Flexible and Semitransparent Organolead Triiodide Perovskite

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Flexible and Semitransparent Organolead Triiodide Perovskite Network Photodetector Arrays with High Stability Hui Deng, Xiaokun Yang, Dongdong Dong, Bing Li, Dun Yang, Shengjie Yuan, Keke Qiao, Yi-Bing Cheng, Jiang Tang, and Haisheng Song Nano Lett., Just Accepted Manuscript • DOI: 10.1021/acs.nanolett.5b03061 • Publication Date (Web): 03 Nov 2015 Downloaded from http://pubs.acs.org on November 4, 2015

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Flexible and Semitransparent Organolead Triiodide Perovskite Network Photodetector Arrays with High Stability Hui Deng1, Xiaokun Yang1, Dongdong Dong1, Bing Li1, Dun Yang1, Shengjie Yuan1, Keke Qiao1, Yi-Bing Cheng1, 2, Jiang Tang1, Haisheng Song1* 1

Wuhan National Laboratory for Optoelectronics (WNLO) and School of Optical

and Electronic Information, Huazhong University of Sciences and Technology, 1037 Luoyu Road, 430074, Wuhan, Hubei, P. R. China 2

Department of Materials Engineering, Monash University, Melbourne, Victoria,

3800, Australia *

Email of corresponding author: [email protected]

1

ACS Paragon Plus Environment

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Abstract Organolead triiodide perovskite (CH3NH3PbI3) as a light-sensitive material has attracted

extensive

attention

in

optoelectronics.

The

reported

perovskite

photodetectors (PDs) mainly focus on individual which limits their spatial imaging applications. Uniform perovskite networks combining transparency and device performance were synthesized on polyethylene terephthalate (PET) by controlling perovskite crystallization. Photodetector arrays based on above network were fabricated to demonstrate the potential for image mapping. The trade-off between the PD performance and transparency was systematically investigated and the optimal device was obtained from 30 wt% precursor concentration. The switching ratio, normalized detectivity and equivalent dark current derived shot noise as the critical parameters of PD arrays reached 300, 1.02×1012 Jones and 4.73×10-15A Hz-1/2, respectively. Furthermore, the PD arrays could clearly detect spatial light intensity distribution thus demonstrating its preliminary imaging function. The perovskite network PD arrays fabricated on PET substrates could also conduct superior flexibility under wide angle and large number of bending. For the common problem of perovskite optoelectronics in stability, the perovskite networks sheathed with hydrophobic polymers greatly enhanced the device stability due to the improved interface contacts, surface passivation and moisture isolation. Taking into consideration transparency, flexibility, imaging and stability, the present PD arrays were expected to be widely applied in visualized portable optoelectronic system.

Key words: photodetector arrays, perovskite networks, semitransparent, image mapping, stability

2


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Introduction Photodetectors (PDs) have a wide range of commercial and scientific applications in imaging, optical fiber communications, spectroscopy and biomedical applications.1-3 The commercially available PDs are typically made by SiC, Si and HgCdTe for detection in UV, visible and infrared regimes, respectively.3-7 Compared with traditional PDs, the light-weight, transparent, flexible and non-cryogenic optical sensors are more suitable for modern portable devices.8-10 Organolead triiodide perovskite (OTP) optoelectronic devices have attracted great attention due to the photoelectric characteristics, such as shallow defect, high light absorption coefficient (>105/cm) at visible range, long diffusion length, etc.11-15 The characteristics have promoted the fast development of perovskite based optoelectronic research. The power conversion efficiency of OTP solar cells has arrived to 20.1% in last 5 years.16-18 Meanwhile, the newly developed PDs based on perovskite thin film and nanowires have also obtained high performances. Dou et al. fabricated photovoltaic hybrid perovskite PDs by solution process and obtained a detectivity of 1014 Jones on FTO rigid substrates.19 Hu et al. obtained OTP thin film photoconductive PDs with a responsivity of 3.49 A/W.20 And perovskite nanowire PDs realized fast response time (~0.3 ms).21-22 The above studies were all based on individual PD. However, the PD practical applications (for example, in imaging) require large number of pixels to construct target images. Therefore, the present work focused on OTP PD arrays and utilized them to preliminarily implement the imaging. In order to achieve the expected detection results, PD arrays should keep high uniformity to avoid the addition of noise signal.23 Furthermore, the PD arrays combining uniformity and transparency may greatly expand their application fields and be conveniently integrated on traditional optoelectronic devices. The reported perovskite PDs were made from nanowires or thin film.20, 22 The randomly distributed NW PD arrays could obtain high transparence but sacrifice the uniformity, while thin film PD arrays could achieve good uniformity but sacrifice the transparence. 3


