Horizontal high temperature rotating graphite drum furnace for ALD and LPCVD on particles and powders 

Session Notes:

PRESENTER

Jonas Sundqvist Ph.D.

BALD Engineering 

LINKS

http://www.blog.baldengineering.com 


ABSTRACT

Conformal ALD and CVD on particles have been demonstrated numerous times using different technologies. ALD that in most cases have superior conformal properties as compared to PVD and CVD has been realized, for instance, using the following reactor technologies:  

  • Fluidized bed  
  • Rotating drum  
  • Vibrating belt  
  • Tubular reactors  

At Fraunhofer IKTS Thin Film Group, an existing R&D LPCVD/ALD high-temperature Furnace platform has been equipped with a rotating particle processing drum. The modular high temperature rotating graphite drum furnace can be operated in LPCVD and ALD mode, i.e., continuous co-injections of precursors or time-resolved pulsing in ALD mode for conformal coating of particles and powders.  

The furnace is designed for developing functional thin films, especially protective coatings and diffusion barrier for hard metal powders such as tungsten carbide (WC), cubic boron nitride (c-BN) that is widely used as an abrasive material and LiNi0,5Mn1,5O4 (LNMO) powder used in lithium ion battery cathode materials for operation at higher voltage (4.7 V).  

The rotating drum has been manufactured in graphite allowing high temperature operation up to the maximum of 1050°C that the outer Inconel furnace with quartz insert can operate at. The ALD/LPCVD furnace have been qualified for two basic processes that are interesting for the applications mentioned above:  

Process 1 : Titanium nitride (TiN) using TiCl4 and NH3 as precursors. This process is well known and understood for as well thermally activated ALD >300 °C and thermal CVD and pulsed CVD >400°C  

Process 2 : Aluminium oxide (Al2O3) using either TMA or in-situ generated AlCl3 and water as precursors. AlCl3 can preferably be used in CVD process mode up to the maximum furnace temperatures whereas, TMA is employed for low temperature ALD in the range of 80 to 400 °C .  

Results from the two processes will be presented, showing basic process window characteristics as well as elemental analysis and particle cross-section analysis. 

