Article

pubs.acs.org/JPCC

Stabilities and Reconstructions of Clean PbS and PbSe Surfaces: DFT

Results and the Role of Dispersion Forces
Volker L. Deringer†,§ and Richard Dronskowski*,†,‡
†
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany
‡
Jülich−Aachen Research Alliance (JARA-HPC), RWTH Aachen University, 52056 Aachen, Germany
*
S Supporting Information

ABSTRACT: Lead sulfide (PbS) and lead selenide (PbSe) are functional
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materials with manifold applications. In particular, nanocrystals and other

nanostructures of PbS and PbSe are of mounting interest, which calls for a
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thorough understanding of the underlying crystal surfaces. Here, we present a

comprehensive density-functional theory (DFT) survey of structures and
stabilities for the (001), (011), and (111) surfaces of rocksalt-type PbS and
PbSe. A representative set of possible reconstructions is explored for the polar
(111) surfaces, allowing us to suggest both 2 × 1 and “octopolar” 2 × 2 motifs
as favorable options; this agrees with previous experiments and could guide
future ones. With regard to methodology, we address the role of dispersion
interactions for studying PbS and PbSe surfaces: interestingly, the prediction of (001) surface energies depends crucially on the
use of dispersion corrections to DFT, and the latter directly influences the computed equilibrium shapes (Wulff constructions).
This study may serve as a starting point for future explorations of surfaces and nanocrystals of PbS, PbSe, and chemically related
chalcogenide materials.

■ INTRODUCTION
Lead chalcogenides have long been known as versatile
functional materials and today are of prime interest for
nanochemistry. New and ingenious synthetic approaches cast
both compounds into precisely controlled particles, nanowires,
and even nanocrystal superlattices with interesting and
sometimes unexpected properties.1−5 So enabled, applications
of “miniaturized” PbS and PbSe encompass solar cells, sensors,
thermoelectrics, and diverse other fields.6−9
The shape and properties of nanostructures are controlled by
the underlying crystal surfaces. For example, the particle
morphology of the homologous SnTe depends on the relative
stabilities of competing {001} and {111} facets, and tuning the
chemical potential (or synthetic conditions) allows one to
modify the shape of SnTe nanostructures.10−13 Unfavorable
surfaces change their atomic connectivity: they reconstruct,
which is not only an interesting phenomenon in itself but
directly affects the electronic nature of surface states.14 Going
one or two length scales larger, the shape of PbSe nanocrystals
has recently been linked to charge-transport properties.15 All
this is important for emerging electronic applications.
The need is hence obvious to know as much as possible
about the surfaces of lead chalcogenides. Besides a range of
experimental techniques, first-principles simulations based on
density-functional theory (DFT) are today routinely employed
in the field of nanochemistry.16,17 We have very recently
reviewed experimental and theoretical work on IV−VI
chalcogenide surfaces,18 and here only reflect on the literature
for the two particular compounds PbS and PbSe. Adsorption of
water molecules on PbS(001) has been computationally
explored in 1999 already,19 and not much later, structures
and properties of clean lead chalcogenide (001) surfaces were
studied by DFT.20,21 Further computations dealt with the
stability of PbSe nanocrystal facets,22 with surface oxidation as
represented by cluster models,23 and with ligand binding to
surfaces of both materials and how this influences nano-
morphology.24−29
Despite these advances, two theoretical questions remain
which both have important practical implications. First, to
describe the morphology both of individual (say, epitaxially
grown) surfaces and of entire nanoparticles, one must consider
all relevant competing surfaces side-by-side, and include surface
reconstructions where appropriate. Second, the choice of DFT
methods affects the prediction of absolute surface energies, with
the popular generalized gradient approximation (GGA)
frequently underestimating them (i.e., erroneously making
surfaces too stable).30−32 In the quest for more accurate DFT
simulations, corrections for dispersion interactions33 have been
recently established as useful and economic tools for inorganic
and materials chemistry, e.g., to achieve correct stability ranking
of polymorphs,34−36 and were previously applied to surfaces of
ternary Ge−Sb−Te phase-change materials.37
In this work, we report comprehensive DFT-based surface
studies for PbS and PbSe, expanding on our previous
investigations of the homologous PbTe38 and also on our
earlier work on germanium and tin telluride surfaces.10,39 We
Received: March 1, 2016
Revised: April 11, 2016
Published: April 12, 2016

