All-Organic Low-Temperature Molecular Layer Deposition on Particle Substrates
Session Notes:
PRESENTER
Tyler J Myers, BS
4th year PhD student at the University of Colorado Boulder
LINKS
0:00:01 everybody thank you for tuning in today and thank you for June and for hosting this first ever p a. 0:00:06 L. D Summit and indulging us all over hang out at home and missing some of those typically well 0:00:11 attended meetings. It's great to see how many people are registered for this summit. This is 0:00:17 wonderful. I'm excited to have the opportunity today to speak with you about molecular deposition on 0:00:22 particles. So we're taking a little bit of a different direction from many of the ale. The talks 0:00:26 that are included today I'm only can be quite challenging due to precursor Chiotis using typical 0:00:32 well vapor pressure, organic precursors becomes even more challenging. And we start to implement 0:00:36 this into a high surface area system like with particles. And we even have something to do this at 0:00:41 low temperatures as well so that it could be implemented into some industry like pharmaceuticals, 0:00:47 where you may be too cosom, thermally sensitive powder. So taking all that into consideration, we're 0:00:52 gonna be discussing considerations for reactor design today to do just this type of process 0:00:58 discussed the characterization of an MLT system that we decided in a matter particles and then also 0:01:03 a brief in yet on using Amel Dakota Street drug delivery applications. So what is not your layer 0:01:11 deposition? If you are familiar with a healthy, this should be pretty intuitive. It's essentially an 0:01:16 analogous process. Toe L. D. Instead of depositing atomic layers were gonna be positive molecular 0:01:22 fragments in this case. So it's still the same process where we use sequential self limiting surface 0:01:27 reactions to create these materials on on the substrate. Good stuff we're doing on Nana media level 0:01:34 control instead of ancient level control. In this case, so referencing this figure here essentially 0:01:39 the same process start out with the surface bringing precursor A because a reacts with all of the 0:01:45 surface sites that are there. And still they are all saturated and precursor A can no longer reactor 0:01:50 the surface. That's a self limiting nature that we all know what above bringing figures would be 0:01:55 that reacts with all surface size that were then generated from dozing precursor a reaction. All of 0:02:00 those And now we have regenerated that original surface we have deposited wanna molecular layer of a 0:02:05 material. 0:02:08 So I mentioned that there our considerations to think about when you are doing a multi. So we 0:02:14 designed a reactor just for doing low temperature, whole organic and multi. I'm particles took a lot 0:02:20 of things into and dip layered to make this design work for us. So the first consideration that we 0:02:26 looked at was condensation of vapour pressure again and precursors. It's very easy for these a 0:02:32 condense and say cold spots in the reactor. In the past, we have had lots of issues with these 0:02:37 organic producers convincing years of cold spots or areas of low conducted its. So the first facet 0:02:45 of the reactor is the entire reactor, and all of its components are how is then a nice with thermal 0:02:50 enclosure. So this is essentially just a fiberglass of it. Holds all of the reactor components, 0:02:55 gives all the same dump here to eliminate the possibility of conversation. Do cold spots. In 0:03:02 addition to this, there are holes in the base plate so that we can plumb in inorganic precursors if 0:03:07 we really needed to, or crackers have much higher vapour pressures. 0:03:16 Second consideration is well precursor conducted since the chamber. We do wanna be utilizing these 0:03:21 precursors as efficiently as possible, so in order to achieve that we have very straight direct 0:03:27 precursor dozing lines right into the chamber. And the chamber is relatively low volume. What you 0:03:34 will you see in the some of the schematics that are that are included a way to run. Now, this 0:03:39 chamber, when I say relatively will buy you, means that we do. We have a little bit of space open 0:03:44 for scale up if if that is something that is necessary for any process that we are doing In addition, 0:03:50 these lines don't have any elbows in them. So we don't have any areas where we're going to limit 0:03:54 that conduct. INTs and each of the precursor lands do have their own perfect and evacuation 0:03:58 mechanisms between the pneumatic valves to help combat this as well. 0:04:05 And the final considerations that we are doing this on particles. So we do need some way to agitate 0:04:10 his particles somewhere to disrupt it and continue to expose the surfaces while the precursors are 0:04:16 dosed into the chamber. Now, the way that we do this, this is a rotary reactor. So what we have is a 0:04:22 magnetic feed through that is in vacuum. Which attach is to a cylinder and the chamber on the 0:04:28 cylinder houses. All of the particles that we're using for the experiments and the future is rotated 0:04:34 by a set of magnets. So as that feeder rotates and rotates canister that is holding all of the 0:04:39 powders, essentially disrupting the powders and agitating them so that we can have, we can have the 0:04:46 surface is continually exposed to the precursors. 