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Dual nature of the excited state in organic–


inorganic lead halide perovskites†
Cite this: Energy Environ. Sci., 2015, 8,
208
Kevin G. Stamplecoskie,a Joseph S. Manserab and Prashant V. Kamat*abc
Received 19th September 2014
Accepted 3rd November 2014
Published on 03 November 2014. Downloaded on 22/04/2017 16:07:49.

DOI: 10.1039/c4ee02988g

www.rsc.org/ees

The rapid increase in efficiency of methylammonium lead halide


perovskite solar cells necessitates further investigation into the nature Broader context
of perovskite absorption features and optical properties. Films The development of thin lm solar cells with efficiencies comparable to
obtained from the deposition of solutions containing lead halides and commercial PV technology is attractive due to simplicity of fabrication and
the CH3NH3+ organic cation is known to yield the CH3NH3PbI3 lower carbon footprint. The recent breakthroughs in developing organic–
perovskite structure upon annealing. In examining the precursor inorganic metal halide perovskite-based solar cells have delivered effi-
ciencies in the range of 17–19%. Whereas the majority of recent efforts
solution used in the processing of CH3NH3PbI3 solar cells, we find that
have focused towards fabrication of high-efficiency perovskite solar cells,
Pb2+ readily forms plumbate complexes in the presence of excess less is known about the nature of the excited state that leads to charge
iodide ions and exhibits characteristic absorption bands at 370 (PbI3 ) separation and ultimately charge extraction. Using femtosecond transient
and 425 nm (PbI42 ). Through comparative spectral analysis of the absorption spectroscopy, we have now identied the dual nature of the
absorption features of charge transfer complexes in the solution phase CH3NH3PbI3 excited state. We nd that both a charge separated state and
charge transfer state explain the overall behavior of the excited state. The
and the final solid-state perovskite films, we are able to fully classify
spectral characterization and kinetic proles presented here provide
the absorption features in the excited state of CH3NH3PbI3 across the insight into the excited state behavior of CH3NH3PbI3 lms. These results
transient absorption spectrum recorded following laser pulse excita- have important implications in understanding the photoinduced
tion. In particular, we attribute the broad photoinduced absorption to processes in perovskite solar cells.
a charge-transfer excited state, and show correlation between the
photoinduced absorption and 480 nm bleach signals. These obser-
their efficacy when coupled with both electron accepting and
vations lead us to propose a band structure composed of two distinct
insulating metal oxides and in planar thin lm photovoltaic
transitions that is consistent with the various spectral features and
architectures.4–7 Additionally, ambipolar carrier diffusion
kinetic behavior of the CH3NH3PbI3 excited state. Characterization of
within lead halide perovskites further highlights the unique
this unique dual excited state nature provides further insight into the
excited state character of this peculiar class of semi-
optoelectronic behavior of hybrid lead halide perovskite films and thus
conductors.8–10 The quest to design high efficiency (>20%)
aids in elucidating their exceptional photovoltaic properties.
perovskite solar cells demands better understanding of the
nature of interactions in the ground state as well as the excited
The unusually high photovoltaic performance of methyl- state behavior leading to efficient charge separation and
ammonium lead halide perovskites has drawn considerable extraction.11,12
attention in understanding the primary photoinduced events One of the most promising attributes of hybrid perovskites
that lead to charge separation.1–3 The excited state properties of for device applications is their ability to be processed from
these hybrid materials are of particular interest considering solution and at low temperatures (100  C). Despite these low-
energy requirements, organic–inorganic perovskites display
surprisingly excellent semiconductor properties, as evidenced
a
Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556, USA. by the limited contribution from trap states to the overall
E-mail: pkamat@nd.edu excited state dynamics and the signicant deviation from
b
Department of Chemical and Biomolecular Engineering, University of Notre Dame, simple Langevin recombination kinetics.13–16 A wide variety of
Notre Dame, Indiana 46556, USA
c
methods for depositing high-quality perovskite thin lms have
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame,
Indiana 46556, USA
been developed, including solution-based sequential deposi-
† Electronic supplementary information (ESI) available. See DOI: tion and co-evaporation of the solid precursor compo-
10.1039/c4ee02988g nents.2,6,7,17,18 However, the most facile technique involves a

