Grain-Size-Limited Mobility in

Methylammonium Lead Iodide Perovskite Thin

Films
Obadiah G. Reid,, Mengjin Yang, Nikos Kopidakis, Kai Zhu, and Garry Rumbles*,,,

Chemistry and Nanoscience Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado
80401, United States

Department of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder, Colorado 80309, United States

Renewable and Sustainable Energy Institute, University of Colorado at Boulder, Boulder, Colorado 80309, United States
S Supporting Information
*

ABSTRACT: We report a systematic study of the gigahertzfrequency charge carrier mobility found in methylammonium lead
iodide perovskite lms as a function of average grain size using timeresolved microwave conductivity and a single processing chemistry.
Our measurements are in good agreement with the Kubo formula for
the AC mobility of charges conned within nite grains, suggesting
(1) that the surface grains imaged via scanning electron microscopy
are representative of the true electronic domain size and not
substantially subdivided by twinning or other defects not visible by
microscopy and (2) that the time scale of diusive transport across
grain boundaries is much slower than the period of the microwave
eld in this measurement (100 ps). The intrinsic (innite grain
size) minimum mobility extracted form the model is 29 6
cm2 V1 s1 at the probe frequency (8.9 GHz).

size increases from panel a to c, and two trends are evident in

the yield-mobility transients: overall signal strength increases
with grain size, and the average lifetime decreases. The initial
yield-mobility product is nearly independent of light intensity
over the order-of-magnitude in uence we measured, between
10101011 photons/cm2 (see Supporting Information) but
seems to increase very slightly with increasing laser uence.
Because the change is slight (40% over more than a factor of 10
in light intensity), we choose to simply average the initial yieldmobility product over all intensities and take the standard
deviation as our measurement uncertainty.
Figure 2 shows the measured yield-mobility product for a
wider sample set as a function of the grain size measured via
SEM. These data are derived from the biexponential ts to our
transients, where the initial photoconductance (at t = 0) is
calculated as the sum of the two exponential amplitudes. The
error bars correspond to the standard deviation for both the
measured grain size (x-axis) and the yield-mobility product (yaxis). Assuming that the charge photogeneration yield in these
lms is 100%, we equate the yield-mobility product with the

he intrinsic charge transport properties of methylammonium lead iodide peroveskite crystals is a matter
of great interest because of its potential utility as a
light-harvesting19 and emitting material.1012 In particular we
seek a quantitative explanation for how dierent processing
conditions and chemistries have inuenced the measured
charge carrier mobility in past reports.13 Here, we describe a
systematic study showing how the crystalline grain size
observed in scanning electron microscopy (SEM) images
correlates with the charge carrier mobility measured at 8.9
GHz. We use a single processing chemistry to vary the grain
size and measure the transient photoconductance of the thin
lms after laser excitation.
Figure 1ac shows representative microwave conductivity
transients (at several incident light intensities) for three
dierent grain sizes, and Figure 1df shows the corresponding
SEM images. The microwave data is plotted as the yieldmobility product calculated by normalizing the measured
photoconductance for the sample geometry and absorbed
photon ux. Calculation of this quantity is detailed elsewhere,14
but it is best understood as the sum of the electron and hole
motilities at the measurement frequency multiplied by the free
carrier yield. The solid black lines show ts to the data using a
biexponential function. As seen in the SEM images, the grain
XXXX American Chemical Society

Received: July 20, 2016

Accepted: August 17, 2016

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DOI: 10.1021/acsenergylett.6b00288
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ACS Energy Letters

