<div dir="ltr">Hello Dr. Diadiuk,<div>at stanford we have worked extensively on PEALD of SiN in the last year, characterizing deposition both on the Fiji systems in the SNF and on a FlexAl in a single PI laboratory. we were particularly interested in low wet etch rate in fluorine chemistries (like HF) and electrical properties such as leakage current and dielectric constant.</div><div><br></div><div>successful deposition was shown to be possible with 3DMAS, BTBAS, DCS (dicholorsilane, which i highly recommend against, reasons below), and TSA (trisilylamine). by far the majority of the work we have done is on 3DMAS, which we have stocked for a long time and are familiar with since we use it for SiO2 deposition as well. there are a couple of papers coming out soon on this work.</div><div><br></div><div>some details about each that may be helpful for you</div><div><b>3DMAS</b> - good recipes established for SiO2 and SiN. most fully characterized precursor from this list. easily obtainable from sigma aldrich and strem and gelleste. price is comparable to other metal amide precursors (TDMA-Hf and TDMA-Ti). etch rate and electrical properties of SiO2 and SiN films are both demonstrably improved over PECVD at the same temperature. GPC ~0.1A/cycle</div><div><br></div><div><b>BTBAS</b> - new precursor to us for this SiN study. not extensively studied, but deposition definitely possible for SiO2 and SiN. GPC ~0.2A/cycle. readily available and reasonably priced from all the typical precursor suppliers</div><div><br></div><div><b>TSA</b> - promising for SiN. we have not looked into SiO2 deposition yet. not extensively explored. GPC ~0.25A/cycle for us, but others have reported even higher (close to 1A/cycle) which we could not reproduce on the FlexAl. low wet etch rate and low leakage currents, similar to what was achieved with 3DMAS. this precursor is pretty hard to stock as we could only source it from air liquid and it look a lot of effort/time/cost to get supply to Stanford. not sure why that is.</div><div><br></div><div><b>DCS</b> - stay away from this. hard to get in a compatible storage cylinder for ALD (much more common to come in large volumes for distribution throughout a facility). dangerous for sure. also, not at all clear that this precursor provides a self limiting surface reaction, so it does not perform ALD so much as CVD. could not achieve etch rate or electrical properties as good as seen with 3dmas and tsa, most likely because of the lack of self-limiting half reactions. since you are already using TiCl4, this may not be as much of a concern, but we've stayed away from chloride chemistries in SNF because of issues with co-deposition in the same chamber with Pt and Ru metals by ALD.</div><div><br></div><div>let me comment further on your specific questions:</div><div><div style="font-size:12.8px"><div><font face="Arial" color="#ff0000"><span style="font-size:12px">Does anyone have any experience w/them & with TDMAT?</span></font></div><div><font face="Arial"><span style="font-size:12px"><br></span></font></div><div><font face="Arial"><span style="font-size:12px">we also have used TDMA-Ti for our Ti precursor since we started ALD work in SNF. we have had great success with TiO2 and TiN deposition with this precursor. as i mentioned above we steered clear of TiCl4 because of HCl by products and compatibility issues since we wanted to deposition Pt and Ru in the same chamber. is it possible this is where the concern you mentioned about TiCl4 with metal amide precursors comes from? similar to the notes from the folks at notre dame, i don't see a safety issue with using these precursors on the same manifold. as an additional datapoint on this, berkeley's nanolab had TiCl4, TMA, and TDMA-Hf all in use on their picosun system.</span></font></div><div><font face="Arial"><span style="font-size:12px"><br></span></font></div><div><font face="Arial" color="#ff0000"><span style="font-size:12px">Any recommendations or suggestions for precursors for SiO2 and SiN?</span></font></div><div><font face="Arial"><span style="font-size:12px"><br></span></font></div><div><font face="Arial"><span style="font-size:12px">see above.