Organic Dye-Sensitized CH3NH3PbI3 Hybrid Flexible Photodetector

Subscriber access provided by The Chinese University of Hong Kong

Article

Organic dye-sensitized CH3NH3PbI3 hybrid flexible photodetector with bulk heterojunction architectures Changjiu Teng, Dan Xie, Mengxing Sun, Shan Chen, Pu Yang, and Yilin Sun ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b09502 • Publication Date (Web): 26 Oct 2016 Downloaded from http://pubs.acs.org on October 29, 2016

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Applied Materials & Interfaces is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 26

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

ACS Applied Materials & Interfaces

Organic dye-sensitized CH3NH3PbI3 hybrid flexible photodetector with bulk heterojunction architectures

Chang-jiu Teng1, Dan Xie1*, Meng-xing Sun1, Shan Chen2, Pu Yang1 and Yi-lin Sun1 1

Institute of Microelectronics, Tsinghua National Laboratory for Information Science

and Technology (TNList), Tsinghua University, Beijing 100084, People’s Republic of China 2

Department of Chemistry, Tsinghua University, Beijing 100084, China.

∗

[email protected]

Abstract A flexible photodetector based on the bulk heterojunction of an organometallic halide perovskites CH3NH3PbI3 and an organic dye Rhodamine B (RhB) has been fabricated via a solution casting process. It showed a high responsivity (Rmax=43.6 mA/W) to visible lights, short response time (tr~60 ms, td~40 ms), high on-off ratio (Ion/Ioff~287) and satisfactory stability because of its Schottky barrier structure and the dye enhanced light absorption.

Key words: CH3NH3PbI3, Rhodamine B, photodetector, bulk heterojunction architectures, dye-sensitized, flexible devices

ACS Paragon Plus Environment


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

Introduction Organometal halide perovskites (CH3NH3PbX3, X=I, Br, Cl) are attractive optoelectronic materials with high carrier mobility, high light absorption coefficients, proper energy band gaps and solution processability1-4,23. Therefore, they have been widely used for fabricating solar cells, photodiodes and phototransistors5-8,24-26, by using their thin films via precursor solution deposition (one or two steps9-10), vapor deposition11 and vapor assisted solution processes12. These devices usually have bilayer-heterojunction architectures just as our present work22. These architectures are convenient for manufacturing and processing, however, their interfaces between perovskites and other functional materials are much smaller than those of bulk-heterojunction architectures (BHJ). On the basis of this consideration, CH3NH3PbI3/rGO13, CH3NH3PbI3/A10C6014 and CH3NH3PbI3/ PC61BM15 hybrid bulk-heterojunction architectures have also been explored for the applications in photodetectors and solar cells. In a photodetector with bulk-heterojunction architecture, organic dye can be used as light- absorbing materials16-17.

As a common dye，Rhodamine shows a narrow absorption range and has been used in hybrid photodetectors as light-absorbing layer16-17. However, organic dye-perovskite hybrid photodetectors has not been widely studied18. Herein, we report a planar flexible CH3NH3PbI3 perovskite photodetector modified by Rhodamine B


Page 2 of 26

Page 3 of 26

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


with bulk-heterojunction architecture. Compared with intrinsic CH3NH3PbI3 perovskite photodetector, the organic dye-perovskite hybrid photodetector showed high responsivity (Rmax=43.6 mA/W) to 550 nm monochromatic light and high on-off ratio (Ion/Ioff ~286) to visible lights at a power of 500 µW cm–2. Furthermore, the hybrid photodetector exhibits ultra-short rise/decay time (tr~60 ms/ td~40 ms), favorable stability and good flexibility, making it has great potential for the applications in future flexible electronics.

Results and Discussions

Scheme

1

illustrates

the

procedures

of

preparing

CH3NH3PbI3/RhB

heterojunction photodetector. Briefly, PEN (Polyethylene naphthalate two formic acid glycol) was selected as the flexible substrate and the interdigitated Au electrodes are designed with 50 µm finger width and interdigital width. Then, the interdigitated electrodes are fabricated by photolithography via a lift-off process after the evaporation deposition 5 nm-thick Cr (for enhancing adhesion of Au layer on PEN substrates) and 50 nm-thick Au on PEN substrate. The interdigitated Au electrodes are ultra-sonicated in acetone, ethanol, and isopropanol successively, treated by UV-Ozone before spin-coating. The perovskite precursor solution was prepared by using a reported method19. Then, a certain amount of Rhodamine B was dissolved into it

to

form

a

hybrid

CH3NH3PbI3/RhB

precursor

solution.