0:04:52 So taking old cast some schematics. Here on the left side, you'll see a from a bird's eye view top 0:04:57 view of the reactor, and on the right, there is a cross section on the left schematic. You can see 0:05:02 the very direct precursor lines. They go straight into the chamber, and they are straight lines next 0:05:07 to the bear times of the left. There is a port for a considerable thermal couple probes, so that's 0:05:12 gonna sit right near the canister so that we can check the temperature. Be very accurate. Make sure 0:05:17 that we are at actualized with thermal temperature compared to the other. You will see gay valve to 0:05:23 isolate from the pump and those kind of cylinders in the back and century. On the top of this 0:05:30 schematic. Those are the magnets that are gonna turn. Turn the few through that is inside the vacuum, 0:05:36 and if you look over on the cross section, you can actually see the feed through. This is the 0:05:41 straight kind of shaft that goes into the chamber and attaches to that canister inside that chamber. 0:05:46 That's where all of the powder is going to be. House. You may also also see a small VCR port just 0:05:53 above where the shaft of the feet through is. This is gonna be for a conducting limited evacuation 0:05:59 line so we don't disrupt the powder essentially, during the initial vacuum come down. You may also 0:06:07 notice that the reactor is on an angle, so it's tilted up at a seven degree angle. This is kind of 0:06:13 the magic angle that was experimentally figured out. In this case, we're using an open ended 0:06:18 canister to house the powders. Many of our rotary system before used a porous canister. Since we are 0:06:24 using sticky will, vapor pressure, organic precursors, we decided the best to go with the open ended 0:06:30 so we don't clock up those pores. So the seven degree angle helps keep powder inside the canister 0:06:35 without having all just sit in the back and not continue to be agitated throughout the process 0:06:43 for additional agitation. We did design this powder scraper. We were having some issues with powder 0:06:49 sticking to the wall of cancer. Whether do the static electricity or that was due to the M. O. D. 0:06:54 Chemistry and gluing It's the wall. So this product scraper attaches to the front conflict of the 0:07:00 reactor and sits right inside the canister, the tip right at the top, so very close to the top. So 0:07:06 as the cancer is rotating around, the scraper is going to catch any of the powder that was stuck to 0:07:11 the wall and not get back off. So just a additional conditional mechanism of agitation. And here 0:07:18 we're showing you the actual s of their own closure on the left is the oven closed? So this is what 0:07:23 it's gonna look like when the reaction I was actually happening on the right is the reactor inside 0:07:29 the enclosure with the enclosure open, just to show you how the reactor is sits inside of the other. 0:07:37 So now let's move on to the actual chemistry that we decided to demonstrate here, and the system 0:07:42 that we decided to to go after is an organic polly and MLD system. So here we're gonna be using a 0:07:48 deep local ride and ethylene di amine to create the so called nylon six to polymer. Now, this may 0:07:55 look familiar to you. If you're familiar with MLD, the nylon 66 power for the typical nylon that 0:08:01 people think of has been deposited in the past. We figured because of that, this would be a good 0:08:06 system to try and demonstrate and establish a baseline for particles. We know the pallium it's gonna 0:08:11 be done. We know they have favorable thermodynamics, and these two producers have relatively high 0:08:17 vapor pressure in those. Well, so I was just a good but we thought easy system to try and implement 0:08:23 into particles substrates. 0:08:28 So since we are dealing with molecular fragments here and not atomic layers, the growth mechanism is 0:08:32 gonna proceed just a little bit differently. So on the left here, I'm showing you ask 67 degrees 0:08:37 Celsius. What? The growth of the poly and it looks like so over a number of some of these cycles, we 0:08:43 get about a four ancient per cycle growth rate for the center of the system. Now you're wondering. 