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Gate-Induced Insulator to Band-Like Transport Transition in Organolead Halide Perovskite Dehui Li, Hung-Chieh Cheng, Hao Wu, Yiliu Wang, Jian Guo, Gongming Wang, Yu Huang, and Xiangfeng Duan J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.6b02841 • Publication Date (Web): 04 Jan 2017 Downloaded from http://pubs.acs.org on January 4, 2017

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The Journal of Physical Chemistry Letters

Gate-Induced Insulator to Band-Like Transport Transition in Organolead Halide Perovskite Dehui Li1,2*, Hung-Chieh Cheng3, Hao Wu3, Yiliu Wang1, Jian Guo3, Gongming Wang1,4, Yu Huang3,4, and Xiangfeng Duan1,4* 1

Department of Chemistry and Biochemistry, University of California, Los Angeles, California

90095, USA. 2School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan, 430074, China; 3Department of Materials Science and Engineering, University of California, Los Angeles, California 90095, USA; 4California Nanosystems Institute, University of California, Los Angeles, California 90095, USA. *Corresponding authors. Email: [email protected]; [email protected].

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Abstract: Understanding the intrinsic charge transport in organolead halide perovskites is essential for the development of high-efficiency photovoltaics and other optoelectronic devices. Despite the rapid advancement of the organolead halide perovskite in photovoltaic and optoelectronic applications, the intrinsic charge carrier transport in these materials remains elusive partly due to the difficulty of fabricating electrical devices and obtaining good electrical contact. Here, we report the fabrication of organolead halide perovskite microplates with mono- or bi-layer graphene as low barrier electrical contact. A systematic charge transport studies reveal an insulator to band-like transport transition. Our studies indicate that the insulator to band-like transport transition depends on the orthorhombic-to-tetragonal phase transition temperature and defect densities of the organolead halide perovskite microplates. Our findings are not only important for the fundamental understanding of charge transport behavior but also offer valuable practical implications for photovoltaics and optoelectronic applications based on the organolead halide perovskite. TOC Graphic


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The organolead halide perovskite materials have recently attracted intensive interest as a most promising material for high efficiency and low-cost solution processable optoelectronic applications.1-10 In particular, due to the high optical absorption coefficient, moderate charge mobility and very long diffusion length, the power conversion efficiency of the organolead halide perovskite solar cells has soared to a certified efficiency of more than 20% within past several years.3, 11 In addition to its application in the field of solar cells, the organolead halide perovskite based light-emitting devices,12 lasers5,

13-14

and photodetectors15 have also been

demonstrated with fairly decent performance. Understanding the charge transport mechanism in organolead halide perovskite materials is essential for further improving the performance of these devices and designing new device architectures. However, despite the rapid advancement in the perovskite-based optoelectronic applications, the studies on the charge transport in organolead halide perovskite is still in its infancy stage and largely limited to spin-coated perovskite thin films due to its solubility of organolead halide perovskite materials in many common solvents such as water, acetone and isopropanol, incompatibility with typical lithographic device fabrication steps and instability in the ambient condition.16-19 Previous studies demonstrated that the charge carrier mobility is modest due to the scattering because the carriers in organolead halide perovskite have low effective mass.20-22 The trap densities are rather low and thus the impurity scattering cannot be the dominant factor that limits the charge carrier mobility in the organolead halide perovskite.20, 23-24

Charge carrier-phonon scattering is believed to be the primary scattering mechanism which

has been demonstrated by several groups via time-resolved carrier dynamics, charge transport measurement and Hall measurement.25-28 X. Y. Zhu and V. Podzorov proposed that the charge carriers in organolead halide perovskite might be protected as large polarons in the tetragonal 3 ACS Paragon Plus Environment


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phase with a large charge carrier effective mass based on a series of experimental facts including the long carrier diffusion length, long lifetime, low electron-hole recombination rate, low scattering rate and temperature dependent mobility29-32, while A. J. Neukirch et al. reported the formation of small polarons in the organolead halide perovskites via in-depth computation.33 The large polaron model predicts a large charge carrier effective mass and is supported by the large difference between the static and high-frequency dielectric constants,29-30 which contradicts the low charge carrier effective mass predicted by first-principle calculation21 and experimentally determined by magneto-absorption.21-22 In terms of the transport within orthorhombic phase, the dielectric constant becomes rather small, which might lead to the free carrier transport. Overall, the charge carrier transport mechanism remains elusive and an actively debated topic that demands for further investigation. Here we report a gate-induced insulator-to-band-like transport transition in the orthorhombic phase of the organolead halide perovskite microplate devices by using monolayer graphene as the low-barrier source-drain electrical contact material.


