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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).
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
561
DOI: 10.1021/acsenergylett.6b00288
ACS Energy Lett. 2016, 1, 561565
Letter
http://pubs.acs.org/journal/aelccp
Letter
DOI: 10.1021/acsenergylett.6b00288
ACS Energy Lett. 2016, 1, 561565
Letter
1
k T (2(k + 1/2))2
B
0
AC = 80 (2(k + 1/2))2
+
1
ieL2
k=0
(1)
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)
DOI: 10.1021/acsenergylett.6b00288
ACS Energy Lett. 2016, 1, 561565
Letter
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.
Notes
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.
REFERENCES
ASSOCIATED CONTENT
S Supporting Information
*
DOI: 10.1021/acsenergylett.6b00288
ACS Energy Lett. 2016, 1, 561565
Letter
ovskite Solar Cells with Efficiency Exceeding 15%. Adv. Mater. 2015,
27, 63636370.
DOI: 10.1021/acsenergylett.6b00288
ACS Energy Lett. 2016, 1, 561565