# Comparing different approaches to model the atomic structure of a ternary decagonal quasicrystal (Comparing different decagonal models)

## 1 Introduction

From the beginning, the existence of quasicrystals has provoked questions about the physical driving force which results in a highly ordered but very complicated structure. Especially, the controversy whether truly deterministic quasicrystals can exist in real systems or whether quasicrystals always contain some inherent random disorder has stimulated much research. The first approach assumes quasicrystals to be stabilized energetically, while the second proposes them to be high–temperature phases due to an entropic contribution.

The quasicrystal structure has often been described and analysed in the framework of quasiperiodic tilings, composed of two or more constituent “unit cells”. Recently, a new approach was made by the covering proposed by Gummelt . By assuming special overlap rules between prototiles of decagonal symmetry, it was shown that the resulting covering of these decagons is equivalent to a deterministic Penrose tiling. Later, Jeong and Steinhardt  gave a simpler proof and further discussed the physical implications of this cluster approach. Especially, they showed that the Penrose tiling corresponds to a maximum density of overlapping decagonal clusters.

The structure of existing quasicrystals has been analysed experimentally. In the case of decagonal quasicrystals, structure determinations were performed e.g. by Steurer et al. . This data was also the base for some further theoretical structure modeling . Experimental analyses have been complicated by the existence of competing structures such as approximants  or microcrystals  which strongly resemble quasicrystals. Furthermore, a problem of all experimental investigations so far, whether electron microscopy or x–ray diffraction, is that it is not possible to distinguish between the different TM atoms in the ternary Al–Co–Cu or Al–Co–Ni decagonal quasicrystals on which research has focussed. Concerning the overlap rules of Gummelt, the common experiment–based models do not provide any crystal chemical motivation.

First attempts to bridge the gap between atomistic structure models and the mathematical algorithm of Gummelt were made recently . However, these models were explicitly designed to impose the Gummelt rules, but without any energetic calculations.

This letter attempts to clarify the relationship of a specific structure model for a decagonal quasicrystal , based on an atomic decoration of a tiling, to the prototile framework. Specific features of the atomic arrangement prevent a strict equivalency of both approaches and can be therefore employed to discriminate between them. Recent experimental data will be discussed and used for comparison with the theoretical models.

## 2 Comparing tiling and covering approaches

### 2.1 Relationship between HBS tiling and prototile covering

In a first step, the hexagon, boat and star (HBS) tiling  will be connected to the overlap rule of decagonal clusters . For this purpose, the Gummelt decagon (including its decoration) can be subdivided into a boat and two hexagons. If we now allow overlaps of the decagons of type A (for the nomenclature see ref. ), the following cases can arise in the HBS framework: i) Two hexagons fall onto each other – no problem. ii) A hexagon falls onto a boat – then the hexagon should be rejected, leaving only the boat as part of the tiling. iii) Two boats overlap, forming a star – then both boats are to be replaced by a star. (Briefly: if two tiles overlap, they should be replaced by the tile which encompasses both. Note that larger and smaller tile always differ by a bowtie shape.) In the case of the type B overlap, the configuration should be replaced by that shown in Fig. 1. Using these rules, we can replace a Gummelt covering by an HBS tiling. Checking the allowed surroundings of a decagon (cf. fig. 14 in ref. ), it can be easily verified that these rules do not lead to any conflicts or ambiguities. As each surrounding in the prototile picture transforms into a different arrangement of HBS tiles (which always contains a star tile), we can conclude that these rules even describe a one–to–one correspondence between Gummelt covering and a HBS tiling. However, as the covering is equivalent to a Penrose tiling , the HBS tiling also has to follow specific matching rules.

### 2.2 The atomic decoration of Cockayne and Widom

Recently, Cockayne and Widom (CW) presented a ternary model for a decagonal quasicrystal  based on Monte–Carlo simulations and consisting of an HBS tiling supposed to impose matching rules which would equivalently allow an description in terms of a Penrose lattice. The atomic arrangement consists of interconnected decagonal clusters of about 2 nm diameter. Its atomic decoration shows remarkable similarities to the schematic Gummelt decoration (Fig. 2). Following the above argumentation, one could assume the CW model could be equivalently described as a overlap of decagonal prototiles. In fact, if an HBS tiling is constructed using the the CW decoration and the above strategy, only a few atoms do not match when placing a boat on top of a hexagon or a star on top of a boat. Part of the incongruencies can be resolved by allowing the two types of TM atoms in a zigzag chain to change places, but not all of them. In the following, the slight but important differences between the CW model and the prototile approach will be elucidated.

