Ultrasensitive broadband phototransistors based on perovskite/organic-semiconductor vertical heterojunctions

ABSTRACT Organolead halide perovskites have emerged as the most promising materials for various optoelectronic devices, especially solar cells, because of their excellent optoelectronic

properties. Here, we present the first report of low-voltage high-gain phototransistors based on perovskite/organic-semiconductor vertical heterojunctions, which show ultrahigh

responsivities of ~109A W–1 and specific detectivities of ~1014 Jones in a broadband region from the ultraviolet to the near infrared. The high sensitivity of the devices is attributed to a

pronounced photogating effect that is mainly due to the long carrier lifetimes and strong light absorption in the perovskite material. In addition, flexible perovskite photodetectors have

been successfully prepared via a solution process and show high sensitivity as well as excellent flexibility and bending durability. The high performance and facile solution-based

fabrication of the perovskite/organic-semiconductor phototransistors indicate their promise for potential application for ultrasensitive broadband photodetection. SIMILAR CONTENT BEING

VIEWED BY OTHERS CONTROLLABLE P- AND N-TYPE BEHAVIOURS IN EMISSIVE PEROVSKITE SEMICONDUCTORS Article 11 September 2024 EFFICIENT LIGHT-EMITTING DIODES FROM MIXED-DIMENSIONAL PEROVSKITES ON A

FLUORIDE INTERFACE Article 19 October 2020 A VERSATILE PHOTODETECTOR ASSISTED BY PHOTOVOLTAIC AND BOLOMETRIC EFFECTS Article Open access 10 September 2020 INTRODUCTION Ultrasensitive

photodetectors with a broadband spectral response from the ultraviolet (UV)–visible region to the near infrared (NIR) are highly desirable for a multitude of industrial and scientific

applications1, 2, 3, 4, 5. The key strategy for realizing an ultrasensitive photodetector is to achieve a high gain, which means that one incident photon can induce many carriers to conduct

current in the device. Conventional high-gain photodetectors, including avalanche photodiodes and photomultipliers, require strictly controlled and complicated fabrication procedures and are

also expensive and bulky6. Moreover, these devices need to be operated at high voltages (>100 V), leading to high power consumption and inconvenience in many applications3, 4, 5. To

date, various novel materials, including nanoparticles, nanorods, organic-semiconductors, graphene and other two-dimensional materials, have been exploited for the development of highly

sensitive photodetectors3, 4, 5, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17. To achieve high gain in a photodetector, one promising strategy is based on the photogating effect, which can cause

photon-activated carriers to recirculate many times before recombining with opposite charges in the channel of a phototransistor3, 5. The photogating effect, similar to field-effect gating,

refers to the modulation of the carrier density, and thus of the conductivity in the channel, by means of light illumination13. The sensitivity of a phototransistor relies on strong light

absorption, efficient charge separation, long carrier lifetimes and high carrier mobilities in the channel. For example, graphene phototransistors modified with PbS colloidal quantum dots or

MoS2 on the surfaces of the graphene have shown responsivities of up to 108 A W–1 and gains of ~108 as a result of pronounced photogating effects13, 14, 15. However, the phototransistors

with the highest previously reported gains cannot be prepared using facile solution processes. Therefore, it is necessary to explore solution-processable ultrasensitive phototransistors for

low-cost and multifunctional applications. Organolead halide perovskite materials have stimulated considerable research interest in relation to high-efficiency and low-cost perovskite solar

cells18, 19, 20. Their excellent optoelectronic properties, including appropriate direct bandgaps21, high light absorption coefficients22 and long carrier transport lengths23, 24, 25, render

them promising candidate materials for photovoltaics and other optoelectronic devices, including photodetectors, light-emitting diodes and semiconductor lasers26, 27, 28, 29, 30. Recently,

organolead halide perovskites have been successfully used in various types of photodetectors, including photodiodes and phototransistors31, 32, 33, 34, 35, 36, 37, 38; however, these devices

have shown relatively low gain in comparison with phototransistors based on other functional materials. Moreover, previously reported perovskite photodetectors show a detectable wavelength

region that is limited by the bandgap of the perovskite material and have not been used for sensing NIR light with wavelengths longer than 800 nm. Here, we report phototransistors based on

perovskite/organic-semiconductor vertical heterojunctions prepared via a solution process. The devices contain double layers of CH3NH3PbI3-_x_Cl_x_ perovskite and an organic-semiconductor