Finally,

the

CH3NH3PbI3/RhB precursor solution (0.35M CH3NH3PbI3+RhB with a concentration of 0.1 mg/mL) was spin-coated onto the flexible interdigitated electrodes at 4000 rpm



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

Page 4 of 26

for 60 s and heated at 90 ℃ for 30 s to give a flexible CH3NH3PbI3/RhB photodetector.

Figure 1. (a) shows the X-ray diffraction (XRD) patterns of pure CH3NH3PbI3 and the hybrid CH3NH3PbI3/RhB thin films. The (110), (220) and (330) diffraction peaks are assigned to crystalline CH3NH3PbI3 films. The introduction of RhB slightly decreased the crystallinity of CH3NH3PbI3, while did induce any new crystal pahse or impurities such as PbI2. Figure 1. (b) shows the UV-visible absorption spectra (from 400 to 700 nm) of pure CH3NH3PbI3, RhB and CH3NH3PbI3/RhB hybrid thin films, respectively. The hybrid film shows an enhanced absorption coefficient in the wavelength range 450 to 570 nm, mainly due to the synergetic effect of CH3NH3PbI3 and RhB. PL (photo luminescence) spectra of the two films on glass substrate inspired by 520 nm monochromatic light are shown in Figure S7. Normally, the pure CH3NH3PbI3 thin film exhibits a characteristic peak at nearly 780 nm. And in the CH3NH3PbI3/RhB hybrid films, the intensity of 780 nm peaks are weaker than the pure which is mainly due to the absorbance of the Rhodamine B to the 520 nm monochromatic light. It is worth noting that Figure 1. (c) and (d) demonstrate the SEM images of CH3NH3PbI3/RhB hybrid films (the SEM images of pure CH3NH3PbI3 films is shown in Figure S1). This film is uniform and compact. RhB represents a flower-like pattern in the hybrid thin film (Inset of Figure 1. (c)). A simlilar morphology has been also

observed

from

the hybrid

film

of

CH3NH3PbI3/R6G20. The EDS (energy dispersive spectrometer) profiles of CH3NH3PbI3/RhB hybrid and pure CH3NH3PbI3 films are shown in Figure S8 which


Page 5 of 26

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


can demonstrate the existence of RhB in the flower-like bulk-architectures due to the obvious N element peak in comparison. These SEM images clearly confirm the formation of a CH3NH3PbI3/RhB bulk-heterojunction architecture. The current-voltage (I-V) curves of the representing the photoelectric characteristics of CH3NH3PbI3/RhB hybrid photodetector are studied by using a Keithley 2600 Source Meter under the dark and illumination condition, respectively. A pure CH3NH3PbI3 flexible photodetector is also fabricated and measured under the same condition for comparison. Various monochromatic lights with diverse wavelengths (from 365 nm to 770 nm) were generated by a 300 W Xe lamp and filtered through the corresponding monochromators. A power meter was used for calibrating the diverse power of monochromatic light (ranging from 8 to 500 µW cm-2) All the measurements were performed in air at room temperature.

Figure 2.(a) shows the I-V curves of flexible CH3NH3PbI3/RhB photodetector illuminated under various monochromatic lights with a power of 500 µW/cm–2 and the bias voltage is from -5V to 5V (time-dependent photoresponse are shown in Figure S3 under the same conditions). For comparison, the I-V curves of the pure flexible CH3NH3PbI3 photodetector are shown in Figure 2. (b) in the same illumination condition. The photoelectric properties of the flexible CH3NH3PbI3/RhB photodetector with different concentrations of RhB are shown in Figure S2. It is easily found that when the wavelength of the monochromatic lights is 445, 550 and 650nm, flexible CH3NH3PbI3/RhB photodetector exhibits an enhancing photoelectric response compared to that of the pure flexible CH3NH3PbI3 photodetector. When the



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

–

applied voltage is 5 V and the power of light is 500 µW cm 2, the current of flexible CH3NH3PbI3/RhB photodetector for 445, 550 and 650 nm is about 2.3, 7.2 and 4.1µA , respectively, which is 2.52, 5.07 and 2.49 times larger than that of pure CH3NH3PbI3 flexible photodetector. Additionally, the on-off ratio of flexible CH3NH3PbI3/RhB photodetector is 287 which is about 11 times higher than that of the pure CH3NH3PbI3 photodetector with a value of 25.