boundaries may act as traps for one of the carriers but

apparently do not serve as ecient recombination centers
because if this were the case one would expect faster
recombination for smaller grains with greater surface area per
unit volume. Previous work15 has shown that the photoluminescence (PL) lifetime does decrease near grain boundaries,
which at rst seems to be in contradiction with our results, if
one assumes that the PL and photoconductance dynamics
report on the same aspects of carrier recombination. In fact, the
two are not so simply related in most thin-lm MAPbI3
samples. In our Supporting Information (Figure S3) we show
a comparison of the PL and photoconductance dynamics for
the extrema of our set of grain sizes. The PL decay is always
much faster than that of the microwave conductivity signal, but
the trend in PL dynamics, though weak, is consistent with
increased grain surface area decreasing the PL lifetime. This
mismatch in the PL and photoconductance dynamics has been
observed before and is explained by the presence of an ecient
trapping mechanism for one of the carriers.16,17 If recombination through the trap-state is slow, this asymmetric trapping
leads to a large remaining population of the other (free) carrier
and a large residual photoconductance but quenches the PL
rapidly. This model is qualitatively consistent with our
observation that smaller grains increase the photoconductance
lifetime while simultaneously decreasing the PL lifetime,
assuming the traps are associated with the free surface and/or
grain boundaries.
We do not attempt to analyze this trend further in the
present work, but why recombination through these inferred
surface traps is so slow merits further investigation as it
mitigates the negative inuence of grain boundaries. It certainly
serves to keep the apparent carrier diusion length high even
for the smallest grain size. Indeed, the mismatch between the
diusion length and the measured grains in all but Figure 1c,f
suggests that while useful, this nomenclature may be
misleading. We will come back to this point below.
The dependence of the minimum microwave-frequency
mobility on the grain size can be understood by invoking the
uctuationdissipation theorem, connecting the random
uctuations of an observable with its linear response coecient;
in this case, mean-squared displacement and mobility. If smaller
grains conne the charge such that its mean-squared displacement on the time-scale of the microwave probe period is
reduced relative to a freely diusing charge, then this will be
reected in the measured mobility. Use of this relationship
depends on quasi-thermal equilibrium conditions and a probing
electric eld that is weak. Quasi-equilibrium is guaranteed
because the carrier scattering time is much shorter than the
period of our probe eld.18 However, the weak-eld condition
merits some explanation as it bears on the conceptual
interpretation of the microwave conductivity measurement. It
is incorrect to suppose that nite grains reduce the microwavefrequency mobility because the carriers are pushed all the way
across a grain by the probe eld and collide with a domain wall.
Rather, the displacement induced by the oscillating probe eld
is small in comparison with the random diusive motion that
takes place during the oscillation period of the probe. If carriers
happen to collide with domain walls through diusion, the
probing eld senses this transport barrier. In our case, the
maximum electric eld at the sample is ca. 35 V/cm. This
corresponds to a maximum displacement of 0.5 nm in each
half-cycle of the probe, using the mobility derived below.

Figure 1. (ac) Microwave photoconductance transients for three

dierent methylammonium lead iodide pervoskite lms with
dierent grain sizes, measured between 10101011 photons/cm2,
600 nm excitation. (df) SEM images of lms prepared with
processing conditions identical to those used for the corresponding
microwave measurements. The minimum carrier diusion length
estimated from the average lifetime and minimum mobility derived
from these ts is (a) 2.4 m, (b) 4.1 m, and (c) 3.6 m.

Figure 2. Yield-mobility product at t = 0, plotted as a function of

average grain size (black symbols) and t using the Kubo relation
for carriers conned in one dimension (blue lines). The solid line
shows the best t for all the data, while the dashed line shows the t
for the rst two data points only.

minimum microwave-frequency mobility consistent with our

data. Here, the trend in mobility is obvious: decreasing grain
size correlates with a sharp decline in the mobility. This is
qualitatively consistent with previous observations that larger
grains produce better solar cells and suggests that the grain
boundaries are not benign toward charge transport.
It is interesting that the photoconductance lifetime decreases
with increasing grain size, because it suggests that the grain
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Thus, we use a special case of the uctuationdissipation
theorem to analyze our data: the Kubo relation.19,20 This
approach has been used numerous times in the past to interpret
microwave conductivity measurements on conned systems.2125 In most preceding cases the system to be modeled
was an explicitly one-dimensional (1D) object. Here, we are
dealing with 3D grains. Nevertheless, the appropriate
expression remains the 1D mobility as previously derived,21,22
because the mean-squared displacement in the direction of the
microwave probe eld depends only on the diusion coecient
and the connement in that direction. The main dierence is
that we do not have to correct the measured mobility for the
random orientation of 1D objects (with zero mobility
perpendicular to their long axis),21 and instead we simply use
the area-weighted average dimensions of each grain in the plane
of the lm to dene the grain size; this is the plane in which the
microwave electric eld is oriented. The expression we use for
the microwave mobility is21,22