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single-step deposition of the perovskite precursors from solu- Using both steady-state and time-resolved absorption spec-
tion. This method entails dissolving both the PbX2 and RNH3X troscopy, we have now probed the formation of iodoplumbate
compounds in a common solvent such as dimethylformamide, complexes in the CH3NH3PbI3 perovskite precursor solution
dimethyl sulfoxide, and/or g-butyrolactone. The solution is then and established the role of charge transfer states in dictating
cast onto a planar or mesostructured lm by spin coating fol- the net photoinduced charge separation in CH3NH3PbI3.
lowed by drying/annealing, during which time the precursor
components self-assemble into the nal perovskite phase with
the general AMX3 stoichiometry.1,19–22 For the 3-dimensional Results and discussion
hybrid perovskites discussed here, A is a small organic cation Complexation between PbI2 and iodide ions
(e.g., CH3NH3+), M is a divalent group 14 metal (Sn2+, Pb2+), and
PbI2 is a well-known semiconductor with limited solubility in
X is a halide ion (I , Br , Cl ).
water,32–34 and colloidal particles of PbI2 have been shown to
The solution-based processing of hybrid perovskites neces-
exhibit semiconducting properties. Interestingly, in the pres-
sarily leads to an intriguing question: what is the nature and
ence of excess iodide ions, PbI2 undergoes complexation to
identity of the species that comprise the precursor solution, and
produce soluble PbI3 , PbI42 , and higher coordinated plum-
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can characterizing their properties help us better understand


bate species. In order to probe the complexation between PbI2
the perovskite excited state? It is well established that transition
and CH3NH3I, we monitored the changes in the absorption
metals with an s2 electron conguration (i.e. Ti+, Sn2+, Pb2+,
spectra of a PbI2 solution at different concentrations of
Sb3+, Bi3+, Te4+) form labile complexes with halogens in a range
CH3NH3I (Fig. 1A). With increasing concentration of CH3NH3I,
of solvents.23 For Pb2+, these complexes are referred to as
two new absorption bands appear with maxima at 370 and
‘plumbates’ (e.g., triiodoplumbate (PbI3 ) and tetraiodo-
425 nm, respectively. The growth of absorbance monitored at
plumbate (PbI42 )) and are investigated herein.23 It is difficult to
these two maxima (Fig. 1B) show different dependence on the
isolate complexes with an exact number of halogens for these
methylammonium iodide concentration. The growth of
metals due to equilibrium between multiple halogenated
absorption at 425 nm saturates at lower concentration than at
complexes. Though these complexes are kinetically labile,
370 nm. The appearance of concentration dependent absorp-
varying the concentration of I allows one to spectroscopically
tion bands suggests the presence of two separate complexation
characterize different forms of the iodoplumbate complex.23
equilibria. These observations are consistent with the reported
Initial investigations into the methylammonium lead halide
complexation between PbI2 and I and calculated absorption
excited state focused primarily on charge mobility and transfer
spectra for each of the tri- and tetra-iodoplumbate complexes
rates to selective electron- and hole-accepting materials.24–26
(equilibria (1) and (2)).23
Since then, additional pump-probe spectroscopic studies in
both the visible and terahertz spectral regions have revealed the PbI2 + I * K1 0 PbI3 (1)
intrinsic nature of photoinduced charge carriers and their
recombination mechanisms within these materials.14,15,25,27–30 PbI3 + I * K2 0 PbI42 (2)
These studies have provided insight into the optoelectronic
properties of hybrid perovskites, including the large fraction of
free carriers generated under non-resonant (Eexcitation > Egap) We further evaluated the complexation process by analyzing
room temperature photoexcitation. This observation, of course, the absorption change using Benesi–Hildebrand plots.35–37 The
is important for photovoltaic applications. Yet given this linear relationship of the double reciprocal plot (1/DA vs. 1/[I ])
growing body of spectroscopic information, full characteriza- (Fig. S1 in the ESI†) for two separate concentration ranges of
tion of the broad and complex spectral features across the iodide conrms the presence of the two equilibria illustrated in
visible region of the lead halide perovskite excited state remains (1) and (2). From the slope and intercept of the linear plot we
elusive. In particular, questions remain regarding the transient obtain equilibrium constants of 54 M 1 for K1 and 6 M 1 for K2.
photoinduced bleaching at 480 nm and induced absorption The average association constant for the tri- and tetra-iodo-
extending from approximately 550 to 680 nm. plumbate in acetonitrile observed in the present experiments
Initially, Xing, et al. attributed the two photoinduced agrees well with the qualitative estimate of 27 M 1 obtained as a
bleaches that arise following laser pulse excitation of combined value for the two equilibria.20 The present study
CH3NH3PbI3 to a dual valence band structure,25 although they enables determination of two separate equilibrium constants.
recognized that this type of conguration could not fully The presence of the organic cation (viz., CH3NH3+) is integral
account for the broad photoinduced absorption. Recently it has in determining the nal hybrid perovskite structure upon
been suggested that the bleaching at 480 nm stems from a PbI2 drying and annealing of the iodoplumbate lm.27 Geometries
passivation layer at the interface between oxide support and ranging from 1-D polymeric chains to 3-D isotropic crystal
lead halide perovskite.31 In both the methylammonium lead structures can form depending on the size and identity of the
iodide structure and the PbI2 rhombus structure (i.e. plumbous organic component.38 The obvious question is whether the
iodide), Pb2+ is coordinated to six I ligands. The obvious organic cation plays a role in the initial complexation process.
question is how the excited state chemistry of the lead iodide We probed the cation effect by repeating the experiment in
inuences the overall excited state behavior of the organic– Fig. 1, replacing CH3NH3I with KI. The absorption changes seen
inorganic metal halide framework under visible excitation. with increasing KI concentration are shown in Fig. S2 (ESI†).