For quantitatively descriptions of the performances of the photodetector, responsivity (R) and external quantum efficiency (EQE) should be studied. The spectral responsivity (R) can be expressed as R = (Iph - Idark)/(P × S), where Iph is the photocurrent, Idark is the dark current, P is the incident power density, S is the effective illuminated area with a value of 33 mm2 in this work. EQE can be expressed as EQE = (R × h × c)/(e × λ), where h is Planck’ s constant, c is the velocity of light, e is the charge of an electron, and λ is the wavelength of incident light. All the following parameters are calculated from the I-V curves of the photodetector. As shown in Figure 2.(c), when the applied voltage is 5 V, the responsivity of CH3NH3PbI3/RhB hybrid photodetector to 445, 550 and 650nm at a power of 500 µW cm–2 is 15.0, 43.6 and 25.2 mA/W, which is 2.5, 4.1 and 2.2 times larger than that of the pure CH3NH3PbI3, respectively. Figure 2. (d) shows the corresponding EQE of the CH3NH3PbI3 and CH3NH3PbI3/RhB photodetector, respectively. It shows the similar tendency with that of responsivity. Compared with the pure CH3NH3PbI3, the photoelectric properties of CH3NH3PbI3/RhB hybrid photodetector increase obviously under the wavelength from 400 to 700nm. And it is also found that the hybrid


Page 6 of 26

Page 7 of 26

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


photodetector is sensitive to 550 nm visible light more than 650 nm, which is different from that of pure CH3NH3PbI3. Figure 3. (a) shows the time-dependent photoresponse of the photodetector to 550nm-monochromatic light at a bias of 5V with diverse power density from 8 to 500 µW cm 2, and the detection limits of the photodetector is larger than 1 µW cm 2. As –

–

shown in Figure 3. (b), the hybrid photodetector exhibits fast rise/decay time (tr~60 ms/ td~40 ms) which is similar to other perovskite photodetector7,13. In practical applications, the lifetime of the photodetector is definitely an important parameter. For the flexible hybrid CH3NH3PbI3 photodetector without any treatment, the relative photoelectric response current reduces to less than 10% after 2 days in the air with 20–30% relative humidity. To improve the stability of the photodetector in the humid air, PMMA is used as a protective layer to eliminate the contact of the photodetector with the surrounding moisture, oxygen. In this case, the stability of the photodetector has been greatly improved and the relativeresponsivity only reduces by 9% in the air with 20–30% relative humidity after 14 days (Figure 3. (c)). The flexibility of the CH3NH3PbI3/RhB hybrid photodetector is also studied by bending to a radius of 9mm and repeated bending test. For reducing the abrasion of the CH3NH3PbI3 thin films during the bending process, flexible detector is protected by PMMA. While the CH3NH3PbI3/RhB hybrid photodetector is bent to a radius of 9 mm in the beginning, its responsivity exhibits a little bit decrease upon illumination with a visible light at 550 nm at 5V bias voltage as shown in Figure 3.(d) (the performance of the device bended in the same condition but illuminated under



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

different monochromatic lights is shown in Figure S5 and Figure S6). At the first 20 times bending cycles, the relative responsivity of the flexible photodetector declines to 94.0% and after 1000 bending/straitening cycles, relative responsivity of the flexible photodetector just declines to 92.7%. These results indicate that our hybrid photodetector has excellent mechanical flexibility and durability.

To explain the photoelectric characteristics of the photodetector, the schematic energy band (energy level) diagram is shown in Figure 4. When the pure perovskite photodetector operates in the dark, an asymmetrical Schottky barrier forms between Au and CH3NH3PbI3 due to the defect ions’ migration to the interface under the operation of bias voltage21. This Schottky barrier reduces the charge transferring in the photodetector resulting in a lower dark current (Figure 4. (a)). Figure S4 shows the influence on the time-dependent photoresponse with different bias. Under the light illumination, large amount of photo-generated carriers produced, leading to the demonstrable decline of the barrier height arises (Figure 4. (b)). Therefore, an obvious light-on current is detected at the fabricated photodetector on macroscopic view. As shown in Figure 4. (c), energy level illustrations briefly indicate the relative situation of the Rhodamine B and CH3NH3PbI3 in the hybrid bulk-heterojunction architectures. When illuminated by specific visible light, basically obeying a dye-sensitized mechanism, Rhodamine B is activated from the highest occupied molecular orbital (HOMO~ -5.3eV) to the lowest unoccupied molecular orbital (LUMO~ -3.2eV), which subsequently injects an electron into the bottom of conducting band (EC~ -3.8eV) of perovskite. At the same time, a hole equally


