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MATERIAL WITNESS

MAKING SPACE FOR SHAPE

Science doesnt quite know what to do
with people like Graham Parkhouse,
a British engineer who surely qualifies
as a maverick. While shoehorned
into a brief academic career at the
University of Surrey he now runs a
civil engineering consultancy nearby
Parkhouse developed ideas on materials
selection and design1 that proved
influential on pioneers of the field
such as MichaelAshby and that now
seem rather prescient. (Sadly, the same
cannot really be said for his published
ideas on cosmic background radiation.)
Parkhouse promoted the idea of
structure as an interplay of material
and shape that can now be seen to
foreshadow notions of hierarchical
materials and metamaterials. His
unusual career trajectory is described
in DonaldBrabens book on blue-skies
thinking, ScientificFreedom: The Elixir
of Civilization (Wiley,2008).
Parkhouses little-remembered
contribution is brought to mind in a
recent exploration by Barthelat and
Mirkhalaf of how material and shape
interact2. The authors have taken an
unusual approach to a well-studied
issue: how best to configure a composite
to achieve an ideal compromise
between the mechanical properties of its
constituents. As Barthelat and Mirkhalaf
point out, while it is well known that
combining a hard and a softer material
can engender a balance of stiffness and
strength (from the hard component)
with toughness and ductility (from the

soft), typically in engineering only a few

microstructures are employed, such as
fibre composites and laminates. Nature
is similarly conservative with its own
microstructural repertoire, favouring in
particular the staggered layering seen in
nacre and bone. But are these really the
best, or even the only, options?
The design of microstructure is
typically conducted as an optimization
process that begins with a certain
topology and refines it. A more
exhaustive search of the space of
microstructural possibilities is generally
thought computationally prohibitive.
But Barthelat and Mirkhalaf describe
a model for which this kind of blanket
survey is tractable: a two-dimensional
composite in which hard, rectangular
inclusions are regularly stacked within
a softer matrix, subjected to extensional
stress. Simple parametrization of this
geometry gives rise to just over 7,000
microstructures for a particular choice
of the hard (brittle) and soft (elastic)
phases. The stressstrain curves and
failure of each of these solutions can
then be calculated.
Most (about 90percent) of the
resulting composites are either very
brittle they contain continuous
hard phases, which yield by brittle
failure or very ductile, failing by
over-extension of the soft matrix. But
the remaining structures look more
useful. Half of these are quasi-brittle:
stiff but ductile, failing at strains much
greater than that supported by the hard

PHILIP BALL
phase alone. The others are labelled
ductile strong, and include staggered
hard platelets comparable to nacre.
The results confirm some expected
general principles: stiffness and strength
usually come together, whereas strength
and toughness tend to be mutually
exclusive. With the microstructural
space fully mapped, however, it becomes
possible to answer design questions
rather precisely: to find exactly which
shapes achieve a particular balance of
properties (if, say, toughness were to
be weighted more than stiffness). The
approach could be extended to include,
for example more degrees of freedom:
dissipation by delamination, hierarchical
structure and anisotropy. It might even
answer questions about natural design:
are natures composites truly optimal, or
constrained by their history?

References
1. Parkhouse, J.G. in Proc. 3rd Int. Conf. Space Structures
(ed. Nooshin, H.) 367 (Elsevier Applied Science, 1984).
2. Barthelat, F. & Mirkhalaf, M.J.R.Soc. Interface
10, 20130711 (2013).

HYBRID SOLAR CELLS

Perovskites under the Sun

Mixed-halide organicinorganic hybrid perovskites are reported to display electronhole diffusion lengths over 1m.
This observation provides important insight into the charge-carrier dynamics of this class of semiconductors and
increases the expectations for highly efficient and cheap solar cells.

