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Printable organometallic perovskite enables large-area, low-dose X-ray


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Article  in  Nature · October 2017


DOI: 10.1038/nature24032

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Letter doi:10.1038/nature24032

Printable organometallic perovskite enables


large-area, low-dose X-ray imaging
Yong Churl Kim1, Kwang Hee Kim1, Dae-Yong Son2, Dong-Nyuk Jeong2, Ja-Young Seo2, Yeong Suk Choi1, In Taek Han1,
Sang Yoon Lee1 & Nam-Gyu Park2

Medical X-ray imaging procedures require digital flat detectors collection efficiency. a-Se has field-dependent sensitivities of up to
operating at low doses to reduce radiation health risks1,2. Solution- 0.44 μ​C mGyair−1 cm−2 at operating electric fields as high11 as 15 V μ​m−1.
processed organic–inorganic hybrid perovskites have characteristics We therefore aimed to produce highly sensitive all-solution-based
that make them good candidates for the photoconductive layer X-ray detectors based on printable polycrystalline MAPbI3 thick films.
of such sensitive detectors3–7. However, such detectors have The X-ray detector was built as illustrated in Fig. 1a and the ­individual
not yet been built on thin-film transistor arrays because it has thin-film transistor (TFT) pixel is depicted in Fig. 1b (see Methods for
been difficult to prepare thick perovskite films (more than a few details). Two interlayers of polyimide (PI)-perovskite c­ omposites (see
hundred micrometres) over large areas (a detector is typically Methods) were inserted by spin-casting to reduce the dark ­current
50 centimetres by 50 centimetres). We report here an all-solution- (that is, the background ‘leakage’ current, which produces noise in
based (in contrast to conventional vacuum processing) synthetic the X-ray detector). The bottom layer of the PI-MAPbI3 composite
route to producing printable polycrystalline perovskites with (Fig. 1b) forms a hole-transporting layer and the top PI-MAPbBr3
sharply faceted large grains having morphologies and optoelectronic layer forms a hole-blocking layer (HBL). The high intrinsic resistivity
properties comparable to those of single crystals. High sensitivities (1018 Ω cm) of PI also reduces electrical crosstalk among the pixels. The
of up to 11 microcoulombs per air KERMA of milligray per square 830-μ​m-thick polycrystalline MAPbI3 (MPC) photoconductor layer
centimetre (μC mGyair−1 cm−2) are achieved under irradiation was printed on the coated PI-MAPbI3 using a doctor blade (Fig. 1b).
with a 100-kilovolt bremsstrahlung source, which are at least one The top electrode (indium tin oxide, ITO) was biased to a positive
order of magnitude higher than the sensitivities achieved with ­voltage source to operate the detector in hole-collection mode. Finally,
currently used amorphous selenium or thallium-doped cesium tape-automated bonding (in which bare integrated circuits are placed
iodide detectors. We demonstrate X-ray imaging in a conventional onto a printed circuit board by attaching them to fine conductors in a
thin-film transistor substrate by embedding an 830-micrometre- polyamide or polyimide film) of readout integrated circuits (ROICs; see
thick perovskite film and an additional two interlayers of polymer/ Methods) was performed on the X-ray detectors. The MAPbI3 has not
perovskite composites to provide conformal interfaces between only a stable three-dimensional perovskite crystal structure, but also
perovskite films and electrodes that control dark currents and its mass attenuation coefficients (obtained from the NIST database12)
temporal charge carrier transportation. Such an all-solution-based are comparable to (or exceed) that of CdZnTe throughout the medical
perovskite detector could enable low-dose X-ray imaging, and could X-ray energy domain (10−​200 keV) thanks to the heavy I and Pb atoms
also be used in photoconductive devices for radiation imaging, that exhibit resonance K-edge absorption at 33.17 keV and 88 keV,
sensing and energy harvesting. respectively (Extended Data Fig. 1a). The X-ray-related measurements
The use of digital flat detectors in many diagnostic and interven- and images were recorded using a 3-mm-thick Al-filtered 100-kV (peak
tional medical applications, including in X-ray imaging procedures, has tube voltage, Vp) tungsten bremsstrahlung source with a dose rate range
increased rapidly over the past decades. This results in higher average of 1−​5  mGyair s−1, resulting in a dose range of 10−​200  μ​Gyair by varying
radiation doses for individuals. Repeated exposure to such ionizing the irradiation pulse width. The measured pixel current (averaged over
radiation can cause cancer. Recent reports of radiation detection by a square centimetre of detector area) as a function of applied voltage
organometallic perovskites (MAPbX3, where MA =​  CH3NH3 and (10−​200 V) yielded a sensitivity range of 0.3−​3.8  μ​C mGyair−1 cm−2
X =​ Cl, Br or I) that are triggered by solar cells8,9 suggest that such (Fig. 1c). These sensitivities are about one-third those measured from a
materials may enable low-dose X-ray imaging. small-sized diode configuration (1−​11  μ​C mGyair−1 cm−2) as described
At present, two flat detector technologies prevail. The dominant below. The μτ product was fitted to 1.0 ×​  10−4 cm2 V−1 by the Hecht
method is based on indirect X-ray conversion using thallium-doped formula13, Q =​  Q0μτVd−2[1 −​ exp(−​d2/μτV)], where V is the applied
cesium iodide (CsI:Tl) scintillators formed on amorphous ­silicon bias, d the thickness, and Q0 the asymptotic collected charge. The cor-
(a-Si) photodetector arrays with a typical sensitivity10 of about responding electron–hole pair generation energy (W±) was e­ stimated
0.3 μ​C mGyair−1 cm−2. The other method uses direct photoconductors to be 12.5 eV at bias 200 V, while 4.7 eV was obtained at the same bias in
such as amorphous selenium (a-Se), which is particularly suitable for the diode measurement (Fig. 1c and Extended Data Fig. 1b), approach-
high-resolution mammography because of its good X-ray conversion ing the theoretically predicted value 3Eg ≈​ 4.5  eV (where Eg is the
efficiency of soft X-ray photons (<​40 keV). These direct-conversion optical bandgap of MAPbI3, about 1.5 eV) by Klein’s rule14.
detectors read out charges by an applied electric field, leading to almost Meanwhile, the spatial resolution of the detector can be determined
none of the optical crosstalk usually suffered by indirect-conversion with the modulation transfer function (MTF), representing the transfer
detectors. However, a-Se has limited use because of its poor absorptivity ability of input signal modulation of the spatial frequency (in-line pair
of hard X-rays, caused by its low-lying K-edge resonance absorption, per millimetre; lp mm−1) relative to its output. Using the slanted-edge
an insufficient charge-carrier mobility lifetime (μτ) product value method15, the MTF of the MPC detector was compared with a state-of-
(about 10−7 cm2 V−1), and the accompanying high operating elect­ the art 250-μ​m-thick a-Se detector with the same pitch (Extended Data
rical fields (10−​40 V  μ​m−1) required to overcome the poor charge Fig. 1c). The MTF of the MPC detector dropped to 0.2 at 3.1 lp mm−1,
1
Samsung Advanced Institute of Technology (SAIT), Samsung Electronics Materials Research Complex, Youngtong, Suwon 443-803, South Korea. 2School of Chemical Engineering and Department
of Energy Science, Sungkyunkwan University, Suwon 440-746, South Korea.