© 2016 American Chemical Society 8813 DOI: 10.1021/acs.jpcc.6b02173

J. Phys. Chem. C 2016, 120, 8813−8820
The Journal of Physical Chemistry C Article

explore surface structures and stabilities, as well as the tendency Table 1. Lattice Parameters and Bulk Moduli of Rocksalt-
of PbS and PbSe (111) surfaces to reconstruct; ultimately, this Type PbS and PbSe
allows us to predict the equilibrium morphology of both
PbS PbSe
materials. In addition, the role of dispersion corrections for the
computation of PbS and PbSe surface energies is critically a (Å) B (GPa) a (Å) B (GPa)
addressed, for the first time to our knowledge. All this is experimentsa−d 5.9143(4)a 52.9b,c 6.1054(5)a 49.4c,d
expected to have important implications for realistic simulations 54.7c,d
of nanoscale lead chalcogenides. LDA (ref 52) 5.906 66.3 6.098 60.8

■ COMPUTATIONAL METHODS
DFT computations were performed using the projector
PBE+SOC (ref 53)
HSE03+SOC (ref 53)
PBE (this work)
6.004
5.963
5.995
51.2
55.0
54.7
6.214
6.170
6.206
44.6
48.3
48.1
augmented-wave (PAW) method40 as implemented in the PBE-D3 (this work) 5.923 56.8 6.127 47.5
a
Vienna ab initio Simulation Package (VASP 5.3.5).41−44 The From ref 58 (X-ray diffraction; 120 K). bFrom ref 59 (at 295 K).
c
cutoff energy for the plane-wave expansion was 500 eV. Isentropic bulk moduli (BS) are quoted. dFrom ref 60 (at 300 K).
Electronic cycles were halted at ΔE < 10−6 eV cell−1, and
structures were optimized until forces on atoms fell below 10−2 the PBE+D3 agreement for a with previous low-temperature
eV Å−1. Exchange and correlation were treated in the GGA experiments 58 is excellent (to within 1.5% and 3.5%,
after Perdew, Burke, and Ernzerhof (PBE).45 Dispersion respectively; Table 1). Regarding bulk moduli, the “D3”
corrections were applied where noted, using the “D3” method correction leads to only minor changes which appear to
of Grimme and co-workers46 together with Becke−Johnson worsen the pure PBE results; the deviations are tiny, however,
damping;47,48 this approach is abbreviated as “PBE-D3” and likely within the error range of different experiments. The
throughout this paper. effect of dispersion corrections on the prediction of bulk
Surfaces were modeled using inversion-symmetric slabs moduli would be clearly more pronounced for other systems,
similar to our previous study on PbTe,38 with in-plane lattice e.g., for the TeO2 polymorphs which are strongly influenced by
dispersion forces.35