Page 8 of 26

Page 9 of 26

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


migrates from the top of valence band (Ev~-5.4eV) of perovskite to HOMO of Rhodamine B as shown in Figure 4. (d) schematically. Furthermore, a part of RhB+ contacting with electrodes may transfer holes into the Au electrode (ϕ~-5.2eV). Under illumination, RhB provides electrons to perovskite and RhB+ gives part of the holes to electrodes, which is favourable for the separation of electrons and holes, thus reducing the recombination of the different carriers efficiently.

Conclusion

In conclusion, a hybrid planar flexible photodetectors are prepared based on perovskite-Rhodamine

bulk-heterojunction

architecture.

The

hybrid

CH3NH3PbI3/RhB flexible photodetectors show higher responsivity of about 43.6mA/W to specific visible light than the pure perovskite. It also exhibits fast rise/decay time (tr~60 ms/ td~40 ms), considerable switching on-off characteristics (Ion/Ioff ~286), good stability and flexibility. Being a dye sensitive to special wavelength illumination, Rhodamine B plays an important role in donating and transferring electrons, which also effectively reduce the recombination of the electrons and holes. Therefore, the hybrid CH3NH3PbI3/RhB flexible photodetectors exhibit excellent photoelectrical properties, which also provides a possibility of dye-sensitized perovskite bulk heterostructures in the photodetector applications.

Supporting information The supporting information contains: (1) SEM images of pure CH3NH3PbI3. (2) I-V curves of the CH3NH3PbI3/RhB hybrid photodetector with different concentrations of



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

Rhodamine B illuminated under 550 nm monochromatic light with a power of 500 µW cm-2. (3) Time-dependent photoresponse of the the CH3NH3PbI3/RhB hybrid photodetector to various monochromatic light at a bias of 5V with a power density of 500 µW cm

–

2

. (4) Time-dependent photoresponse behaviors of the the

CH3NH3PbI3/RhB hybrid photodetector to 550 nm monochromatic light at different bias with a power density of 500 µW cm–2. (5) The relative responsivity to 650 nm light of the CH3NH3PbI3/RhB hybrid photodetector by bending at a radius of 9 mm for 1000 cycles. (6) The relative responsivity to 445 nm light of the CH3NH3PbI3/RhB hybrid photodetector by bending at a radius of 9 mm for 1000 cycles. (7) PL spectra of the pure CH3NH3PbI3 and CH3NH3PbI3/RhB hybrid films inspired by 520 nm monochromatic light. (8) EDS profiles of the pure CH3NH3PbI3 part and CH3NH3PbI3/RhB hybrid flower-like part in the Figure 1. (c). Acknowledgements The authors are grateful for the financial support from National Natural Science Foundation of China (51372130, and 61401251), the Open Research Fund Program of the State Key Laboratory of Low-Dimensional Quantum Physics under Grant KF201517, and the Open Foundation of State Key Laboratory of Electronic Thin Films and Integrated Devices (KFJJ201402).

Notes and references

1.

Wehrenfennig C.; Eperon G. E.; Johnston M. B.; Snaith H. J. and Herz L. M. High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide


Page 10 of 26

Page 11 of 26

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


Perovskites Adv. Mater. 2014, 26, 1584.

2.

Leijtens T.; Stranks S. D.; Eperon G. E.; Lindblad R.; Johansson E. M. J.; McPherson I. J.; Rensmo H.; Ball J. M.; Lee M. M. and Snaith H. J. Electronic Properties of Meso-Superstructured and Planar Organometal Halide Perovskite Films: Charge Trapping, Photodoping and Carrier Mobility ACS Nano 2014, 8, 7147.

3.