</span></font></div><div><font face="Arial"><span style="font-size:12px"><br></span></font></div></div><div style="font-size:12.8px"><font face="Arial" color="#ff0000"><span style="font-size:12px">We'd like to assess all of these precursors and films with respect to:</span></font></div><div style="font-size:12.8px"><font face="Arial" color="#ff0000"><span style="font-size:12px">1) Cost and availability of precursor</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px">addressed above</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div style="font-size:12.8px"><font face="Arial" color="#ff0000"><span style="font-size:12px">2) Robustness of precursor (A precursor that degrades rapidly over time wld not be preferred)</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px">i didn't mention this above, but we never saw any of these decay over time. the only precursor we have stocked for a long time (meaning months to a year) to know for sure that it has good shelf life is 3DMAS. however, TSA at least is chemically stable and requires no heating for introduction into the chamber, so i would surmise it is also stable. </span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px">bonus info: TDMA-Ti is quite stable on the shelf or even heated (we keep it at 75C on the tools), and will last for months.</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div style="font-size:12.8px"><font face="Arial" color="#ff0000"><span style="font-size:12px">3) Quality of film: Electrical data would be nice but even indices of refraction would do</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px">because we have papers coming out soon, i've stopped short of supplying raw data, but gave a general level of results above. indices of refraction for the optimized recipes are on the order of 2.0 at 655nm for 3DMAS and TSA. closer to 1.9 at 655nm for BTBAS, and 1.8 at 655nm for DCS.</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div style="font-size:12.8px"><font face="Arial" color="#ff0000"><span style="font-size:12px">4) Any chemical compatibility issues.</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div><font face="Arial"><span style="font-size:12px">nothing established in this regard. everything looks fine.</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div style="font-size:12.8px"><font face="Arial" color="#ff0000"><span style="font-size:12px">5) Existence of recipes on the Oxford ALD tool at other places. This will reduce the amount of optimization that we will need to do.</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div style="font-size:12.8px"><span style="font-family:Arial;font-size:12px">on our FlexAl</span><font face="Arial"><span style="font-size:12px"><br></span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px">recipes in existence for SiN and SiO2 for 3DMAS. SiN for TSA and BTBAS, and starting points for SiO2.</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px"><br></span></font></div><div><font face="Arial"><span style="font-size:12px">additionally a starting point recipe for SiO2 for BTBAS on a different reactor (Cambridge Nanotech FijI)</span></font></div><div><font face="Arial"><span style="font-size:12px"><br></span></font></div><div><font face="Arial"><span style="font-size:12px">please feel free to contact me if you would like recipe details, and i can be in touch regarding our forthcoming papers related to this topic if you wish.</span></font></div><div><font face="Arial"><span style="font-size:12px"><br></span></font></div><div><font face="Arial"><span style="font-size:12px">i hope this was helpful.</span></font></div><div style="font-size:12.8px"><font face="Arial"><span style="font-size:12px">dr j</span></font></div></div></div><div class="gmail_extra"><br><div class="gmail_quote">On Tue, Oct 13, 2015 at 6:03 AM, Mike Young <span dir="ltr"><<a href="mailto:myoung6@nd.edu" target="_blank">myoung6@nd.edu</a>></span> wrote:<br><blockquote class="gmail_quote" style="margin:0 0 0 .8ex;border-left:1px #ccc solid;padding-left:1ex"><div style="word-wrap:break-word">Hi Vicky. See below for relevant comments from two of my esteemed colleagues, regarding our FlexAL and its sources.