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Figure 1. (a) Schematic of the back-gate, back-contact halide perovskite microplate field-effect transistor fabricated on a 300 nm SiO2/Si substrate with monolayer graphene stripes as contact. (b) An optical image of the graphene contact device with graphene outlined by red dashed lines. The scale bar is 6 µm. (c-d) The output (Vg= 60, 70, 80, 90 V) (c) and transfer (Vsd=4, 8, 10, 12 V) (d) characteristics of the graphene contact field-effect transistor at 77 K. (e) The temperature dependent field-effect mobility measured with a source-drain voltage of 10 V. The blue arrow indicates the tetragonal-to-orthorhombic phase transition temperature. (f) Temperature dependent photoluminescence spectra for the same halide perovskite microplate under the excitation of a 633 nm laser with a power of 3 µW. Figure 1a displays the schematic of a two-terminal organolead halide perovskite microplate field-effect transistor (FET) with monolayer graphene as the source-drain contacts. Figure 1b exhibits an optical image of such device with the monolayer graphene stripes outlined by red dashed lines. The graphene-contacted devices are fabricated via mechanical exfoliation and dry alignment transfer method (See Experimental Section).34-35 We made the Au electrodes be as close to perovskite microplate as possible so that the contribution from graphene can be neglected, similar to the graphene-contacted MoS2 transistors.36-37 All electrical measurements are carried out in dark from room temperature to liquid nitrogen temperature by using a cryogenic probe station. To avoid any possible mechanical contact problems due to the very different temperature-dependent mechanical properties of Au, graphene and perovskite, we changed the temperature in a very low rate (1-2 K/minute) such that there is efficient time allowing those contacted materials to achieve thermal relaxation to avoid the mechanical failure. Since the monolayer graphene has a finite density of states, the work function of monolayer graphene can be easily tuned by the back-gate voltage,34 which opens the possibility to tune the barrier height between the graphene and organolead halide perovskite microplates. In addition, our previous studies indicate that unipolar n-type behavior can be observed in monolayer or bilayer graphene contacted organolead halide perovskite microplate FETs, which could be attributed to the relative small difference between the work function of graphene and the 5 ACS Paragon Plus Environment


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conduction band edge of organolead halide perovskite, in contrast to the Au electrode contact where ambipolar behavior was observed both in spin-coated thin film and microplate devices. The small or negligible contact barrier between the monolayer graphene and organolead halide perovskite leads to the presence of the insulator to band-like transport transition in our FETs. The output characteristics (Isd vs. Vsd) of the monolayer graphene-contacted organolead halide perovskite microplate FET at 77 K show that the source-drain current Isd continuously increases with increasing positive gate voltage, indicating an n-type semiconductor behavior (Figure 1c). The transfer characteristics also exhibit a unipolar n-type behavior for the monolayer graphene-contacted device (Figure 1d). The similar unipolar n-type behavior has been observed for bilayer graphene contacted perovskite microplate FETs (Figure S1). Nevertheless, the unipolar n-type behavior evolves to ambipolar behavior for Au contacted FETs (Figure S1), which further confirms that the observed unipolar behavior for mono- and bi-layer graphene contacted organolead halide perovskite microplate FETs is due to the smaller difference between the work function of graphene and the conduction band edge of organolead halide perovskite. The electron field-effect mobility can be extracted from transfer characteristics (Figure 1e). Similar to what observed in spin-coated thin film organolead halide perovskite FETs, our devices show considerable hysteresis in the transfer curves (Figure S1), which prevents the precise evaluation of the mobility and can lead to systematic errors for mobility determination and misinterpretation of temperature dependent source-drain current under different gate voltages. The origin of the strong hysteresis in transfer curves is not yet fully understood to date. A number of origins including the ion migration, ferroelectricity, surface dipole and trap states has been proposed16. Among those factors, ion migration plays an important role in the hysteresis at higher temperatures and has been proven by experimental results16. Surface dipole and 6 ACS Paragon Plus Environment

