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Darn Near Flatland

Graphene is the most famous of the two-dimensional solids, and with good reason. We’ve all seen graphite in pencils, and it’s strange to think that this same substance, plus some household adhesive tape, led to a Nobel. (You probably wouldn’t want to try that experiment with actual pencils – the graphite is often blended with other materials. And even if you have a chunk of good-quality graphite, the single-atom-thick sheets, which is what you end up with after you do the adhesive-tape peel a few times, become basically invisible without a handy electron microscope). Graphene has very interesting properties, starting with it being much stronger than steel, and these are directly related to it being a completely bonded flat sheet of carbon atoms. It’s like some sort of mathematical ideal, a Platonic substance that showed up down here in the cave instead of just being a shadow on the wall. The shift from the bulk phase to the individual layers is a huge one, and has huge implications in optics, electronics, and materials science in general.

There are, by now, a number of other two-dimensional substances that have joined the ranks. Sticking with the pure elements, you have phosphorene, which can be produced by running the tape trick on flaky black phosphorus. (Similarly, arsenene has been predicted to exist, but I don’t think it’s been isolated yet). Borophene has been prepared on a metal substrate, but is overall much less well characterized. Then there’s germanene, which also (so far) has to be painstakingly grown on a surface, silacene (shown at right – it’s not flat like its graphene cousin, but rather is gently rippled), and stanene, which has been reported a couple of times but whose existence would benefit from some further shoring up. Almost all of this work is from 2010 on, and most of it is only from about 2014 or so: the field of two-dimensional materials is very new indeed, and it’s definitely still in the land-rush look-over-here phase.

Moving to single-layer compounds with more than one element in them opens the wild frontier up even wider. There have long been crystals known that have a “layer cake” structure, such as molybdenite, which has molybdenum and sulfur single-element layers. It has a similar slippery, scaly feel like graphite in the bulk phase, due to those sulfur layers sliding past each other, and is similarly used as an industrial lubricant. You can get this down to a two-dimensional layer of molybdenum sulfide, which is a material that’s showing up in the literature these days with great regularity. And it’s just the best-known example of a whole slew of metal-sulfur (or metal-selenium) 2D materials, the exploration of which is a very lively field (palladium selenide, anyone?). Two-dimensional boron nitride is also a hot topic, since its properties would seem to make it ideal for many nanotech applications (better, in fact, than graphene, could it only be produced in quantity). 2D thallium oxide has just been calculated to be stable and may even be available through exfoliation (tape or otherwise), and the list most certainly goes on.

Why stop there, though? Last year, a three-way graphenelike compound of silicon, boron, and nitrogen was predicted to exist, and no doubt there are people whacking away right now trying to prepare it. And even now, people are taking these 2D compounds and stacking them on top of each other, looking for unusual electronic properties and more. There are, beyond doubt, a huge number of artificial materials, which could be produced by the techniques now emerging – for instance, start with a layer of molybdenum sulfide, and then layer a completely different metal sulfide on top of that. Rinse and repeat – you could end up with a Dobosh-tort solid with two (or more, why not) metals along with sulfur, all present as single-atom layers piled on top of each other. The magnetic, optical, electrical, thermal, and mechanical properties of such things are anyone’s guess; I’m not sure if current modeling is up to calculating them after a certain point.

But as it stands, there’s a lot of chemistry (and physics) to be done. Once you get past the naturally occurring 2D-layer materials (graphite, black phosphorus, molybdenum sulfide), you’re faced with some rather large synthetic difficulties. Just because some allotrope or compound is predicted to be stable enough to exist doesn’t mean that you have a route to it, of course. Vapor deposition and other semiconductor-industry techniques can be a way in (although not a universal one), but there are surely chemical tricks to laying these things down that we haven’t learned yet, since it’s only (relatively) recently that we’ve had the tools to see what’s going on. Flatness, it turns out, looms large.

26 comments on “Darn Near Flatland”

  1. Hap says:

    Thallium oxide would have to have some really cool properties to make me think about making it, though.

    1. John Wayne says:

      I bet it would be awesome at some reactions. Everybody knows that really toxic reagents tend to work better. I used a ton of organotin in my PhD and swore I would never use it again. Unfortunately, that crap just works great and I still end up there from time to time.

      1. Derek Lowe says:

        I’m getting that sensation in my nose and my teeth just thinking about all that tin. . .

        1. John Wayne says:

          Don’t forget that persistent taste in your mouth …

          1. n2o3 says:

            After getting used to it I guess I can tell ‘you might even like it’ 😉

        2. Me says:

          My thoughts exactly – that was almost like a gourmet post: I could literally smell stannanes as I read it.

      2. Pennpenn says:

        This may sound like a dumb question, but is the toxicity and the effectiveness related? As in, the fact that a reagent works on a lot of things means it’s more likely to dive in and start screwing around with your body whereas less effective reagents are also less likely to be “effective” on you? In a general sense, I mean.