<div><br></div><div>--Mike<br><div><br><blockquote type="cite"><div>Begin forwarded message:</div><br><div style="margin-top:0px;margin-right:0px;margin-bottom:0px;margin-left:0px"><span style="font-family:-webkit-system-font,Helvetica Neue,Helvetica,sans-serif;color:rgba(0,0,0,1.0)"><b>From: </b></span><span style="font-family:-webkit-system-font,Helvetica Neue,Helvetica,sans-serif">Mark Richmond <<a href="mailto:Mark.M.Richmond.7@nd.edu" target="_blank">Mark.M.Richmond.7@nd.edu</a>><br></span></div><div style="margin-top:0px;margin-right:0px;margin-bottom:0px;margin-left:0px"><br></div><br><div><div dir="ltr">Mike,<div> I was never informed of any manifold compatibility issues of precursors by Oxford, and Dr. Xing didn't have any objections to that either. I found that odd but the system is under vacuum and is purged well before and after recipes are executed. As you can see from Dave's screen capture we have had this setup for the last few years, although we do not perform many Titanium growths. </div><div><br></div><div> As for the SiO2 and SiN we use BDEAS in our recipes, Nitride growth is very slow though. We never purchased a BTBAS source but we did have a 3DMAS source. The 3DMAS source was used up in attempting to characterize the material and we never had a good material growth so we have not replaced that material. It used to be in the empty spot that is now on the machine.</div><div><br></div><div> Vicky should be able to contact Oxford for their information sheets on different film recipes per precursor or I have in the past anyway. </div><div><br></div><div>Thanks</div><div>Mark</div></div><div class="gmail_extra"><br><div class="gmail_quote">On Mon, Oct 12, 2015 at 2:09 PM, David Heemstra <span dir="ltr"><<a href="mailto:David.Heemstra.1@nd.edu" target="_blank">David.Heemstra.1@nd.edu</a>></span> wrote:<br><blockquote class="gmail_quote" style="margin:0 0 0 .8ex;border-left:1px #ccc solid;padding-left:1ex"><div dir="ltr"><div>Mike:<br>We also have two separate manifolds. Below is a screen capture for our system.</div><div>Maybe im missing something but - it sounds like they don't want to put TiCl4 and TMA on the same manifold? I believe that is how ours is currently setup.</div><div>I thought we had 3DMAS or BTBAS a long time ago - but currently Si source is BDEAS.</div><div>Possible (if we are doing something that isn't ideal) it is OK as long as you use sufficient purges afterwards?</div><div>Not really sure that this helps. Mark may have a better understanding.</div><div>Dave</div><div><br></div><div><br></div><div class="gmail_extra"><br></div><div class="gmail_extra"><br></div><div class="gmail_extra"><img width="506" height="691" alt="Inline image 1" src="cid:ii_1505d3a713a9534c"><br></div></div></blockquote></div></div></div></blockquote><div><br></div><br><blockquote type="cite"><div><div class="gmail_extra"><div class="gmail_quote"><blockquote class="gmail_quote" style="margin:0 0 0 .8ex;border-left:1px #ccc solid;padding-left:1ex"><div dir="ltr"><div class="gmail_extra"><div class="gmail_quote">On Sun, Oct 11, 2015 at 10:26 AM, mike young <span dir="ltr"><<a href="mailto:mike.young@nd.edu" target="_blank">mike.young@nd.edu</a>></span> wrote:<br><blockquote class="gmail_quote" style="margin:0px 0px 0px 0.8ex;padding-left:1ex;border-left-color:rgb(204,204,204);border-left-width:1px;border-left-style:solid">
<div text="#000000" bgcolor="#FFFFFF">
dave/mark, can you advise Vicky regarding this ALD question?<div><div class="h5"><br>
<br>
<div><br>
<br>
-------- Forwarded Message --------
<table border="0" cellspacing="0" cellpadding="0">
<tbody>
<tr>
<th align="RIGHT" nowrap valign="BASELINE">Subject:
</th>
<td>[labnetwork] ALD of SiO2 and SiN with precursors 3DMAS
and BTBAS</td>
</tr>
<tr>
<th align="RIGHT" nowrap valign="BASELINE">Date: </th>
<td>Fri, 9 Oct 2015 15:56:30 -0400</td>
</tr>
<tr>
<th align="RIGHT" nowrap valign="BASELINE">From: </th>
<td>Vicky Diadiuk <a href="mailto:diadiuk@mit.edu" target="_blank"><diadiuk@mit.edu></a></td>
</tr>
<tr>
<th align="RIGHT" nowrap valign="BASELINE">To: </th>
<td><a href="mailto:labnetwork@mtl.mit.edu" target="_blank">labnetwork@mtl.mit.edu</a></td>
</tr>
</tbody>
</table>
<br>
<br>
<div><font face="Arial"><span style="font-size:12px">Hi,</span></font></div>
<div><font face="Arial"><span style="font-size:12px"> We are
interested in adding SiO2 and SiN deposition capabilities to
at least one of our ALD systems (specifically the Oxford
FlexAL).</span></font></div>