■
vectors locked to multiples of the respective optimized bulk
parameters (see below). The thickness of the slabs was >17 Å
(7 layers) for (001), > 16 Å (9 layers) for (011), and >23 Å (15 RESULTS AND DISCUSSION
layers) for (111) surfaces; vacuum regions of >11, >16, and >17 Pristine Surfaces. The initial step in theoretical surface
Å, respectively, were introduced to separate periodically science is to model the pristine, unreconstructed crystal faces;
repeated images. All atoms were fully relaxed in the slab the optimized structures are shown in Figure 1 for PbS. The
supercells. Reciprocal space was sampled on dense Γ-centered
Monkhorst−Pack meshes49 sized 16 × 16 for the (001), 16 ×
24 for the (011), and 9 × 9 for the (111) surface simulation
cells. To accommodate reconstructions, all (111) terminations
were modeled in 2 × 2 expansions of the conventional surface
unit cell, as done and discussed before.38,39 Structural models
were handled using wxDragon,50 and visualizations and Wulff
constructions were created with the help of VESTA.51
As a necessary reference, computations for bulk PbS and
PbSe were performed at the outset. Both bulk phases have been
widely studied by theory;52−56 exemplarily, we compare our
results to previous linearized augmented plane-wave (LAPW)
computations52 in the local density approximation (LDA), and
to a more recent work which explicitly includes spin−orbit
coupling (SOC).53 As discussed and justified earlier,38,57 SOC
is not taken into account in the present work: it has only small
effects on geometric structures but would increase computa- Figure 1. Low-index surfaces of PbS, structurally optimized at the
tional costs significantly. On the other hand, studies of PBE-D3 level of theory. Labels for interatomic distances d are given
electronic band structures, which have been done for bulk Pb that will be used in the following. The Pb- and S-terminated slabs
chalcogenides, e.g., in ref 53, would make the inclusion of SOC (panels c and d) are equally thick, but they have been shifted in the
mandatory and may in fact be a rewarding target for future drawings to visualize how both are derived from the same bulk
surface studies. structure. The respective, homologous PbSe surfaces are similar in
connectivity but naturally differ in bond lengths (cf. Figures 2 and 3).
Table 1 provides results for the bulk phases of the title
compounds and thereby compares the computational method-
ology we use both to experiment and to previous theoretical rocksalt-type (001) and (011) surfaces are “stoichiometric”,
studies. It is noteworthy that the simplistic LDA already that is, they bear equal amounts of cations and anions (“type I”
performs exceedingly well with respect to the a parameters of surfaces according to Tasker’s scheme; ref 61). By contrast, for
both compounds albeit it overshoots their bulk moduli (ref 52). the (111) surfaces two pristine terminations exist (Figure 1c−
The latter are better reproduced from gradient corrections d), and these are both polar unless reconstructed (Tasker “type
(PBE) and in particular from more accurate and costly hybrid- III”). Before looking at energies, we inspect the computed
functional computations (HSE03).53 The economic “D3” atomic structures of the pristine surfaces and refer to earlier
dispersion correction on top of PBE re-establishes LDA quality work where possible. The labeling convention we use is
for the lattice parameters together with reasonable bulk moduli; illustrated in Figure 1.
8814 DOI: 10.1021/acs.jpcc.6b02173
J. Phys. Chem. C 2016, 120, 8813−8820
The Journal of Physical Chemistry C
As there are previous reports on the structures of these
particular (001) surfaces,20,21 we will here focus on a
comparison between the pure PBE and the PBE-D3 results.
Nonetheless, we mention that at the PBE level, the computed
changes in bond lengths are in line with earlier simulations: we
obtain an average shortening of d1 by ∼6%, and an expansion of
d2 by ∼4% for both compounds. The relaxations are slightly
stronger at PbS(001) than at PbSe(001). All this agrees
reasonably with previous computations.20,21
Here, instead, we focus on a quantity characteristic for
rocksalt (001) terminations: their rumpling, which measures the
shifts of cations and anions relative to each other at the relaxed
surface. We use the definition of the rumpling parameter Δzi