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Therefore, we developed OTP networks for PD arrays by controlling the crystallization. And the synthesized method for uniform and transparent OTP network could widely expand OTP material application fields in cascade visualized optoelectronic devices such as building-integrated photovoltaics (BIPV)24, smart touch screen25, transparent display26 and so on. Herein, OTP network PD arrays which balanced uniformity and transparency were designed and synthesized via controlling the crystallization. The optimized OTP network PD arrays obtained the normalized detectivity of ~1012 Jones and switching ratio of ~300. Furthermore, the PD arrays could clearly detect the spatial light source intensity distribution. The flexible network PD arrays deposited on polyethylene terephthalate (PET) could stand for wide angle and large number of bending. The stability of OTP PD arrays was greatly improved by hydrophobic organic material passivation and the devices could be stored in air for one month with little degradation. The full consideration of present network PD arrays was expected to promote the research progress of OTP PDs. Material growth. All starting materials were obtained from commercial suppliers and used without further purification. Methylamine iodide (CH3NH3I) was synthesized according to a previous study.27 The OTP precursor solution was prepared by mixture of equimolar PbI2 and CH3NH3I dissolved in N, N-dimethylformamide (DMF) solvent. The substrates (PET and glass, 2.5 cm2.5 cm) were ultrasonically washed with acetone, ethanol and deionized water. Then the washed substrates were treated by UV-ozone for 30 minutes. Three different morphologies of OTP film (thin film, nanowires, networks) were synthesized by following procedures. For thin film growth, two-step method was adopted.28 The PbI2 layer was deposited by spin coating (6500 rpm) at 70°C. Then the PbI2 film was dipped in CH3NH3I solution (10 mg/mL) for 60 s, rinsed with 2-propanol and finally heated at 70°C for 30 minutes to obtain the OTP thin film. For nanowire growth22, small amount (~5 µL) of the precursor was dropped onto the substrate to crystalize by natural evaporation and annealed for final phase conversion. For OTP network growth, the precursor solution (~100 µL) was 4


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dropped on PET and then spin-coated at 2500 rpm for 30 s. After that they were kept in glovebox for 2 minutes and heated at 80 °C for 30 minutes to obtain the final products. The prepared OTP products were characterized by scanning electron microscopy (SEM, Nova NanoSEM 450), XRD (XRD-7000S/L), UV-Vis absorption spectra (Cary, Lambda 950) and photoluminescence (PL, LabRAM HR800). Device fabrication and measurements. The OTP networks were uniformly deposited on PET substrates which were pre-patterned with ordered Au electrodes by thermal evaporation. The active channels were 200 µm in length and 500 µm in width. For protective layer deposition, 50 mg/mL polymethyl methacrylate (PMMA) toluene solution was spin-coated on PD array at 3000 rpm for 30 s. Photodetector performance was measured by Agilent B1500A semiconductor characterization system assisted with a probe station. The devices were further covered with an aluminum cap to provide optical and electromagnetic shielding. The irradiation was generated from monochromatic light-emitting diodes (650 nm) controlled by a functional generator (Agilent 33210A). Light intensity was calibrated by a silicon optical power meter (Newport 818-UV).

Results and discussions Organolead halide perovskite crystals with different morphologies were widely applied in optoelectronic devices such as solar cells, PDs and lasers.24-26 For present PD arrays, various kinds of OTP crystal film were synthesized to investigate their optoelectronic performances. Figure 1a-1d showed three different morphologies of OTP crystals and their corresponding XRD spectra. The XRD spectra (Fig.1d) of as-synthesized products (marked as red stars) agreed well with the standard OTP spectra22 without any PbI2 residue. The peak of OTP networks at (110) plane located at 14.2°was stronger than that of thin film, which demonstrated the preferential growth of networks. Compared with OTP thin film (Fig. 1a) and OTP nanowires (Fig. 1b), the networks constructed by uniform crisscross belt-like crystals (Fig.1c and inset) demonstrated good uniformity and transparence combining the advantages of thin 5