that form staggered heterojunctions. Although perovskite/organic heterojunctions have previously been successfully applied in photovoltaics and even in biological systems as artificial

synapses39, they have never been used in phototransistors until now. We have found that phototransistors based on CH3NH3PbI3-_x_Cl_x_ and

poly-(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) exhibit a broadband photoresponse from the UV–visible region to the NIR region, with a responsivity and specific

detectivity of higher than 109 AW−1 and 1014 Jones, respectively, at a low operating voltage of only 0.5 V. This excellent performance is attributed to a significant photogating effect at

the vertical heterojunction, mainly due to the long carrier lifetimes and strong light absorption in the perovskite layers. MATERIALS AND METHODS DEVICE FABRICATION A SiO2 (300 nm)/Si or

polyimide (PI) substrate was ultrasonically cleaned sequentially in alcohol, acetone and deionized water and dried under a stream of nitrogen gas. Cr (10 nm)/Au (100 nm) electrodes with a

channel width (_W_) and length (_L_) of 1000 and 2 μm, respectively, were patterned via photolithography and magnetron sputtering. Then, a PEDOT:PSS film was deposited onto the substrate via

the spin coating of a PEDOT:PSS aqueous solution (Clevios PH 500, Heraeus Precious Metals GmbH & Co. KG, Leverkusen, Germany). The thickness of the PEDOT:PSS film was controlled by

adjusting the solution concentration and the spin-coating speed. Afterward, the substrate was transferred into a glovebox filled with high-purity nitrogen gas and baked at 150 °C for 1 h.

Methylammonium iodide (CH3NH3I) and lead chloride (PbCl2) (99.5 wt.%) were dissolved in anhydrous N,N-dimethylformamide (DMF) (99.8 wt.%) at a 3:1 molar ratio of CH3NH3I to PbCl2, and the

solution was stirred at 45 °C for 12 h inside a nitrogen-filled glovebox to produce a mixed halide perovskite precursor solution. Then, the precursor solution was spin coated onto the

PEDOT:PSS film for 1 min to form a CH3NH3PbI3-_x_Cl_x_ perovskite film. The device was then annealed at 100 °C for 45 min. The thickness of the perovskite film was controlled by adjusting

the spin-coating speed while keeping the other conditions unchanged. In this work, perovskite films with approximate thicknesses of 180, 205, 250, 300 and 330 nm were obtained at

spin-coating speeds of 6200, 4500, 3300, 2500 and 2000 r.p.m., respectively. MATERIAL CHARACTERIZATION The morphology of the perovskite/PEDOT:PSS films was characterized using scanning

electron microscopy (SEM, FEI Nova 450 Nano, FEI Company, Hillsboro, OR, USA). Transmittance and UV–vis absorption spectra were recorded using a Perkin Elmer (Waltham, MA, USA) Lambda 900

UV/VIS/NIR spectrometer. The PEDOT:PSS surface morphology was characterized by means of atomic force microscopy (AFM, Veeco NanoScope V, Bruker Corporation, Billerica, MA, USA). A surface

chemical analysis of the PEDOT:PSS was conducted using an X-ray photoelectron spectrometer (VG ESCALAB 220i-XL, Thermo Fisher Scientific, Waltham, MA, USA). DEVICE CHARACTERIZATION

Electrical and optoelectrical measurements were performed using a semiconductor parameter analyzer (Agilent 4156 C, Santa Clara, CA, USA) under light illumination at various intensities in a

glovebox. The light sources were light-emitting diodes with wavelengths of 370, 598 and 895 nm. The flexible devices were measured both before and after bending tests. In the bending tests,

each sample was pressed against a small glass bottle with a radius of 7 mm up to 300 times. Spectral response tests were performed using a standard quantum efficiency measurement system

equipped with a xenon lamp (Oriel 66902, 300 W, Newport Corporation, Irvine, CA, USA), a monochromator (Newport 66902, Irvine, CA, USA), a Si detector (Oriel 76175-71580, Newport

Corporation), and a dual-channel power meter (Newport 2931-C). Neutral density filters were used to attain light with a constant intensity, and a source meter (Keithley 2420, Cleveland, OH,

USA) was used to collect the electrical signals. The devices were wire-bonded and encapsulated using glass caps and epoxy in the glovebox before the spectral response tests in air. RESULTS

