The formation of methylammonium lead iodide (CH3NH3PbI3) perovskite into mesoporous titania (TiO2) scaffold via a sequential deposition method is known to offer high quality films for good photovoltaic device performance. The local kinetics at the lower interface between the mesoporous TiO2 film and the collecting electrode govern perovskite growth and formation. Here, we have used a NanoPlasmonic Sensing (NPS) approach with gold (Au) nanosensors to monitor the formation of CH3NH3PbI3 perovskite at the lower interface of up to 650 nm mesoporous TiO2 films. This technique provides time-resolved spectral shifts of the localized surface plasmon resonance at different operating temperatures and methylammonium iodide (CH3NH3I3) concentrations by recording changes in the local vicinity of the Au nanosensors at the mesoporous TiO2 film interface. Analytical studies included ellipsometry, scanning electron microscopy, X-ray diffraction, and photoluminescence spectroscopy. The results show that both the intensity of the NPS response and NPS rate constants are correlated with the operating concentrations and temperatures of CH3NH3I3 as well as CH3NH3PbI3 perovskite growth in mesoporous TiO2.

Perovskite solar cells based on alkylammonium metal trihalide light-absorption layer offer the promise for a breakthrough for next generation solar devices.1–7 Particularly, the attractive class of methylammonium lead iodide (CH3NH3PbI3: MAPbI3) exhibit several advantages of unique optical characteristics with bandgap tunability, high mobility and long carrier lifetime, and long-range electron-hole diffusion lengths.8–13 Perovskite films have been deposited via either thermal evaporation14,15 or solution processing.5,11,12 The two common pathways often applied during film formation are the one-step method in which the reactants are thoroughly mixed prior to deposition16,17 and the two-step route where the precursors are sequentially deposited.1,8,13 Remarkably, much better control over the perovskite morphology was observed using the two-deposition route to either thick or thin mesoscopic metal oxides.11,12,18 The growth and fabrication conditions of these films significantly affect the performance of the fabricated photovoltaic devices.

In the pioneering work of Burschka et al.,1 they have applied a sequential solution deposition protocol to deposit a thin film of PbI2 into ∼350 nm thick mesoporous TiO2, followed by an appropriate dipping in a CH3NH3I/isopropanol solution for perovskite conversion. The small crystallite size of PbI2 deposited in the mesoporous TiO2 host matrix allows remarkable perovskite conversion upon diffusion of CH3NH3I. The complete conversion of crystalline perovskite was notably obtained within a few seconds. They monitored the perovskite formation integrally by optical absorption emission and X-ray diffraction (XRD) spectroscopy, without providing insight into reaction dynamics of perovskite formation at the interface between the mesoporous TiO2 film and the collecting electrode.

In this paper, we demonstrate the use of nanoplasmonic sensing (NPS) to detect the formation kinetics of CH3NH3PbI3 perovskite at the interface of up to ∼650 nm compact/mesoporous TiO2 films with Au nanodisks. We monitor time-resolved spectral shifts of the Localized Surface Plasmon Resonance (LSPR) peak induced by the embedded plasmonic Au sensors. We assess the formed materials at the interface according to analytical results obtained by NPS and other characterization techniques.

Insplorion sensors with a dense TiO2 coating were purchased from Insplorion AB (Gothenburg, Sweden). TiO2 paste (average particle size of 20 nm) was acquired from Dyesol. Lead iodide (PbI2) and methyl ammonium iodide (CH3NH3I: MAI) were purchased from Solaronix. Dimethylformamide (DMF), propanol, and ethanol were purchased from Sigma-Aldrich.