Dong Q.; Fang Y.; Shao Y.; Mulligan P.; Qiu J.; Cao L. and Huang J. Electron-Hole Diffusion Lengths> 175 µm in Solution-Grown CH3NH3PbI3 Single Crystals Science 2015, 347, 967.

4.

Wang L.; McCleese C.; Kovalsky A.; Zhao Y. and Burda C. Femtosecond Time-Resolved Transient Absorption Spectroscopy of CH3NH3PbI3 Perovskite Films: Evidence for Passivation Effect of PbI2 J. Am. Chem. Soc. 2014, 136, 12205.

5.

Dou L.; Yang Y.; You J.; Hong Z.; Chang W.-H.; Li G. and Yang Y. Solution-Processed Hybrid Perovskite Photodetectors with High Detectivity Nat.Commun. 2014, 5, 5404.

6.

Dong R.; Fang Y.; Chae J.; Dai J.; Xiao Z.; Dong Q.; Yuan Y.; Centrone A.; Zeng X. C. and Huang J. High-Gain and Low-Driving-Voltage Photodetectors Based on Organolead Triiodide Perovskites Adv. Mater. 2015, 27, 1912.

7.

Hu X.; Zhang X.; Liang L.; Bao J.; Li S.; Yang W. and Xie Y. High-Performance



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

Flexible Broadband Photodetector Based on Organolead Halide Perovskite Adv. Funct. Mater. 2014, 24, 7373.

8.

Lee Y.; Kwon J.; Hwang E.; Ra C.-H.; Yoo W. J.; Ahn J.-H.; Park J. H. and Cho J. H. High-Performance Perovskite-Graphene Hybrid Photodetector Adv. Mater. 2015, 27, 41.

9.

Kim H.-S.; Lee C. R.; Im J.-H.; Lee K.-B.; Moehl T.; Marchioro A.; Moon S.-J.; Humphry-Baker R.; Yum J.-H.; Moser J. E.; Gratzel M. and Park N.-G. Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9% Sci. Rep. 2012, 2, 591.

10. Burschka J.; Pellet N.; Moon S.-J.; Humphry-Baker R.; Gao P.; Nazeeruddin M. K. and Gratzel M. Sequential Deposition as a Route to High-Performance Perovskite-Sensitized Solar Cells Nature 2013, 499, 316.

11. Liu M.; Johnston M. B. and Snaith H. J. Efficient Planar Heterojunction Perovskite Solar Cells by Vapour Deposition Nature 2013, 501, 395.

12. Chen Q.; Zhou H.; Hong Z.; Luo S.; Duan H.-S.; Wang H.-H.; Liu Y.; Li G.and Yang Y. Planar Heterojunction Perovskite Solar Cells via Vapor-Assisted Solution Process

J. Am. Chem. Soc. 2014, 136, 622.

13. He M.; Chen Y.; Liu H.; Wang J.; Fang X. and Liang Z. Chemical Decoration of CH3NH3PbI3 Perovskites with Graphene

Oxides for Photodetector

Applications Chem. Commun. 2015, 51, 9659.


Page 12 of 26

Page 13 of 26

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


14. Wang K.; Liu C.; Du P.; Zheng J. and Gong X. Bulk Heterojunction Perovskite Hybrid Solar Cells with Large Fill Factor Energy Environ. Sci. 2015, 8, 1245-1255.

15. Liu C.; Wang K.; Du P.; Yi C.; Meng T.; and Gong X. Efficient Solution-Processed Bulk Heterojunction Perovskite Hybrid Solar Cells Adv. Energy Mater. 2015, 5, 1402024.

16. Lee Y.; Yu S.; Jeon J.; Kim H.; Lee J.; Kim H.; Ahn J.-H.; Hwang E. and Cho J. Hybrid Structures of Organic Dye and Graphene for Ultrahigh Gain Photodetectors Carbon 2015, 88, 165–172. 17. Yu S. H.; Lee Y.; Jang S. K.; Kang J.; Jeon J.; Lee C.; Lee J. Y.; Kim H.; Hwang E.; Lee S.; and Cho J. H. Dye-sensitized MoS2 Photodetector with Enhanced Spectral Photoresponse ACS NANO 2014, 8, 8285.