AND DISCUSSION Figure 1a presents a schematic diagram of a perovskite photodetector consisting of CH3NH3PbI3-_x_Cl_x_ perovskite and PEDOT:PSS films on a SiO2/Si substrate. Cr/Au electrodes

were patterned on the substrate by means of photolithography and magnetron sputtering, followed by the sequential coating of PEDOT:PSS and CH3NH3PbI3-_x_Cl_x_ perovskite layers. The surface

morphology of the perovskite film on the PEDOT:PSS was observed under SEM (see the Supplementary Information and Supplementary Fig. S1). We found that the perovskite layer exhibited

reasonably full coverage on the PEDOT:PSS layer, with only a few pinholes, and cross-sectional SEM imaging showed the film to have a double-layer stacked structure. Figure 1b shows the band

structure of the device29, in which a staggered heterojunction is formed between the CH3NH3PbI3-_x_Cl_x_ perovskite and the PEDOT:PSS. Under light illumination, excitons or electron–hole

pairs are generated in the perovskite film, depending on the film morphology, as reported by Grancini _et al._40. Moreover, excitons can easily dissociate into electrons and holes at the

perovskite/PEDOT:PSS interface or in the perovskite film because of the low-exciton binding energy41. Holes tend to diffuse into the PEDOT:PSS layer because of the decreased energy, whereas

electrons must accumulate in the perovskite layer since the conduction band level of the perovskite is lower than the lowest unoccupied molecular orbital level of the PEDOT:PSS. Thus, the

channel current of the device can be attributed to the electrons and holes in the perovskite and PEDOT:PSS layers, respectively. We found that the electron mobility in the perovskite layer

is only ~1.7 × 10−4 cm2 V−1 s−1 (Supplementary Information and Supplementary Fig. S2), whereas the hole mobility in the PEDOT:PSS layer is estimated to be ~5.6 cm2 V−1 s−1 (Supplementary

Information, Parts 1 and 2). Therefore, the channel current is mainly due to the hole transport in the PEDOT:PSS layer, and the current across the perovskite layer is negligible. The

current–voltage (_I_–_V_) curves between the two Au electrodes of the perovskite photodetectors were first measured in the dark. The devices exhibited linear _I_–_V_ curves, indicating good

ohmic contacts between the perovskite/PEDOT:PSS bilayer films and the Au electrodes. Then, the perovskite photodetectors were characterized under light illumination at wavelengths from the

UV–visible region to the NIR region. Figure 1c shows the photocurrent (_I_ph=_I_light– _I_dark) of a device as a function of the applied voltage between the two Au electrodes under

illumination with NIR light (wavelength: ~895 nm) at various intensities. The photocurrents of the same device under UV (~370 nm) and visible (~598 nm) light are shown in the Supplementary

Information (Supplementary Fig. S3). The photocurrent was found to depend almost linearly on the applied voltage, with a maximum value of ~4 mA at an applied voltage of only 0.5 V. To

confirm that the photocurrents reported above were not due solely to either the perovskite or the PEDOT:PSS film, control experiments were performed on devices prepared with the individual

films. We found that the photocurrent of a transistor based on CH3NH3PbI3-_x_Cl_x_ perovskite alone was ~10 nA at a bias voltage of 0.5 V under light illumination at the same intensity (see

the Supplementary Information, Supplementary Fig. S4). Another control device, based on pure PEDOT:PSS, exhibited a negligible current response to light illumination. The photocurrents (~1 

μA) were three orders of magnitude lower than the values observed in the perovskite/PEDOT:PSS phototransistors under the same light intensity from the UV–visible to the NIR region

(Supplementary Fig. S5). Therefore, the increase in the channel current of a perovskite/PEDOT:PSS phototransistor under light illumination can be attributed to a photogating effect, and the

photocurrent _I_ph is given by where _I_light and _I_dark are the currents in the device under light illumination and in the dark, respectively; _W_ and _L_ are the channel width and length

of the device, respectively; _q_ is the elementary charge; Δ_p_ is the increase in the density of holes per unit area in the PEDOT:PSS layer in the channel; _μ_ is the hole mobility in the

PEDOT:PSS layer; and _V_ is the voltage applied to the two Au electrodes. The responsivity (_R_), which is an essential figure of merit for a photodetector, is given by6 where _E__e_ is the

light intensity. Figure 1d shows the device responsivity as a function of the applied voltage for various light intensities (wavelength: 895 nm), exhibiting a maximum value of 7.6 × 108 A 