The NPS sensors monitor changes taking place on the surface of spacer layer (a 10 nm dielectric layer aimed to tailor surface chemistry and protect Au nanosensors) via locally, strongly enhanced electromagnetic (EM) field that often extends a few tens of nanometers. Standard films comprising fused silica coated with Au nanodisks (100 nm diameter and 20 nm height) and 10 nm dense layer of compact TiO2 as a dielectric spacer layer have been used in various NPS experimental system arrangements.19–22 In our work, these films were used following a procedure adapted from the pioneer work in Ref. 1. We spin-coated an additional layer of mesoporous TiO2 prepared by mixing a commercial TiO2 paste from Dyesol and ethanol (2:7 wt. %) at 5000 rpm for 30 s. The films are calcined at 500 °C for 30 min. The thickness of mesoporous TiO2 films was 650 nm, which is measured using the VASE Ellipsometer VB-400. Then, 1M (462 mg/ml) of lead iodide (PbI2) in dimethylformamide (DMF) was prepared under stirring at 70 °C. The mesoporous TiO2 films were consequently infiltrated with PbI2 by spin coating at 6000 rpm for 90 s and dried at 70 °C for 30 min. Different concentrations of CH3NH3I (MAI) in 2-propanol ranging from 5 to 15 mg/ml at various temperatures (25–53 °C) were prepared for in situ monitoring of perovskite formation.

Insplorion Xnano was used to monitor nanoplasmonic peaks during MAPbI3 perovskite formation.

Initially, a blank measurement was taken for a fused silica substrate for subtraction. The coated Au sensor film was placed inside the system chamber, and the wavelength scan shows that the nanoplasmonic peak position of a sensor is located at 800 nm–900 nm depending on the Au disk size and distribution of the gold nanoparticles. The Au nanodisks, which act as optical antennas, respond to events occurring at the interface between the sensor surface and the sample material [Figs. 1(a), 1(c), and 1(d)]. As a result, it is possible to probe the kinetics of the reactions occurring at the lower interface. A peak-fitting method proposed by Dahlin et al.23 is applied to enable monitoring the spectral shifts on the order of 1 nm or less with a 0.01 nm resolution limit.

FIG. 1.

(a) Schematic illustration of the sensor structure with mesoporous TiO2 infiltrated with PbI2, (b) schematics of NPS simultaneous readout, and typical SEM images of (c) Au nanosensors and (d) mesoporous TiO2 film.

FIG. 1.

(a) Schematic illustration of the sensor structure with mesoporous TiO2 infiltrated with PbI2, (b) schematics of NPS simultaneous readout, and typical SEM images of (c) Au nanosensors and (d) mesoporous TiO2 film.

Close modal

A fresh pure solvent was injected via the system pump to flush the tubes and to take a baseline measurement as settings are set at a continuous, optimum flow rate of 0.1 μl/min to avoid the bulk concentration gradient. At this point, minor spectral shifts were observed in both the nanoplasmonic peak position and extinction due to the change in the dielectric constant of the medium near the sensors. Upon diffusion of CH3NH3I into the mesoporous TiO2 film at different concentrations and temperatures, the refractive index at Au nanodisks changes with the film color change (dark brown), known as perovskite reaction, as major spectral shifts of resonance wavelength and extinction of the previously located, sensor-specific peak are simultaneously, in real time, collected and monitored via the Insplorer software [Fig. 1(b)].

For comparison, fresh solvent can be pumped again for rinsing the films. The sensors were removed for characterization. A set of 5 sensors were used for each experimental condition. Additionally, X-ray diffraction (XRD) Bruker AXS D4 Endeavour X diffractometer using Cu Kα1/2, λα1 = 154.060 pm, λα2 = 154.439 pm radiation and room temperature photoluminescence (PL) (RF-5301 PC, SHIMADZU, 400 W, 50/60 Hz) average spectra were obtained. Scanning electron microscopy (SEM) (JEOL-6300F, 5 kV) images were analyzed using the Image J software to generate histograms of average particle size distributions.

The nanoplasmonic sensor peak position [Fig. 2(a)] and extinction shifts [Fig. 2(b)] occur as a result of changing the sensor environment at the coated Au sensors prior and post injection of the MAI containing solvent. The mesoporous TiO2/PbI2 coated Au sensors were run without postrinsing. However, a fast rinsing at stagnant conditions has been reported with almost no effects on the perovskite phase formed. Additionally, the coated Au sensors were found to be sensitive to the change in the heating program (25–53 °C) prior to the MAI injection (Fig. S1, supplementary material); however, the actual sensor peak position and extinction shifts detected in this work are tailored to present the sensor response after MAI injections as addressed hereafter.

