ARTICLES

PUBLISHED ONLINE: 19 JUNE 2017 | DOI: 10.1038/NPHOTON.2017.94

High-performance direct conversion X-ray

detectors based on sintered hybrid lead
triiodide perovskite wafers
Shreetu Shrestha1,2, René Fischer3, Gebhard J. Matt1*, Patrick Feldner4, Thilo Michel5, Andres Osvet1,
Ievgen Levchuk1, Benoit Merle4, Saeedeh Golkar6, Haiwei Chen1, Sandro F. Tedde3, Oliver Schmidt3,
Rainer Hock7, Manfred Rührig3, Mathias Göken4, Wolfgang Heiss1, Gisela Anton5
and Christoph J. Brabec1,8

Lead halide perovskite semiconductors are in general known to have an inherently high X-ray absorption cross-section and
a significantly higher carrier mobility than any other low-temperature solution-processed semiconductor. So far, the
processing of several-hundred-micrometres-thick high-quality crystalline perovskite films over a large area has been
unresolved for efficient X-ray detection. In this Article, we present a mechanical sintering process to fabricate
polycrystalline methyl ammonium lead triiodide perovskite (MAPbI3) wafers with millimetre thickness and well-defined
crystallinity. Benchmarking of the MAPbI3 wafers against state-of-the-art CdTe detectors reveals competitive conversion
−1
efficiencies of 2,527 µC Gyair cm−2 under 70 kVp X-ray exposure. The high ambipolar mobility–lifetime product of
−4 2 −1
2 × 10 cm V is suggested to be responsible for this exceptionally high sensitivity. Our findings inform a new generation
of highly efficient and low-cost X-ray detectors based on perovskite wafers.

D
ue to their outstanding physical properties, hybrid organic–
inorganic perovskites (HOIP), and most notably
CH3NH3(Pb,Sn)(I,Br)3 , have received extraordinary atten-
tion from the research community. Especially significant are the
charge-transport properties of MAPbI3 , which has demonstrated
long minority-carrier lifetimes and diffusion lengths that are
comparable with single-crystalline covalent semiconductors1–5.
A new application for this material class is the sensitive detection
of high-energy radiation such as X-ray6,7 and γ radiation8. The
search for an ideal X-ray-sensitive photoconductor (PC) is of
ongoing interest because most semiconductors with good charge-
transport properties do not absorb high-energy radiation effectively.
The latter, however, is an intrinsic property of HOIPs due to the
presence of heavy metal and halide ions. Current state-of-the-art
materials for direct X-ray detection9 include stabilized amorphous
Se (a-Se)10, PbI2 (ref. 11), HgI2 (refs 12, 13), CdTe (ref. 14) and
CdZnTe (ref. 15). a-Se detectors have been successfully commercia-
lized but are limited to mammography applications due to their low
absorption coefficient in the spectral regime higher than 50 keV.
PbI2 and HgI2 detectors face stability issues that hinder their wide-
spread application. Significant effort is being directed at Cd(Zn)Te
(ref. 16), but upscaling to larger wafers and charge carrier trapping
remain issues yet to be overcome.
Generally, for efficient X-ray absorption, the PC layer should be
approximately three times larger than the attenuation length, which
is the length at which 63% of photons are absorbed17. As discussed
later in detail, HOIPs have attenuation lengths on the order of
hundreds of micrometres for the X-ray energies commonly used
in medical applications. Although the widely reported solution-
process protocols for fabricating thin films of HOIPs are efficient
in the sub-micrometre regime, producing several-hundred-micro-
metres-thick, high-quality films covering a large area is extremely
difficult. In this Article, we present a room-temperature sintering
process for MAPbI3 microcrystals to form thick (200 µm to 1 mm)
rigid wafers of virtually any size.
MAPbI3 wafer sintering process
In contrast to covalent semiconductors such as Si and Cd(Zn)Te,
which require high-temperature crystallization processes, ionic crys-
tals can be processed from solution at low temperatures. An easily
overlooked property of ionic crystals is their plasticity, which
results in pressure-induced flow processes18. Although HOIPs
are not pure ionic crystals, this material class does exhibit
pressure-induced agglomeration effects.
The MAPbI3 microcrystals presented here were synthesized by
precipitation from a precursor solution at room temperature19 (see
Methods). The precipitated microcrystals were irregular in shape,
with sizes ranging from 50 nm to 1 µm (Supplementary Fig. 1).
By applying a pressure of 0.3 GPa to the microcrystals for 5 min
using a hydraulic press, a compact MAPbI3 layer (which will
be referred to as a wafer) was formed. A series of wafers with
1/2 inch diameter and thickness ranging from 200 µm to 1 mm
were prepared. It is remarkable that these free-standing MAPbI3
wafers have a mirror-like reflective surface with a root-mean-square