given by Satta and de Gironcoli:20
zianion − ziPb
Δzi =
d0
where zi denotes the respective position along [001] of an atom
located in the ith layer (the i = 1 atoms are directly at the
surface, i = 2 denotes the first subsurface layer, and so on). d0 is
the Pb−anion distance in the optimized bulk structure.
The results are provided in Figure 2. Interestingly, the
qualitative rumpling behavior is inverted between the two lead
Figure 2. Surface rumpling at PbS(001) and PbSe(001) surfaces from
DFT simulations at the PBE and PBE-D3 levels. The parameter Δzi is
described in the text and visualized in simplified cartoons. The more
Δzi deviates from zero, the more the atoms within a layer are shifted
relative to one another.20
chalcogenides:21 at PbS(001), the anions relax toward the
crystal interior, whereas they move to the outside at
PbSe(001); consequently, the Pb atoms relax outward (inward)
for PbS (PbSe), respectively. This has previously been
rationalized at the hand of different ionic radii:20,21 it was
argued that, compared to the small sulfide anion, its selenide
counterpart is larger and more diffuse, and so it moves to the
outside, away from the crystal lattice;20,21 similar behavior has
been seen and discussed for the heavier homologue PbTe.20,57
Our simulations reproduce this contrast well; “D3” slightly but
consistently increases the predicted rumpling at PbS(001), and
lowers it at PbSe(001), but using dispersion corrections does
not change the qualitative conclusions. Unfortunately, precise
experimental benchmarks regarding the quantitative extent of
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surface rumpling are difficult to attain, and a final verdict may
come from high-level computational techniques beyond
DFT.31,62 In what follows, we will report structures at the
dispersion-corrected PBE-D3 level and provide pure PBE data
in the Supporting Information as they do not lead to any
changes in interpretation.
The pristine, dense (111) surfaces (Figure 1c−d) have been
less studied so far; recall that those are likely metastable with
regard to surface reconstructions (the latter will be discussed
below). Figure 3 compiles computed, absolute distances at the
Figure 3. Course of Pb−S and Pb−Se bond lengths near relaxed,
pristine lead chalcogenide (111) surfaces. Computational results at the
PBE-D3 level are shown; those based on PBE are qualitatively similar
(Supporting Information).
unreconstructed surfaces, which outline the formation of
characteristic bilayers (“short−long” alternation), similar to
what was found for α-GeTe(111) and PbTe(111).38,39 The
scattering in surface bond lengths spans a range of ∼0.4 Å both
for PbS and PbSe; the anion-terminated surfaces (squares in
Figure 3) show this effect more strongly than their Pb-
terminated counterparts (blue circles). While the present work
is concerned with slab modeling exclusively, we do mention in
passing that other studies have been reported on isolated, entire
particles: for example, PbSe nanocrystals were simulated by
Franceschetti.63 The distribution width of surface bond lengths
in the latter work compares well to the present results from slab
models.
Let us now turn to surface energies, that is, stabilities which
are the key determinants for nanocrystal morphology.17,18 The
surface energies γ are obtained using similar expressions as in
previous studies, e.g., on the homologous PbTe (see ref 38 and
references therein). We begin by discussing the neutral pristine
surfaces, (001) and (011). Here, there are a number of previous
PBE computations in the literature to which we compare our
results in Table 2. The differences between previous studies and
ours are marginal; in fact, we have listed decimal places only to
make comparison feasible. At the PBE level, the (011) surfaces
come out approximately twice as costly as (001), in line with
previous work;22 this agrees well with the fact that no {011}
facets are observed in equilibrium.22 Using dispersion
corrections (rightmost column in Table 2), the relative
difference is smaller, but the surface energies still attain a
γ
ratio of γ011 ≈ 1.5; this is higher than what would be required
001
for the {011} facets to appear in the equilibrium shape
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The Journal of Physical Chemistry C Article