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RESEARCH Letter

a X-ray photons b

V+ PI-MAPbI3 on TFT
ITO

TFT
PI-MAPbBr3

MPC

Printed MPC I3
PI-MAPbI3 APb
TFT backplane PI-M

ITO c
Measured; pixellated detector
d Fitted to the Hecht equation 4

air per pixel)

X-ray sensitivity (μC mGyair


1,200
µτ = 1.0 × 10−4 cm2 V−1

Signal current (×106 e mGy–1


800
12.5 eV 2

W± (eV)
10
400

–1 cm–2)
1
4.7 eV
1 0 50 100 150 200
Bias voltage (V)
0 0
0 30 60 90 120 150 180 210
Bias voltage (V)
Figure 1 | Building an X-ray detector based on hybrid perovskites. panel shows a photograph of printed MPCs on the PI-MAPbI3. c, Charge
a, Illustration of an all-solution-processed digital X-ray detector. b, The collection and sensitivity characteristics of the MPC detector measured at
left panel shows an optical image of spin-cast PI-MAPbI3 on an a-Si:H 100 kVp. The inset shows W± in the pixellated (blue symbols) and diode
TFT backplane. The inset shows a single-pixel structure of TFT (scale (red symbols) detectors. d, A hand phantom X-ray image obtained from an
bar 30 μ​m) in which the collection electrode (white outline) is connected MPC detector (using 100 kVp and 5 mGyair s−1 for 5 ms exposure, resulting
to the drain contact of the TFT through a via (circular pad). The right in a dose of 25 μ​Gyair and a bias voltage of 50 V).