1
Friedrich-Alexander-University Erlangen-Nürnberg, Institute of Materials for Electronics and Energy Technology (i-MEET), Martensstrasse 7, 91058
Erlangen, Germany. 2 School of Advanced Optical Technologies (SAOT), Paul-Gordan-Strasse 6, 91052 Erlangen, Germany. 3 Siemens Healthineers,
Technology Center, Guenther-Scharowsky-Str. 1, 91058 Erlangen, 91058 Erlangen, Germany. 4 Materials Science and Engineering I, Friedrich-Alexander-
University Erlangen-Nürnberg, Martensstrasse 5, 91058 Erlangen, Germany. 5 Friedrich-Alexander-University Erlangen-Nürnberg, Centre for Astroparticle
Physics, Erwin-Rommel-Straße 1, 91058 Erlangen, Germany. 6 Institute of Particle Technology (LFG), Haberstrasse 9a, 91058 Erlangen, Germany.
7
Friedrich-Alexander-University Erlangen-Nürnberg, Lehrstuhl für Kristallografie und Strukturphysik, Staudtstrasse 3, 91058 Erlangen, Germany.
8
Bavarian Center for Applied Energy Research (ZAE Bayern), Am Weichselgarten 7, 91058 Erlangen, Germany. * e-mail: gebhard.matt@fau.de

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NATURE PHOTONICS DOI: 10.1038/NPHOTON.2017.94 ARTICLES
a b

100 nm

200 μm

Figure 1 | Images of the sintered MAPbI3 wafer. a, Free-standing MAPbI3 wafer (1/2 inch × 1 mm). b, SEM cross-section of a sintered MAPbI3 wafer.
Inset: higher-magnification image. Circles indicate two interconnected microcrystals.

roughness of only ∼75 nm (Fig. 1a; for atomic force microscopy I4cm space group previously reported by Stoumpos et al. and
topography see Supplementary Fig. 3). Scanning electron microscopy Kawamura and co-authors21,29. The full-width at half-maximum
(SEM) of a wafer cross-section shows that the wafer is homogeneous (FWHM) of the diffraction peaks from the wafer and microcrystals
and dense (Fig. 1b). The density of the wafer is 3.76 g cm–3, which is are comparable. Also, the maximum of the photoluminescence
close to the density of single-crystalline MAPbI3 (4.15 g cm–3), as
calculated from lattice parameters20,21. a 1.2
It is evident from the SEM cross-section that the grain boundaries MAPbI3 single crystal
of the microcrystals remain well defined in the wafer. Furthermore, MAPbI3 wafer
1.0
grain boundary interconnections can be easily recognized (circles in
the inset of Fig. 1b).
Hardness (GPa)

0.8

Structural and mechanical investigations 0.6

Nanoindentation has emerged as the method for evaluating the
hardness and Young’s modulus of small material volumes and 0.4
thin films22,23. Measurements were performed with a Berkovich
tip, which was pressed 2.5 µm into the MAPbI3 wafer surface 0.2
using a constant strain rate of 0.05 s−1. Single-crystal MAPbI3
synthesized in house served as a reference for this measurement. 0.0
To provide a measurement with continuous stiffness, a sinusoidal 0.0 0.5 1.0 1.5 2.0 2.5
oscillation was superimposed to the load to evaluate the hardness Indentation depth (μm)
and Young’s modulus as a function of indentation depth24.
b 150
110
(counts s−1)

220

Hardness is defined as the ratio of the load on the tip to the MAPbI3 single crystal
Intensity

100
004

projected tip contact area.