W−1. Figures 1e–1g show the responsivities to wavelengths of 370, 598 and 895 nm, respectively. The responsivity increased as the light intensity decreased, following a relationship of the

form , as previously observed in many other phototransistors3, 14. Notably, the highest responsivity at low light intensity was 1.91 × 109 A W−1 (wavelength: ~598 nm), which is much higher

than the corresponding responsivities of previously reported perovskite photodetectors and other state-of-the-art photodetectors6, 13, 14, 15, 31, 32, 33, 34, 35, 36, 37, 38. Moreover, the

gain (_G_) of a phototransistor is given by42 where _c_ is the speed of light, _λ_ is the wavelength of the incident light and _h_ is Planck’s constant. Thus, the gain corresponding to the

maximum responsivity is estimated to be 4.0 × 109. In addition to the responsivity, the specific detectivity (_D_*) is another key parameter of a photodetector and is given by6, 42, 43, 44

where _A_ is the effective area of the photodetector, _B_ is the bandwidth, _NEP_ is the noise equivalent power, is the root mean square value of the noise current and _R_ is the

responsivity of the device. The noise level per unit bandwidth (1 Hz) of the perovskite photodetectors was measured to be ~60 nA Hz−1/2 (see the Supplementary Information, Part 3 and

Supplementary Fig. S10). Therefore, the specific detectivities (_D_*) of a device at an applied voltage of 0.5 V and at wavelengths of 598 and 895 nm were 1.4 × 1014 and 5.6 × 1013 Jones (cm

 Hz1/2 W−1), respectively, far superior to those of traditional Si photodetectors6. Figure 2a shows a schematic diagram of a perovskite/PEDOT:PSS phototransistor under light illumination, in

which electrons and holes have accumulated in the perovskite and PEDOT:PSS layers, respectively. The density of photocarriers (that is, photo-generated holes) in the PEDOT:PSS layer can be

calculated based on the photocurrent. If the hole mobility under light illumination is assumed to be constant, then the density of photocarriers in the PEDOT:PSS layer is given by the

following equation6: where _μ_ is the hole mobility in PEDOT:PSS. As shown in Figure 2b, the maximum hole density that can be achieved is ~2 × 1013 cm−2, which is one order of magnitude

higher than that typically induced in a field-effect transistor6. Therefore, an extremely strong photogating effect is observed in the devices under light illumination. We further

characterized the spectral response of the perovskite photodetectors as shown in Figure 2c. The normalized spectral responsivity of a device at a given light intensity exhibits a sharp

rising edge near a wavelength of 800 nm, corresponding to the band-edge absorption of the CH3NH3PbI3-_x_Cl_x_ perovskite (~1.55 eV), as shown in the same figure. Although the responsivity is

rather low at wavelengths longer than 800 nm, it can be as high as 7.6 × 108 A W–1 at 895 nm, corresponding to a gain of 1.1 × 109. Notably, the spectral response of the phototransistors is

different from the external quantum efficiency of a perovskite solar cell, which shows a sharp decrease to 0 for wavelengths longer than 800 nm (see the Supplementary Information and

Supplementary Fig. S11)45. To better understand this effect, the light absorption of a pure perovskite film was characterized from the UV to the NIR region. As shown in Figure 2c, a

perovskite film can absorb light at wavelengths of up to 1.9 μm because of the existence of traps in the film46. Therefore, the photoresponse of the devices at wavelengths longer than 800 nm

can be attributed to the excitation of carriers from the valence band to the trap states within the perovskite bandgap, as shown in Figure 1b. In such a phototransistor, the photo-generated

electrons are not necessarily mobile in the perovskite film, and thus, an ultrahigh responsivity in the NIR region can be achieved, unlike in the case of a solar cell-based photodetector33,

34. The photoresponse of a device also depends on the thicknesses of the perovskite and PEDOT:PSS layers, as shown in Figures 2c and 2d. The responsivity increases with increasing

perovskite thickness because of the enhanced light absorption and tends to saturate when the perovskite thickness is larger than 300 nm. Similarly, the responsivity increases with increasing

PEDOT:PSS thickness and reaches a maximum when this thickness is ~43 nm. Therefore, the thicknesses of the perovskite and PEDOT:PSS layers were optimally chosen to be 300 nm and 43 nm,

respectively, in our experiments. The time-dependent photoresponse of the perovskite photodetectors was studied by periodically turning the light illumination on and off. As shown in Figure