0:00:01   Hello Jonas Sundqvist from dressed in Germany. So I'm here today to talk about the
0:00:08   particular alien city on hard metals on some other powders. Um, this work I've done during my time
0:00:19   in frowned over. So since about two months now, I'm independent consultant. Full time for bold
0:00:26   engineering Swedish company. So this is joint presentation with my former colleagues that brown over
0:00:35   i Q tests in Dressed on more recruit Monday. Turn on the the new pitch. Did your Aunt Marco rodders
0:00:44   get started?
0:00:47   So we have been developed Alien city process on Thanks, Tyne car, but it on cubic boron nitride for
0:00:56   a while now. So the gold with this process is Teoh Increase the hardness off the scented product
0:01:05   that you do out of the powders The powder ihsaa wide range off hard materials like if you have here
0:01:14   single crystalline diamond poorly crystalline diamond on different types of hot metal based on
0:01:24   either tungsten carbide Cubic boron nitrites As you noticed this whole graphics and German But it's
0:01:32   sort of universal language in this business. Um, on what you do there, it put in cobalt Ah,
0:01:44   promoter Teoh before the centering process to act as, ah, glue between the grains that stick
0:01:54   together on. But we are trying to control this process and more data. And there's old range of other
0:02:03   ah additives like you can do a Coleman based core bite. Stanton Khobar. Nobody called but titanium
0:02:11   carbide. So it's like a secret brew that the company's developed over the years and put in there to
0:02:17   go along this car here. So a minimum increased the rupture strength on the hardness, the perfect
0:02:27   situation. Would they like always to be a a pair and the impossible corner where everything is good,
0:02:33   but you don't reach that if you look at the structures are here. So on the left side is the single
0:02:40   crystalline material. So in this case, it's war tanks and Corbett on. On the right side is a poorly
0:02:46   crystalline thanks in Korbut, and that's what they're developing. So we want to coat the individual
0:02:53   grains hair with the titanium nitride, uh, activity or indeed, process to create Soviet. What we do
0:03:03   is that they changed wetting function off the times ago, but surface on this is beneficial for the
0:03:11   cobalt when you do is entering process. Andi that increase this done? It has two functions. It
0:03:20   reduces the risk of getting Kubu diffusing into the tax and Corbett, which reduces the hardness of
0:03:25   the core but on also improves the wedding. Off the surface,
0:03:31   you hear same graph. But now to confuse Teoh a switch. So we Hanauer hardness down here on fracture
0:03:39   toughness or as the y axis on. Yeah, we want to go here. You want to be harder, faster, make a
0:03:47   tougher material because this then eventually we're gonna be shaped into three D form and used for
0:03:55   cutting tools to cut steel and aluminum And are the metal operating them at high temperature? Um, on
0:04:05   the harder material, this doesn't have low rapture strengthen. The longer you can use this tool bit
0:04:13   on, if you can use it for long. Your aunt out of this pit that often on, then you're can run more
0:04:19   productive and yours save, of course, money. Because this tool which cost a lot of money over time
0:04:26   So So some people, they were just on the hard metal and try to improve that Andi yours. You have a
0:04:34   coating on top of that which we also do with a lady So what? It's a whole different field s. So now
0:04:42   we're optimizing the only city process for the powder. So you have to think this is big business, so
0:04:49   I don't know exactly, but its metric tones off tungsten carbide powder every year that is used for
0:04:57   this on it all. If this would go into production, it wouldn't all have to be coated by Save 80 or a
0:05:05   lady. So I guess you're all hoping enough for a day. Of course, that's it. Here's one example is
0:05:12   cubic boron nitride powder that we have coated the cubic border night. Or those have art
0:05:18   applications? Look, you use it for as a publishing granite that you're done mold into polishing
0:05:27   discs on such things. So they're also co today. This doesn examples Beautiful 10. I tried coating on
0:05:34   one of those grains on Iran. Used a hair sample size up 200 grams. So this is enough to do centering
0:05:42   tests on a lot of custom requests in this size of the movement because you know, are in data pick.
0:05:50   It's not any pilot. Production was so hard underground, miss. Definitely enough. Ah! So before
0:05:59   setting this up, there was all types of considerations. What type of shame? The technology to use.
0:06:05   So I think you're well aware off the main types of you know, the good old fluid. I bet that has been
0:06:12   used for quite a long time for particle ale de on a rotating drum. So they decided to use a rotating
0:06:21   drum. I will explain more data. Why House Integrated on There's other technologies, like if you want
0:06:27   to scale up and go to metric tones done, maybe want tohave road or vibrating belt type of wrecked or
0:06:36   or or spatial type of fluids. That director or something like that. But the route rotating promise
0:06:43   very versatile, and it can be easily integrated in stand out l Piscitelli foreigners in different us.
0:06:50   This is what we did. So we have normally this horizontal Haledon festivity, foreign US three stone
0:06:56   fullness. You can stick in
0:07:00   anything you like. We have different models like there are roll to roll wire modules. They have this
0:07:06   rotating drum that was your next light on. We can go up to 2050 degrees so that the Incan Elwood to
0:07:15   Well, if we go above that to the internal out, Director and and it's ah, courts insert, which is
0:07:21   easier than when you spoke between process different materials. You can just remove the insult and
0:07:26   clean it and go to next powder or two bit coating. Experiment so this furnace can run in a lady and
0:07:35   70 mode and has a lot of big ah cocktail bar here behind with different precursors along the typical
0:07:45   ones on also a lot of activity gases that you need forward so opposes pressure separate one millibar
0:07:54   up to one bore waken do atmospheric for carbon nanotubes. Temperature 52,050 51 day model If it
0:08:02   around that we can run up to tuna millimeter per minute on, ESA said, all the powder up 200 grand
0:08:08   goes into a drum they used. Typically, we do a lot of time. I tried aluminum oxide, Thai aluminum,
0:08:16   Nightline, stuff like this. They use either tick lt May or instated gent generated aluminum, three
0:08:23   chlorate and water. If the oxides are the ones who have doubted correct aunts like ammonia itself
0:08:30   hydrant, Hold on, Notre on. We can also didn't see to generate basically any metal chloride, which
0:08:38   is volatile enough. So happening. Karadzic on um, chloride texting core. It can all be made
0:08:43   insensitive. So we just have metal ships on Run it through special furnace on the inside to generate
0:08:50   those free courses. Um so rotating Trump's So it's mounted on the chef. You can see here it's a
0:08:59   rotating shaft. It wrote us a different speeds on. On the end of this, we have a graphic trump,