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trapping states are believed to contribute to the hysteresis at low temperatures. However, due to complex of this problem, there is no solid evidence to support which one is the dominant factor or any other potential factors that could contribute to the hysteresis as well. Nevertheless, both positive and negative sweepings give the same trend of mobility and source-drain current versus temperature. In the rest of this report, we focus on the mobility and source-drain current extracted from the positive sweeping for the simplicity of discussion. In general, the mobility continuously increases with the decrease of temperature, but with a sudden fall around 170 K and starts to increase again with further decreasing temperature below 170 K. The sudden fall of mobility around 170 K can be attributed to the tetragonal-to-orthorhombic phase transition,38 which was further confirmed by the temperature dependent photoluminescence (PL) spectra (Figure 1f). The presence of two emission peaks below 170 K is an evidence of the tetragonal inclusions within orthorhombic phase (Figure 1f), with the lower energy emission peak originates from the tetragonal phase inclusions, and the orthorhombic phase leads to the higher energy emission peak.38 Since the tetragonal to orthorhombic phase is a first-order solid-solid phase transition,38 the phase transition undergoes a phase mixing and the orthorhombic phase gradually transits to tetragonal phase with temperature. As the temperature approaches to the phase transition temperature (160-180 K), the portion of orthorhombic phase is becoming negligibly small, leading to unremarkable orthorhombic phase emission. While the increase of the mobility with the decreasing temperature above 170 K might be ascribed to the reduction of carrier-phonon interaction or due to large polaron transport which can be protected from scattering and trapping,28 the increase of mobility below 170 K is a result of reduction of electron-phonon interaction and the decrease of the small inclusions of tetragonal phase domains



within orthorhombic phase, as demonstrated by low temperature transmission electron microscopy and temperature dependent PL spectra.38

(a) 10-7

(b) 10-7 90 V 100 K 120 K 140 K 160 K

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(c)

0

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40 Vg (V) Tetragonal

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VgVt EF

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EF Localized trap states

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Density of States Density of States Density of States

Figure 2. (a) The temperature dependent transfer characteristics of the same monolayer graphene-contacted field-effect transistor for positive sweeping. The source-drain voltage is 10 V. (b) The temperature dependent source-drain current under different gates voltage. (c) The schematic diagrams of electronic structures for tetragonal phase (left panel) and orthorhombic phase under gate voltage smaller (middle panel) and larger (right panel) than the voltage (Vt) that the insulator to band-like transport transition occurs. The presence of the tetragonal phase introduces extra grain boundary disorders, which might introduce in-gap electronic states and thus significantly alter the charge transport. To investigate how the tetragonal inclusion introduced disorders influences the charge transport, we display the temperature dependent transfer characteristics of a monolayer graphene contacted device below phase transition temperature around 170 K (Figure 2a). By varying temperature below 170 K, there is a source-drain current crossover for the positive sweeping near the gate voltage of 60 V: while the source-drain current increases with the decrease of temperature for the gate voltage larger than 60 V, a complete opposite trend of source-drain current was observed for


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the gate voltage smaller than 60 V (Figure 2a). In order to view this trend more clearly, we extract the source-drain current against temperature under different gate voltages as shown in Figure 2b. A clear insulator to band-like transport transition was found with increasing gate voltage within orthorhombic phase (below 180 K), while the source-drain current increases with decreasing temperature under all gate voltages investigated in tetragonal phase (above 180 K). This trend is rather different from that of Au contacted perovskite microplate transistors, where the source-drain current always increases with the decreasing temperature within both tetragonal and orthorhombic phase (Figure S2). This continuous increase might be attributed to the contact barrier due to the large difference between the Au work function and the conduction band edge of perovskite, which will be discussed in details later. When organolead halide perovskite is in tetragonal phase above 180K, the continuous increase of source-drain current with the decreasing temperature under all gate voltages within tetragonal phase might be due to the fact the charge carriers are protected as large polarons, which has been proposed previously and primarily supported by optical measurement.20, 32 In contrast to the small polarons where the thermally activated hopping dominates the charge transport, the large polarons with a large charge carrier effective mass can effectively reduce the carrier-phonon and carrier-defect scattering, leading to the increase of the source-drain current with the decreasing temperature.29, 39 Below 180 K within the orthorhombic phase, the small inclusions of tetragonal phase would introduce more grain boundaries and thus the in-gap electronic states (Figure 2c). As a consequence, the Fermi level locates within the bandgap at low gate voltages due to a large amount of in-gap electronic states, leading to the insulating behavior (Figure 2c). As the gate voltage increases, all in-gap electronic states are filled and the Fermi level shifts close to or into 9 ACS Paragon Plus Environment