0:08:48 OK, that seems a little low on the right figure here. This is one ideal model air. Would it look 0:08:55 like if we were depositing a polymer? We would expect to just go straight up, kind of like a forest 0:08:59 of Palmer. And in that case, the ideal model later would be around 18 extremes. So if we're 0:09:05 depositing straight one on top of each other and continue to grow straight up, we should, in theory, 0:09:10 get 18 ancient per cycle of growth. Three. However, we don't see that 0:09:17 because the polymer is going straight up initially. Eventually, it's going to collapse under its own 0:09:22 weight. We're gonna have bond rotation, and we're going to end up with something that looks like 0:09:27 what we see on the bottom right of the slide here. This man ideal amount aware, so resembles more of 0:09:32 a plate of spaghetti than it does a forest of of polymer. And that's what's going to end up, 0:09:38 resulting in this some on a layer growth. 0:09:43 Even so, we can look at different temperatures here, and even with that interesting growth mechanism, 0:09:49 we do still get when you're growth rate over a range of temperatures. So here we're showing two 0:09:53 different curves on. This was done on Sacconi, um, dioxide witness wafers and then submitted for ex 0:09:58 situ analysis with extra reflectivity and spectroscopic ellipse summitry I'm over showing. Here are 0:10:04 a few different growth rates and different temperatures. The green curve is the same that I showed 0:10:10 in the last lead. So that's that for ancient percent growth, three as 67 degrees Celsius and I'm 0:10:15 also showing to other temperatures here as well. This is a temperature above and below that 67 0:10:21 degrees Celsius. So above 50 67 we have occurred in the red, which is 90 degree Celsius. We get 0:10:26 about 1.3 ancient per second growth rate and below 67. We use 57 degrees Celsius and we get about 0:10:33 1.6 ancient percent growth rate. That's his blue curve here. Now it's interesting to see that both 0:10:38 above and below that 67 degrees Celsius we see a decrease growth rate. 0:10:46 Looking at the data just a little bit differently, we can see some very interesting temperature 0:10:50 dependence on the throw three here so again that for ancient per second growth rate is seen at 67 0:10:55 degrees Celsius, which is a peak in this curve here. But if you go above or below that temperature, 0:11:01 you get a decrease growth rate. Now. This isn't so surprising for the higher temperatures. Many m of 0:11:07 these systems in the past of demonstrated that higher temperatures will result in a lower growth 0:11:13 rate, and this is due to the short residents. Time of the precursors on the surface is not enough 0:11:19 time for the reaction to proceed before Diz Orbs that many haven't with that the the weather 0:11:25 temperatures. And in this case we do see a D whose birth rate that we're attributing Teoh not quite 0:11:31 reaching the thermal activation barrier needed for the reaction. Proceed, We did attempt to do some 0:11:38 experimental both if you degrees Celsius. We had a negligible growth. Didn't really see anything 0:11:44 happen here. Another interesting thing that look as that the decrease seems to go more rapidly on 0:11:50 the lower side of the temperatures and it does on the fest are on the higher side. Excuse me, 0:11:57 suggesting that maybe the thermal activation barrier plays more of a role in this from the system 0:12:03 that a residence time does that case, which is very interesting to see these trade offs those we 0:12:08 start to see maybe an MLT window opening up here and you get these trade offs here that you are 0:12:15 using low vapor pressure precursors. So maybe a higher temperature would help you out in terms of 0:12:21 getting vapor pressure in terms of better purging. But you're going to sacrifice your growth rate 0:12:25 for that higher temperature and those better vapor pressures. 0:12:30 Now, of course, we have good growth we have when you're growth. You wanted to make sure that we're 0:12:34 actually depositing the correct composition and the right polymer that would be hoping to hear. 0:12:39 We're looking at an XPS survey scan of a zirconium dioxide witness. Wait for that. We deposited and 0:12:45 I won 6 to 1, referencing the polymer down in the right hand corner. Here. What would be expected to 0:12:52 see in this XPS is oxygen, carbon and nitrogen. And that is exactly what we see in the SPS. Very 0:12:58 large signals from those three elements are interestingly, we do see a small P for Korean as well, 0:13:06 popping over to the table and working out the expected at Howard Percentages there relatively close 0:13:11 to view, looking at 16.7% for both oxygen and nitrogen, 66.7% for carbon. And of course, if this 0:13:19 proceeded in a perfect fashion, we wouldn't have any Korean in the film at all for a little bit on 0:13:24 the low one for the oxygen and nitrogen and a little bit on the high end for the carbon. We are 0:13:29 attributing that increased amount of carbon to add petitions. Carbon. This wasn't ex situ analysis, 0:13:35 so the sample did have to be transferred from the MLB reactor over to the XPS. There are a couple 0:13:44 reasons why there might be Korean in the film. First of all, we are operating in a static dose 0:13:50 regime here. So the precursors are sitting in a chair for