whereas the MTF of the a-Se detector was 0.2 at 7.1 lp mm−1. The perovskites or possible desorption of residual solvents21. Loss of the
enlarged resolution test image resolved between 2.8 lp mm−1 and CH3NH2 species followed by loss of the HI was observed between
3.1 lp mm−1. A side-by-side comparison is not clear owing to differ- 300 °C and 370 °C, with corresponding infrared absorption peaks
ences in the photoconductor layer thickness, material packing and related to CH3NH2. Loss of PbI2 started at around 410 °C by melting.
morphology, applied field, and radiation energy between the two To characterize the optoelectronic properties, we fabricated MPC
detectors. However, the most probable cause of the MPC detector’s photoconductor devices by printing on the ITO-coated glasses that
lower MTF (than that of the a-Se detector) is the 20−​100  μ​m size of form the cathodes and contacting the top layer (on the illuminated
the MPC crystallites: those crystallites larger than a pixel can overlap side) by sandwiching other ITO glasses to form anodes. The optical
neighbouring pixels, leading to charge sharing, which degrades MTF ­properties were compared with those of thin MAPbI3 films (0.5 μ​m in
substantially. The resolution of the demonstrated MPC detector could ­thickness) p ­ repared by an adduct method (hereafter referred to as the
be much improved by uniform material preparation and a greater adduct film)22. The MPC films showed an absorption band extended
understanding of pixel-to-pixel charge collections and trap-assisted to 840 nm, whereas the thin adduct films had an absorption edge at
charge behaviours in the MPC detectors. X-ray images of a hand 760 nm (Fig. 3a). Such absorption extension is similar to the ­behaviour
phantom and a smaller smartphone produced under low doses of reported for MAPbI3 single crystals23. The photoluminescence peak
25 μ​Gyair and 10 μ​Gyair, respectively, are shown in Fig. 1d and Extended of the MPCs red-shifted from 760 nm (adduct film) to 810 nm. We
Data Fig. 1d. note here that the photoluminescence intensity of the MPCs is about
Though an ideal photoconductor would be a single crystal, such 100-fold stronger than that of the thin adduct films (Extended Data
crystals are difficult and expensive to assemble on large flat panels. In Fig. 2a), which is thought to be due to a reduced number of non-
photo­conductive devices such as solar cells, larger crystal grain size radiative surface defects in the MPC crystallites. The optical bandgap
has been predicted16 to increase the power-conversion efficiency, and estimated by the Tauc method was lowered to 1.50 eV from the 1.60 eV
this has been proved experimentally in doctor-bladed MAPbI3 films17 of the thin adduct film (Fig. 3b). This bandgap reduction is strongly
and spin-cast thin MAPbI2Cl films18. In the preparation of viscous related to the fewer grain boundaries and corresponding lower locali­
MPC paste, an anti-solvent method was used (see Methods). We chose zed defects in our large-grain MPCs. Carrier lifetime τ was estimated
γ​-butyrolactone as a primary polar solvent and α​-terpineol ­(relative by using time-resolved photoluminescence. We compared the transient
dielectric constant εr =​ 2.75 at room temperature) as our anti-­solvent. fluorescence from the photoexcitation peaks at 810 nm (MPC) and
The as-grown MPCs have an average grain size of 30 μ​m, and the 760 nm (adduct film) (Fig. 3c). Biexponential fitting (Extended Data
­largest grains of up to 100 μ​m are found to have crystal habits ­typical Fig. 2b) revealed both fast and slow dynamics, with slow component
of a body-centred tetragonal lattice exhibited as sharply ­faceted lifetime values of τ2 =​ 1,052 ns for the MPC and τ2 =​ 128 ns for the thin
­rhombo-hexagonal dodecahedra (Fig. 2a and b). Powder X-ray adduct film. Meanwhile, impedance spectroscopy24 gave a much longer
­diffraction (Fig. 2c) reveals the well crystallized tetragonal (I4/mcm) carrier recombination lifetime of 6−​300  μ​s measured under 0.1 Sun
phase of the prepared MPCs, distinguishable from the cubic phase and 1 Sun (where 1 Sun =​ 100 mW cm−2) illumination conditions
by the presence of the (211) peak19,20. Additional t­ hermogravimetry (Extended Data Fig. 2d). The large measured difference in the lifetime
­a nalysis coupled with gas-phase Fourier-transform infrared results is also found in other reports4,16. We chose the smaller τ of time-
­spectrometry did not show any notable mass loss below 230 °C (Fig. 2d), resolved photoluminescence result (1,052 ns) as the carrier lifetime. The
unlike other reports of MAPbI3, which typically show mass loss in charge-carrier mobility was measured by a time-of-flight method using
the temperature range of 80−​130 °C, attributed to dehydration of 400-μ​m-thick MPC films (Fig. 3d and Extended Data Fig. 2c). The