mobility edge40, resulting the band-like transport.41-42 Similar gate-induced metal to band-like transport transition has been observed in organic polymer transistor and quantum dot films. The source-drain current in the insulating regime for gate voltage around 40 and 50 V can be described by43

I ∝ exp(−

T0 ) T

where T0 is a characteristic temperature (Figure S3). Similar temperature dependent behavior has been identified in polymers and organic semiconductors and can be attributed to variable range hopping transport with Coulomb interaction.43-45 Hence, the behavior observed in the insulating regime in our devices might be assigned as variable range hopping for gate voltage around 40-50 V, which is resulted from the carrier hopping between randomly distributed localized electronic states. Nevertheless, the number of disorders varies with the temperature, which renders it difficult to precisely determine the hopping mechanism in the insulating regime.

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100 10

-1

50V

10-5 10-6 10-7 10-8

10-2 50

100 150 200 250 T (K)

90

120 T (K)

- 20V 150

Figure 3. (a) The temperature dependent transfer characteristics of the monolayer graphene contacted field-effect transistor for a thinner organolead halide microplate device (positive sweeping). The source-drain voltage is 10 V. The channel length is 10 µm and length is 3 µm. (b) The temperature dependent field-effect mobility measured under a source-drain voltage of 10 V. The blue arrow indicates the tetragonal-to-orthorhombic phase transition temperature. (c) The temperature dependent source-drain current under different gate voltages. 10 ACS Paragon Plus Environment

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To further confirm our hypothesis that the insulator to band-like transport transition indeed originates from the phase transition induced disorders, we carried out the same electrical measurement for a thinner organolead halide perovskite microplate transistor, which has a lower phase transition temperature.38 The transfer characteristics of the monolayer graphene-contacted microplate device with a smaller thickness shows the similar unipolar n-type behavior (Figure 3a).

The very similar mobility versus temperature behavior was observed for the thinner

microplate devices and the temperature dependent mobility curve indicates that the orthorhombic-to-tetragonal phase transition occurs at a lower temperature ~130 K (Figure 3b), consistent with previous temperature dependent studies. It should be noted that the thinner device has much higher mobility and source-drain current compared with the thicker device, which might be originated from the different crystalline quality of the microplates introduced during the growth of the PbI2 microplates and/or during the vapor phase intercalation. The source-drain current versus temperature under different gate voltages show that a similar insulator to bandlike transport transition is present as well in the thinner microplate device right after the orthorhombic-to-tetragonal phase transition, demonstrating that this transition is indeed due to the phase transition induced disorders (Figure 3c). The observation of the insulator to band-like transport transition in our devices can be attributed to the better crystalline quality of our organolead halide microplates and graphene electrical contact. Previous studies indicate that the defect states are close to the both the valence and the conduction bands with a lower defect density of 1010-1011 cm-3 for the perovskite single crystals.23-24 Our field-effect transport measurement exhibits a transition from a unipolar n-type behavior at higher temperature to an ambipolar behavior at lower temperature, which also verifies that the defect density is low and thus the Fermi level significantly shifts with the 11 ACS Paragon Plus Environment