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film and nanowires. The OTP materials were easy to crystallize which promised the convenient tuning of OTP morphologies.29-30 The present three different morphologies were implemented by controlling the velocity of crystallization. By evaporating solvent over a short time or adding anti-solvent, rapid crystallization obtained compact thin film.27, 31 On the contrary, natural crystallization in air made it grow into nanowires.22 Inspired from above two growth methods, we combined the spin coating and natural growth to synthesize OTP networks by controlling the speed of crystallization. Figure 1e showed the schematic diagram of individual device structure (top). The dimension of active channel between two adjacent Au pads was 200 µm in length, 500 µm in width and 100 nm for film thickness. The network PD array (bottom of Fig. 1e) was consisted of 49 groups of PDs and each group was made up of 4 pieces. Such device distribution was convenient with the measurement system. In order to characterize the uniformity of different PDs, The boxplot of photocurrent ranges were plotted in Fig 1f. The photocurrent ranges of thin film and network PD arrays were narrow, which revealed excellent uniformity. By contrast, the OTP nanowire PD arrays showed poor uniformity because of the random distribution of nanowires. The OTP network combining the advantages of thin film and nanowires demonstrated novel properties in PD applications: uniformity, semitransparency, photosensitivity and flexibility. For the following part, all the PD arrays were made up of OTP networks. For a photoconductive PD, switching ratio (SR), responsivity (R) and normalized detectivity (D*) are the figures of merit to compare the performances of different devices. The PD switching ratio was calculated by SR = was calculated by R =

Ip Id

=

I on − I d ; Responsivity Id

I on − I d ; For photoconductive PD, shot noise dominates the PA

total noise of detector. Shot noise derived normalized detectivity can be calculated by

D* =

I on − I d , where Ip is photocurrent, Ion is on-state current, Id is dark current, P P 2qI d A 6


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denoted light power density and A denoted the device area, q represents elementary charge. All the data of SR, R and D* were calculated according to above equations in present work. In order to optimize the devices’ transparence and performance, precursor concentrations were investigated to unfold the relationship between them. As shown in Fig. 2a, the OTP network absorption spectra covered the full visible spectrum. The transmittance gradually diminished with the increase of the precursor concentrations. The inset of Fig. 2a showed a photograph of semitransparent OTP networks grown from 30 wt% concentration. The flowers can be clearly watched through the network film. Once the precursor concentration exceeded 50 wt%, the transmittance was too weak (~20%) to be watched by naked eyes. The effect of precursor concentration to PD performance had been investigated as shown in Fig. 2b-d. The photocurrent increased as the precursor concentration increased (Fig. 2b). On the other hand, the transmittance decreased all the time and the normalized detectivity gradually saturated (Fig. 2c). The other two key parameters, switching ratio and responsivity, presented different evolution trends as shown in Fig. 2d. The switching ratio from the concentration of 30 wt% obtained a peak value ~340. In order to balance performance and transmittance, the optimal concentration of 30 wt% was selected for PD array fabrication. The corresponding normalized detectivity and responsivity were 1.021012 Jones and 0.10 A/W, respectively. The obtained uniform semitransparent networks fabricated by versatile and mild conditions could be conveniently integrated on surveillance, imaging and portable optoelectronic devices. Photodetector arrays made from 30 wt% precursor concentration were further detailedly investigated their performances. The working principle of photoconductive network PD was schematically depicted in Fig. 3a. When the device was irradiated by light source, the electron-hole pairs were generated in perovskite according to the photoelectric effect. Then the electron-hole pairs were rapidly separated and collected by electrodes under the applied electric field. Figure 3b showed I-V curves under different intensities of light illumination. The linear curves demonstrated ohmic 7


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contact due to the energy alignment between OTP networks and Au electrode. From the I-t curves of Fig. 3c, the sequential PD response to the switch of light was stable and abrupt. The extracted photocurrent and dark current were ~22 nA and ~0.07 nA, respectively. And the SR exceeded 300 at a bias voltage of 10 V under a light power density of 100 µW/cm2. In photoconductive PD, the equivalent dark current derived shot noise32 estimated from