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Fig. 1 (A) Absorption spectra of 250 mM PbI2 solution in dimethylformamide (a) with increasing concentration of MAI from 6 mM (b) to 24 mM (e),
and (B) the change in absorbance monitored at the 370 nm peak for PbI3 and 425 nm for PbI42 as a function of the MAI/Pb2+ ratio.
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The appearance of absorption bands at 370 nm and 425 nm, the fundamental properties of these perovskite lms in the
similar to Fig. 1A and B, conrms that PbI2 undergoes excited state.14,24–26,39
complexation with iodide ions irrespective of the nature of the The transient absorption spectra recorded following 387 nm
cation. Thus, the yellow-colored precursor solution employed in laser pulse excitation of the PbIxn precursor solution are shown
the preparation of organometal halide perovskite lms for solar in Fig. 2A. The transient bleaching below 410 nm is accompa-
cell devices is essentially a lead halide complex (PbIxn ). The nied by an induced absorption with a maximum around
ratio of PbI2 : I determines the type of initial complex formed 460 nm. The absorption-time prole recorded at 500 nm shows
in this system and hence careful control of this complex is a quick decay of the transient with a lifetime of 3.6  0.2 ps,
important to obtain perovskite structure in the annealed lms. followed by a longer lived component with a lifetime of 698 
Given its ability to coordinate with six ligands, we can expect up 92 ps (Fig. 2B). In order to establish the identity of the transient
to six I ions to associate with a single Pb2+ ion in the lm. absorption peak at 460 nm, we compared the induced absorp-
Because of the solubility limitation of iodide, it is not possible tion spectrum with various iodide species (I , I3 , I2 etc.). It is
to probe higher order complexes in solution. interesting to note that the induced absorption has close
spectral match with the spectrum of I2 in dimethylformamide
solution (see Fig. S3 in ESI†). Given this spectral similarity, we
assign this transient formed following the excitation of the
Excited state behavior of PbIxn complex in solution
PbIxn complex to a species similar to I2.
The photochemical activity of PbI2 semiconductor colloids as
well as lead halide complexes is well documented in the liter- PbIxn + hn / (PbIx 2
n
/I2) (3)
ature.34 The absorption properties of plumbate complexes are
determined by the octahedrally coordinated Pb and have been
associated with the halide-to-metal charge transfer absorp- As shown previously,23,39 ligand-to-metal charge transfer in
tions.23,39 Despite the intense efforts to fabricate high efficiency the excited state leads to transfer of electrons from I3 to Pb2+.
solar cells with varying composition of lead and halide coun- The formation of I2 species formed within the complex is short-
terparts, relatively few studies have focused on elucidation of lived, as it decays to regenerate the complex. The appearance of