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Letter RESEARCH

a b

c d
Tetragonal I4/mcm 100 420 °C
(400)

350 °C

Absorbance (arbitrary units)


Derivative of weight (% ºC–1)
0.0
Counts (arbitrary units)

345 °C
80 C–N stretch C–H stretch
for amine (1,143–1,214) (2,965)
Weight (%)
–0.5 335 °C
(200)

N–H bending N–H stretch


60 (3,288)
(211)

(1,600)
–1.0 330 °C
C–N stretch
40 (900–1,200)
–1.5 320 °C
300 °C
150 °C
10 20 30 40 50 60 70 80 90 20
0 100 200 300 400 500 1,000 1,500 2,000 2,500 3,000 3,500
2θ (deg) Temperature (°C) Wavenumber (cm–1)
Figure 2 | MPC perovskite basic properties. a, A scanning electron prepared MPC film (right; scale bar 30 μ​m). c, X-ray diffraction pattern of
microscope (SEM) image of a 400-μ​m-thick printed MPC film using the powdered grains from an MPC film. d, Analysis of thermal behaviour
a doctor blade. Scale bar, 400 μ​m. b, SEM images showing surface of MPC films using thermogravimetry analysis coupled with gas-phase
morphology(left; scale bar 50 μ​m) and a polygon of crystallites of the Fourier-transform infrared spectrometry.

hole mobility was 139 ±​ 14 cm2 V−1 s−1, and the electron mobility was To make use of MPC film for medical imaging devices, the dark
66 ±​  7 cm2 V−1 s−1. The μτ products of the MPC films estimated for the c­ urrent must be tightly controlled. A high dark current limits the
demonstrated X-ray detector (1.0 ×​  10−4 cm2 V−1) agrees reasonably dynamic range of the detector as well as increases noise levels, thus
well with the μτ product (1.46 ×​  10−4 cm2 V−1) obtained independently degrading the signal-to-noise ratio. The MPC detectors should be
from the time-of-flight and time-resolved photoluminescence. Though ­operated in the hole-collection mode because of the longer carrier
the μ​τ product measured here is two orders of magnitude lower than lifetime and hole mobility. In addition to requiring the HBL on the
for those record-high single crystals of perovskite4,5, it is comparable anode side, a hole-transporting layer on the cathode side providing
to that of HgI2 single crystals and better than the vapour-deposited good adhesion between the MPC film and the TFT substrate (back-
polycrystalline CdZnTe in the range25 10−5 cm2 V−1. plane) is required. Using TiO2 for the HBL and Spiro-OMeTAD for the
a b 8
1.2 1.2 12
Normalized photoluminescence

MPC Adduct MAPbI3


Normalized absorbance

6
0.8 0.8 9
(arbitrary units)

(arbitrary units)

(αhυ)2 (× 1010)
(αhυ)2 (×107)

4 6
0.4 0.4
Eg = 1.50 eV Eg = 1.60 eV
2 3
0.0 MPC 0.0
Adduct MAPbI3
400 500 600 700 800 900 0 0
1.4 1.5 1.6 1.7 1.4 1.5 1.6 1.7
Wavelength (nm) hυ (eV) hυ (eV)
c d
100 0.9 0.6
Normalized photoluminescence

MPC 0.8
0.7 0.5
Adduct MAPbI3
intensity (arbitrary units)

0.6 0.4
Normalized current

Normalized current

10–1
(arbitrary units)

(arbitrary units)