FIG. 2.

Simultaneous readouts of (a) adapted nanoplasmonic peak position shift showing the behavior after MAI injection and upon postrinsing the perovskite in propanol solvent and (b) peak extinction shift of the coated gold sensor showing the nanoplasmonic behavior upon MAI injection and perovskite formation.

FIG. 2.

Simultaneous readouts of (a) adapted nanoplasmonic peak position shift showing the behavior after MAI injection and upon postrinsing the perovskite in propanol solvent and (b) peak extinction shift of the coated gold sensor showing the nanoplasmonic behavior upon MAI injection and perovskite formation.

Close modal

The effect of changing MAI concentrations (from 5 to 15 mg/ml at 25 °C) and temperature (from 25 to 53 °C at MAI concentration of 10 mg/ml) on NPS position and extinction shifts using Au sensors/compact TiO2/650 nm mesoporous TiO2/PbI2 are shown in Figs. 3(a)–3(c) and Figs. S2(a) and S2(b). The response of NPS is inherently dependent on the thickness of the support structure. For the 650 nm mesoporous TiO2, NPS extinction shifts are inversely proportional to MAI concentrations and proportional to temperatures. This implies that diffusion at the lower interface is not limited under these conditions. Rate constants of perovskite formation are obtained from the corresponding NPS extinction shifts where the slope values (point of rise, initial point after plateau, duration of time in seconds) are accurately obtained from the Insplorer software. The reaction rates are dependent on the concentrations of MAI at the lower interface and the obtained rate constants. According to the results in the sequential work by Rajab,24 when the morphology of mesoporous titania structure is changed as in a mimic photoelectrode of solar cells using Au sensors/compact TiO2/350 nm mesoporous TiO2/PbI2, the NPS extinction shifts follow different trends reflecting different perovskite structural formation.

FIG. 3.

Characteristic MAI concentration curves measured for Au sensors/compact TiO2/650 nm mesoporous TiO2/PbI2 prepared by the step spin coating program showing (a) the nanoplasmonic peak position shifts and (b) the rate constant vs MAI concentration obtained from the nanoplasmonic peak extinction shifts for MAI concentrations ranging from 5 to 15 mg/ml at 25 °C. The slowest reaction is recorded for the 10 mg/ml of MAI compared with the other concentrations highlighted in the dashed box. The rate constant is nonlinear with temperature as shown in (c), which is obtained from the nanoplasmonic peak extinction shifts for temperatures ranging from 25 to 53 °C at 10 mg/ml of MAI.

FIG. 3.

Characteristic MAI concentration curves measured for Au sensors/compact TiO2/650 nm mesoporous TiO2/PbI2 prepared by the step spin coating program showing (a) the nanoplasmonic peak position shifts and (b) the rate constant vs MAI concentration obtained from the nanoplasmonic peak extinction shifts for MAI concentrations ranging from 5 to 15 mg/ml at 25 °C. The slowest reaction is recorded for the 10 mg/ml of MAI compared with the other concentrations highlighted in the dashed box. The rate constant is nonlinear with temperature as shown in (c), which is obtained from the nanoplasmonic peak extinction shifts for temperatures ranging from 25 to 53 °C at 10 mg/ml of MAI.

Close modal

The effect of operating temperature (from 25 to 53 °C at MAI concentration of 10 mg/ml) on NPS extinction shifts using Au sensors/compact TiO2/650 nm mesoporous TiO2/PbI2 is shown in Fig. 3(c) and Fig. S2(b), which shows an increase in NPS extinction with higher temperature (except for the highest temperature of 53 °C). The highest extinction increase was observed for the TiO2/PbI2 film temperature of 41 °C.