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decreasing temperature.38 We do not anticipate to observe such insulator to band-like transport transition in the spin-coated perovskite films due to the small crystalline size, which introduced a large amount of grain boundaries. The large amount of grain boundaries would increase the density of defect states, leading to the observed insulating behavior under all gate voltages we investigated, which has been supported by transport measurement of the graphene-contacted devices after thermal annealing. The thermal annealing would introduce more defect states, which results in that only insulating behavior can be observed under the gate voltage range we investigated. In addition, the difference between the work function of mono- or bi-layer graphene and the conduction band edge of organolead halide perovskite is smaller compared with that of Au contact, leading to a smaller contact barrier. As a result, the intrinsic insulator to band-like transport transition is not smeared by the contact effect and can be observed here. In summary, we have observed the insulator to band-like transport transition induced by the gate voltage within the orthorhombic phase in organolead halide perovskite microplate devices with monolayer graphene as electrical contacts. This gate-induced insulator to band-like transport transition might be attributed to the disorders introduced by the tetragonal inclusions within the orthorhombic phase. Our findings are not only important to the fundamental research but also have important practical implications in the development of the electronic and optoelectronic devices at low temperatures, which would have applications in the airplanes and satellites. Fabrication of field-effect transistors using graphene as contact: To fabricate the graphene contact devices, graphene strips (as electrodes) were exfoliated on a clean silicon/ silicon oxide (300 nm) substrate, while the lead di-iodine (PbI2) plates were peeled on polymer stack PMMA spun on a silicon wafer. First, the peeled PbI2 plate was aligned and transferred onto the 12 ACS Paragon Plus Environment

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graphene strips and 5 nm Cr/50 nm Au electrodes for graphene stripes were defined by electronbeam lithography and followed by thermal evaporation and lift-off. Finally, the PbI2 plate was converted to organolead halide perovskite (CH3NH3PbI3) by using the vapor phase intercalation.35 Electrical measurements and optical characterizations: Temperature dependent FET device measurements were carried out in a probe station ((Lakeshore, TTP4) coupled with a precision source/measurement unit (Agilent B2902A). The scanning rate for the transport measurement is 20 V/s and the devices were pre-biased at the opposite voltage for 30 s before each measurement. The PL measurement was conducted under a confocal micro-Raman system (Horiba LABHR) equipped with a 600 gr/mm grating in a backscattering configuration excited by a solid-state laser (633 nm) with a power of 3 µW. For the low temperature measurement, a liquid nitrogen continuous flow cryostat (Cryo Industry of America) was used to control the temperature varying from 77 K to 300 K. Corresponding Authors *D.L.: Email: [email protected] *X.D.: Email: [email protected] Acknowledgements We acknowledge the Nanoelectronics Research Facility (NRF) for technical support. D. L would like to acknowledge the financial support from National Young 1000-Talent Program and the National Natural Science Foundation of China, Grant No. 61674060. X. D. and Y. H. acknowledge the support from the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering through Award DE-SC0008055. Supporting Information Available: The transfer characteristics of the individual organolead



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halide perovskite microplate field-effect transitions with different electrical contact; The temperature dependent source-drain current under different gate voltages for Au-contacted devices; The temperature dependent source-drain current under different gates voltage for the inverse square root scale x-axis.

References 1.

Lee, M. M.; Teuscher, J.; Miyasaka, T.; Murakami, T. N.; Snaith, H. J. Efficient hybrid

solar cells based on meso-superstructured organometal halide perovskites. Science 2012, 338, 643-647. 2.

Liu, M.; Johnston, M. B.; Snaith, H. J. Efficient planar heterojunction perovskite solar

cells by vapour deposition. Nature 2013, 501, 395-398. 3.

Yang, W. S.; Noh, J. H.; Jeon, N. J.; Kim, Y. C.; Ryu, S.; Seo, J.; Seok, S. I. High-

performance photovoltaic perovskite layers fabricated through intramolecular exchange. Science 2015, 348, 1234-1237. 4.

Burschka, J.; Pellet, N.; Moon, S.-J.; Humphry-Baker, R.; Gao, P.; Nazeeruddin, M. K.;

Grätzel, M. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 2013, 499, 316-319. 5.

Xing, G.; Mathews, N.; Lim, S. S.; Yantara, N.; Liu, X.; Sabba, D.; Grätzel, M.;

Mhaisalkar, S.; Sum, T. C. Low-temperature solution-processed wavelength-tunable perovskites for lasing. Nat. Mater. 2014, 13, 476-480. 6.