attribute to grain size and how much to the diering chemical

origins of the lms. Our results, using a unied synthesis route,
indicate that grain size is indeed the controlling factor, and the
agreement between our data and the Kubo formula, a standard
transport model, supports this assertion.
We conclude that there is little evidence either that grains are
subdivided or that transport across grain boundaries is
unusually facile; the good agreement between the model and
our data indicates that what you see is what you get and that
the grain boundaries are signicant barriers to charge transport,
with diusion across them taking place on a time scale much
longer than the period of the microwave eld used here to
probe charge transport (100 ps). Moreover, the contradiction
between the nominal charge carrier diusion lengths calculated
from the microwave-frequency mobility and the average
photoconductance lifetime in Figure 1 suggests a fundamental
danger in equating carrier diusion length with an actual
transport distance. The diusion length jointly characterizes
local mobility and lifetime, but when an AC technique is used
for this measurement, such as time-resolved microwave
conductivity (TRMC) or transient terahertz, it may give the
erroneous impression of long-distance transport in a system
where charges are actually conned to rather small grains.31
Similarly, the apparent lifetime (and thus diusion length) may
be increased by an asymmetric trapping process; while clearly
not devastating to performance because of the slow throughtrap (ShockleyReadHall) recombination, one would prefer
to avoid such trapping entirely. Finally, the complex relationship between the photoluminescence and photoconductance
dynamics shows that the two measurements need to be
interpreted together in order to obtain a complete picture of
carrier dynamics in these materials.

1

k T (2(k + 1/2))2

B
0

AC = 80 (2(k + 1/2))2
+
1

ieL2
k=0
(1)

where 0 is the intrinsic (innite grain size) mobility, k a

summation integer, e the electron charge, the microwave
probe frequency, and L the average grain length.
The solid blue line in Figure 2 shows the best t to our data
using this expression, where 0 is the only variable parameter.
The t was done by orthogonal-distance regression to
incorporate both x- and y-error estimates and yields a value
of 0 = 29 6 cm2 V1 s1 (95% condence). The agreement
between the model and our data is reasonably good; however,
there is an evident deviation between the mobility measured for
our smallest grain size samples and the t. One can force eq 1
to t through these points, as shown by the dashed curve in
Figure 2, leading to an alternative interpretation of our data: the
intrinsic mobility is actually much higher (250 cm2 V1 s1),
and the electronic domain size saturates at around 100 nm
despite the increase in grain size evident in SEM images. We
nd this quite unlikely, primarily because terahertz measurements, which should be less sensitive to grain sizes in this range,
have not shown such high mobility13 except where the yield
was assumed to be small.26,27 To put this another way, the yield
mobility product has never been reported to be much higher
than that found here. Nevertheless, the eective carrier masses
in methylammounium lead iodide are low enough to make this
high mobility plausible,28 and we cannot entirely discount it.
Still, we speculate that a more likely explanation for the smallgrain samples appearing with lower mobility than predicted by
the free-t of the Kubo model is that there is an increase in
amorphous or nanocrystalline material in these small-grain
samples. The rapid nucleation and growth conditions used for
the small-grain samples could conne the intergrain regions in a
way similar to that in mesopourous TIO2.29 Thus, counting up
crystalline domains visible in SEM images could eectively
overestimate the average grain size, leading to the slight
deviation we observe between our smallest grain size sample
and the Kubo t.
Other authors have previously observed a similar trend in the
charge carrier mobility of methylammonium lead iodide
perovskite lms as a function of the grain size,30 but dissimilar
processing conditions used in that study complicate the
interpretation, as it is not clear how much of this eect to