The change in dielectric constants of the materials upon injection of MAI into the Au sensor-coated TiO2/PbI2 films provides insight into the interface interactions. The conversion of PbI2 with a dielectric constant (ε∞ = 6) to MAPbI3 perovskite with much higher (ε∞ ∼ 20)25 explains the red shifts observed in NPS extinction. The structural, optical, and morphological details of the MAPbI3 materials were thus investigated by XRD, PL, and SEM measurements. First, the XRD patterns on different substrate surfaces were acquired as control samples. As revealed in Fig. S3, peaks of tetragonal MAI at 2θ = 19.74° and 29.79° along with a hexagonal PbI2 at 2θ = 12.8° were identified. Figures 4 and 5 show the XRD patterns and the PL spectra of MAPbI3 perovskites prepared into Au sensors/compact TiO2/650 nm mesoporous TiO2 at different MAI concentrations and temperatures, respectively, with the corresponding SEM images.

FIG. 4.

(a) XRD patterns of MAPbI3 perovskites prepared into Au sensors/compact TiO2/650 nm mesoporous TiO2 structures at different concentrations at a temperature of 25 °C. (b) The corresponding photoluminescence spectra measured at room temperature with 400 nm excitation wavelength. [(c-1)–(c-5)] Typical SEM images of as-formed perovskites at different MAI concentrations: 5, 7.5, 10, 12.5, and 15 mg/ml, respectively. As revealed, the PL peaks detected at ∼1.631 eV show correlation in intensity with particle size distribution. Films of larger particle size distribution show higher PL intensity: 15 > 12.5 > 5 > 7.5 > 10 mg/ml.

FIG. 4.

(a) XRD patterns of MAPbI3 perovskites prepared into Au sensors/compact TiO2/650 nm mesoporous TiO2 structures at different concentrations at a temperature of 25 °C. (b) The corresponding photoluminescence spectra measured at room temperature with 400 nm excitation wavelength. [(c-1)–(c-5)] Typical SEM images of as-formed perovskites at different MAI concentrations: 5, 7.5, 10, 12.5, and 15 mg/ml, respectively. As revealed, the PL peaks detected at ∼1.631 eV show correlation in intensity with particle size distribution. Films of larger particle size distribution show higher PL intensity: 15 > 12.5 > 5 > 7.5 > 10 mg/ml.

Close modal
FIG. 5.

(a) XRD patterns of MAPbI3 perovskites prepared into Au sensors/compact TiO2/650 nm mesoporous TiO2 structures at different temperatures using 10 mg/ml MAI. (b) The corresponding photoluminescence spectra measured at room temperature with 400 nm excitation wavelength. [(c-1)–(c-5)] Typical SEM images of the as-formed perovskites at different temperatures: 25, 31, 36, 41, and 53 °C, respectively. As revealed, the PL peaks detected at ∼1.631 eV show correlation in intensity with particle size distribution. Films of larger particle size distribution show higher PL intensity: 25 > 53 > 36 > 31 > 41 °C.

FIG. 5.

(a) XRD patterns of MAPbI3 perovskites prepared into Au sensors/compact TiO2/650 nm mesoporous TiO2 structures at different temperatures using 10 mg/ml MAI. (b) The corresponding photoluminescence spectra measured at room temperature with 400 nm excitation wavelength. [(c-1)–(c-5)] Typical SEM images of the as-formed perovskites at different temperatures: 25, 31, 36, 41, and 53 °C, respectively. As revealed, the PL peaks detected at ∼1.631 eV show correlation in intensity with particle size distribution. Films of larger particle size distribution show higher PL intensity: 25 > 53 > 36 > 31 > 41 °C.

Close modal

As revealed from Fig. 4(a), a series of diffraction peaks (at 2θ = 14.25°, 28.57°, and 31.95°) corresponding to the tetragonal phase of MAPbI3 perovskite has been detected at all MAI concentrations but with different extents, consistent with the literature data.17,26 Furthermore, the PL spectral lines of Fig. 4(b) exhibited characteristic PL bands at 1.631 eV, attributed to the near-band-edge (NBE) transition in tetragonal MAPbI3 perovskite,27,28 but with different PL intensities. Additionally, the SEM images taken at different MAI concentrations for the 650 nm films revealed well-crystalline phase formation with different crystal morphologies [Figs. 4(c–1)]. Correlation in PL intensity [Fig. 4(b)] with crystal size distribution [Figs. S4(a)–S4(e)] can be seen as films of larger particle size distribution show higher PL intensity.