Yan, W.; Li, Y.; Li, Y.; Ye, S.; Liu, Z.; Wang, S.; Bian, Z.; Huang, C. Stable high-

performance hybrid perovskite solar cells with ultrathin polythiophene as hole-transporting layer. Nano Res. 2015, 8, 2474-2480. 7.

Yan, W.; Li, Y.; Ye, S.; Li, Y.; Rao, H.; Liu, Z.; Wang, S.; Bian, Z.; Huang, C.

Increasing open circuit voltage by adjusting work function of hole-transporting materials in perovskite solar cells. Nano Res. 2016, 9, 1600-1608.


Page 15 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


8.

Song, J.; Li, J.; Li, X.; Xu, L.; Dong, Y.; Zeng, H. Quantum Dot Light‐Emitting Diodes

Based on Inorganic Perovskite Cesium Lead Halides (CsPbX3). Adv. Mater. 2015, 27, 71627167. 9.

Song, J.; Xu, L.; Li, J.; Xue, J.; Dong, Y.; Li, X.; Zeng, H. Monolayer and Few-Layer

All-Inorganic Perovskites as a New Family of Two-Dimensional Semiconductors for Printable Optoelectronic Devices. Adv. Mater. 2016, 28, 4861-4869. 10.

Li, X.; Yu, D.; Cao, F.; Gu, Y.; Wei, Y.; Wu, Y.; Song, J.; Zeng, H. Healing All-

Inorganic Perovskite Films via Recyclable Dissolution–Recyrstallization for Compact and Smooth Carrier Channels of Optoelectronic Devices with High Stability. Adv. Funct. Mater. 2016, 26, 5903-5912. 11.

Bi, D.; Tress, W.; Dar, M. I.; Gao, P.; Luo, J.; Renevier, C.; Schenk, K.; Abate, A.;

Giordano, F.; Baena, J.-P. C. Efficient luminescent solar cells based on tailored mixed-cation perovskites. Sci. Adv. 2016, 2, e1501170. 12.

Tan, Z.-K.; Moghaddam, R. S.; Lai, M. L.; Docampo, P.; Higler, R.; Deschler, F.; Price,

M.; Sadhanala, A.; Pazos, L. M.; Credgington, D. Bright light-emitting diodes based on organometal halide perovskite. Nat. Nanotechnol. 2014, 9, 687-692. 13.

Zhang, Q.; Ha, S. T.; Liu, X.; Sum, T. C.; Xiong, Q. Room-Temperature Near-Infrared

High-Q Perovskite Whispering-Gallery Planar Nanolasers. Nano Lett. 2014, 14, 5995-6001. 14.

Zhu, H.; Fu, Y.; Meng, F.; Wu, X.; Gong, Z.; Ding, Q.; Gustafsson, M. V.; Trinh, M. T.;

Jin, S.; Zhu, X. Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors. Nat. Mater. 2015, 14, 636-642. 15.

Dou, L.; Yang, Y. M.; You, J.; Hong, Z.; Chang, W.-H.; Li, G.; Yang, Y. Solution-

processed hybrid perovskite photodetectors with high detectivity. Nat. Commun. 2014, 5, 5404. 16.

Chin, X. Y.; Cortecchia, D.; Yin, J.; Bruno, A.; Soci, C. Lead iodide perovskite light-

emitting field-effect transistor. Nat. Commun. 2015, 6, 7383. 17.

Li, F.; Ma, C.; Wang, H.; Hu, W.; Yu, W.; Sheikh, A. D.; Wu, T. Ambipolar solution-

processed hybrid perovskite phototransistors. Nat. Commun. 2015, 6, 8238. 18.

Mei, Y.; Zhang, C.; Vardeny, Z.; Jurchescu, O. Electrostatic gating of hybrid halide

perovskite field-effect transistors: balanced ambipolar transport at room-temperature. MRS Commun. 2015, 5, 297-301.



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19.

Page 16 of 18

Li, D.; Cheng, H.-C.; Wang, Y.; Zhao, Z.; Wang, G.; Wu, H.; He, Q.; Huang, Y.; Duan,

X. The Effect of Thermal Annealing on Charge Transport in Organolead Halide Perovskite Microplate Field-Effect Transistors. Adv. Mater. 2016, DOI: 10.1002/adma.201601959. 20.