Fig. 2 (A) Time-resolved transient absorption spectra recorded following 387 nm laser pulse excitation of methylammonium lead iodide
precursor solution with 250 mM PbI2 and 24 mM MAI in dimethylformamide and (B) absorption-time profile of the induced absorption for the
same precursor solution monitored at 500 nm (the difference absorption maximum is normalized to value 1).

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Fig. 3 (A) Ground state absorption spectra of (a) the perovskite precursor solution in DMF, (b) as-deposited film from a 1 : 1 CH3NH3I : PbI2
solution on alumina, and (c) after annealing the deposited film at 100  C for 20 min. (B) Excited state spectra of the same samples recorded 5 ps
after 387 nm femtosecond laser pulse excitation in an evacuated cell.
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this transient following laser pulse excitation indicates that the temperatures to drive mass loss and initiate perovskite crystal
excited state is photoactive and is capable of undergoing charge formation.15,41
transfer within the complex. The charge transfer characteristics Though we observe partial perovskite formation upon thin
of PbIxn and its ability to undergo photochemical charge lm deposition, the similarity of spectral features at wave-
separation remains an important feature of the unannealed lengths below 500 nm in spectra a and b (Fig. 3A) and the lack of
perovskite lms. features near the band edge transition (760 nm, spectrum b)
indicate that the electronic transitions in both cases are
dictated primarily by the PbIxn complex. Thus the organic
Excited state behavior of perovskite lms cation acts largely as a spectator (viz., charge neutralizer) at this
In designing CH3NH3PbI3 thin lms, one usually casts a layer of early stage, with minimal inuence on the ground state
the yellow-colored precursor solution prepared with PbI2 and absorption characteristics. Earlier reports have shown other
CH3NH3I on a conducting electrode surface or mesoscopic plumbate complexes possess optical properties that are domi-
metal oxide lm. Fig. 3A shows the absorption spectra recorded nated by the hexagonally coordinated lead, and that the various
following the deposition of the precursor solution onto a mes- cations balance charges but have little effect on the light
oporous alumina scaffold, along with the spectrum of the absorption properties.38,42
precursor solution. The wide band gap alumina support When annealed at 100  C for 20 min, the color of the lm
prevents unwanted charge transfer events that could convolute changes from light yellow-brown to dark brown, indicating
the intrinsic excited state properties of CH3NH3PbI3 (see ESI† structural transformations to produce the perovskite
for experimental details on perovskite lm preparation). morphology. The absorption peaks seen at 365 and 420 nm
The absorption spectrum of the as-deposited lm before disappear and broadened peaks now appear at 480 and 760 nm
annealing (spectrum b in Fig. 3A) shows absorption maxima at (spectrum c in Fig. 3A). The changes seen in the absorption
365 and 420 nm that closely resemble the plumbate complexes features following the annealing process reect full trans-
seen in solution (spectrum a). Given the anionic nature of the formation of the [PbIxn (CH3NH3)+] complex into the
complex, the cation (CH3NH3+) is expected to be associated with CH3NH3PbI3 perovskite. Additionally, the characteristic
the complex in the lm as the solvent molecules are removed CH3NH3PbI3 X-ray reections become more intense with
during the drying process. The absorption of the unannealed annealing (Fig. S4, ESI†). Although we cannot discern various
lm extends into the visible as a result of partial conversion of degrees of order in the XRD analysis reported here, previous
the plumbate complex to the perovskite structure upon drying. X-ray scattering measurements have revealed an interplay
The X-ray diffraction (XRD) pattern of the solid-state lm before between crystalline and amorphous hybrid perovskite phases
annealing indeed reveals reections in good agreement with the within mesoporous supports.43 While annealing of perovskite
tetragonal phase of CH3NH3PbI3 (see Fig. S4 in ESI†), indicating lms increases the fraction of crystalline domains,27 further
some degree of perovskite crystallite formation within the studies are required to pinpoint the specic absorption char-
mesoporous support.2,40 This initial perovskite formation prior acteristics of both disordered and ordered CH3NH3PbI3 regions.
to annealing is expected given the stoichiometric ratio of the We can however rule out a transition from amorphous to crys-
precursor components (CH3NH3I : PbI2) and the tendency of talline perovskite as the sole cause for the change upon
the precursors to rapidly crystallize when deposited from a annealing, as the unannealed sample exhibited no character-
relatively weak coordinating solvent such as DMF (compared to istic band edge peak and closely resembled the absorbance of
the stronger coordination between PbI2 and DMSO).7 It has the precursor solution.
been reported previously that increasing the CH3NH3I : PbI2 Several studies employing XRD, grazing incidence wide-
molar ratio requires longer annealing times and/or higher angle X-ray scattering, and scanning electron microscopy have