0:09:06   which began council for a change to design off. This is where we placed the powder and they sold.
0:09:11   Sharpton is stuck into the horizontal honest and sailed with Caldas soaring so we can also look at
0:09:19   the Globe books hair so they do Some bacteria probably research castle material and stuff the
0:09:27   biggest corporate materials you can use, I note of Mr On Load it and unload. And there's also had
0:09:34   applications, powder applications. We do video ultraviolet lightning powder, some, uh, this wide
0:09:45   range off applications. So the lost three years. So we get many customer request on this too. So
0:09:53   first there could get the first results video station or activity test. So we just loaded up
0:09:59   tungsten carbide in ceramic boats on used to our old small other civilly furnace for these tests,
0:10:06   and one this post our process, experts said, was the process for the best con formalities. Very,
0:10:16   really wanted to do a test there. Do we need to go through the hassle of having held a protest?
0:10:22   There can be diversity process. So this waas what she said under here that that's morbid. Best
0:10:29   compromisers. A ticket based instead of you getting ammonia, they use high during the night trim
0:10:33   mixture of nine out of 50 degrees C and it's horizontal foreigners on. They run that for, uh, hoping
0:10:41   our so And they got
0:10:45   very decent. It's quite nice. Conformance is their life. Um uh, coating around the darker tungsten
0:10:54   carbide grains. Andi So what he could say. Sometimes you have sort of a shadowing effect. So you
0:11:02   have here senior coating on one side and then a sick of coating on the other side. So it's not
0:11:09   perfectly confirm. Er conformers Oh, yeah, for sure. We need to try out a day instead. We want to do
0:11:16   it. Perfect. So that's where we're done, loaded up in the drum. So you see this drum? This has now
0:11:23   you say it has sort of bronze color because we coated it so many times with tonight, right on the
0:11:30   powder fall. So this rotating czar, unfortunately, a roast and wrong direction is roses in the other
0:11:36   direction, of course. So So you say it creates sort of a waterfall here on one side to the powder
0:11:42   falls from the top down on Demi posts Bail the interest tickle, parch. I'm on our porch, Onda.
0:11:55   Originally they had open here in the back, but they have covered that with nickel foil. No, because
0:12:01   we lost too much powder out this way. So they now actually pals into the chamber. And then we suck
0:12:08   out the guests on policy in chamber cycle together. It's not really optimum, so we have some
0:12:14   filtering ideas here to optimize it for so what am I? But this foiled have sort of 75% deal, so of a
0:12:23   loose 25% of the powder, it's going in the general direction off the pump. Um, if you want there, I
0:12:33   can email you the original presentation than you can click here. There's direct links and embedded
0:12:39   movies off different rotating tests so you can see this waterfall nicely being formed. But I dont
0:12:45   show it now because it's typically fails when you click it. So first test second test on day it and
0:12:56   it s so has powder poorly Crystalline fine, grand Thanks, Tyne Korbut Super hard stuff. This has
0:13:05   been coated it the tonight Are they all day, but 29 minute recipe I think there's there are 400
0:13:12   cycles. Want to the greasy? That's Sarah 0.333 on strong for cycle on some incubation cycles. That
0:13:23   should be something like that. Um, on here, low energy, you can see a rod is smooth surface, so they
0:13:34   used low energy in there. Sam, that means we're surface sensitive only look basically at the surface.
0:13:40   Now, we don't see this structure that they expect to say from times and Corbett the individual
0:13:47   thinkers and grains. But if you increase tentative, it then used to the coating sort of disappears.
0:13:53   You see through the coating, and you can see the structure of tanks and Corbett So it looks like
0:13:58   they have Ah, very good. Uh, cover it on. Duh. Um, we were happy with this. Or some. There was a
0:14:10   checked addicts, so you can see here take different points. This is just a rip. Something different
0:14:15   to see. Tanks, Temple, shore, some condemnation. But chlorine here because there's a relatively low
0:14:24   temperatures of the definitely gets imploring left over from 10 chlorate on to Nice to attaining
0:14:30   picks and the big one over here. So we definitely have time tonight. Right here.
0:14:36   Uh, yeah. So that's they have done centering tests. Um, on they are working with industrial partners
0:14:47   on that or testing this, but they are not prepared to disclose any more data test yet. So that's why
0:14:56   they will do that in the future conference. But for now, you're just show here that it works on.
0:15:03   What we will do were this is ongoing test on. We are now discussing scale up to build a bigger part
0:15:09   of machine that go to next level, you know, to be supply every supply up to 10. Kill a powder piston.
0:15:16   Explain on they have also, uh, other program. It's for better materials. So in this case, do it's
0:15:26   nothing fancy. It's what everybody's doing. Aluminum oxide, very thin, conform a layer on the castle
0:15:32   powder material. We don't work anymore with the COBOL based. So they have moved the whole found off
0:15:40   like a test program on this, And batteries has moved ahead on, uh, push. It would do some cobalt,
0:15:48   and I'm saying material, but the main focus is cobalt three. You know, you know, the store about
0:15:54   cobalt, its mind in the Democratic Republic of Congo on the conditions are really crap There on.
0:16:02   This is definitely nothing that you want to be part of if you can, the doctor death and the whole
0:16:07   Kubel chair. But here are supply. Shane is also been suspect, so we have decided to switch
0:16:14   technology or cobalt print. So the future material, it's not really on the market yet. Everybody's
0:16:21   still using cobalt on. Instead, that nickname agonists a little mixed up on What's this? Now they
0:16:31   did. 20 cycles worth 200 seconds will be new. 200 sectors would be definitely would kill the cells,
0:16:38   basically, but were surprised we could measure something on dumb. It's it's in the details. It's
0:16:48   more like engineering. It's not huge improvement, but we think if you look at the slopes and so off
0:16:54   the curbs
0:16:57   special the endpoint capacity. You can clearly see if you have a thick coating. The capacity drops
0:17:02   of course, But if you keep in the thin range so they think reacts, elliptical even seem now they
0:17:09   will be able to have extenders likability on Do not get big capacitors
0:17:19   penalty. So this is all the ongoing working to have. Ah, bigger long term project starting this. But
0:17:25   some industrial consults him in Germany. So I think that's a level seven on This is our process
0:17:33   catalog What we can do on this equipment. So anything you say here on this table can be realized
0:17:40   there has older been realized This machines it's mixed of city and sea. So thank you very much. Andi
0:17:49   was really great to be part of this Onda. I hope my presentation came out in time. I see so 18
0:17:59   minutes some time for questions. Take care, Stay said.