Table 2. Computed Surface Energies of Pristine PbS and

PbSe (001) and (011) Surfaces
γ (meV Å−2)
a
Previous PBE PBE-D3
PbS (001) 13.7,b 11.2c 11.9 26.0
(011) 24.3 39.7
PbSe (001) 11.0,c 11.5d 11.6 25.5
(011) 19.8d 22.1 36.7
a
All previous studies employed the PBE level of DFT, and slightly
different but overall comparable computational parameters. bFrom ref
64. cFrom ref 65. dFrom ref 22.

γ
( γ011 = 2 ; see below). Accordingly, the (011) surfaces have
001
been neglected in the above discussion of pristine surfaces.
Looking at the computed absolute surface energies (Table 2),
there is a significant difference in the latter dependent on
whether dispersion corrections are added or not. The mere fact
that both results do differ is not surprising: for example, Ončaḱ
et al. computed γ = 56 meV Å−2 for the MgO(001) surface at
the PBE level, and γ = 80 meV Å−2 for the same surface using
PBE-D2.66 For comparison, an earlier quantum Monte Carlo
study of MgO(001) had arrived at γ = 74 meV Å−2 (ref 31),
much closer to the above dispersion-corrected result (−7%)
than to the uncorrected one (+32%). This observation is also
reminiscent of the fact that absolute surface energies depend on
the choice of exchange−correlation functional, as mentioned
above.30−32 A more extreme influence of dispersion has
previously been encountered for “van der Waals” type (0001)
surfaces of layered Ge−Sb−Te materials:37 there, switching on
dispersion corrections to GGA increases the computed γ’s for
the stable “vdW” surfaces by an order of magnitude (or, to put
it more plainly: the uncorrected GGA functional fails by a
factor of 10).37 In this regard, the lead chalcogenides seem to
be intermediate between MgO (with which they share the
rocksalt structure) and the aforementioned layered chalcoge-
nide materials.
(111) Surface Reconstructions. The (111) surfaces are
special in the rocksalt type, as they are densely covered by one
or the other atomic species exclusively. In ionic compounds
such as MgO, this causes electrostatic instabilities which are
remedied by surface reconstructions67−69 or roughening.70 For
the significantly less ionic GeTe39 and SnTe,10,14 this need not
be the case throughout, and indeed an unreconstructed α-
GeTe(111)-(1 × 1) surface structure has recently been
observed in reflection high-energy electron diffraction
(RHEED) experiments.71 On the contrary, pure dense
PbSe(111) surfaces did turn out to be unstable, both in
transmission electron microscopy (TEM) and in simula-
tions.22,72 Likewise, a recent study revealed that an as-prepared
dense PbTe(111)-(1 × 1) surface does not prevail but
transforms into a stable (2 × 1) reconstruction upon heating.73
Clarifying atomic mechanisms which might stabilize the PbS
and PbSe (111) surfaces now seems to be a natural task for
DFT.
To this end, we proceed to sample representative surface
reconstructions (Figure 4a). The number of the latter is
necessarily finite, and limited by the size of simulation cells
available; this makes the choice of models even more
important, and the latter will ideally include patterns known
from earlier experiments. While evidence for PbSe(111) surface
reconstructions has indeed been found by Rutherford back-
8816
Figure 4. Reconstructions of lead chalcogenide (111) surfaces. (a)
Schematic drawing (after refs 38 and 74) of candidate structural
models. Smaller open and larger filled circles denote surface and
subsurface atoms, respectively, and thus they can represent either
cations or anions depending on the particular surface termination. (b)
The Pb-terminated 2 × 1 reconstruction of PbS(111), relaxed at the
PBE-D3 level of theory and shown in top view. Two characteristic
bond lengths di are labeled, and the boundary of the simulation box is
indicated. (c) Same for the S-terminated octopolar reconstruction; the
inset shows an isolated Pb4S4 motif at the surface. The complementary
2 × 1/S and oct/Pb reconstructions, as well as those at PbSe(111),
show similar connectivities (with atomic species exchanged and
structural parameters adjusted, of course).
scattering, 75 we do not know of atomically resolved
observations (say, by scanning tunneling microscopy), and
again we resort to previous findings for the “textbook” surfaces
of MgO. For example, the “octopolar” A4B4 moiety is a well-
known way to alleviate surface polarity.67 Later, an additional
reconstruction pattern was proposed for the MgO(111)
surface, which we label “MgO” here.68 The interested reader
is referred to ref 74 for an instructive survey of rocksalt-type
(111) reconstructions.
Computed energies for all candidate reconstructions are
summarized in Table 3. The “MgO” reconstruction does not
significantly stabilize the surfaces and in some cases has even
slightly higher γ than the pristine alternatives (top row in Table
3); the “SV” motif does provide some stabilization but is not
globally competitive. While the aforementioned two motifs are
polar (and thus their surface energies depend on the chemical
environment), the lower two, “2 × 1” and “oct” are not, and
these two do significantly stabilize the surfaces. For PbSe, 2 ×
1-reconstructed surfaces have been studied before at the PBE
level;22 note that in the latter work, they have been dubbed
“(111)-Pb nonpolar” and “(111)-Se nonpolar”, respectively.
There, and here, the Pb-terminated 2 × 1 reconstruction is
found visibly more stable than the anion-terminated alter-
native;22 the same holds for PbS (Table 3) and PbTe (ref 38),
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The Journal of Physical Chemistry C Article