0.5
0.4 h+ 0.3
10–2 time of flight e–
0.3 30 V time of flight
0.2
40 V –30 V
10–3 50 V –40 V
0.2 60 V –50 V
70 V –60 V
80 V –80 V
10–4 0.1 0.1
0.0 0.5 1.0 1.5 0.2 0.3 0.4 0.5 0.2 0.4 0.6 0.8 1.0
Time (μs) Time (μs) Time (μs)
Figure 3 | Optoelectronic characterization of MPC thick films. frequency. c, Photoluminescence lifetime of the MPC and adduct films.
a, Normalized photoluminescence and absorption spectra of the MPC d, Normalized time-of-flight h+ (hole carrier) and e− (electron carrier)
and thin adduct MAPbI3 films. b, Optical bandgap (Eg) estimation from charge transient curves for an MPC film under CO2 laser illumination
absorption spectra of the MPC and thin adduct MAPbI3 films, where (wavelength 337.1 nm) with various bias voltages.
α​is the absorption coefficient, h is the Planck constant, and υ is the light

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© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
RESEARCH Letter

a b
ITO / MPC / ITO
102 ITO / TiO2 / MPC / Spiro-MeOTAD / ITO PI-MAPbI3
ITO / MAPbBr3 (adduct) / MPC / PI-MAPbI3 / ITO
Current density (mA cm–2) ITO / PI-MAPbBr3 / MPC / PI-MAPbI3 / ITO
100 ITO / PI-MAPbBr3 (dilute) / MPC / PI-MAPbI3 / ITO

10–2

10–4
MPC d = 830 μm
PI-MAPbBr3
10–6

0 50 100 150 200


Bias voltage (V)
c
200 V
100 kV
10–2 150 V d
1 mGyair s–1, 0.2 s
125 V
X-ray response (mA cm–2)

Device d = 830 μm
75 V
Bias 50 V (0.06 V μm–1)

X-ray response (mA cm–2)


Device 50 V 10–2
10–3 d = 830 μm S1 S10 X-ray 50 ms shuttered
25 V
100 kV, 1 mGyair s–1
10 V

10–3
10–4
Idark (t)
Idark (0)

10–4
10–5

0.0 0.2 0.4 0.6 0 1 2


Time (s) Time (s)
Figure 4 | Diode MPC device characterization. a, Dark-current plots MPC device response to X-ray pulses with varying applied bias voltage.
as a function of applied bias voltage with various interlayers, where d is d, A response under 50 V to a train of short X-ray pulses with a pulse
MPC thickness. b, Typical SEM images of PI-MAPbI3 and PI-MAPbBr3 width 50 ms.
composite films used for interlayers (scale bars, 5 μ​m and 400 μ​m). c, An