Complete conversion of MAPbI3 formation, confirmed by film XRD testing at an MAI concentration of 10 mg/ml, in Fig. 4(a), corresponds with the lowest NPS rate constant of 2.5–3.0 ms−1 in Fig. 3(b), smallest particle size (90 nm) and smallest particle size distribution (<500 nm) in Fig. S4(c) and lowest PL spectra in Fig. 4(b). Other MAI concentrations ranging from 5 to 15 mg/ml which indicate the presence of reactants correspond with higher NPS rate constants of 4.8–5.3 ms−1 and larger particle size distributions, due to crystallization of MAI [peaks of tetragonal MAI at 2θ = 19.74° and 29.79° for MAI concentration of 7.5, 12.5, and 15 mg/ml, Fig. 4(a)] and the presence of unreacted PbI2 [peak of hexagonal PbI2 at 2θ = 12.8° for MAI concentration of 5 mg/ml in Fig. 4(a)], as well as higher PL spectra shift. Although the extinction shifts are inversely proportional to MAI concentration, the lowest NPS rate constant for the intermediate MAI concentration is a criterion of complete MAPbI3 perovskite formation which happens at a lower time scale compared with incomplete conversion. Hence, the local kinetics at the lower interface between the mesoporous TiO2 film and the collecting electrode govern perovskite growth and formation.

Similarly, as revealed from Fig. 5(a), a series of diffraction peaks (at 2θ = 14.25°, 28.57°, and 31.95°) corresponding to the tetragonal phase of MAPbI3 perovskite has been detected at all temperatures ranging from 25 to 53 °C at a concentration of 10 mg/ml. However, the MAPbI3 formation at temperatures of 25 °C corresponds with rate constants of ∼2.5 to 3.0 ms−1, seen in Fig. 3(c) with a median particle size of 165 nm. The MAPbI3 formation at other temperatures of 31–41 °C corresponds with higher NPS rate constants of around 6.8–8.9 ms−1, larger median particle size, and smaller particle size distributions. MAPbI3 formation at a temperature of 53 °C corresponds with a NPS rate constant of ∼3.0 ms−1 with spread out particle size distribution. This behavior of perovskite formation is highly non-Arrhenius as higher temperatures beyond the optimum conditions lead to slower rate constants and spread out growth regions. In summary, MAPbI3 perovskite particle size distribution is reduced as temperature is increased to 53 °C [Figs. S5(a)–S5(e)], which correlate well with PL intensity in Fig. 5(b). Here, the NPS rate constant from the NPS technique is a direct indicator of MAPbI3 perovskite crystal growth as higher rates indicate faster conversion as well as smaller particle size distribution, which can be utilized in solar cell applications using Au sensors/compact TiO2/350 nm mesoporous TiO2/PbI2, as illustrated in the sequential work by Rajab.24 

The formation of MAPbI3 perovskite at the lower interface of mesoporous TiO2 films via a sequential deposition method was performed in situ using a nanoplasmonic sensing approach. We used nanoplasmonic sensing to detect CH3NH3PbI3 perovskite formation at the interface of thick TiO2 films with Au nanodisks, where complete conversion of perovskite formation was characterized by slow NPS red shifts, while incomplete reactions were characterized by fast methylammonium iodide (CH3NH3I) crystallization. When complete reaction activation energies were reduced, perovskite formation was characterized by relatively fast NPS red shifts. The research findings lead to the pursuit of utilizing the NPS approach to characterize CH3NH3PbI3 perovskite formation in a mimic photoelectrode of solar cells.

See the supplementary material for additional NPS characterization, XRD, and SEM particle size distribution histograms.

The authors would like to acknowledge the support of the Ministry of Higher Education, Kingdom of Saudi Arabia, through a grant (Grant No. PCSED-003-16) under the Promising Centre for Sensors and Electronic Devices (PCSED) at Najran University, Kingdom of Saudi Arabia. Acknowledgment is made to Professor Osman Bakr at KAUST (King Abdullah University of Science and Technology) for his support.