First, the CW decoration breaks the symmetry both of the boat and the star tiles. In the case of the boat tile, the asymmetry of positions 1 and 2 in Fig. 2 could be resolved, although this would require also changes of all other positions marked with a cross. Furthermore, to symmetricise the boat while allowing a Gummelt overlap of type A would require not only position 3 but also position 4 to be occupied with a Cu atom. Together with the Co atom in between, this would result in a zipper–like interconnection of two zigzag chains of TM atoms. It is doubtful that such an arrangement would be stable.

An even more ”dramatic” conflict concerns the bottleneck region of the bowtie. There, the two vertices (designated by 5 and 6 in Fig. 2) approach each other too closely for pentagonal Al clusters to be centered around both of them.

Similar difficulties arise also with the decorated star tile.

Therefore, the pentagonal Al clusters at the vertices and the zigzag chains are stumbling stones to any attempt to construct a decagonal cluster following the overlap rules exactly. In fact, these two features are also absent from such atomic models . In the case of the model of Steinhardt et al.  this is all the more remarkable as part of the authors already proposed these zigzag chains in a previous paper .

The covering forced by the Gummelt decoration is a deterministic Penrose tiling . Assuming the constituting cluster to be preferred on energetic reasons, the approach gives a physical mechanism for producing stable deterministic quasicrystals . On the other hand, the energetic stability of the cluster has been only postulated so far. In the specific proposal , the cluster is built of several hundred atoms, which makes it difficult to imagine that slightly different clusters will not be energetically degenerate.

One could argue that such a cluster remains essentially unaffected by the exchange or displacement of a few of the about hundred atoms inside. Then, the CW model can be considered as a covering of a single decagonal prototile following the overlap rules of Gummelt, if only the atomic decoration of the prototile is not strictly fixed but slight changes and reshufflements are allowed. Therefore, the results of CW would come close to provide us with a crystal chemical motivation for the cluster decoration of the Gummelt model. However, the conceptual beauty of the prototile approach has been lost.

In contrast, the CW model already contains an argument for stability, namely matching rules induced by ordering of TM atoms. This offers an explanation at a more fundamental level than having to postulate special stability of a specific cluster composed of hundreds of atoms.

## 3 Comparison of the structure models with experimental results

In the following, some experimental results will be reviewed and compared with the above approaches. Tab. 1 contains a summary of the major differences between the models (including the often–discussed Burkov model ) and their comparison with the experiments.

### 3.1 Atomic positions in the 2 nm cluster

A very peculiar feature of the CW model is the lack of a central atom in the 2 nm cluster. Instead, the center point is surrounded by triangular patterns of TM zigzag chains and pentagonal clusters comprising mainly Al atoms. This contradicts an established consensus that the 2 nm cluster should have perfect tenfold symmetry which is at the base of the common structural models . High–resolution transmission electron microscopy (HRTEM) images usually also show a tenfold cluster symmetry . Only in the case of decagonal Al–Pd–Mn , a triangular pattern in the center of the cluster was reported. However, it was interpreted to indicate columns in between the atomic positions, retaining the existence of a central atom.

On the other hand, HRTEM micrographs contain strong dynamical contributions and phase contrast due to the microscope lens system. Therefore, the patterns are not easy to interprete. These disadvantages can be avoided by using the high–angle annular dark–field method which directly uses the electrons scattered from an incident beam into an annular detector. The resulting high–resolution images directly show the atomic structure. Using this method, images of the decagonal phase with composition Al<sub>72</sub>Co<sub>8</sub>Ni<sub>20</sub> have been obtained recently . As the scattering power of the Al atoms is five times less than that of the TM atoms, the latter show up prominently. Their positions fit remarkably well to the CW model. Even the triangular arrangement in the center of a 2 nm cluster column predicted by CW can be clearly recognized in the experimental images. The HBS tiles of CW are indicated by broken lines in fig. 3a of ref. . Matching rule violations are not observed. The vertices of the tiling show only a weak scattering contrast, indicating an Al atomic position, which is surrounded by a pentagonal arrangement of strong scatterers. Saitoh et al.  explain this arrangement by a cluster (named S and marked with a star) motivated by its resemblance to clusters found in the Al<sub>13</sub>Fe<sub>4</sub>–type approximant. However, to account for the experimental observation, the central TM atom had to be arbitrarily substituted by Al, which gives unrealistic bond lengths. Furthermore, the tips of the stars indicating clusters of type S always overlap, as the bright dots forming these pentagons seem to be slightly elongated. This should not occur with the cluster proposed by Saitoh et al., but fits perfectly well to the TM zigzag chains in the model of ref. . As the two TM atomic positions are only 1.5 Å apart, they could not be directly resolved due to the experimental resolution of about 2 Å.