        1. Me says:

          ‘In a general sense’ yes. But there’s a whole lotta minutiae in there that make life interesting for drug discovery peeps.

        2. Joeylawn says:

          An example of positive correlation between toxicity and effectiveness is with Alkylating agents. Dimethyl Carbonate is a rather weak alkylating agent, but it’s also much less toxic than dimethyl Sulfate, which is a really good alkylating agent, but is also extremely toxic.

  2. Uncle Al says:

    the single-atom-thick sheets…basically invisible without a handy electron microscope

    http://heinz.phys.columbia.edu/publications/Pub193.pdf
    DOI:10.1016/j.ssc.2012.04.064

    Absorption = (pi)(alpha) 2.2925% Naked eye VISiBLE! alpha = 1/137.036
    Transmittance T = 1/sqrt[1 +1/2(pi)(alpha)]
    Reflectance R = 1/[4(pi)²(alpha)²(T)]

  3. oldnuke says:

    IIRC, pencil “lead” is graphite compounded with clay.

    Clay is an amazing material in itself, I can remember my late father explaining the impact of clay properties in formulating pesticide dusts.

    1. Clay, like graphite, takes the form of thin sheets. Makes it a decent filler for graphite in pencil “lead.”

      I have a suspicion that, at the molecular level we’re talking about here, steel is much stronger than steel. Various crystal defects at the larger scale weaken it. I suspect the same is true of graphene.

      1. Derek Lowe says:

        Good point! Metallurgy must get pretty weird as you scale down to something like that. . .

        1. zero says:

          Monocrystalline iron whiskers are absurdly strong. Putting that to use remains elusive.

        2. Eric says:

          It certainly does. Theoretical strength of most metals is usually 3 orders of magnitude larger than the actual strength. Outside of extremely small volumes of very carefully prepared samples, the concentration of intrinsic defects even in well annealed and prepared samples leads to dramatically different meso and macro scale properties.

          1. Falanx says:

            And graphene is always a very small sample of a very carefully manufactured materials. The present upper strength limit of carbon nanotubes in bulk (still *millimetre* long samples) is lower than the strength of bulk steels – a 2mm tube was measured at 1.4GPa, when MLG on aircraft are made from steels with UTS in sections inches thick of 2GPa.

            The equilibrium thermodynamic defect level is an inescapable reality. Scaling anything up that is perfect on a microscale cannot fail to introduce them, and in materials like graphene that rely on structural perfection from strength, it’s disastrous. Modern ultra high strength steels and other alloys derive their strength from the very opposite; defects that in the majority of modes are nonmetallic in bonding, or crystallography, or order – such as dislocation density via coherent intermetallics, substantial grain boundary area from ultrafine grain.

      2. regdoug says:

        Even on a macro scale, steel is stronger than steel. ASTM A228 music wire (used to make springs of all kinds) is nearly 10x as strong as “CQ” (for commercial quality) sheet steel.

        1. Falanx says:

          And the present manufacturing limits of steels are about 5GPa for samples big enough to see readily with the naked eye. You can drive a horse and cart though “As strong as steel”

      3. Scott says:

        You get some interesting things in jet engines. Single-crystal castings for turbine blades are insanely heat-resistant, but expensive to make since you need to grow a single crystal that is a good 10cm in all directions, and then you need to machine it without shattering. At least you can re-use the cuttings.

  4. Ryan says:

    Graphite is carbon, diamonds are carbon, no kidding it’s stronger. Would be curious about molecular gold.

  5. gippgig says:

    Graphene with B or N substituted at specific locations might have really interesting properties. So might graphene with C-13 at specific locations.

    1. Me says:

      Was thinking about this myself: two sheets with very different redoc/electronic properties layered one on top of the other = a nano-scale capacitor/logic gate/solar cell…..etc. etc.

      Thanks for the post Derek – not often I think about stuff outside of the chem/pharm sphere.

      1. cookingwithsolvents says:

        Devices made this way are a VERY active area of research! 🙂 Lots of problems, including deposition, defects/doping, scalabilty, etc.

    2. eyesoars says:

      I’m trying to think what properties…

      The thermal conductivity of pure carbon-12 diamonds is substantially higher than that of natural diamonds (~1% C-13), especially at low temperatures. Diamonds conduct heat very well, and are electrical insulators, so there has been some interest in the chip business in carbon-12 diamond paste.

      That’s pretty much the difference: phonons tend to scatter off C-13 atoms in a mixed-atom lattice, and the effect is much enhanced at low temperatures where phonon energies are more strongly quantized.

      1. GladToMoveToProcess says:

        IIRC, there was a patent fight going on 5-10 years ago over single isotope diamond for insulation uses. Maybe GE and someone else?

  6. Barry says:

    Because graphene is a good electrical conductor in-plane and a good insulator perpendicular to the plane, it may be possible to make capacitors out of a single material (gotta seal the edges, of course). That would be a big density improvement. But over such small distances, tunneling could compromise even a great insulator?

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