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probed the structural transformation from a lead halide the origin of these two bands to transitions between two valence
complex to the nal perovskite phase.1,44,45 In particular, Tan, bands (VB1 & VB2) and a common conduction band minimum
et al. identied a crystalline precursor phase following deposi- (CB1).25 As discussed in our earlier study, the lower energy
tion of a mixed halide precursor solution containing CH3NH3I transition (760 nm bleach) arises from intrinsic charge sepa-
and PbCl2 that appears prior to perovskite crystal formation.44 ration corresponding to the band edge transition
Manifestation of this unknown crystalline precursor was shown (reaction (4)).14
to be a function of processing conditions such as annealing
atmosphere and time/temperature. It was posited that this CH3NH3PbI3 + hn / CH3NH3PbI3 [h + e] / CH3NH3PbI3 (4)
precursor compound inuences the nal perovskite thin lm
morphology and ultimately the device performance. These
recent results suggest that characterizing the individual Based on the observed second order recovery of the 760 nm
components and precursors that precede hybrid lead halide bleach, we suggested that charge recombination proceeds
perovskite formation can enable improved control over material principally through nongeminate bimolecular recombination
and optoelectronic properties. across a broad range of excitation intensities.14 The band lling
model established in this study further corroborated this
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To investigate the excited state properties of the iodo-


plumbate complex in the solid state, the as-deposited and conclusion and revealed the limited contribution from excitonic
annealed lms were transferred into a spectroscopic cell, states in CH3NH3PbI3 following room temperature laser pulse
evacuated, and subjected to laser pulse excitation. The transient excitation. The relatively low exciton binding energy (30–
spectra recorded following 387 nm laser pulse excitation are 50 meV) estimated for CH3NH3PbI3 facilitates the direct
shown in Fig. 3B. The excited state spectrum of the as-deposited formation of a large fraction of photogenerated free charge
lm displays bleaching at 440 and 680 nm, whereas the carriers in CH3NH3PbI3.12,46 Furthermore, theoretical investi-
annealed lm exhibits bleaching at 480 and 760 nm. The gations into possible dielectric screening by the organic cation
bleaching centered at 680 nm of the as-deposited lm arises suggest the binding energy may be well below the 26 meV of
most likely as a result of formation of a small amount of CH3- thermal energy at room temperature.47
NH3PbI3 upon drying (vide supra). Both samples exhibit a broad One of the distinguishable features of the two bleaching
photoinduced absorption. Shown also in Fig. 3B is the excited bands seen in the transient spectra (Fig. 4A) is the narrowing of
state spectrum of the precursor solution, which has a similar the 760 nm bleaching band with time. The spectral narrowing,
photoinduced absorption in the visible and a probable which is also reected as a red-shi in the zero absorbance
bleaching below 400 nm. The red-shied spectral features in cross over point with time, can be well described by the dynamic
the as-deposited lm compared to the precursor solution are Burstein–Moss or band lling model.14 As a result of this shi,
expected considering higher order coordination between Pb2+ we fail to observe a clean isosbestic point between the bleaching
and I dominates in the solid-state lms. Qualitative compar- band in the 680–740 nm region and induced absorption. This
ison of these spectral signals suggests that a charge transfer spectral behavior in the 680–800 nm region fails to correlate
complex nature persists in the excited state of the as-deposited with the other parts of the transient absorption spectrum,
and annealed lms. indicating the presence of additional transient species.
Time-resolved transient absorption spectra recorded In addition to examination of the excited state spectral
following 387 nm laser pulse excitation of the annealed lm are features, we also observed signicant discrepancies in the
shown in Fig. 4A. Two bleaching bands prominently seen at 480 excited state recovery kinetics at 480, 600, and 760 nm. Inter-
and 760 nm were attributed to the transitions seen in the estingly, the induced absorption seen in the 550–680 nm region
ground state absorption spectrum. A previous study attributed and the bleaching at shorter wavelengths (<500 nm) in the
annealed lms are closely associated. We base this argument on