18. Lin Q.; Armin A.; Burn P. L. and Meredith P. Filterless Narrowband Visible Photodetectors Nat. Photon. 2015, 9, 687.

19. Zuo C. and Ding L. An 80.11% FF Record Achieved for Perovskite Solar Cells by Using the NH4Cl Additive Nanoscale 2014, 6, 9935. 20. Zhou X.; He S.; Brown K.; Mendez-Arroyo J.; Boey F. and Mirkin C. Locally Altering the Electronic Properties of Graphene by Nanoscopically Doping It with Rhodamine 6G Nano Lett. 2013, 13, 1616.

21. Kwon K. C.; Hong K.; Le V. Q.; Lee S. Y.; Choi J.; Kim K.-B.; Kim S. Y. and



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

Jang H. W. Inhibition of Ion Migration for Reliable Operation of Organolead Halide Perovskite-Based Metal/Semiconductor/Metal Broadband Photodetectors Adv. Funct. Mater. 2016, 26, 4213.

22. Chen S.; Teng C.; Zhang M.; Li Y.; Xie D.; and Shi G. A Flexible UV–Vis– NIR Photodetector based on a Perovskite/Conjugated‐Polymer Composite Adv. Mater. 2016, 28, 5969.

23. Zhao Y. and Zhu K. Organic– inorganic hybrid lead halide perovskites for optoelectronic and electronic applications Chem. Soc. Rev. 2016, 45, 655.

24. Zhang Y.; Du J.; Wu X.; Zhang G.; Chu Y.; Liu D.; Zhao Y.; Liang Z. and Huang J. Ultrasensitive Photodetectors Based on Island-Structured CH3NH3PbI3 Thin Films ACS Appl. Mater. Interfaces 2015, 7, 21634.

25. Gong X.; Li M.; Shi X.-B.; Ma H.; Wang Z.-K. and Liao L.-S. Controllable Perovskite Crystallization by Water Additive for High-Performance Solar Cells Adv. Funct. Mater. 2015, 25, 6671–6678.

26. Qian M.; Li M.; Shi X.-B.; Ma H.; Wang Z.-K. and Liao L.-S. Planar perovskite solar cells with 15.75% power conversion efficiency by cathode and anode interfacial modification J. Mater. Chem. A, 2015, 3, 13533-13539

Graphic for manuscript


Page 14 of 26

Page 15 of 26

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


Scheme 1 Schematic illustrations of CH3NH3PbI3 crystal structure and the fabrication of CH3NH3PbI3/RhB photodetector.

Figure 1. (a) XRD patterns of pure CH3NH3PbI3 and CH3NH3PbI3/RhB thin films. (b) UV-visible

absorption

spectra

of

pure

CH3NH3PbI3,

Rhodamine

B

and

CH3NH3PbI3/RhB thin films. (c) SEM images of CH3NH3PbI3/RhB hybrid thin films on interdigitated Au electrodes and inset of (c) is the flower-like pattern of RhB in the hybrid thin films. (d) SEM images of CH3NH3PbI3/RhB hybrid thin films with



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

Page 16 of 26

obvious CH3NH3PbI3 grains.

Figure 2. (a) I-V curves of the CH3NH3PbI3/RhB hybrid photodetector illuminated –

under various monochromatic lights with a power of 500 µW cm 2. (b) I-V curves of the pure CH3NH3PbI3 photodetector illuminated under the same condition. (c) Calculated responsivity of the hybrid photodetector. (d) Calculated EQE of the hybrid photodetector.


Page 17 of 26

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


Figure 3. (a) Time photoresponse behaviors of the flexible CH3NH3PbI3/RhB hybrid photodetector to 550nm-monochromatic light at a bias of 5V with diverse power density. (b) Photocurrent rise and decay time of the device under the irradiation with 550nm-monochromatic light. (c) The relative responsivity of the photodetector in the air with 20–30% relative humidity for 2 weeks. (d) The relative responsivity to 550 nm light of the photodetector by bending at a radius of 9 mm for 1000 cycles.



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

Figure 4. Indicated energy band diagram (a, b, d) and energy level illustrations (c) in this work. (a) Energy band diagram in the dark for pure perovskite. (b) Energy band diagram under illumination for pure perovskite. (c) Energy level illustrations under illumination for hybrid photodetector. (d) Energy band diagram under illumination for hybrid photodetector.

Figure Captions Scheme 1 Schematic illustrations of CH3NH3PbI3 crystal structure and the fabrication of CH3NH3PbI3/RhB photodetector.