The importance of the experimental findings of Saitoh et al. was already pointed out by Steinhardt et al. . Although their model is able to reproduce the observed positions of strong scatterers quite well by single TM atoms, it does not offer any explanation for their elongated shape. It was demonstrated that the model is also able to reproduce conventional HRTEM reasonably well, but the same is claimed by part of the coauthors for a different model . Here, the comparison is made with images interpreted originally to support a cluster model with tenfold symmetry . These contradictions only reflect the well–known fact that there is no unique relation between an HRTEM image and a structure model (even in the case of simple crystalline structures).

Unfortunately, literature data do not provide a complete set of microscope parameters and imaging conditions which would be necessary to compare with image simulations of the CW model. Therefore, a more quantitative comparison of the CW model with standard HRTEM images has to be left for some future research.

Meanwhile, another investigation using the same material and the same method has been published . This time, the resolution of the microscope was sufficient to resolve the zigzag chains of TM atoms (called “buckled columns” in this reference), thereby giving further evidence for the correctness of the CW approach and refuting the model of Steinhardt et al. . According to the study of Yan et al. , the material is composed from two types of clusters, one with the characteristic triangular pattern in the center, the other where the decagonal symmetry is retained even in the central part. The latter would contradict both the CW and the Steinhardt et al. model. However, it should not be forgotten that all HRTEM images inherently project all atomic positions along the direction of observation. The second type of cluster can be easily explained by assuming clusters of the first type, but stacked on top of each other rotated by multiples of 36. What has been called chemical disorder  could also be interpreted as stacking disorder. These rotations, if acting in an ordered way, could also explain superstructures along the decagonal axis. Indeed, higher periods of 0.8, 1.2 and 1.6 nm were experimentally observed . If acting in a random way, they constitute a source of entropy. As every structure determination, whether by HRTEM or by Patterson analysis, contains an averaging, it also can be suggested why the majority of models contain a cluster of perfect decagonal symmetry .

### 3.2 Further comparison

So far, the comparison was focussed only on the atomic positions projected along the decagonal axis. In the following, other features will be checked.

The experimentally investigated phase contains a $`10_5`$ screw axis which is correctly reproduced by both models of CW and Steinhardt et al.

Steinhardt et al.  calculate a composition of Al<sub>72.5</sub>Co<sub>8.9</sub>Ni<sub>18.6</sub> for their model, which is equal to the experimental composition within the error margins.

Starting from the composition Al<sub>64.8</sub>Co<sub>19.6</sub>Cu<sub>15.6</sub> of the CW model  and bearing in mind that Cu substitutes for Al and Co in equal proportions, we obtain a pseudo–binary Al<sub>72.6</sub>TM<sub>27.4</sub> phase, which also compares remarkably well with the composition Al<sub>72</sub>TM<sub>28</sub> of the experimental studies . However, the Monte–Carlo simulations of binary Al–Co would suggest a quite different structure for the decagonal phase of such a composition . The quasicrystal of Saitoh et al. also does not correspond to the basic Co–rich but to the basic Ni–rich phase. Both variants are connected by several superstructures along the Al<sub>72</sub>Co<sub>x</sub>Ni<sub>28-x</sub>–line . As Co and Ni would be treated similarly by the Monte Carlo approach, one would not expect any variations with $`x`$. Therefore, the rôle of transition metals seems to be more subtle. It should be admitted, however, that there remains a major aspect of the CW model which still awaits experimental verification, namely the alternation of the two different TM atoms along a zigzag chain. As Co and Cu or Ni cannot be distinguished by electron microscopy or standard x–ray techniques, this test will be rather difficult to perform.

Some caution should be applied in generalizing the results obtained on the above composition to “the” decagonal phase. It is by now commonly accepted that even in one alloy system different variants exist . Their structures might be more different than previously assumed. In this respect it is interesting to recall the neutron scattering experiments performed on Al<sub>72.5</sub>Co<sub>11</sub>Ni<sub>16.5</sub> exhibiting superstructure reflections which, however, were concluded not to be due to a Co/Ni ordering but a true structural feature .