202
211

The steep decrease in hardness at shallow indentation depths 150

shown in Fig. 2a is typical for such measurements and is attributed 0
to uncertainties in the geometry of the tip apex25. At higher indenta- 10 20 30 40 50 60
tion depths, the hardness of the MAPbI3 wafer and that of the single 2θ (°)
crystal levels off at ∼0.36 GPa and ∼0.47 GPa, respectively. The latter
(counts s−1)

value is in good agreement with previously reported values26. The

Intensity

40 MAPbI3 microcrystals
mechanical investigations were complemented by strain rate jump 20
tests, which are a measure of the dynamic mechanical behaviour of 0
a material, that is, the dependence of its strength on the imposed
10 20 30 40 50 60
deformation rate27. With this technique, a strain rate sensitivity m
2θ (°)
value of 0.065 was estimated (Supplementary Figs 4 and 5). This
value is in the upper range of m values found for metallic nanocrys-
(counts s−1)
Intensity

100 MAPbI3 wafer

tals28 and indicates that time-dependent deformation mechanisms
such as diffusion, dislocation activity and plastic flow due to grain 50
boundary sliding are dominant. This viscoplasticity is interpreted as 0
the underlying mechanism for the mechanical rigidity of the wafers. 10 20 30 40 50 60
To investigate the structural properties we performed X-ray dif- 2θ (°)
fraction (XRD) measurements. Figure 2b clearly shows that the dif-
fraction peaks of the MAPbI3 wafer, microcrystals and single crystal Figure 2 | Mechanical and structural properties of the MAPbI3 wafer.
are at the same positions. Major diffraction peaks at angles of 14.0, a, Nanointendation measurements on a MAPbI3 wafer and single crystal.
23.4, 24.4, 28.0 and 28.3° correspond to (110), (211), (202), (004) b, X-ray diffraction spectra of MAPbI3: single crystal (top), microcrystals
and (220) lattice planes, and are consistent with the tetragonal (middle) and sintered wafer (bottom).