Maria Antonietta Loi and Jan C. Hummelen

aterials that have a generic

chemical formula ABX3
and a cubic structure are
defined as perovskites, named after the
mineral CaTiO3. The A and B sites can
accommodate inorganic cations of various

valency and ionic radius. Alternatively,

suitable organic species can replace
cationA and create organicinorganic
hybrid materials1 (Fig.1). A number of
exciting physical properties, like colossal
magnetoresistance, ferroelectricity and

NATURE MATERIALS | VOL 12 | DECEMBER 2013 | www.nature.com/naturematerials

2013 Macmillan Publishers Limited. All rights reserved

superconductivity, have been discovered

in this prolific family of compounds
during the past century 1,2. Recently,
organicinorganic hybrid perovskites (in
particular CH3NH3PbX3, where X=I, Cl,
Br) came to the fore as a result of their
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news & views

H
C
N
Pb

Cl

Figure 1 | Crystal structure. Possible structure of the hybrid perovskite CH3NH3PbI3xClx. At present,
crystallographic data on the precise position of the organic ligands are not available.

high performance in converting solar

light into electrical power 3, with powerconversion efficiencies (PCE) exceeding
15% (refs4,5). This result is even more
impressive considering that the first
perovskite solar cells were only reported
in 2009, and displayed PCE values as low
as 3.8% (ref.6). These initial prototypes
were based on the classical architecture of
dye-sensitized solar cells, with the organic
inorganic compounds deposited on top of a
mesoporous TiO2 structure (Fig.2a). More
recent works demonstrated that a simpler
geometry a perovskite layer sandwiched
between a compact thin film of TiO2 and
a hole-conducting organic compound
(Fig.2b) is also able to convert light
with efficiencies higher than 10%, provided
that a uniform and dense morphology is
achieved in the deposited layer 5,7. Such
a steep learning curve in the design and
processing of hybrid perovskites is certainly
unprecedented in the field of photovoltaic
research. However, the understanding
of the mechanisms underlying such
exceptional performance has not grown
at the same pace. Writing in Science, the
groups of HenryJ.Snaith and colleagues8
and NripanMathews, TzeC.Sum and
collaborators9 now independently report
on diffusion-length measurements
performed on hybrid perovskites, which
shed light on the dynamics of photoexcited
species (excitons or charge carriers) in
these materials.
Both teams used photoluminescence
quenching experiments to measure the
electronhole diffusion length. They
deposited on top of a perovskite thinfilm a layer of quenching molecules,
which act as a sink for the photoexcited
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species that, travelling in the film, reach

the interface between the perovskite and
the quencher. The photoluminescence
dynamics of the material under study
are therefore dependent on the thickness
of the thin film and on the diffusion
length LD of the photoexcitations; this last
parameter can be extracted by modelling
the photoluminescence decay curves
according to a simple one-dimensional
diffusion equation. One of the most
challenging aspects of this technique is
the exact determination of the travelling
distance of the photoexcitations in other
words, the thickness of the tested layer
must be precisely controlled to minimize
the uncertainty of the extracted LD values.
In this respect, efforts reported in previous
works by Snaith and co-workers to optimize
the deposition of the perovskite layers5,7
have been fundamental in allowing a
reliable estimation of the electronhole
diffusion length. Both teams obtain LD of
about 100nm for electrons and holes in
CH3NH3PbI3. Furthermore, the group of
Snaith also investigated the mixed-halide
perovskite CH3NH3PbI3xClx, obtaining in
a