2qI d was about 4.73×10-15 A Hz-1/2 at 1 Hz. The high

SR and low noise could have great potential in high-sensitivity applications. It might result from better crystallization and interface passivation between the network and PET. From a high resolution scan of one cycle in Fig. 3d, the extracted rise and decay times were 0.3 ms and 0.4 ms, respectively. The response time was similar to the value of single crystal nanowire PD thus demonstrating the fast response of network PD arrays.21-22 The superior performance of network PD arrays promised the preliminary application in imaging. To verify the imaging capability of PD array, light fringes with varied intensities (Fig. 4a) were utilized as light source to illuminate on the PD arrays. The detected photocurrent results of thin film PD array and network PD array were extracted to plot the detecting images as shown in Fig. 4b and 4c. All the PDs were functional and each can work as a pixel. The detected two-dimensional mappings extracted from network PD array and thin film PD array were similar. Both of them were well coincident with the signal of light resource. More detailed data extracted from a typical OTP network array’s response was listed in Fig. 4d. The PD detected signal was clearly separate to each other without any interlaced signal. The resolution of detection was ~20 µw/cm2, which was enough for common optical sensors. The implementation of present two-dimensional imaging might be attributed to the high uniformity and complete crystallization. Owing to the novel network structure, PD arrays can release part of bending stress which helps to improve the flexibility. The device fixed in a vernier caliper was bended at varied angles to test their flexibility as shown in Fig. 5a. The PD array performance was tested at a bias voltage of 10 V under 100 µW/cm2 light illumination. 8


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When the device was bended for 1000 times at different angle (20° to 80°), the photocurrent evolution was shown in Fig. 5b. The response signals were almost invariant at fixed angle (no more than 60°). When it was bended at a large angle (~80°), the photocurrent had a decrease of ~20%. Similarly, I-t evolution curves were obtained in larger number of bending cycles at fixed angle (Fig. 5c). The photocurrent shrank less than 10% after 10000 cycles. Therefore, the network PD arrays on PET demonstrated excellent flexibility which may greatly expand their application fields especially in portable devices. It was well known that the fatal problem of OTP was the instability in air.33-34 The perovskite was easily decomposed once water was introduced.35 In order to improve the stability of present OTP network PD arrays, a series of control experiments were designed and implemented. The device structures of Sample 1 to Sample 4 were Glass/OTP, Glass/PMMA/OTP, PET/OTP, PET/OTP/PMMA, respectively. All samples were stored in a dark environment with the humidity of about 70 % and taken out to characterize their evolution at different storing time. Figure 6a was the schematic images of four types of samples and each layer of them was labeled. From the evolution photographs in Fig. 6b, Sample 1 was degraded in less than one day and Sample 2 stood for a few days. By contrast, Sample 3 and Sample 4 had a little change in color even they were stored for one month. The samples after one month storing were further characterized by XRD (Fig. 6c). Sample 1 was fully decomposed; Sample 2 and Sample 3 contained both the phases of OTP and PbI2 impurity; and Sample 4 kept intact of OTP phase without any PbI2 peaks. Therefore, the PET substrate and PMMA protecting layer as normal hydrophobic polymers36 contributed to the stability improvement. The

enhancement mechanism

of OTP stability was investigated

by

photoluminescence (PL) spectra. The PL peaks from fresh samples (Fig. 6d) revealed blue shift once the PET or PMMA was introduced. The blue-shift of PL peaks indicated better crystallization and lower defect concentration37 which had great contributions to device stability38. Figure 6e showed the PL intensities of above four 9


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samples after a month storing. As reported by previous study, the peak intensity indicated the degradation degree.39 The intensity of Sample 4 was stronger than those of the others which demonstrated little degradation. The four samples were also utilized to fabricate PD arrays and the photocurrent degradation was shown in Fig. 6f. The decomposition of OTP seriously degraded the performances of PD arrays. By contrast, the photocurrent signal of Sample 4 decreased less than 30% after a month storing in air. In above four types of samples, both PMMA and PET as protective polymer film not only passivated surface defects but also blocked atmosphere moisture. On the other hand, the OTP had a better contact with hydrophobic polymers than the one with inorganics,40 which was verified from above control experiment results. Therefore, the improvement of OTP stability was mainly attributed to defect passivation, moisture block and enhancement of interface contact quality.