Brenner, T. M.; Egger, D. A.; Kronik, L.; Hodes, G.; Cahen, D. Hybrid organic-inorganic

perovskites: low-cost semiconductors with intriguing charge-transport properties. Nat. Rev. Mater. 2016, 1, 15007. 21.

Miyata, A.; Mitioglu, A.; Plochocka, P.; Portugall, O.; Wang, J. T.-W.; Stranks, S. D.;

Snaith, H. J.; Nicholas, R. J. Direct measurement of the exciton binding energy and effective masses for charge carriers in organic-inorganic tri-halide perovskites. Nat. Phys. 2015, 11, 582587. 22.

Tanaka, K.; Takahashi, T.; Ban, T.; Kondo, T.; Uchida, K.; Miura, N. Comparative study

on the excitons in lead-halide-based perovskite-type crystals CH3NH3PbBr3 CH3NH3PbI3. Solid state Commun. 2003, 127, 619-623. 23.

Shi, D.; Adinolfi, V.; Comin, R.; Yuan, M.; Alarousu, E.; Buin, A.; Chen, Y.; Hoogland,

S.; Rothenberger, A.; Katsiev, K. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. Science 2015, 347, 519-522. 24.

Adinolfi, V.; Yuan, M.; Comin, R.; Thibau, E. S.; Shi, D.; Saidaminov, M. I.;

Kanjanaboos, P.; Kopilovic, D.; Hoogland, S.; Lu, Z. H. The In-Gap Electronic State Spectrum of Methylammonium Lead Iodide Single-Crystal Perovskites. Adv. Mater. 2016, 28, 3406-3410. 25.

Oga, H.; Saeki, A.; Ogomi, Y.; Hayase, S.; Seki, S. Improved understanding of the

electronic and energetic landscapes of perovskite solar cells: high local charge carrier mobility, reduced recombination, and extremely shallow traps. J. Am. Chem. Soc. 2014, 136, 13818-13825. 26.

Savenije, T. J.; Ponseca Jr, C. S.; Kunneman, L.; Abdellah, M.; Zheng, K.; Tian, Y.; Zhu,

Q.; Canton, S. E.; Scheblykin, I. G.; Pullerits, T. Thermally activated exciton dissociation and recombination control the carrier dynamics in organometal halide perovskite. J. Phys. Chem. Lett. 2014, 5, 2189-2194. 27.

Milot, R. L.; Eperon, G. E.; Snaith, H. J.; Johnston, M. B.; Herz, L. M. Temperature‐

Dependent Charge‐Carrier Dynamics in CH3NH3PbI3 Perovskite Thin Films. Adv. Funct. Mater. 2015, 25, 6218-6227.


Page 17 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


28.

Karakus, M.; Jensen, S. A.; D’Angelo, F.; Turchinovich, D.; Bonn, M.; Cánovas, E.

Phonon-Electron Scattering Limits Free Charge Mobility in Methylammonium Lead Iodide Perovskites. J. Phys. Chem. Lett. 2015, 6, 4991-4996. 29.

Zhu, X.-Y.; Podzorov, V. Charge Carriers in Hybrid Organic–Inorganic Lead Halide

Perovskites Might Be Protected as Large Polarons. J. Phys. Chem. Lett. 2015, 6, 4758-4761. 30.

Brivio, F.; Walker, A. B.; Walsh, A. Structural and electronic properties of hybrid

perovskites for high-efficiency thin-film photovoltaics from first-principles. APL Mater. 2013, 1, 042111. 31.

Juarez-Perez, E. J.; Sanchez, R. S.; Badia, L.; Garcia-Belmonte, G.; Kang, Y. S.; Mora-

Sero, I.; Bisquert, J. Photoinduced giant dielectric constant in lead halide perovskite solar cells. J. Phys. Chem. Lett. 2014, 5, 2390-2394. 32.

Zhu, H.; Miyata, K.; Fu, Y.; Wang, J.; Joshi, P. P.; Niesner, D.; Williams, K. W.; Jin, S.;

Zhu, X.-Y. Screening in crystalline liquids protects energetic carriers in hybrid perovskites. Science 2016, 353, 1409-1413. 33.