NATURE PHOTONICS | VOL 11 | JULY 2017 | www.nature.com/naturephotonics 437

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ARTICLES
spectrum at 770 nm (Supplementary Fig. 6) is in good agreement
with the literature30–33.
To conclude, the observed time-dependent flow process triggers
a pressure-induced agglomeration of the microcrystals due to defor-
mations on their grain boundaries, and photoluminescence, XRD
and SEM investigations confirm that the crystallinity of the micro-
crystals is retained. These results are consistent with in situ XRD
measurements performed on MAPbBr3 and MAPbI3 crystals,
which indicate that amorphization is observed at a much higher
pressure of 2 GPa, and it is reversible up to 34 GPa (ref. 34) and
50 GPa, respectively33.
Charge-transport investigations
In polycrystalline materials, the macroscopic charge-carrier
mobility and the free charge-carrier lifetime are dominated by the
nature of the grain boundaries; that is, boundaries will scatter car-
riers being transported from grain to grain, surface defects may
lead to deep trap states, and space-charge layers will act as potential
barriers35. To investigate the charge-carrier transport properties of
the polycrystalline MAPbI3 wafers, the time-of-flight (TOF) tech-
nique was used. TOF is an elegant method frequently used for
organic36 and inorganic semiconductors37. Generally, a laser pulse
generates a carrier reservoir Q in a thin layer near the illuminated
surface, which is subsequently extracted by the applied electric
field. The laser pulse intensity was kept low to prevent a distortion
of the electric field (Q < CV, where C is the sample capacitance and
V is the bias voltage). At too high laser intensities the excess charge-
carrier concentration distorts the electric field and the temporal
response features an overshoot38,39. Consequently, the laser intensity
was reduced until the temporal response of the transient current
remained unaltered. The device stack consisted of glass/indium
tin oxide (ITO)/poly(methyl methacrylate) (PMMA)/MAPbI3
wafer/Au. The 0.5-µm-thick PMMA layer was used to suppress
current injection from the ITO electrode. The sample was optically
excited from the glass side using a nanosecond laser emitting at
532 nm. The transient photocurrent response for holes, shown in
Fig. 3a, represents a characteristic and well-resolved TOF transient,
in which the transit time ttr of the fastest charge carriers is defined as
the intersection of asymptotes from the plateau and tail in a double
logarithmic I(t) plot40,41. The TOF transients show a clear trend
towards non-dispersive transport at higher electric fields.
The mobility is calculated from ttr using μ = d/(Ettr), where d
is the sample thickness and E is the applied electric field. For
holes, the mobility is in the range of 0.53–0.70 cm2 V−1 s−1, with a
negative field dependency (that is, due to increased scattering at
higher E fields, Fig. 3b). Under the same experimental conditions
but with reversed bias polarity, a slightly lower mobility of
0.50–0.56 cm2 V−1 s−1 and a more dispersive transport for electrons
(Supplementary Figs 7 and 8) is measured.
This observed ambipolar transport is remarkable, as very low or
even missing charge transport of either electrons or holes is com-
monly observed in amorphous and polycrystalline systems11,42.
The field dependency of the charge transport indicates potential
barriers (that is, at the grain boundaries), while quenching of free
charge-carrier lifetime and of the macroscopic mobility via deep
traps is unlikely to be present. These findings are consistent with
recent theoretical investigations that show that MAPbI3 is a
defect-tolerant semiconductor and that vacancy-type defects (that
is, iodine vacancies) are resonant in the bands43.
Direct X-ray to current conversion
The device stack of the X-ray detector is shown in Fig. 4a. The
electric contacts of the 1-mm-thick MAPbI3 wafer are formed by
poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:
PSS) and phenyl-C61-butyric acid methyl ester (PCBM) and ZnO
as hole-selective and electron-selective contact and buffer layers,
438
© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
NATURE PHOTONICS DOI: 10.1038/NPHOTON.2017.94
a 1
0.57 V μm−1
Photocurrent (a.u.)
0.39 V μm−1
0.20 V μm−1
0.1
1 10
Time (μs)
b 0.70
Hole mobility (cm2 V−1 s−1)
0.65
0.60
0.55
0.24 0.32 0.40 0.48 0.56
Electric field (V μm−1)
Figure 3 | Charge transport investigations. a, Time-of-flight transients of
holes. b, Electric field dependency of hole mobility.
respectively. A bottom ITO/glass substrate and a silver top electrode
finish the device stack.
The sample was irradiated with X-ray radiation of 70 kVp from
the silver electrode side for 2 s. The most intense emission was at
38 keV (see Supplementary Information, pages 7 and 8 for the
set-up with the X-ray source and the simulated X-ray photon-
density spectrum). A simulation using the XCOM database esti-
mates an attenuation depth in the MAPbI3 wafer at 38 keV of
∼125 µm (Supplementary Fig. 11). Consequently, the fraction of
incident X-ray photons that are attenuated approaches unity17
(Supplementary equation (3)).
The photocurrent response under constant reverse bias (the
electrodes are selectively e/h extracting) and increasing dose rates
is presented in Fig. 4b. The extracted charge shows a nearly linear
X-ray dose dependency up to 5 mGyair (Fig. 4d). The slope of a
linear fit (red line in Fig. 4d) is defined as the sensitivity of the
detector and we obtained a conservatively estimated sensitivity of
−1
∼2,527 µC Gyair cm−2 at an electric field of 0.2 V µm–1. Figure 4c
shows the dependence of the extracted charge from the MAPbI3
sample on the electric field at a constant dose rate of 6.72 mGyair s−1.
A fit with the Hecht equation gives a tentative μτ product of
2 × 10–4 cm2 V−1 (red line in Fig. 4c).
To compare and validate the X-ray response of the MAPbI3 wafer-
based detector, we measured the charge released from a 1-mm-thick
single-crystalline CdTe sensor layer on the photon-counting pixel
detector ‘Timepix’ (see ref. 44 and the Supplementary Information,
page 12, for a technical description). For comparison, the CdTe
sensor layer has the same thickness as the MAPbI3 wafer and was
biased with the same electric field. As is evident from Fig. 4d, the
amount of extracted charge Q from the MAPbI3 sample is comparable
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NATURE PHOTONICS DOI: 10.1038/NPHOTON.2017.94 ARTICLES
a b 25