hole-transporting layer, as widely used in perovskite solar cells, reduced falling (reaching 10% of the saturated X-ray signal) times both
the dark current by about one order of magnitude (Fig. 4a). decreased as the bias increased between 10 V and 200 V (Extended Data
We developed improved composites of PI and perovskites. These Fig. 4a). This relatively fast response of our device structure is clearly
composites are motivated by the fact that (i) PI films have been reported shown in a train of short X-ray pulses with a pulse width of 50 ms
as effective HBLs in a-Se detectors26, and PI precursors are usually formed using a shuttered X-ray irradiation (Fig. 4d), which indicates
polymerized in polar solvents such as N-methyl-2-pyrrolidone (NMP) relatively lower trap states in our electrode/interlayer/MPC interfaces
and γ​-butyrolactone, which are compatible with perovskite precursors and that any bulk traps existing in the MPC have relatively low detrap-
(Extended Data Fig. 3a); and (ii) other hybrid perovskites having larger ping energy.
bandgaps than MAPbI3, such as MAPbBr3 or MAPbCl3, can be used The temporal performance of the direct-converting X-ray detectors
as HBLs, as confirmed by dark-current measurements using MAPbBr3 can be characterized by ‘lag’ and ‘ghosting’26,28. As analysed using the
synthesized by the adduct method (Fig. 4a)22 as an HBL. Both spin-cast repeated pulse train measurement on the diode structure (Extended
interlayers—the PI-MAPbBr3 composite as HBL and the PI-MAPbI3 Data Fig. 4b and c), the ‘lag’ showed almost the same behaviour for
composite as the hole-transporting layer—reduced dark current to each exposure. Charge trapping in the bulk of the MPC film can
one order of magnitude less than the dark current of the device sand- ­contribute to ‘lag’ by releasing trapped charges after exposures, which
wiched by TiO2/Spiro-OMeTAD. The PI-MAPbBr3 composite further take longer to be released when the trapping energy is larger (deep
reduced the dark current by controlling the concentration of MAPbBr3 traps). Another contribution to ‘lag’ is charge injection through contact
­precursors in the composite system (Fig. 4a and Extended Data electrodes being under a constant bias potential, in which the charge
Fig. 3b). The coated PI-MAPbI3 formed uniform composite films traps generated by X-ray illumination increase the electric field at the
about 2.5 μ​m thick with MAPbI3 polycrystalline grains underneath electrode interfaces, causing a dark current injection that leads to a ‘lag’
the p ­ olymer-like layer (Fig. 4b), which adhered well to the MPC increase. ‘Ghosting’ is represented as a change in sensitivity with each
films as a result of partial dissolution of the PI overlay by the solvent X-ray exposure by the generated charge traps. No apparent sensitivity
(γ​-­butyrolactone) incorporated in the printed MPC. The PI-MAPbBr3 decrease trend is observed with increase in the number of exposures.
composites showed an interesting morphology (Fig. 4b and Extended We consider that in our devices, with relatively high dark current (about
Data Fig. 3a and b) having orange-coloured fourfold symmetric two orders higher than in stabilized a-Se devices), these unusual lag
­dendrite structures. Such dendritic figures are usually found in metal and ghosting behaviours may be attributable to the extremely short
alloys27 or snowflakes. X-ray pulses were illuminated on the diode-­ charge trap release time as a result of the shallowness of the charge
configured devices for the measurement of the X-ray photoresponse vacancy traps in the MAPbI3 crystallites29 or injected hole carriers
(Fig. 4c). Electrical fields in the range 0.01−​0.24 V  μ​m−1 were through blocking contacts effectively recombining with the charge
applied to collect charges through the bottom ITO electrode. X-ray traps and leading to invariant sensitivity behaviours. Our demonstrated
­sensitivities in the range 1−​11  μ​C mGyair−1 cm−2 were observed (versus device protocol could be applied to low-dose inexpensive detectors in
0.3−​3.8  μ​C mGyair−1 cm−2 in the pixelated detector) as discussed in the full medical X-ray range. The remaining technological challenges
Fig. 1. The rising (reaching 90% of the saturated X-ray signal) and are ­further lowering the dark current, and improving the relatively slow

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Letter RESEARCH

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(2010). Acknowledgements N.-G.P. acknowledges partial financial support from
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tribromide perovskite single crystals. Nat. Photon. 10, 333–339 (2016). Frontier R&D Program on Center for Multiscale Energy System) and NRF-
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crystals of hybrid lead halide perovskites. Nat. Photon. 10, 585–589 (2016). S.Y.L. are indebted to all the members of SAIT (especially H. Kim and Y. Kim)
6. Wei, W. et al. Monolithic integration of hybrid perovskite single crystals with and the Healthcare & Medical Equipment Division of Samsung Electronics
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8. Kojima, A. et al. Organometal halide perovskites as visible-light sensitizers for Author Contributions I.T.H. initialized this project. Y.C.K. and N.-G.P. organized
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xcom-photon-cross-sections-database (NIST Phys. Lab., 1998). www.nature.com/reprints. The authors declare no competing financial
13. Kasap, S. O. X-ray sensitivity of photoconductors: application to stabilized a-Se. interests. Readers are welcome to comment on the online version of the paper.
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14. Que, W. & Rowlands, J. A. X-ray photogeneration in amorphous selenium: claims in published maps and institutional affiliations. Correspondence and
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5 o c t o b e r 2 0 1 7 | V O L 5 5 0 | N A T U RE | 9 1
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RESEARCH Letter