Table 3. Surface Energies of Pristine and Reconstructed For now, we focus on the two most favorable (111)
(111) Surfaces reconstructions so identified, which are practically degenerate
in their surface energies (Table 3). The optimized atomic
γ (meV Å−2), PBE-D3a
structures have been visualized in Figure 4b (“2 × 1”) and
PbS PbSe Figure 4c (“octopolar”). We collect characteristic bond lengths
term Pb poorb Pb richc Pb poord Pb richc for these in Table 4. For PbS in particular, the respective
pristine Pb 107 68 99 63
S/Se 62 102 52 88 Table 4. Structural Properties of Reconstructed Lead
SV Pb 63 44 60 42 Chalcogenide (111) Surfacesa
S/Se 52 71 47 65 d1 (Å) d2 (Å) d3 (Å)
MgO Pb 90 70 85 68
PbS (2 × 1) Pb-term 2.64 2.77
S/Se 83 103 74 91
S-term 2.63 2.78
2×1 Pb 38 38 36 36
oct. Pb-term 2.72 2.82 2.85
S/Se 44 44 43 43
S-term 2.73 2.78 2.95
oct Pb 39 39 38 38
PbSe (2 × 1) Pb-term 2.77 2.88
S/Se 39 39 38 38
a
Se-term 2.79 2.89
Results at the PBE level are given as Supporting Information (and are oct. Pb-term 2.83 2.95 2.95
also visualized in Figure 5). bDefined as μPb = E(bulk)
PbS − ES
(bulk) c
. Defined
Se-term 2.87 2.90 3.07
as μPb = EPb . Defined as μPb = EPbSe − ESe .
(bulk) d (bulk) (bulk)
a
The parameters d1, d2, and d3 are defined in Figure 4. All data given
and also when moving from the PBE level to the PBE-D3 level have been obtained at the PBE-D3 level of theory. The optimized
bond lengths in the bulk are 2.96 Å (PbS) and 3.06 Å (PbSe),
in Table 3.
respectively (Table 1).
It is again interesting to compare the results with and without
dispersion corrections, and the larger number of reconstruc-
tions allows us to probe this difference in a more systematic shortest bond (d1) is significantly compressed at the 2 × 1
way (Figure 5). All data refer to the “Pb-rich” case; that is, to reconstruction compared to the octopolar motif. Relative to the
bulk (Table 1), the computed d1 are shorter by ∼11% (2 × 1)
and ∼8% (octopolar) at PbS(111) surfaces. They are likewise
compressed at PbSe(111), by ∼10% at most.
Finally, the question that emerges is that of global stability:
can the reconstructed surfaces discussed here compete with
their important (001) counterparts?
Surface Phase Diagrams. The global stability of different
surfaces is addressed using surface phase diagrams.76 Results for
the lead chalcogenides are presented in Figure 6, side by side
such as to detect chemical trends. Regardless of computational
methodology, the pristine and polar (111) surfaces (dashed
lines) are higher in energy for PbS than for PbSe, due to the
higher electronegativity difference in the lighter sulfide
compound. By contrast, all charge-neutral surfaces (horizontal
lines) are practically indifferent to the anionic species. Both for
PbS(111) and PbSe(111), reconstructions are clearly favored
and significantly lower the surface energies; for clarity, we show
Figure 5. Scatterplot of PBE versus PBE-D3 computed surface only the most stable option in each of the surface phase
energies, combining data for pristine and reconstructed (111) surfaces diagrams. It should be stressed that the energy difference
of PbS (circles) and PbSe (squares). The dashed line is the result of a between the 2 × 1/Pb and both octopolar motifs is only 1−2
least-squares fit (y = 0.9759x + 17.33; R2 = 0.997). meV Å−2 both at the PBE and the PBE-D3 level of theory
(Table 3); the deviation is likely within the error range of the
computations. In short, both types of reconstructions appear to
μPb = E(bulk)
Pb , where neither anionic species enters in the be viable.
definition of γ; this makes side-by-side comparison straightfor- Wulff Constructions. The comprehensive set of surface
ward. stabilities thus obtained may be translated into equilibrium
Clearly, the outcomes of the two methods are closely shapes using the Wulff construction77,78 (Figure 7). One
correlated (dashed line in Figure 5). There is, however, not a observes mainly cube-like morphologies for both lead
scaling factor between the results, but an of fset: PBE-D3 chalcogenides, not unexpectedly, but the results are different
predictions are higher than those of PBE by ∼17 meV Å−2. This in detail depending on whether dispersion corrections are used
suggests that long-range dispersion interactions affect surfaces or not. The shapes predicted at the PBE level are perfect cubes,
of similar area in a roughly similar way, and are less sensitive to whereas those at the PBE-D3 level are truncated at the corners,