Ag ZnO

M 20
PCB

Photocurrent (μA cm−2)

PbI 3
MA 15
:PSS
OT
PED
ITO
10
ss
Gla

5
0.048 5.86 mGyair s−1

20 40 60 80 100 120 140 160

Time (s)

c 25 d
50 CdTe 'Timepix' detector

MAPbI3 sample
20 40
Charge (μC cm−2)

Charge (μC cm−2)

30
15

20

10
10

μτ E d
Q = Q0 1 − exp −
5 d μτ E 0

0.00 0.05 0.10 0.15 0.20 0 2 4 6 8 10 12

Electric field (V μm−1) Dose (mGyair)

Figure 4 | Direct X-ray to current conversion. a, Device stack of the MAPbI3-wafer-based X-ray detector. The MAPbI3 wafer is 1 mm thick. b, Time-resolved
photocurrent at E = 0.2 V µm–1 with different dose rates. c, Extracted charge versus electric field. The dose rate is kept constant at 6.72 mGyair s–1.
d, Extracted charge at constant E = 0.2 V µm–1 for the MAPbI3 wafer-based sample and the CdTe ‘Timepix’ reference detector. All exposures are
2-s-long pulses from an X-ray source operated at 70 kV.

to the commercial CdTe ‘Timepix’ reference detector. For doses
<5 mGyair , Q is almost identical to that of the CdTe reference (∼5%
higher for the CdTe sample). For doses >5 mGyair , Q deviates from
the CdTe reference (due to enhanced recombination).
Another essential parameter is the ionization energy W± , which
is the amount of radiation energy absorbed to create a single free
electron and/or hole. Stated differently, it is the total adsorbed
energy divided by the total number of extracted electrons.
For the MAPbI3 wafer, an ionization energy of ∼5 eV at 0.2 V
µm–1 electric field is calculated (see Supplementary equation (7)).
This value is in close agreement with the Que-Rowlands45 and
Klein rules46, which predict the lowest limit of W± according to
W± = 2.2Eg + Ephonon ≤ 3.9 eV and W± = 3Eg = 4.65 eV, respectively,
where Eg = 1.55 eV is the bandgap and Ephonon ≤ 0.5 eV is the
phonon energy. We conclude that the low W± is due to an excellent
collection efficiency (CE) and a low geminate recombination rate.
This finding is in agreement with recent investigations on
MAPbI3 single crystals claiming a CE of 75% using 20–35 keV
soft X-ray irradiation with an electrode distance of 2.5 mm (ref. 47).
Despite these excellent electronic properties, one important
drawback of these devices is the high and rather unstable dark-
current density of 6 µA cm–2 at 0.2 V µm–1 reverse bias (see baseline
drift in Fig. 4b). In MAPbI3 , the dark conductivity is dominated by
ionic conduction (free iodine migration48) and the current instabil-
ity at reverse bias is caused by the non-ideal e/h selective electrodes.
Carrier-selective electrodes featuring improved e/h selectivity
are currently an area of intense research. Improvements in this
direction are expected to further advance the performance of
perovskite-based X-ray converters.
A comparison of previously reported sensitivities, as shown in
the Supplementary Information (Supplementary Fig. 14), reveals
that the sensitivity value, the μτ product9 and the ionization
energy W± are on par with the best available technologies, such as
HgI2 and Cd(Zn)Te (refs 9, 13). In addition to its toxicity, the elec-
tronic parameters of HgI2 are strongly dependent on the deposition
process and can vary from sample to sample49. Conversely, crystal-
line Cd(Zn)Te wafers offer close to ideal properties but require
energy-demanding production processes such as zone melting, the
Bridgman method, epitaxial growth, or the travelling heater
method (THM)50. Furthermore, wafer inhomogeneities due to Cd,
Te inclusions51 and upscaling to larger areas remain issues with
these technologies16. Many of theses shortcomings are resolved by
the presented sintering method for MAPbI3 microcrystals, which
allows the formation of rigid wafers of virtually any size.
In conclusion, in this Article, we present a sintering process to
manufacture rigid, several-hundred-micrometres-thick MAPbI3
wafers. The wafer conserves the structural and optical properties of
the microcrystalline starting material. Ambipolar charge transport is
demonstrated with a mobility of 0.45–0.7 cm2 V−1 s−1. Under X-ray
exposure, a μτ product of ∼2 × 10–4 cm2 V−1 is measured with an