Methods Japan, Inc. We used a part of the active layer for the coating of PI-MAPbI3
Growth of MPC. We used a two-step solvothermal process with addition of and MPC photoconductors. The imaging area consists of 1,428 ×​  1,428 pixels
α​-terpineol to grow MPCs, and the resulting mixture is dense and viscous, readily (10 cm ×​ 10 cm) with a pixel pitch of 70 μ​m. The individual pixel capacitance is
printed using doctor blades. The thickness of the coated MPC films was controlled 0.4 pF with a geometric fill factor of 76%. The geometric fill factor is defined as
by the guide frames. Equivalent molar ratios of CH3NH3I (prepared as in ref. 22) the fraction of effective pixel area occupied by the charge collection electrode. The
and PbI2 (99%, Sigma-Aldrich) made up to be 78 wt% in total were mixed with MAPbI3 may react with metals (for example, aluminium, which is commonly used
22 wt% of γ​-butyrolactone (≥​99%, Sigma-Aldrich) in a closed bottle. This mixture in TFT backplanes), resulting in defective pixels and lines forming over hours to
was put in the 90 °C convection oven for 4−​6 h with periodic vibration every half days after manufacture. Therefore, the metal lines (such as the address and data
hour. Then 30−​40 wt% of α​-terpineol with respect to γ​-butyrolactone was mixed lines) were protected by a passivation overcoat on which ITO (which is inert to
and put in the same 90 °C oven for 4−​6 h with periodic vibration every half-hour. MAPbI3) collection electrodes were formed. The ITO electrodes are electrically
The final viscous solution was printed on substrates using a doctor blade. The connected by holes to the drain contacts of the TFT pixels. The TFTs are protected
coated substrates were cured on a hot plate at 120 °C for 1.5 h. The blend solution by electrostatic shield structures to prevent permanent damage by the applied bias
kept under ambient temperature was vibrated and then warmed to 80 °C before on the photoconductors.
the printing process owing to its large viscosity increase during ambient storage. ROIC. The ROICs are supplied from Analogue Devices Inc. The used ROICs
Adduct MAPbI3 and MAPbBr3. Adduct MAPbI3 films were prepared by the contains a 256-channel/16-bit analogue front end with low noise of 560e (where
method described in ref. 22. A solution of molar ratio 1:1:6.7:2 of CH3NH3Br was e is the electron charge).
prepared in-house by mixing PbBr2 (≥​98%, Sigma-Aldrich), dimethyl formamide X-ray characterization and imaging in the pixellated detector. The dark current
(DMF) and dimethyl sulfoxide (DMSO). Stirring this mixture for 1 h resulted in the for the prototype MPC detector presented here reached 0.4 ±​ 0.1 pA per pixel
adduct solution. The final transparent solution was spin-cast for 30 s at 2,000 r.p.m. (areal density 80 ±​  20 pA mm−2), which is up to two orders of magnitude higher
with diethyl ether sprayed over it. than state-of-the-art direct (a-Se) and indirect (CsI:Tl) detectors. Dark-current
PI-MAPbI3 composite. Polyimide (PI) precursors p-phenylenediamine and subtraction was applied for the image acquisition.
biphenyl tetracarboxylic acid dianhydride (BPDA) with a molar ratio of 1:0.975 The pixel X-ray signal was saturated in the exposure range 50−​55  μ​Gyair at
in total 15 wt% was mixed with 85 wt% of NMP, then the solution was stirred for 50 V bias. Up to 70% of the saturated pixel value, the detector response showed a
5 h in a N2 purged reactor at room temperature, and then the reactor temperature good linearity in about 1% deviation. With exposure increase, the deviation from
was increased to 40 °C for additional 12-h reaction. The resultant poly(pyrom- linearity was exaggerated until the pixel was saturated. The MTF presented here
ellitic dianhydride-co-4,4′​-oxydianiline) (which is called polyamic acid) formed was measured under 15 μ​Gyair of exposure (1.5 mGyair s−1 for 10 ms), which is
the PI-NMP solution. 4.61 g of PbI2 and 1.59 g of CH3NH3I were added to the within a good linear response range.
prepared PI-NMP (4.8 g) with extra addition of 2.4 g DMF (other solvents such Pixel-to-pixel signal non-uniformity in the prototype MPC detector presented
as NMP or γ​-butyrolactone are also acceptable). After overnight stirring of this here was in the range of 5% (high exposure; 20 μ​Gyair) to 12% (low exposure;
mixture at room temperature, the PI-MAPbI3 solution was spin-cast at 2,000 r.p.m. 1 μ​Gyair) with respect to exposure levels. This level of non-uniformity is larger than
for 30 s, and then cured for 10−​30 min on a 120 °C hot plate. can be accounted for by the variation of MAPbI3 thickness (under 5%) across the
PI-MAPbBr3 composite. We used the same process for the synthesis of full prepared sample (under 1% in the local region of interest, about 1 cm2). Other
PI-MAPbI3. For example, PbBr2 [3.835 g (for dilute)−​7.670 g (for concentrated)] factors such as the interlayer–photoconductor contact and the existence of small
+​ CH3NH3Br [1.170 g (for dilute)−​2.340 g (for concentrated)] +​PI-NMP (9.6 g) irregular voids in the MPC film can also contribute to this non-uniformity. After
+​DMF (4.8 g). gain correction, the non-uniformity of the pixel response was reduced to 3%−​4%.
a-Si:H TFT backplane. The TFT backplane (active area 25.088 cm ×​ 28.672 cm) Data availability. The data sets analysed during the study are available from the
was specifically customized for commercial a-Se detectors supplied from CMO corresponding authors upon request.