EXPERIMENTAL SECTION
Methylammonium lead iodide perovskite lms were grown on
quartz substrates by following a general procedure we
developed previously.32 In brief, stoichiometric PbI2 and MAI
were dissolved in a mixed solvent of NMP and GBL (7:3,
weight ratio) to form a 50 wt % precursor solution. A smooth
wet lm on top of quartz was formed after a spin-coating at
4500 rpm for 25s. Quartz substrate was transferred into
dimethyl ether solution for 1 min, and the wet lm was
converted into perovskite lm by the solventsolvent
extraction process. The perovskite lms were subsequently
annealed at temperatures ranging from 100 to 150 C for
various durations. This procedure results in lms with uniform
lm thickness (see Figure S2) but variable crystalline grain size
due to the dierent annealing temperature and duration.
SEM images were obtained by using a eld-emission
scanning electron microscopy instrument (FESEM, Quanta
600 and Nova 630 NanoSEM, FEI).
Analysis of SEM images was done in Adobe Illustrator. A
random representative area within each image was dened, and
every visible grain that was fully contained in the boundary (not
clipped at the edge) was measured along two orthogonal axes.
The rectilinear area was computed, and the grain size is taken
as the geometric mean:
a=

xy

(2)

where a is the average geometric length of the grain and x and y

are the dimensions measured for each grain during image
analysis. These grain sizes were tabulated for the whole dened
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area we analyzed (typically 30 grains in total), and the areaweighted arithmetic mean and standard deviation were taken:

a =

i aiAi
i Ai

A (aa )2 1/2
i
i

a = i

i i

(3)

(4)

AUTHOR INFORMATION

Corresponding Author

*E-mail: garry.rumbles@nrel.gov.

where a is the ensemble average grain size, ai the size of the

ith grain, Ai its area, and a the area-weighted standard
deviation.
Time-resolved microwave conductivity measurements were
performed in a standard system that has been extensively
reported elsewhere.14 Briey, the sample is mounted in a
microwave cavity, and a microwave probe beam is coupled to it
by waveguide circuitry, with the microwave frequency tuned to
be on resonance with the cavity. We photoexcite the sample
with a short laser pulse (5 ns, Nd:YAG pumped OPO
systems: Continuum Powerlite/Panther or Spectra Physics
QuantaRay/GWU PremiScan) and measure the transient
change in absorption of the CW microwave probe as a
function of time after the laser pulse. The fractional change in
microwave power reected from the cavity is directly
proportional the transient conductance of the sample; the
proportionality constant, K, is calculated by numerically solving
Maxwells equations for microwave propagation through the
sample and cavity materials and geometry. Two dierent
cavities were used in this work, having K = 28 000 and K =
18 000. Note that this method of determining the cavity
sensitivity factor, K, is a novel feature of this work and the
subject of a forthcoming dedicated publication. We have found
this method of determining our sensitivity to be more accurate
than the analytical formulas that we and others have used in the
past,14 which inevitably contain simplifying assumptions that
limit accuracy. Our present numerical calculation takes into
account every detail of the cavity geometry and, particularly, the
dielectric materials integral to it.
TRMC data was analyzed in custom software developed for
Igor Pro. Each photoconductance transient was t using a
convolution between the instrument response function and a
double-exponential decay, and error estimates on the t
coecients were obtained by weighting the t with the
standard error associated with each transient (itself the mean
from many laser pulses). The sum of the pre-exponential
coecients and a pooling of their associated error estimates
provides an initial photoconductance, corresponding to the
maximum transient signal deconvoluted from resolved decay
processes.
We routinely measure many transients as a function of laser
uence in order to obtain kinetic data related to carrier
recombination processes. In this case the initial photoconductance is linear with laser uence in the range we
measured, indicating constant yield. Thus, in order to obtain
the best estimate of yield-mobility product for each sample, we
simply average these numbers across all measured uences.

Initial photoconductance and average lifetime as a

function of uence, absorbance spectra of several
representative lms with dierent grain sizes, and a
comparison of photoluminescence and photoconductance dynamics in small and large grain size samples
(PDF)

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This work was supported by the Solar Photochemistry
Program, Division of Chemical Sciences, Geosciences, and
Biosciences, Oce of Basic Energy Sciences, U.S. Department
of Energy under Contract DE-AC36-08-GO28308 with the
National Renewable Energy Laboratory.

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ASSOCIATED CONTENT

S Supporting Information
*

The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acsenergylett.6b00288.
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