Figure 1. (a) XRD patterns of pure CH3NH3PbI3 and CH3NH3PbI3/RhB thin films. (b)


Page 18 of 26

Page 19 of 26

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


UV-visible

absorption

spectra

of

pure

CH3NH3PbI3,

Rhodamine

B

and

CH3NH3PbI3/RhB thin films. (c) SEM images of CH3NH3PbI3/RhB hybrid thin films on interdigitated Au electrodes and inset of (c) is the flower-like pattern of RhB in the hybrid thin films. (d) SEM images of CH3NH3PbI3/RhB hybrid thin films with obvious CH3NH3PbI3 grains.

Figure 2. (a) I-V curves of the CH3NH3PbI3/RhB hybrid photodetector illuminated –

under various monochromatic lights with a power of 500 µW cm 2. (b) I-V curves of the pure CH3NH3PbI3 photodetector illuminated under the same condition. (c) Calculated responsivity of the hybrid photodetector. (d) Calculated EQE of the hybrid photodetector.

Figure 3. (a) Time photoresponse behaviors of the flexible CH3NH3PbI3/RhB hybrid photodetector to 550nm-monochromatic light at a bias of 5V with diverse power density. (b) Photocurrent rise and decay time of the device under the irradiation with 550nm-monochromatic light. (c) The relative responsivity of the photodetector in the air with 20–30% relative humidity for 2 weeks. (d) The relative responsivity to 550 nm light of the photodetector by bending at a radius of 9 mm for 1000 cycles.

Figure 4. Indicated energy band diagram (a, b, d) and energy level illustrations (c) in



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

this work. (a) Energy band diagram in the dark for pure perovskite. (b) Energy band diagram under illumination for pure perovskite. (c) Energy level illustrations under illumination for hybrid photodetector. (d) Energy band diagram under illumination for hybrid photodetector.


Page 20 of 26

Page 21 of 26

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


TOC graphic 141x158mm (96 x 96 DPI)



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

Scheme 1 Schematic illustrations of CH3NH3PbI3 crystal structure and the fabrication of CH3NH3PbI3/RhB photodetector. 217x116mm (96 x 96 DPI)


Page 22 of 26

Page 23 of 26

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


Figure 1. (a) XRD patterns of pure CH3NH3PbI3 and CH3NH3PbI3/RhB thin films. (b) UV-visible absorption spectra of pure CH3NH3PbI3, Rhodamine B and CH3NH3PbI3/RhB thin films. (c) SEM images of CH3NH3PbI3/RhB hybrid thin films on interdigitated Au electrodes and inset of (c) is the flower-like pattern of RhB in the hybrid thin films. (d) SEM images of CH3NH3PbI3/RhB hybrid thin films with obvious CH3NH3PbI3 grains. 230x175mm (96 x 96 DPI)



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

Figure 2. (a) I-V curves of the CH3NH3PbI3/RhB hybrid photodetector illuminated under various monochromatic lights with a power of 500 µW cm–2. (b) I-V curves of the pure CH3NH3PbI3 photodetector illuminated under the same condition. (c) Calculated responsivity of the hybrid photodetector. (d) Calculated EQE of the hybrid photodetector. 388x304mm (96 x 96 DPI)


Page 24 of 26

Page 25 of 26

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


Figure 3. (a) Time photoresponse behaviors of the flexible CH3NH3PbI3/RhB hybrid photodetector to 550nm-monochromatic light at a bias of 5V with diverse power density. (b) Photocurrent rise and decay time of the device under the irradiation with 550nm-monochromatic light. (c) The relative responsivity of the photodetector in the air with 20–30% relative humidity for 2 weeks. (d) The relative responsivity to 550 nm light of the photodetector by bending at a radius of 9 mm for 1000 cycles. 242x180mm (96 x 96 DPI)



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

Figure 4. Indicated energy band diagram (a, b, d) and energy level illustrations (c) in this work. (a) Energy band diagram in the dark for pure perovskite. (b) Energy band diagram under illumination for pure perovskite. (c) Energy level illustrations under illumination for hybrid photodetector. (d) Energy band diagram under illumination for hybrid photodetector. 263x223mm (96 x 96 DPI)


Page 26 of 26

Organic Dye-Sensitized CH3NH3PbI3 Hybrid Flexible Photodetector

Recommend Documents