1.
J.
Burschka
,
N.
Pellet
,
S.-J.
Moon
,
R.
Humphry-Baker
,
P.
Gao
,
M. K.
Nazeeruddin
, and
M.
Grätzel
, “
Sequential deposition as a route to high-performance perovskite-sensitized solar cells
,”
Nature
499
,
316
319
(
2013
).
2.
W. S.
Yang
 et al., “
Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells
,”
Science
356
,
1376
1379
(
2017
).
3.
Q.
Hu
,
J.
Wu
,
C.
Jiang
,
T.
Liu
,
X.
Que
,
R.
Zhu
, and
Q.
Gong
, “
Engineering of electron-selective contact for perovskite solar cells with efficiency exceeding 15%
,”
ACS Nano
8
,
10161
10167
(
2014
).
4.
D. W.
deQuilettes
,
S. M.
Vorpahl
,
S. D.
Stranks
,
H.
Nagaoka
,
G. E.
Eperon
,
M. E.
Ziffer
,
H. J.
Snaith
, and
D. S.
Ginger
, “
Impact of microstructure on local carrier lifetime in perovskite solar cells
,”
Science
348
(
6235
),
683
686
(
2015
).
5.
J.-H.
Im
,
I.-H.
Jang
,
N.
Pellet
,
M.
Grätzel
, and
N.-G.
Park
, “
Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells
,”
Nat. Nanotechnol.
9
,
927
(
2014
).
6.
M.
Saliba
 et al., “
A molecularly engineered hole-transporting material for efficient perovskite solar cells
,”
Nat. Energy
1
,
15017
(
2016
).
7.
A.
Kojima
,
K.
Teshima
,
Y.
Shirai
, and
T.
Miyasaka
, “
Organometal halide perovskites as visible-light sensitizers for photovoltaic cells
,”
J. Am. Chem. Soc.
131
,
6050
6051
(
2009
).
8.
T.
Zhang
,
M.
Yang
,
Y.
Zhao
, and
K.
Zhu
, “
Controllable sequential deposition of planar CH3NH3PbI3 perovskite films via adjustable volume expansion
,”
Nano Lett.
15
,
3959
3963
(
2015
).
9.
N. J.
Jeon
,
J. H.
Noh
,
Y. C.
Kim
,
W. S.
Yang
,
S.
Ryu
, and
S. I.
Seok
, “
Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells
,”
Nat. Mater.
13
,
897
(
2014
).
10.
J. B.
Patel
,
R. L.
Milot
,
A. D.
Wright
,
L. M.
Herz
, and
M. B.
Johnston
, “
Formation dynamics of CH3NH3PbI3 perovskite following two-step layer deposition
,”
J. Phys. Chem. Lett.
7
,
96
102
(
2016
).
11.
P.
Docampo
,
F. C.
Hanusch
,
S. D.
Stranks
,
M.
Döblinger
,
J. M.
Feckl
,
M.
Ehrensperger
,
N. K.
Minar
,
M. B.
Johnston
,
H. J.
Snaith
, and
T.
Bein
, “
Solution deposition-conversion for planar heterojunction mixed halide perovskite solar cells
,”
Adv. Energy Mater.
4
,
1400355
(
2014
).
12.
D.
Liu
and
T. L.
Kelly
, “
Perovskite solar cells with a planar heterojunction structure prepared using room-temperature solution processing techniques
,”
Nat. Photonics
8
,
133
(
2013
).
13.
H.
Zhang
,
X.
Qiao
,
Y.
Shen
,
T.
Moehl
,
S. M.
Zakeeruddin
,
M.
Gratzel
, and
M.
Wang
, “
Photovoltaic behavior of lead methylammonium triiodide perovskite solar cells down to 80 K
,”
J. Mater. Chem. A
3
,
11762
11767
(
2015
).
14.
M.
Saliba
,
K. W.
Tan
,
H.
Sai
,
D. T.
Moore
,
T.
Scott
,
W.
Zhang
,
L. A.
Estroff
,
U.
Wiesner
, and
H. J.
Snaith
, “
Influence of thermal processing protocol upon the crystallization and photovoltaic performance of organic–inorganic lead trihalide perovskites
