Stamplecoskie 2015
Stamplecoskie 2015
Stamplecoskie 2015
Environmental
Science
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COMMUNICATION View Journal | View Issue
DOI: 10.1039/c4ee02988g
www.rsc.org/ees
208 | Energy Environ. Sci., 2015, 8, 208–215 This journal is © The Royal Society of Chemistry 2015
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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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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, conrms 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 prole 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).
210 | Energy Environ. Sci., 2015, 8, 208–215 This journal is © The Royal Society of Chemistry 2015
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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 inuence 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 reect 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 reections 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 reections 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 specic 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. identied 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 inuences 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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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).
212 | Energy Environ. Sci., 2015, 8, 208–215 This journal is © The Royal Society of Chemistry 2015
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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 proles 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 proles below
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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 signicant 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,
and an excited charge transfer state (reaction (5)). These two M. Grätzel, S. Mhaisalkar and T. C. Sum, Nat. Mater., 2014,
states remain coupled to form a dual excited state. Both these 13, 476–480.
states undergo charge recombination to regenerate the ground 17 K. Liang, D. Mitzi and M. T. Prikas, Chem. Mater., 1998, 10,
state. The unusual dual nature of the excited state presented in 403–411.
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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.
processes leading to charge separation in organic–inorganic Phys. Chem. Lett., 2014, 5, 3308–3312.
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.
Energy at Notre Dame (cSEND) for partial funding of the project. 23 O. Horváth and I. Mikó, J. Photochem. Photobiol., A, 1998,
This work was completed with the use of the cSEND Material 114, 95–101.
Characterization Facility's Bruker D8 Advance Davinci powder 24 S. D. Stranks, G. E. Eperon, G. Grancini, C. Menelaou,
X-ray diffractometer. We thank Barry Reid for his assistance in M. J. P. Alcocer, T. Leijtens, L. M. Herz, A. Petrozza and
recording XRD spectra. This is contribution number NDRL no. H. J. Snaith, Science, 2013, 342, 341–344.
5036 from the Notre Dame Radiation Laboratory. 25 G. Xing, N. Mathews, S. Sun, S. Lim, Y. Lam, M. Gratzel,
S. Mhaisalkar and T. Sum, Science, 2013, 342, 344–347.
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