<div><font face="Arial"><span style="font-size:12px">The system
has two sets of independent precursor manifolds. </span></font></div>
<div><font face="Arial"><span style="font-size:12px">Currently,
one manifold is completely filled up with TMA, the Hf source
and the W source, while the second manifold only has TiCl4
for depositing TiN and TiO2. </span></font></div>
<div><font face="Arial"><span style="font-size:12px">The
problem is that the TiCl4 source (and other such metal
halide sources) is not compatible with metal amide sources
and thus we can't put any metal amide precursors on the two
open slots on the second precursor manifold. </span></font></div>
<div><font face="Arial"><span style="font-size:12px"><br>
</span></font></div>
<div><font face="Arial"><span style="font-size:12px">Our users
are interested in depositing SiO2 and SiN by using metal
amide precursors like 3DMAS and BTBAS but that requires that
the TiCl4 source be replaced with a compatible Ti precursor,
such as TDMAT to deposit TiN.</span></font></div>
<div><font face="Arial"><span style="font-size:12px">The
precursors we are considering based on what people seem to
be using at other universities and a quick literature search
are:</span></font></div>
<div>
<div><font face="Arial"><span style="font-size:12px"><br>
<b>SiO2</b></span></font>
<div><font face="Arial"><span style="font-size:12px">3DMAS/TDMAS <br>
BTBAS<br>
<br>
</span></font></div>
<div><b style="font-size:12px"><font face="Arial">SiN</font></b></div>
<div><font face="Arial"><span style="font-size:12px">3DMAS <br>
<br>
</span></font></div>
<div>
<div><font face="Arial"><span style="font-size:12px">Does
anyone have any experience w/them & with TDMAT?</span></font></div>
<div><font face="Arial"><span style="font-size:12px">Any
recommendations or suggestions for precursors for SiO2
and SiN?</span></font></div>
<div><font face="Arial"><span style="font-size:12px"><br>
</span></font></div>
</div>
<div><font face="Arial"><span style="font-size:12px">We'd
like to assess all of these precursors and films with
respect to:</span></font></div>
<div><font face="Arial"><span style="font-size:12px">1)
Cost and availability of precursor</span></font></div>
<div><font face="Arial"><span style="font-size:12px">2)
Robustness of precursor (A precursor that degrades
rapidly over time wld not be preferred)</span></font></div>
<div><font face="Arial"><span style="font-size:12px">3)
Quality of film: Electrical data would be nice but even
indices of refraction would do</span></font></div>
<div><font face="Arial"><span style="font-size:12px">4) Any
chemical compatibility issues.</span></font></div>
<div><font face="Arial"><span style="font-size:12px">5)
Existence of recipes on the Oxford ALD tool at other
places. This will reduce the amount of optimization
that we will need to do.</span></font></div>
</div>
</div>
<div><font face="Arial"><span style="font-size:12px"><br>
</span></font></div>
<div><font face="Arial"><span style="font-size:12px">We really
appreciate any comments you might have.</span></font></div>
<div><font face="Arial"><span style="font-size:12px">Thx,</span></font></div>
<div><font face="Arial"><span style="font-size:12px"> Vicky</span></font></div>
<div>
<div><br>
</div>
</div>
<br>
</div>
<br>
</div></div></div>
</blockquote></div><br></div></div>
</blockquote></div><br></div><span class="HOEnZb"><font color="#888888">
</font></span></div></blockquote></div><span class="HOEnZb"><font color="#888888"><br><div>
<div style="color:rgb(0,0,0);letter-spacing:normal;text-align:start;text-indent:0px;text-transform:none;white-space:normal;word-spacing:0px;word-wrap:break-word">-- <br><font face="Consolas"><span style="font-size:11px">Michael P. Young <a href="tel:%28574%29%20631-3268" value="+15746313268" target="_blank">(574) 631-3268</a> (office)<br>Nanofabrication Specialist <a href="tel:%28574%29%20631-4393" value="+15746314393" target="_blank">(574) 631-4393</a> (fax)<br>Department of Electrical Engineering <a href="tel:%28765%29%20637-6302" value="+17656376302" target="_blank">(765) 637-6302</a> (cell)<br>University of Notre Dame <a href="mailto:mike.young@nd.edu" target="_blank">mike.young@nd.edu</a><br>B-38 Stinson-Remick Hall<br>Notre Dame, IN 46556-5637</span></font></div>
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