Fig. 4 (A) Transient absorption spectra recorded following 387 nm excitation of annealed CH3NH3PbI3 on a mesoporous alumina support at
various pump-probe delay times. (B) Difference absorption-time profiles recorded at 480 (blue trace), 600 (grey trace), and 760 nm (red trace).

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two facts: (1) the presence of a 530 nm isosbestic point between (6). The generation of an I2-like species in the excited state may
the two bands and (2) similar decay lifetimes at 480 and 600 nm. have interesting effects on the long term stability and photo-
A set of transient decay proles are compared in Fig. 4B. Fitting voltaic performance of CH3NH3PbI3-based devices. In the
the kinetics to a biexponential decay reveals that the recovery at present study, we observe full recovery of this excited state and
480 and induced absorption at 600 nm match well with an no indication of photodegradation of the lms with repeated
average lifetime of 97  7 and 105  6 ps, respectively (see ESI† experiments.
for details on data tting). These average lifetimes deviate The dual valence band model considered previously was
markedly from that seen at 760 nm (313  37 ps). It should be derived to account for behavior of the two photoinduced
noted that these lifetimes are shorter than those determined in bleaches at 480 and 760 nm in CH3NH3PbI3.25 However, this
other studies utilizing time-resolved spectroscopic techniques model cannot account for the discrepancy in recovery kinetics at
due to the relatively high excitation uence employed here the two spectral positions. Given a common conduction band
(19 mJ cm 2).24,25 As we have demonstrated previously, the minimum, one would expect the transient kinetics to be
intrinsic bimolecular recombination kinetics are a strong homogeneous across the visible spectrum, assuming the
function of excitation intensity in CH3NH3PbI3.14 difference absorbance signal stems principally from state
lling. The kinetics of the bleaching recovery proles below
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Based on the complete analysis of the spectral data for the