quite a long time, and it has been shown 0:13:56 that there can be diffusion of precursors into these polymer films. So what likely happens is we 0:14:02 don't send a typical chloride into the into the chamber, sits in the chamber for some predetermined 0:14:08 amount of time, cut off from the vacuum, and we have some dual core I'm diffusing into the MLD film 0:14:15 now sufficient purging may end up, may end up taking out all of the diffused precursor, but that 0:14:24 would be pretty difficult to get all of it out in the end. Another reason we might have Korean in 0:14:29 the film is we are operating and stuff on away or growth here. It's possible that some of the 0:14:35 polymer chains are not totally reacting 100% so it might have some chains in the film that are 0:14:41 terminated after in difficult chloride does, which would mean the end of the polymer chain is a 0:14:46 Korean it corn. From that and then also with the nylon 66 works show that there could be possible 0:14:52 core insults that are incorporating to the film as well. So a lot of reasons why there might be some 0:14:57 Korean in the film. Thankfully, it is relatively low in this case, only at about 1.3 percent. So the 0:15:04 XPS was the end of the characterization witness wafers and our moving to characterization on powder. 0:15:09 How the first we did here was FBI are at the end of the end. Zirconium dioxide, you know, powder, 0:15:14 the Emily was quoted on the powder and the president to Thompson grid and put it into through the IR 0:15:19 instrument we're looking for is a few different functional groups. Here I have those color 0:15:24 coordinated from the reference polymer on the left and then where they correspond to in the actual 0:15:29 FT Iris scans. So it would be looking for are the carbon hydrogen, the Amit and then the nitrogen 0:15:35 hydrogen as well Taking a look at the highway of number region Here we do see the nitrogen hydrogen 0:15:41 stretch coming in at just under 3300. So at 30 to 90 wave numbers now we do see the carbon hydrogen 0:15:48 stretch coming and just below 3000 way of numbers as well. So good to see those moving down to the 0:15:54 low way of number of region. We do see a number of modes that correspond to the to the Amit 0:15:59 functional group. So the amad carbon double bond action stretch and then the carbon oxygen, nitrogen, 0:16:07 hydrogen bending road as well as a sanity check. We didn't make sure that these were the same 0:16:11 functional groups and same wave numbers that we saw in the nylon 66 work, and they are so way were 0:16:19 pretty happy to see that those were those were consistent with each other. Find a little bit of 0:16:25 characterization of the film in Terms of Composition is a TDs map here of the MLT film coated on and 0:16:32 organic substrate. This organic strip straight was first coated with a lady aluminum oxide, and we 0:16:39 do see very clear layers of the polymer of the aluminum oxide and of the substrate from that 0:16:45 aluminum where is very nice and showing the separation between the two and you can see where the 0:16:49 polyamory film is due to the very clear nitrogen and Corrine signals in this case as well. Again, we 0:16:57 do see, according to the film. But the atomic percentages that were backed out with with this 0:17:01 experiment showed only 0.8% according so, you know, lower than the XPS. But it's nice to see that 0:17:07 the composition as deposited on a powder, is the same composition and consistent with the XPS survey 0:17:12 scan. So now, moving on to actual images of the Kennedy family wanted to make sure that the growth 0:17:19 on the on the particles was consistent as well with what we saw in the witness waivers. So here I'm 0:17:26 showing the TM of the M L D on a zirconium dioxide nanoparticles. Glamorous. So this was 60 cycles 0:17:32 of MLD performed at 67 degrees Celsius. Now, if we take that original growth rate of four ancients 0:17:38 per cycle that we saw a 67 degree Celsius on the witness wafer, we would be expecting around 24 0:17:44 Manny meters of M o d film in this case. And that is exactly what we see here. Maybe a little bit 0:17:50 more on the edges, but the outer edges so very confortable in smooth film where they thickness, 0:17:56 that's consistent. Without four action per second birthday, we would hope to see a 67 degrees 0:17:59 Celsius. Now we do see a thicker film and some areas of low conduct ins. As you can see where kind 0:18:07 of the glamorous are coming together, there's a much thicker film there That's unsurprising, I think, 0:18:14 and sufficient purging high temperatures could likely combat that at the end and a sacrifice for 0:18:20 growth rate and first cycle time as well. But this would suggest that maybe and all are gonna gamble. 