Neukirch, A. J.; Nie, W.; Blancon, J.-C.; Appavoo, K.; Tsai, H.; Sfeir, M. Y.; Katan, C.;

Pedesseau, L.; Even, J.; Crochet, J. J. Polaron stabilization by cooperative lattice distortion and cation rotations in hybrid perovskite materials. Nano Lett. 2016, 16, 3809–3816. 34.

Cheng, H.-C.; Wang, G.; Liu, D.; Wu, H.; Ding, M.; Huang, Y.; Liu, Y.; Yin, A.; Duan,

X.; He, Q. Van der Waals heterojunction devices based on organohalide perovskites and twodimensional materials. Nano Lett. 2015, 16, 367–373. 35.

Wang, G.; Li, D.; Cheng, H.-C.; Li, Y.; Chen, C.-Y.; Yin, A.; Zhao, Z.; Lin, Z.; Wu, H.;

He, Q.; Ding, M.; Liu, Y.; Huang, Y.; Duan, X. Wafer-scale growth of large arrays of perovskite microplate crystals for functional electronics and optoelectronics. Sci. Adv. 2015, 1, e1500613. 36.

Liu, Y.; Wu, H.; Cheng, H.-C.; Yang, S.; Zhu, E.; He, Q.; Ding, M.; Li, D.; Guo, J.;

Weiss, N. O.; Huang, Y.; Duan, X. Toward Barrier Free Contact to Molybdenum Disulfide Using Graphene Electrodes. Nano Letters 2015, 15, 3030-3034. 37.

Cui, X.; Lee, G.-H.; Kim, Y. D.; Arefe, G.; Huang, P. Y.; Lee, C.-H.; Chenet, D. A.;

Zhang, X.; Wang, L.; Ye, F.; Pizzocchero, F.; Jessen, B. S.; Watanabe, K.; Taniguchi, T.; Muller, D. A.; Low, T.; Kim, P.; Hone, J. Multi-terminal transport measurements of MoS2 using a van der Waals heterostructure device platform. Nat. Nanotechnol. 2015, 10, 534-540.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

38.

Page 18 of 18

Li, D.; Wang, G.; Cheng, H.-C.; Chen, C.-Y.; Wu, H.; Liu, Y.; Huang, Y.; Duan, X. Size-

dependent phase transition in methylammonium lead iodide perovskite microplate crystals. Nat. Commun. 2016, 7, 11330. 39.

Emin, D. Polarons. Cambridge University Press: UK, 2013.

40.

Turk, M. E.; Choi, J.-H.; Oh, S. J.; Fafarman, A. T.; Diroll, B. T.; Murray, C. B.; Kagan,

C. R.; Kikkawa, J. M. Gate-Induced Carrier Delocalization in Quantum Dot Field Effect Transistors. Nano Lett. 2014, 14, 5948-5952. 41.

Dhoot, A. S.; Yuen, J. D.; Heeney, M.; McCulloch, I.; Moses, D.; Heeger, A. J. Beyond

the metal-insulator transition in polymer electrolyte gated polymer field-effect transistors. Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 11834-11837. 42.

Podzorov, V.; Menard, E.; Borissov, A.; Kiryukhin, V.; Rogers, J.; Gershenson, M.

Intrinsic charge transport on the surface of organic semiconductors. Phys. Rev. Lett. 2004, 93, 086602. 43.

Dhoot, A. S.; Wang, G. M.; Moses, D.; Heeger, A. J. Voltage-Induced Metal-Insulator

Transition in Polythiophene Field-Effect Transistors. Phys. Rev. Lett. 2006, 96, 246403. 44.

Sakanoue, T.; Sirringhaus, H. Band-like temperature dependence of mobility in

a solution-processed organic semiconductor. Nat. Mater. 2010, 9, 736-740. 45.

Chen, T.; Reich, K.; Kramer, N. J.; Fu, H.; Kortshagen, U. R.; Shklovskii, B. Metal-

insulator transition in films of doped semiconductor nanocrystals. Nat. Mater. 2015, 15, 68696877.


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