precursor solution and solid-state samples, we propose the 500 nm and identication of the transient species responsible
existence of a dual excited state composed of a charge transfer for the induced absorption need to be reconciled in order to
band (480 nm) and charge separated band gap state (760 nm) in obtain a complete understanding of the excited state.
CH3NH3PbI3 (Fig. 5). We assign the spectral features below It is evident from the present investigation that the annealed
680 nm (induced absorption and bleach) in the fully formed CH3NH3PbI3 perovskite lm retains the charge transfer
CH3NH3PbI3 perovskite to those of the excited complex that complex character that is inherited from the parent lead halide
undergoes charge transfer to produce an I2-like species. complex. Despite the larger extinction coefficient of the transi-
Furthermore, the charge transfer excited state can be generated tion at 480 nm (as compared to the 760 nm transition), the
with lower energy (590 nm) excitation as well (Fig. S5†), indi- magnitude of the observed bleaching is relatively small. This
cating that the absorption is broad. However, the relative suggests that the contribution of the charge transfer complex to
intensities of the 760 and 480 nm bleaches differ when using the overall excited state is relatively small. The model depicted
590 nm laser excitation from that of 387 nm excitation, which in Fig. 5 also helps in understanding why the photoinduced
excites with energy above the absorption maximum for both bleaches at 480 and 760 nm have different recovery dynamics,
transitions. Following photoexcitation, this species recombines since the charge transfer (480 nm) and charge separated
to regenerate the ground state according to reactions (4) and (5). (760 nm) excited states can decay at different rates.
Such a dual excited state with diverse characteristics could
CH3NH3PbI3 + hn / [CH3NH3PbI/I2] (5) serve as a model for explaining the unusual semiconductor
properties of organic–inorganic perovskites. The 760 nm charge
[CH3NH3PbI/I2] / CH3NH3PbI3 (6) separated state is well understood based on the semiconductor
band gap model.14 The 480 nm charge transfer excited state,
however, does not display the same simple free carrier kinetics
The similarity of the kinetic traces recorded at the 480 nm
previously reported for the 760 nm bleach. Although kinetically
bleach and 600 nm photoinduced absorption (Fig. 4B) represent
we observe no evidence for carrier cooling from the 480 nm
the regeneration of the charge transfer ground state via reaction
charge transfer state to the band edge, these two states remain
in equilibrium. Furthermore, these two states are active in solar
cell operation as evidenced by the photocurrent action spec-
trum (quantum efficiency at various excitation wavelengths),
with external quantum efficiency of approximately 80% across
the visible spectrum.48
Gottesman et al. have provided insight into the charge
transfer nature (I / Pb) of the interband transitions in
CH3NH3PbI3 and the important role it plays in the low binding
energy for electrons.39 Both of the lowest lying unoccupied
bands in CH3NH3PbI3 are composed of Pb (6p) orbitals as the
accepting states in what are referred to as the 480 nm charge
transfer and 760 nm charge separated transitions here.39,46 The
low binding energy is an important factor in realizing highly
efficient perovskite photovoltaics.11,12
The charge transfer nature of the interband transitions
makes it possible for methylammonium ions to align in the
Fig. 5 Scheme illustrating the dual nature of the organic–inorganic electric eld in working photovoltaic devices and contribute to
perovskite excited state. the high open circuit voltages and photocurrents achieved.39

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Moreover, weak localization of charges within the hybrid 12 H. J. Snaith, J. Phys. Chem. Lett., 2013, 4, 3623–3630.
perovskite lattice has been proposed to explain the surprisingly 13 F. Deschler, M. Price, S. Pathak, L. E. Klintberg,
low recombination rates in perovskite thin lms.15 The charge D.-D. Jarausch, R. Higler, S. Hüttner, T. Leijtens,
transfer nature described here corroborates these postulations S. D. Stranks, H. J. Snaith, M. Atatüre, R. T. Phillips and
and spatial separation of charges within organic–inorganic R. H. Friend, J. Phys. Chem. Lett., 2014, 5, 1421–1426.
perovskites could help explain the signicant deviation from 14 J. S. Manser and P. V. Kamat, Nat. Photonics, 2014, 8, 737–
Langevin recombination kinetics observed previously. 743.
To summarize, the spectroscopic investigation of methyl- 15 C. Wehrenfennig, G. E. Eperon, M. B. Johnston, H. J. Snaith
ammonium lead halide perovskite lms reveals two different and L. M. Herz, Adv. Mater., 2014, 26, 1584–1589.
excited state behaviors, viz., charge separated state (reaction (4)) 16 G. Xing, N. Mathews, S. S. Lim, N. Yantara, X. Liu, D. Sabba,
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this work provides further insight into the initial photoinduced 18 P. Pistor, J. Borchert, W. Fränzel, R. Csuk and R. Scheer, J.
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metal halide perovskite lms. 19 J. M. Ball, M. M. Lee, A. Hey and H. J. Snaith, Energy Environ.
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Acknowledgements 20 V. M. Burlakov, G. E. Eperon, H. J. Snaith, S. J. Chapman and
A. Goriely, Appl. Phys. Lett., 2014, 104, 091602.
We thank the Division of Chemical Sciences, Geosciences, and 21 J. A. Christians, R. C. M. Fung and P. V. Kamat, J. Am. Chem.
Biosciences, Office of Basic Energy Sciences of the U.S. Soc., 2013, 136, 758–764.
Department of Energy for their support through award DE- 22 G. E. Eperon, V. M. Burlakov, P. Docampo, A. Goriely and
FC02-04ER15533. We also thank the Center for Sustainable H. J. Snaith, Adv. Funct. Mater., 2014, 24, 151–157.
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