Conclusions By controlling the crystallization, OTP networks were successfully fabricated and further applied in flexible PD arrays. Compared with thin film and nanowires, the networks deposited on PET held unique advantages of uniformity, transparency and flexibility. To make a balance between the PD performance and transparence, the optimized PD arrays were obtained from 30 wt% precursor concentration. The responsivity and normalized detectivity of PD arrays reached 0.1 AW-1 and 1.02× 1012 Jones, respectively. Besides, the switching ratio was more than 300 and the response time was about 0.3 ms. The OTP PD arrays was further applied in imaging and successfully obtained clear mapping of the light source signal. The network PD arrays showed superior flexibility which could stand under wide angle (20-80 degree) and numerous (~10000 times) bending. Moreover, the sandwiching structure (PET/OTP/PMMA) could greatly improve the device stability and the network PD arrays easily kept intact for one month storing in air. The presented semitransparent, flexible and stable OTP network PD arrays are expected to apply in wide application fields, especially in portal optoelectronics. 10


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Notes The authors declare no competing ﬁnancial interest.

Acknowledgement This work was financially supported by the National Natural Science Foundation of China (61306137) and the Fundamental Research Funds for the Central Universities (HUST：2014QN014). The authors also thank Testing Center of HUST and the Center for Nanoscale Characterization and Devices, Wuhan National Laboratory for Optoelectronics (WNLO) for facility access.

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Figures and captions Fig. 1 (a-c) Perovskite morphologies from thin film (a), nanowires (b), and networks (c). The inset in Fig. 1c was the high resolution image of network. (d) XRD spectra of thin film, nanowires and networks deposited on PET. The peaks of OTP and PET substrates were marked as red stars and blue squares, respectively. (e) The schematic description to a PD (top) and photograph of network PD arrays (bottom). The length, width, and thickness of channel between two adjacent square pads were 200 µm, 500 µm and 100 nm, respectively. (f) Photocurrent statistical boxplots of PD arrays made by thin film, nanowires and networks. The photocurrents of PDs were tested at a bias voltage of 10 V under 650 nm light illumination with a power density of 100 µW/cm2. Fig. 2 Precursor concentration effect to PD performances. (a) Transmittance spectra of OTP networks evolved with the precursor concentrations. And the inset showed a photograph of semitransparent OTP networks grown from 30 wt% concentration. (b) I-t curves of network PD arrays. The bias voltage was 10V and the 650 nm light power density was 100 µW/cm2. (c) Transmittance and normalized detectivity evolved with precursor concentrations. (d) Responsivity and switching ratio changed with precursor concentrations. Fig. 3 (a) The working principle of photoconductive OTP network PD. (b) I-V curves under different illumination power densities at a bias voltage of 10 V. (c) I-t curve illuminated by 650 nm light (100 µW/cm2) at a bias voltage of 10 V. (d) High resolution scan to one cycle of I-t curves. The time interval was 0.1 ms. Fig.4 (a) The spatial distribution mapping of light source intensity. The four colors denoted the four light power densities of 10 µW/cm2, 40 µW/cm2, 80 µW/cm2 and 100 µW/cm2, respectively. (b, c) Mapping results obtained from thin film PD arrays (b) and network PD arrays (c). (d) Current statistic values of 49 pieces of network PDs excited by 650 nm light in different power densities (0 to 100 µW/cm2) at a bias voltage of 10 V. Fig. 5 (a) Photographs of bended PD array at varied angles from 0° to 80°. (b) I-t 14


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curves of network PD arrays at different angles (20° - 80°) after 1000 time bending. (c) I-t curve evolution at different bending cycles (0 - 10000 times) at a fixed angle of 40°. Fig. 6 (a) The diagrammatic drawing of four samples. (b) Time evolving photographs of the four samples. (c) XRD spectra of the four samples after one month storing. The peaks of OTP, PET and PbI2 were marked as red stars, purple squares and blue dots, respectively. (d, e) PL spectra of four samples at fresh (d) and a month later (e) states. (f) Photocurrent degradation percent at different storing time. All measurements were tested at 10 V bias voltage under 100 µW/cm2 light illumination.

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Fig. 1

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Fig. 2

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Fig. 3

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Fig. 4

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Fig. 5

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Fig. 6

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Flexible and Semitransparent Organolead Triiodide Perovskite

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