3a, the photocurrent of a device increases rapidly during the initial stage (within the first few seconds) of illumination and then increases slowly for several minutes; this behavior can be

fitted using a double exponential function with two relaxation times where _τ_1 and _τ_2 are two time constants and _A_1 and _A_2 are magnitudes. As shown in Figure 3b, the time constants

_τ_1 and _τ_2 for the fitted curve are 4.5 and 57.5 s, respectively. We note that these response times are relatively long compared with previously reported perovskite photodetectors31, 32,

35, 36, which is not strange since slow responses are typically expected in phototransistors with ultrahigh gains13, 14, 15, 47. In our devices, the photoresponse is associated with the

accumulation processes of holes and electrons in the PEDOT:PSS and perovskite layers, respectively. During the initial stage, holes diffuse from the perovskite to the PEDOT:PSS layer, and

thus, the channel current rapidly increases with time. As the hole density in the channel increases, more holes will recombine with electrons at the perovskite/PEDOT:PSS interface. Moreover,

a reverse electric field induced by the increased number of separated charge carriers will depress the injection rate of holes. Consequently, the increase in channel current subsequently

slows under continued illumination for the above reasons. Only once the recombination rate is equal to the rate of injection of holes from the perovskite to the PEDOT:PSS can the device show

a stable photocurrent. At the same time, holes will transfer and recirculate many times in the PEDOT:PSS channel throughout their long carrier lifetimes, which explains the ultrahigh gain

achieved in our phototransistors. According to Equation (3), the gain of a device can be calculated based on its time-dependent photocurrent. Figure 3c shows the gain of a device as a

function of illumination time for two different light intensities. The gain of the device increased over time and saturated at values of 1.2 × 109 and 2.9 × 106 for light intensities of

14.15 and 76 μW cm−2, respectively. Thus, the gain decreases with increasing light intensity, which is consistent with the decreased responsivity with increasing light intensity shown in

Figure 1. Since the photoresponse of our devices is due to the accumulation of electrons in the perovskite layer, it is reasonable to consider that the response speed of a device is closely

related to the properties of its perovskite layer. We measured a phototransistor with a thinner perovskite layer (thickness: ~180 nm) prepared under the same annealing conditions as the

other devices (see the Supplementary Information, Part 4 and Supplementary Fig. S12). Although the responsivity of the device was lower, which is consistent with the data shown in Figure 2d,

the response speed was dramatically improved, indicating that a thinner perovskite layer can lead to a shorter response time. During the charge accumulation process in the

perovskite/PEDOT:PSS heterojunction, electrons will fill the trap states from deeper to shallower levels and will then fill the conduction band in the perovskite. The deep trap states can be

filled throughout the entire perovskite layer because of their low-energy levels, whereas the shallow trap states and conduction band will be filled only close to the heterojunction.

Consequently, as the film thickness decreases, fewer deep trap states will be involved in the charge accumulation process. Since the capture cross section of deep trap states is typically

smaller than that of shallow trap states6, a thinner perovskite layer with fewer deep trap states can result in a phototransistor with a faster response speed. Next, we investigated the

properties of the perovskite and organic-semiconductor layers that might influence the device responsivity. Although the perovskite material shows strong light absorption and can generate

electron–hole pairs with high quantum efficiency, some holes recombine with electrons in the perovskite and are unable to be injected into the PEDOT:PSS layer, especially when a high density

of electrons accumulates in the perovskite layer. Therefore, the responsivity and gain of a device strongly depend on the lifetime of holes in the perovskite, which is related to two

factors. First, the density of electrons in the perovskite layer increases with increasing light intensity, leading to a decrease in the hole lifetime in the perovskite and, consequently, a

decrease in device responsivity. Second, the hole lifetime in CH3NH3PbI3-_x_Cl_x_ perovskite has been found to be longer than those in many other semiconductors because of the low density of

recombination centers in the perovskite48. To further confirm this understanding, we tested phototransistors based on CH3NH3PbI3/PEDOT:PSS heterojunctions (see the Supplementary

Information, Part 5 and Supplementary Fig. S13) and found that the maximum responsivity was only ~106 A W−1 at the lowest light intensity. It has been reported that the hole lifetime in a

CH3NH3PbI3 film is much shorter than that in a CH3NH3PbI3-_x_Cl_x_ film under the same illumination conditions23, 49. Therefore, it is reasonable to find that a phototransistor based on