this case a LD exceeding 1m; this high

value reinforces hope for the future of
hybrid perovskite solar cells, because it
makes possible the fabrication of devices
with thicker active layers, where the
absorption of light can be increased without
affecting the collection efficiency of the
generated charges. That is to say, PCE values
of more than 15% may be possible.
But what is so exciting about these
materials, given that their PCE are still far
from those displayed by other common
photovoltaic examples such as singlecrystalline silicon devices (PCEof25%) or
thin-film copper indium gallium selenide
cells (PCEof20.4%)? The answer is the
lower manufacturing costs expected for
this future perovskite-based photovoltaic
technology. In fact, these materials can be
directly deposited from solution, a cheap
and scalable approach that is also the main
strength of alternative technologies such as
organic photovoltaics, dye-sensitized solar
cells and colloidal quantum dot-based solar
cells. In contrast to these latter devices,
which at the moment do not seem to be able
to boost the efficiency much above 10%,
perovskites are easy to fabricate and have
a higher power-conversion performance,
and this combination is likely to be because
of their hybrid nature. Indeed, the organic
component makes the perovskite soluble
and facilitates its self-assembly, thus
enabling its deposition from solution. At the
same time, the inorganic component forms
an extended framework bound by strong
covalent and/or ionic interactions, which
most likely preserves a precise crystalline
structure in the deposited films and ensures
a high carrier mobility 1. As shown by Snaith
and collaborators, the structural order
of mixed-halide hybrid perovskites leads
to a carrier (or exciton) diffusion length
above 1,000nm, in stark contrast with the
maximum values of about 10nm reported
for the diffusion length of excitons in solar
cells based on inherently less-ordered
polymerfullerene solar cells10.
The studies reported by the two teams
highlight that, after the initial excitement
b

Gold

Gold

Hole-transporting layer
Hybrid perovskite
TiO2

Hole-transporting layer
Hybrid perovskite

TiO2
Fluorine-doped tin oxide
Glass

TiO2
Fluorine-doped tin oxide
Glass

Figure 2 | Architectures of perovskite solar cells. a, Hybrid perovskite solar cell on mesoporous TiO2.
b, Planar hybrid perovskite solar cell.
NATURE MATERIALS | VOL 12 | DECEMBER 2013 | www.nature.com/naturematerials

2013 Macmillan Publishers Limited. All rights reserved

news & views

and surprise of the high efficiency of the
solar cells, it is now time to investigate
the physical properties that make hybrid
perovskites so promising for solar-energy
conversion. The next point to be addressed,
as Snaith and colleagues put forward in
their work, is whether the photoexcited
species in this class of materials are
excitons or free charges. We can further
suggest other aspects deserving thorough
analysis: what is the mobility of electrons
and holes? What is the exact chemical
structure of the hybrid perovskites and
how does it influence the transport
behaviour of the photoexcitations? What
is the precise role of each interface in the
device architectures proposed so far? Are
perovskite solar cells stable? And finally,
is it possible to reach analogous optical
and electrical performance using lead-free

organicinorganic compounds, thus

reducing the toxicity and environmental
impact of this future technology? Only a
large multidisciplinary effort will be able
to answer these questions, and create from
this exciting research topic a new and less
expensive photovoltaic technology.

5. Liu, M., Johnston, M.B. & Snaith, H.J. Nature

501, 395398 (2013).
6. Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T.
J.Am. Chem. Soc. 131, 60506051 (2009).
7. Eperon, G.E., Burlakov, V.M., Docampo, P., Goriely, A. &
Snaith, H.J. Adv. Funct. Mater http://dx.doi.org/10.1002/
adfm.201302090 (2013).
8. Stranks, S. etal. Science 342, 341344 (2013).
9. Xing, G. etal. Science 342, 344347 (2013).
10. Mikhnenko, O. etal. Energy Environ. Sci. 5, 69606965 (2012).

Maria Antonietta Loi 1 and Jan C.Hummelen1,2

are at 1Zernike Institute for Advanced Materials,
University of Groningen, Nijenborgh 4, Groningen,
9747AG, The Netherlands, 2Stratingh Institute for
Chemistry, University of Groningen, Nijenborgh 4,
Groningen, 9747AG, The Netherlands.
e-mail: m.a.loi@rug.nl; j.c.hummelen@rug.nl
References
1.
2.
3.
4.

Mitzi, D.B. Prog. Inorg. Chem. 48, 1121 (1999).

Polyakov, A.O. etal. Chem. Mater. 24, 133139 (2012).
Lee, M.M. etal. Science 338, 643647 (2012).
Burschka, J. etal. Nature 499, 316319 (2013).

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2013 Macmillan Publishers Limited. All rights reserved

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