,”
J. Phys. Chem. C
118
,
17171
17177
(
2014
).
15.
M.
Liu
,
M. B.
Johnston
, and
H. J.
Snaith
, “
Efficient planar heterojunction perovskite solar cells by vapour deposition
,”
Nature
501
,
395
(
2013
).
16.
W.
Nie
 et al., “
High-efficiency solution-processed perovskite solar cells with millimeter-scale grains
,”
Science
347
,
522
(
2015
).
17.
D.
Shi
 et al., “
Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals
,”
Science
347
,
519
(
2015
).
18.
D.
Li
,
J.
Cui
,
H.
Li
,
D.
Huang
,
M.
Wang
, and
Y.
Shen
, “
Graphene oxide modified hole transport layer for CH3NH3PbI3 planar heterojunction solar cells
,”
Sol. Energy
131
,
176
182
(
2016
).
19.
V.
Gusak
,
L.-P.
Heiniger
,
M.
Graetzel
,
C.
Langhammer
, and
B.
Kasemo
, “
Time-resolved indirect nanoplasmonic sensing spectroscopy of dye molecule interactions with dense and mesoporous TiO2 films
,”
Nano Lett.
12
,
2397
2403
(
2012
).
20.
V.
Gusak
,
L.-P.
Heiniger
,
V. P.
Zhdanov
,
M.
Gratzel
,
B.
Kasemo
, and
C.
Langhammer
, “
Diffusion and adsorption of dye molecules in mesoporous TiO2 photoelectrodes studied by indirect nanoplasmonic sensing
,”
Energy Environ. Sci.
6
,
3627
3636
(
2013
).
21.
E. M.
Larsson
,
C.
Langhammer
,
I.
Zorić
, and
B.
Kasemo
, “
Nanoplasmonic probes of catalytic reactions
,”
Science
326
,
1091
(
2009
).
22.
C.
Langhammer
,
E. M.
Larsson
,
B.
Kasemo
, and
I.
Zorić
, “
Indirect nanoplasmonic sensing: Ultrasensitive experimental platform for nanomaterials science and optical nanocalorimetry
,”
Nano Lett.
10
,
3529
3538
(
2010
).
23.
A. B.
Dahlin
,
J. O.
Tegenfeldt
, and
F.
Höök
, “
Improving the instrumental resolution of sensors based on localized surface plasmon resonance
,”
Anal. Chem.
78
,
4416
4423
(
2006
).
24.
F.
Rajab
, “
Nanoplasmonic sensing of CH3NH3PbI3 perovskite formation in mimic of solar cell photoelectrodes
,”
AIP Adv.
8
,
115303
(
2018
).
25.
M. H.
Du
, “
Efficient carrier transport in halide perovskites: Theoretical perspectives
,”
J. Mater. Chem. A
2
,
9091
9098
(
2014
).
26.
T.
Baikie
,
Y.
Fang
,
J. M.
Kadro
,
M.
Schreyer
,
F.
Wei
,
S. G.
Mhaisalkar
,
M.
Graetzel
, and
T. J.
White
, “
Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications
,”
J. Mater. Chem. A
1
,
5628
5641
(
2013
).
27.
W.
Kong
,
Z.
Ye
,
Z.
Qi
,
B.
Zhang
,
M.
Wang
,
A.
Rahimi-Iman
, and
H.
Wu
, “
Characterization of an abnormal photoluminescence behavior upon crystal-phase transition of perovskite CH3NH3PbI3
,”
Phys. Chem. Chem. Phys.
17
,
16405
16411
(
2015
).
28.
Y.
Yasuhiro
,
N.
Toru
,
E.
Masaru
,
W.
Atsushi
, and
K.
Yoshihiko
, “
Near-band-edge optical responses of solution-processed organic–inorganic hybrid perovskite CH3NH3PbI3 on mesoporous TiO2 electrodes
,”
Appl. Phys. Express
7
,
032302
(
2014
).

Supplementary Material