the particular local reconstruction. In turn, the dispersion slightly more strongly so for PbSe. This reflects an observation
correction affects the most stable surfaces (with lowest γ) most we have made above: the surface energies for the competing
strongly in relative terms. This will become important when {001} facets are notably higher when “D3” is switched on. It
performing Wulff constructions, because those precisely reflect would now seem interesting to tackle this question
the relative stability of competing {hkl} facets. experimentally, for example, by utilizing vapor−liquid−solid
8817 DOI: 10.1021/acs.jpcc.6b02173
J. Phys. Chem. C 2016, 120, 8813−8820
The Journal of Physical Chemistry C
Figure 6. Computed surface phase diagrams for PbS (left) and PbSe
(right), excluding (a) and including (b) dispersion corrections to
DFT. Among the (111) reconstructions, only the respective most
stable one is given. Note, however, that for both compounds and at
both levels of theory, the respective pairs of “2 × 1” and “oct” motifs
are degenerate within a few meV Å−2. For further candidate
reconstructions, as well as the definition of chemical potentials (“Pb-
poor”, “Pb-rich”), see Table 3.
(VLS) routes similar to those used previously for growing SnTe
nanostructures.11−13,79 This would rule out effects of surface
ligands which have been described for PbSe nanocrystals,22 and
enable better comparison with the results of Figure 7. It should
also be noted that surface energies will additionally depend on
vibrational contributions at finite temperature, which have been
neglected here. These vibrational contributions have been
estimated to be on the order of ≤10 meV Å−2 in a seminal
study on RuO2(110),76 but how they affect the particular
surfaces studied here remains to be explored before quantitative
comparison to experiment can be made. Finally, with wet-
chemical syntheses in mind, the Wulff construction concept has
been nicely expanded to adsorbate-covered surfaces for the
particular case of PbSe.27 It would now seem very interesting to
explore the influence of dispersion corrections to DFT on the
outcome of such a model.
■ CONCLUSIONS
We have studied crystal surfaces of PbS and PbSe by
comprehensive first-principles simulations and have so obtained
fundamental insight into the materials’ properties at the
8818
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Figure 7. Equilibrium shapes of PbS and PbSe nanoparticles, obtained
using the Wulff construction77 based on computed surface energies.
The {001} facets (gray) are predominant regardless of methodology.
Using PBE-D3 (lower panels), one obtains slightly truncated
polyhedra which expose {111} surfaces with a 2 × 1/Pb termination
(blue). No {011} facets are observed in any case.
nanoscale. Dispersion corrections to DFT do affect the
computed surface energies, in particular those of (001), and
thus they indirectly affect the computed equilibrium shapes.
Lead chalcogenide (111) surfaces are prone to reconstruct (as
observed in previous experimental and theoretical studies); our
surface phase diagrams clearly identify viable candidates,
namely, Pb-terminated (2 × 1) motifs as well as both cation-
and anion-terminated “octopolar” reconstructions. Structural
parameters and trends have been predicted and may be probed
by surface-sensitive experiments in the future. Finally, our
findings for the clean surfaces may provide starting points for
further endeavors: for simulations of few-layer nanosheets,
reactivities of reconstructed (111) surfaces, their surface
oxidation, and likely some more.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.6b02173.
Computational results at the DFT-PBE level (as
supplements to Figure 3 and Tables 3 and 4) (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: drons@HAL9000.ac.rwth-aachen.de. Telephone: +49
241 80 93642. Fax: +49 241 80 92642.
Present Address
§
Engineering Laboratory, University of Cambridge, Trumping-
ton Street, Cambridge CB2 1PZ, United Kingdom.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We thank Philipp Konze for useful discussions and remarks on
this manuscript. This study received financial support from
Deutsche Forschungsgemeinschaft (DFG) through SFB 917
“Nanoswitches”. CPU time was allocated by the Jülich−Aachen
Research Alliance (Project jara0033).
DOI: 10.1021/acs.jpcc.6b02173
J. Phys. Chem. C 2016, 120, 8813−8820
The Journal of Physical Chemistry C
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