0:18:25 These system isn't the best for doing Cody's in high aspect ratios, which I don't think anybody 0:18:31 would be would be telling you to do that at this time. Anyway. We also find that there's consistency 0:18:39 in the control over a number of cycles. In this case, I'm showing 10 psychos, 30 cycles and 60 0:18:45 cycles again, all the positive at a 67 degrees Celsius. So taking that same for ancient procreate, 0:18:51 you would expect we'd be looking for foreign anti meters for 10 cycles 12 90 million films for 30 0:18:57 cycles and then 24 90 meter films for the 60 cycles. That is exactly what we see here on the very 0:19:02 first figure figure. A. We do see about four nanometers around the outside of these nanoparticles. 0:19:08 Very nice and weaken formal film. It looks really nice moving over to day 30 cycles. Again, we do 0:19:14 seek about 12 millimeters, which is what we would expect, and then seeing the 60 cycles is the same 0:19:20 image that I showed in the previous slide. Here. We do get that 24 manu meter per cycle growth three 0:19:25 here. So not only can we do this Emily system on powders, but we do have, and though the control 0:19:30 over the thicknesses and get to quite substantial thicknesses of this Palmer as well. 0:19:37 So, in an attempt to get around some of the agglomeration issues that we're having with the 0:19:41 nanoparticles, we decided to attempt this on some larger powder. So here we're doing the empathy on 0:19:46 a cellulose polymer. Micro powder thes are quite large particles on the hundreds of micron size. We 0:19:53 did the same 60 cycles as 67 degrees Celsius, hoping to see a 24 90 meter film with that for action 0:20:00 percent growth. Three and again that is will receive. Here is a 24 90 meter film around the outer 0:20:06 edges of these particles conform all coating that agrees with the witness way for measurements. And 0:20:11 what's really exciting is that we're showing consider CIA both across size and composition of 0:20:17 substrate that we're trying to do this and all the system on. So we're not showing any were nuclear 0:20:22 a Shinto ways or something like that, from going from an inorganic to an organic powder final 0:20:28 particle substrate that we decided to test this system on is a Matt Foreman powder, and this is an 0:20:34 anticipation of moving towards some industry application, particularly the pharmaceutical industry. 0:20:39 So if you're familiar, metformin is an aural diabetes medication. And we essentially thought that if 0:20:44 we could coat this system onto an actual active pharmaceutical ingredient, this could pave the way 0:20:50 for MLD actually being used for for something like a drug delivery coating. So we did again the same 0:20:57 60 cycle of amoled, the A 67 degree Celsius. And I'm sure you caught on. By now, we would be looking 0:21:02 for a 24 Nana meter film on these powders. And again, this is what we see you. We see about 24 90 0:21:10 meter film fairly smoothly conform on the outside of these particles. So not only do we have the 0:21:16 ability to coat inorganic particles polymer particles, but we can also call molecular solids with 0:21:23 this MLD system as well. And I think this is very exciting to not only be able to do the M of these 0:21:29 systems are a pharmaceutical powder, but to also demonstrate that system at a low temperature, which 0:21:35 may let us do these types of coatings on third with sensitive powders as well. 0:21:41 Now, the reason that we would want to use MLT on these types of pharmaceutical powders is for an 0:21:48 application and, say, drug delivery. So there are plenty of Palmer's that have been used for drug 0:21:54 delivery applications for many decades. Now, at this point on, there are a ton of sophisticated, 0:21:59 sophisticated systems that are used for direct delivery as well. There's not enough time to go 0:22:04 through every single type. I will only briefly talk about these two here and really only spend a 0:22:11 good amount of time on the U. F. One the time release. So there two types that I discuss the time 0:22:16 release on the left is to kind of eliminate the having to dose over and over again, a meditation so 0:22:24 typically taken medication. You have an increase in the concentration of the drug in your 0:22:28 bloodstream that passes out, you take another dose and you get this a Silla torrey fashion of 0:22:33 concentration of the drug in your body. Instead, we can have a time release system where the system 0:22:40 keeps a control. Standard amount of concentration in the blood had a particular for a particular 0:22:47 amount of time, and that way you don't have to continue taking medication over and over again at the 0:22:51 touch of systems are typical used for these time release methods are either a monolithic polymer 0:22:57 drug system, meaning that the polymer coating and the drug are homologous in this case. So as the 0:23:04 Palmer is dissolving, it is also dissolving the drug into the bloodstream as well. Now the other way 0:23:10 is to have just a simple polymer coating, and this is going to be a diffusion based mechanism where 0:23:15 the a. P I is diffusing through the film at a particular rate that's determined by the thickness of 0:23:20 that coating. Now the other interesting applications