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ARTICLES
−1
excellent conversion sensitivity of 2,527 µC Gyair cm−2 at 0.2 V µm–1
electric field.
Methods
Methods and any associated references are available in the online
version of the paper.
Received 20 October 2016; accepted 12 May 2017;
published online 19 June 2017
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Acknowledgements
The Cluster of Excellence Engineering of Advanced Materials (EAM) at the FAU
University Erlangen and the Gradko 1896 ‘in situ Microscopy’ (DFG) is acknowledged for
support. The authors thank C.O. Quiroz and M. Salvador for reading the manuscript.
Author contributions
S.S., R.F., G.J.M., T.M., O.S., M.R. and S.F.T. performed the electrical characterization under
X-ray exposure at the Siemens Healthineers Technology Center. I.L. and S.S. synthesized
the MAPbI3 single crystals and microcrystals. H.C. helped with processing of the X-ray
detectors. S.S., A.O. and G.M. performed TOF experiments. B.M. and P.F. carried out the
mechanical investigations. R.H. interpreted the XRD data. S.S. and S.G. performed the SEM
investigation. G.J.M. wrote the manuscript. M.G., W.H., G.A. and C.J.B. initiated and
supervised the work. All authors reviewed the manuscript.
Additional information
Supplementary information is available in the online version of the paper. Reprints
and permissions information is available online at www.nature.com/reprints.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in
published maps and institutional affiliations. Correspondence and requests for materials
should be addressed to G.J.M.
Competing financial interests
The authors declare no competing financial interests.
NATURE PHOTONICS | VOL 11 | JULY 2017 | www.nature.com/naturephotonics
NATURE PHOTONICS DOI: 10.1038/NPHOTON.2017.94
Methods
MAPbI3 single-crystal and microcrystal synthesis. The MAPbI3 microcrystals were
synthesized by a precipitation reaction as reported in ref. 19. A 1 M precursor
solution was prepared by dissolving an equimolar ratio of methylammonium
iodide CH3NH3I (synthesized in house) and lead(II) iodide (Sigma Aldrich) in
γ-butyrolactone (GBL) at 60 °C and stirred for 3 h. Chloroform was
added to the filtered precursor solution, which immediately precipitated
CH3NH3PbI3 microcrystals. The microcrystals were washed twice with chloroform
in a centrifuge, and then dried in a vacuum oven at 40 °C overnight. The synthesis of
the single crystals followed procedures in refs 52 and 53. In brief, the precursor was
heated at 100 °C for 3 h, which produced small MAPbI3 crystals. One small
crystal was used as a seed in 1 M precursor solution and allowed to grow overnight
at 100 °C.
Sintering process. A hydraulic press (Specac) with a 1/2-inch die was used for
sintering. A polished stainless-steel cylinder was placed in the bore of the cylinder
body followed by 250–500 mg of CH3NH3PbI3 powder. Next, a second polished
cylinder and a plunger were inserted into the cylinder body. A vacuum membrane
pump was connected to the die. After about 2 min of turning on the vacuum pump,
a pressure of 0.3 GPa was applied to the plunger for about 5 min to form the
MAPbI3 wafer.
Fabrication of the MAPbI3 wafer based photodetector. Glass substrates with
sputtered ∼100-nm-thick ITO were cleaned in an ultrasonic bath with acetone and
isopropanol for 10 min and then placed in an oxygen plasma oven for 2 min.
PEDOT:PSS (VP Al 4083 from H.C. Starck) was spin-coated onto the cleaned