### 3.3 Thermodynamical considerations

Experimentally, the basic–Ni decagonal structure was observed to be stable only as a high–temperature phase , indicating an entropic contribution which stabilizes the structure. On the other hand, the prototile approach was advanced mainly to provide a plausible mechanism for energetic stabilization via maximizing the density of clusters assumed to have minimum energy . Therefore, the prototile idea lacks experimental support also from the thermodynamic viewpoint. Although the CW model was also derived by energetic arguments, it might be more flexible to accomodate random components.

The concept of random tilings  is able to provide an entropic term for stability. However, a recent tiling analysis  showed the high–temperature basic Ni–rich phase to be a perfect Penrose tiling. (This contrasts to a variant with superlattice ordering where even single phasons could be identified by HRTEM .) The evident entropic term was attributed to chemical disorder  without specifying its exact origin.

In the following some mechanisms will be listed which can introduce disorder easily and in a into the CW model without changing the underlying tiling: i) Switching between the two mirror–related variants of the boat tile, or rotating the star tile which also results in non–equivalent atomic configurations due to the symmetry breaking of the decoration; ii) rotating the 2 nm cluster, as mentioned above; iii) exchange of Co and Cu in the zigzag chains.

## 4 Summary

An algorithm is presented which transforms a covering with decagonal prototiles and the overlap rules of Gummelt into an HBS tiling. The atomic decoration of an HBS tiling proposed Cockayne and Widom, although it resembles the Gummelt decoration very much, contains features which do not allow it to be interpreted as a reasonable realization of such a covering in the strict sense. Only if minor variations in the constituting decagonal cluster are allowed, the approaches could be reconciled. Experimental investigations render support to the major features of the model of Cockayne and Widom, but contradict the competing proposal of Steinhardt et al. Tab. 1 contains a brief overview of the comparison. Chemical disorder has been proposed as a means to obtain an entropic stabilization which is suggested by the experimentally determined phase diagram.

## Acknowledgment

The author gratefully thanks Eric Cockayne for fruitful discussions and valuable comments. The project was supported by the Deutsche Forschungsgemeinschaft (grant no. Wi1645/1).

## Table

|  | Cockayne and | Steinhardt | Burkov  | Saitoh | Yan |
| --- | --- | --- | --- | --- | --- |
|  | Widom (CW) | et al.  |  | et al.  | et al.  |
| construction | HBS tiling | covering | covering / |  |  |
|  |  |  | tiling |  |  |
| central atom | no | no | yes | no | no |
| tenfold symmetry |  |  |  |  | sometimes |
| in cluster center | broken | broken | perfect | broken | broken |
| zigzag chains |  |  |  |  |  |
| of TM atoms | yes | no | no | not resolved | yes |
| Co/Cu ordering | yes | yes | no | ? | ? |
| screw axis | $`10_5`$ | $`10_5`$ | $`10_5`$ | $`10_5`$ | $`10_5`$ |
| composition | Al<sub>64.8</sub>Co<sub>19.6</sub>Cu<sub>15.6</sub> | Al<sub>72.5</sub>Co<sub>8.9</sub>Ni<sub>18.6</sub> | Al<sub>60</sub>TM<sub>40</sub> | Al<sub>72</sub>Co<sub>8</sub>Ni<sub>20</sub> | Al<sub>72</sub>Co<sub>8</sub>Ni<sub>20</sub> |
|  | = Al<sub>72.6</sub>TM<sub>27.4</sub> |  |  |  |  |
| stabilisation | energetic | energetic |  | (entropic ) | (entropic ) |

Tab. 1:   
Comparison of special features of the different structure models (left part), especially those suitable for comparison with the experimental results (right part).

## Figure captions

Fig. 1:   
Part of an HBS tiling corresponding to a type B overlap of two decagonal clusters. The boundaries of the original decagonal clusters are indicated by broken lines.

Fig. 2:   
Atomic cluster of 2 nm diameter taken from ref.  (fig. 2) and formed by a boat and two hexagons of the CW model. The Al atoms at the vertices of the HBS tiling and the few Al atoms marked by a cross are located at $`z=0\text{ or }0.5`$ whereas all other atoms occupy positions at $`z=0.25\text{ or }0.75`$ (in units of the $`c`$–axis periodicity). The cluster is superposed on the Gummelt decoration (indicated by thick lines) of a decagonal prototile, showing large similarities. The relevance of the atoms designed by numbers 1 to 6 is discussed in the text.

Fig. 1

Fig. 2