with stimuli responsive films. These are 0:23:28 typically more complex films as well. So we're looking at hydrogel is my cells, maybe some Marasco 0:23:33 polymers and crosslink networks as well, and you can imagine all different kinds of environmental 0:23:39 stimuli that could change the morphology of these of these methods. So something like a pH change 0:23:46 going from, say, stomach to intestines, a temperature change, maybe ultrasonic or electromagnetic 0:23:52 stimulus as well. You can imagine a my cell hitting some difference to be a lie. It's morphology 0:23:59 flipping around and really see the drug that way. But due to the actual current state of MLD, I 0:24:07 think the best way to look at is the time release applications. So these more simple polymer 0:24:14 coatings he's more monolithic polymer drug type type methods and one in particular I would like to 0:24:22 discuss is this reservoir methods. So this is essentially the simple polymer coating that I 0:24:27 mentioned before. So you essentially have a pharmaceutical ingredient and you have an MLB film. That 0:24:33 is, it's coating on the outside of this AP I. So as time goes on the AP, eyes going to diffuse 0:24:41 through the MLT film into the blood stream has some controlled rate that's based on the film 0:24:47 thickness. So as time goes on and concentration of the AP, I inside the film is going to decrease as 0:24:54 it's released into the body, but that this would be controlled by the MLB thickness. So if we're 0:25:03 looking at what the expected release profiles, but it looked like we'd be looking at something that 0:25:07 should look like the figure on the right here. So we would imagine that a thicker MLD film would 0:25:13 result in a slower drug release because we have a larger distance for the A P I to diffuse to 0:25:20 actually get to the bloodstream. So looking at these three red curves, the top curve so the fastest 0:25:25 regulars would be your fin ist MLD film and the bottom curve where you have the slowest virtually so 0:25:33 that would be your thickest motu film. So you increase the thickness of the MLT film, you would have 0:25:38 a much markedly slower, really something drug. Now this is corroborated with some literature already. 0:25:46 So there's a nice our journal article and come communications by the only group in the Netherlands 0:25:51 where they use an ability system to coach some protein powder in this case, and then look at the 0:25:56 control were released of that protein into a solution. And as you can see, just as that, those 0:26:04 figures suggest in the previous slide here that a thicker MLD film will give you a solo release of 0:26:11 whatever family film is coating. So, looking at this figure here, the red dots are going to be a 0:26:17 bear protein in this case, and then you go from two cycles to six cycles to 10 cycles of penalty on 0:26:24 the protein powder. The two psychos of any of these shows the fastest release other than Bebear 0:26:30 protein and then as you increase the thickness, increased the number of cycles of the MLD. You do 0:26:35 get a slow release of the protein into solution. So this does corroborate that there is quite a bit 0:26:42 of potential for using about the to control drug release profiles. We are working on some some 0:26:48 testing of our films as well to get some figures and curbs that look like this. So we're very 0:26:53 excited to to see what those what those released profiles they're going to look like in the end, 0:27:01 just a sum everything up first. I believe that reactor's design is quite important for doing such 0:27:07 English application for something that is is difficult to do as a low temperature MLD on part of 0:27:14 those substrates. So there a lot of considerations taken place when you're working with a process is 0:27:19 very fickle, and making sure equipment can do it is I was going Teoh Onley benefit you in the end. 0:27:26 The second is we're able to deposit films with expected compositions using this low temperature. I 0:27:32 saw thermo approach, so we're getting the right composition of Palmer and we are getting good growth 0:27:37 rate as well. Third weekend do control deposition of an MLT film on particles. So we showed. And not 0:27:45 only can we do out over a very number of cycles, but we can also show control and consistency of the 0:27:51 system over a various number of sizes of particles and composition of particles as well. And then 0:27:57 finally, we believe that this could have applications in the pharmaceutical industry. There is a 0:28:02 literature showing that Ahmadi can do some extended release of a P I. We're hoping that our films 0:28:08 may show something similar when we are done testing them as well. So with that, I'd like to thank 0:28:14 everybody for listening. I hope I was able to get everybody's questions in the Q and A. Please feel 0:28:19 free to email me or Professor George with any other questions that you might have about this project 0:28:25 and enjoy the remain of the summit. Thank you