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Letter RESEARCH

Extended Data Figure 1 | MPC X-ray detector. a, Calculated mass study, the panel sensitivities should coincide with those measured from
attenuation coefficient for a-Se, CdZnTe and MAPbI3, and two normalized simple diodes. At this stage this discrepancy is probably mainly due to
bremsstrahlung X-ray spectra used in medical applications as a function of the incomplete charge collection in the gap between pixels by the limited
X-ray energy. The linear attenuation coefficient (in cm−1) can be obtained geometric fill factor‚ imperfect MPC contact on the pixel electrode, and a
by multiplying mass attenuation and mass density (a.u., arbitrary units). possible reduction in the effective applied bias on the MPC layer caused
b, An X-ray spectrum of a 3-mm-filtered 100-kVp tungsten source in by the thicker interlayers formed in the processing of large-area detectors
1 mGyair (black line), the absorption by 830-μ​m-thick MPC film (blue (rather than smaller diodes). c, The MTF of an MPC detector and a
line), and the resulting absorbed spectrum by the MPC film (red line). conventional a-Se direct converting detector with a same pixel pitch of
The integral of the absorbed spectrum equals the total deposited energy 70 μ​m. The inset shows a magnified 100-kVp X-ray image of a resolution
(Eabs) in the MPC film of about 2.91 ×​  1011 keV cm−2 mGyair−1. The W± is phantom. The MTF presented here was measured under 15 μ​Gyair of dose
defined as EabsS−1, where S is the X-ray sensitivity. There are various loss (dose rate of 1.5 mGyair s−1 for 10 ms exposure time). d, A smartphone
mechanisms that reduce the sensitivity in the pixelated detector. Provided X-ray image at dose rate 1 mGyair s−1 with exposure time 10 ms (10 μ​Gyair
that all the specific loss factors are understood and corrected by further of dose).

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RESEARCH Letter

Extended Data Figure 2 | Optoelectronic properties of MPC film. impedance (Z) spectra for the 400-μ​m-thick MPC film measured under
a, Photoluminescence spectra of the MPC and the thin adduct 1 Sun and 0.1 Sun irradiation conditions. The inset shows the equivalent
MAPbI3 film using an excitation source wavelength of 505 nm. circuit for analysis, where Rs is the series resistance of the MPC, Rrec is the
b, Photoluminescence lifetime of the MPC film. The fitted recombination recombination resistance related to the recombination current, and CPE
lifetime is 1.052 μ​s. c, Full time-of-flight current behaviour for both is the chemical capacitance represented as a constant phase element. Here,
charge carriers: left for hole and right for electron. d, Nyquist plots of the lifetime is estimated by multiplying Rrec and CPE.

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Letter RESEARCH

Extended Data Figure 3 | Interlayers of PI–perovskite composites. a, Additional images of interlayer films and their precursor solutions. Scale bar
for the upper middle image, 30 μ​m. b, Morphology changes in PI-MAPbBr3 film with decreasing precursor concentration of MAPbBr3. All scale bars,
200 μ​m.

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RESEARCH Letter

Extended Data Figure 4 | Temporal X-ray response characterization. where Idark(t) is the dark current measured at time t after each exposure,
a, Rise and fall time response dependent on the applied bias. b, ‘Lag’ Idark(0) is the initial dark current level before any exposures, S1 is the
measurement as a function of time after each X-ray pulse signal. X-ray sensitivity for the first exposure, and Sn is the sensitivity of the nth
c, ‘Ghosting’ measured using the sensitivity change for each X-ray pulse exposure, respectively.
signal. Lag can be defined as [Idark(t) – Idark(0)]Sn−1, and ghosting as SnS1−1,

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