Sunday, June 02, 2024

Materials families: Halide perovskites

Looking back, I realized that I haven't written much about halide perovskites, which is quite an oversight given how much research impact they're having.  I'm not an expert, and there are multiple extensive review articles out there (e.g. here, here, here, here, here), so this will only be a very broad strokes intro, trying to give some context to why these systems are important, remarkable, and may have plenty of additional tricks to play.

From ACS Energy Lett. 5, 2, 604–610 (2020).

Perovskites are a class of crystals based on a structural motif (an example is ABX3, originally identified in the mineral CaTiO3, though there are others) involving octahedrally coordinated metal atoms.  As shown in the figure, each B atom is in the center of an octahedron defined by six X atoms.  There are many flavors of purely inorganic perovskites, including the copper oxide semiconductors and various piezo and ferroelectric oxides.  

The big excitement in recent years, though, involves halide perovskites, in which the X atom = Cl, Br, I, the B atom is most often Pb or Sn.  These materials are quite ionic, in the sense that the B atom is in the 2+ oxidation state, the X atom is in the 1- oxidation state, and whatever is in the A site is in the 1+ oxidation state (whether it's Cs+ or a molecular ion like methylammonium (MA = [CH3NH3]+) or foramidinium (FA = [HC(NH2)2]+).  

From Chem. Rev. 123, 13, 8154–8231 (2023).

There is an enormous zoo of materials based on these building blocks, made even more rich by the capability of organic chemists to toss in various small organic, covalent ligands to alter spacings between the components (and hence electronic overlap and bandwidths), tilt or rotate the octahedra, add in chirality, etc.  Forms that are 3D, effectively 2D (layers of corner-sharing octahedra), 1D, and "OD" (with isolated octahedra) exist.  Remarkably:

  • These materials can be processed in solution form, and it's possible to cast highly crystalline films.
  • Despite the highly ionic character of much of the bonding, many of these materials are semiconductors, with bandgaps in the visible.
  • Despite the differences in what chemists and semiconductor physicists usually mean by "pure", these materials can be sufficiently clean and free of the wrong kinds of defects that it is possible to make solar cells with efficiencies greater than 26% (!) (and very bright light emitting diodes).  
These features make the halide perovskites extremely attractive for possible applications, especially in photovoltaics and potentially light sources (even quantum emitters).  They are seemingly much more forgiving (in terms of high carrier mobility, vulnerability to disorder, and having a high dielectric polarizability and hence lower exciton binding energy and greater ease of charge extraction) than most organic semiconductors.  The halide perovskites do face some serious challenges (chemical stability under UV illumination and air/moisture exposure; the unpleasantness of Pb), but their promise is enormous

Sometimes nature seems to provide materials with particularly convenient properties.  Examples include water and the fact that ordinary ice is less dense than the liquid form; silicon and its outstanding oxide; gallium arsenide and the fact that it can be grown with great purity and stoichiometry even in an extremely As rich environment; I'm sure commenters can provide many more.  The halide perovskites seem to be another addition to this catalog, and as material properties continue to improve, condensed matter physicists are going to be looking for interesting things to do in these systems. 

3 comments:

Anonymous said...

Are there any products or things we can buy with these perovskites?

Douglas Natelson said...

Almost. There are a number of startups. See here: https://sauletech.com/product/
And https://www.pv-magazine.com/2023/10/31/commercial-perovskites-imminent/

Sankaran Ramesh said...

One of the fascinating and enigmatic aspects of these materials is the interaction of charges with vibrations in the polar crystal - the dressing of charges by phonons seems to be consequential for many of the positive aspects of these materials that you have mentioned here...