Fiveling

A fiveling, also known as a decahedral nanoparticle, a multiply-twinned particle (MTP), a pentagonal nanoparticle, a pentatwin, or a five-fold twin is a type of twinned crystal that can exist at sizes ranging from nanometers to millimetres. It contains five different single crystals arranged around a common axis. In most cases each unit has a face centered cubic (fcc) arrangement of the atoms, although they are also known for other types of crystal structure. They nucleate at quite small sizes in the nanometer range, but can be grown much larger. They have been found in mineral crystals excavated from mines such as pentagonite or native gold from Ukraine, in rods of metals grown via electrochemical processes and in nanoparticles produced by the condensation of metals either onto substrates or in inert gases. They have been investigated for their potential uses in areas such as improving the efficiency of solar cell or heterogeneous catalysis for more efficient production of chemicals. Information about them is distributed across a diverse range of scientific disciplines, mainly chemistry, materials science, mineralogy, nanomaterials and physics. Because many different names have been used, sometimes the information in the different disciplines or within any one discipline is fragmented and overlapping. At small sizes in the nanometer range, up to millimetres in size, with fcc metals they often have a combination of {111} and {100} facets, a low energy shape called a Marks decahedron. Relative to a single crystal, at small sizes a fiveling can be a lower energy structure due to having more low energy surface facets. Balancing this there is an energy cost due to elastic strains to close an angular gap (disclination), which makes them higher in energy at larger sizes. They can be the most stable structure in some intermediate sizes, but they can be one among many in a population of different structures due to a combination of coexisting nanoparticles and kinetic growth factors. The temperature, gas environment and chemisorption can play an important role in both their thermodynamic stability and growth. While they are often symmetric, they can also be asymmetric with the disclination not in the center of the particle.

History

Dating back to the nineteenth century there are reports of these particles by authors such as Jacques-Louis Bournon in 1813 for marcasite, and Gustav Rose in 1831 for gold. In mineralogy and the crystal twinning literature they are referred to as a type of cyclic twin where a number of identical single crystal units are arranged in a ring-like pattern where they all join at a common point or line. The name fiveling comes from them having five members (single crystals). Fivelings have also been described as a type of macle twinning. The older literature was mainly observational, with information on many materials documented by Victor Mordechai Goldschmidt in his Atlas der Kristallformen. Drawings are available showing their presence in marcasite, gold, silver, copper and diamond. New mineral forms with a fiveling structure continue to be found, for instance pentagonite, whose structure was first decoded in 1973, is named because it is often found with the five-fold twinning. Most modern analysis started with the observation of these particles by Shozo Ino and Shiro Ogawa in 1966-67, and independently but slightly later (which they acknowledged) in work by John Allpress and John Veysey Sanders. In both cases these were for vacuum deposition of metal onto substrates in very clean (ultra-high vacuum) conditions, where nanoparticle islands of size 10-50 nm were formed during thin film growth. Using transmission electron microscopy and diffraction these authors demonstrated the presence of the five single crystal units in the particles, and also the twin relationships. They also observed single crystals and a related type of icosahedral nanoparticle. They called the five-fold and icosahedral crystals multiply twinned particles (MTPs). In the early work near perfect decahedron (pentagonal bipyramid) and icosahedron shapes were formed, so they were called decahedral MTPs or icosahedral MTPs, the names connecting to the decahedral ( D 5 h {\displaystyle D_{5h}} ) and icosahedral ( I h {\displaystyle I_{h}} ) point group symmetries. Parallel, and apparently independent there was work on larger metal whiskers (nanowires) which sometimes showed a very similar five-fold structure, an occurrence reported in 1877 by Gerhard vom Rath. There was fairly extensive analysis following this, particularly for the nanoparticles, both of their internal structure by some of the first electron microscopes that could image at the atomic scale, and by various continuum or atomic models as cited later. Following this early work there was a large effort, mainly in Japan, to understand what were then called "fine particles", but would now be called nanoparticles. By heating up different elements so atoms evaporated and were then condensed in an inert argon atmosphere, fine particles of almost all the elemental solids were made and then analyzed using electron microscopes. The decahedral particles were found for all face centered cubic materials and a few others, often together with other shapes.

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