substrate to form a 100-nm-thick thin film. MAPbI3 wafers were pressed onto the
PEDOT:PSS/ITO substrates at about 15 MPa for 2 min using a hydraulic press.
PCBM (20 mg ml–1) then ZnO were subsequently spin-coated onto the wafers. The
Ag top contacts (6.6 mm2 in area and 70–100 nm thick) were deposited by
thermal evaporation.
SEM. SEM measurements were performed on MAPbI3 wafers and the
microcrystalline particles supported on standard adhesive carbon pads using an
ULTRA 55 Carl Zeiss AG SEM under 10 kV acceleration voltage. For the image of
the cross-section, the wafers were ‘broken’ with a hammer.
Atomic force microscopy measurements. An NT-MDT nano-educator AFM in
contact mode was used.
Photoluminescence. Photoluminescence spectra were measured using a 450 nm
laser diode as the excitation source in a back-scattering configuration at room
temperature. The laser beam was focused to a spot with a diameter of ∼10 µm. The
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ARTICLES
emission was recorded with a Si charge-coupled device camera (Syncerity, Horiba
Jobin-Yvon) attached to an iHR320 monochromator (Horiba Jobin-Yvon) with a
resolution of 5 nm. The spectra were corrected for the spectral sensitivity of the
system, determined with the help of a calibrated halogen lamp (Stellarnet).
Nanoindentation. Nanoindentation measurements were performed using a
Keysight G200 Nanoindenter. A Berkovich tip was pressed 2.5 µm into the sample
surface, using a constant strain rate of 0.05 s–1. Nanoindentation was carried out in
continuous stiffness mode (CSM), where a small oscillation is superposed on the
indentation load. A 2 nm sinusoidal oscillation was superposed to the loading signal.
The hardness values were average over 25 measurements taken at least 100 µm apart.
Strain-rate jumps tests were implemented during the nanoindentation loading
segment. The corresponding strain rates ranged between 0.025 s–1 and 0.005 s–1.
Strain-rate sensitivity was determined as the slope of a linear fit in a double
logarithmic plot of hardness versus strain rate.
TOF. PMMA (Sigma Aldrich) in chlorobenzene (100 mg ml–1) was spin-coated on
cleaned ITO substrates to form a 500-nm-thick layer. MAPbI3 wafers were pressed
into the PMMA/ITO substrates at ∼50 MPa for 2 min using the hydraulic press. The
Au top contacts (70 nm thick and 0.2 cm2 in area) were thermally evaporated to
provide the charge-collecting electrode. As excitation, a nanosecond pulse laser
(532 nm, CryLaS) was used. The bias voltage was applied to the sample using a
function generator (Agilent 33500B) and a voltage amplifier (Falco Systems
WMA 300). The transient current was measured as the voltage drop over a load
resistor and recorded with a digital oscilloscope (Tektronix DPO 3034).
Photocurrent under X-ray exposure. A 70 kV X-ray source (Siemens MEGALIX
Cat Plus 125/40/90, 124 GW) with a tungsten anode was used. The X-ray spectrum
was filtered with a 2.5-mm-thick Al plate. The dose rate was changed by changing
the X-ray tube current and was calibrated with a PTW Diados T11003-001896
dosimeter. A Keithley 2400 SMU measuring at 10 Hz was used to record the
photocurrent. See Supplementary Information for additional details.
Data availability. The data that support the plots within this paper and other
findings of this study are available from the corresponding author upon
reasonable request.
References
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