CH3NH3PbI3/PEDOT:PSS shows a much lower responsivity than a device based on CH3NH3PbI3-_x_Cl_x_/PEDOT:PSS. This experiment clearly indicates that the ultrahigh responsivity and gain of our

phototransistors are due to the long lifetime and diffusion length of holes in the CH3NH3PbI3-_x_Cl_x_ perovskite films. To better understand the photogating effect of the

perovskite/organic-semiconductor heterojunction, we prepared devices based on another organic-semiconductor, poly(3-hexylthiophene) (P3HT), and CH3NH3PbI3-_x_Cl_x_. P3HT is a typical

organic-semiconductor with a carrier mobility of up to 0.1 cm2 V−1 s−1(Ref. 50). Under light illumination, the transfer curve of such a transistor shifts toward higher gate voltages because

of the injection of holes into the P3HT layer (see the Supplementary Information and Supplementary Fig. S14). The increase in hole density induced by light illumination is given by , where

_C__i_ is the gate capacitance and Δ_V_ is the light-induced shift in the gate voltage. The maximum shift is ~20 V, corresponding to the increase in the hole density in the channel to 4 ×

1012 cm−2, which is much lower than the value (2 × 1013 cm−2) observed for devices based on CH3NH3PbI3-_x_Cl_x_/PEDOT:PSS. More importantly, the responsivity (see the Supplementary

Information and Supplementary Fig. S14 and S15) is several orders of magnitude lower than that of a device based on CH3NH3PbI3-_x_Cl_x_/PEDOT:PSS for two reasons. First, the hole mobility of

P3HT is only 2.7 × 10−2 cm2 V−1 s−1, which is two orders of magnitude lower than that of PEDOT:PSS. Second, the maximum density of accumulated carriers in a heterojunction is related to the

status of the energy level alignment on both sides. Under light illumination, a CH3NH3PbI3-_x_Cl_x_/P3HT heterojunction has band bending on both sides, whereas a

CH3NH3PbI3-_x_Cl_x_/PEDOT:PSS heterojunction has band bending only on the perovskite side because the PEDOT:PSS is highly doped and the Fermi level inside it is pinned by the dopant (see the

Supplementary Information and Supplementary Fig. S16). Consequently, a much higher density of electrons can accumulate in the CH3NH3PbI3-_x_Cl_x_/PEDOT:PSS heterojunction. Meanwhile, the

strong photogating effect can be attributed to the high relative dielectric constant (~60) of the perovskite material41, which is much higher than that of organic-semiconductors (~3) or Si

(11.9)6. It has been proven that the density of accumulated carriers is proportional to the dielectric constant under identical band bending conditions51. Therefore, the strong photogating

effect observed in the CH3NH3PbI3-_x_Cl_x_/PEDOT:PSS vertical heterojunction is also due to the high dielectric constant of the perovskite material and the high hole mobility in the

PEDOT:PSS layer. Flexible photodetectors have recently received considerable attention because of their potential applications in several emerging areas, such as wearable electronics and

artificial eyes52. As shown in Figure 4, perovskite photodetectors were fabricated on flexible polyimide (PI) substrates with a thickness of 50 μm. Figure 4b shows the _I_ph–_V_

relationships for a representative flexible photodetector under infrared light illumination (wavelength: ~895 nm) at various light intensities. The device was also characterized after being

bent to a radius of 7 mm 300 times. Figure 4c shows the relationships between the responsivity and bias voltage of the device under different light intensities. The maximum responsivity was

found to be ~8.3 × 108 A W−1, and the performance showed little change before and after the bending test. Figure 4d shows the time-dependent photoresponse of the device under alternating

light illumination conditions before and after 300 bending repetitions. Interestingly, the response time of the flexible device was faster than that of a device prepared on a SiO2/Si

substrate under the same processing conditions, and the photocurrent could reach a stable value within tens of seconds. We characterized the crystalline quality of two perovskite films

prepared on PI and SiO2/Si substrates and found that the two films showed similar diffraction patterns and peak widths (Supplementary Information and Supplementary Fig. S17). Therefore, the

faster response speed cannot be attributed to a different quality of the perovskite in the flexible device. To better understand this effect, we characterized the thickness of the perovskite

layer on the flexible substrate using a stylus profiler (Bruker: DektakXT, Billerica, MA, USA). We found that the thickness of the perovskite layer was only ~240 nm, thinner than the

perovskite layer (~300 nm) prepared on the SiO2/Si substrate. This difference in thickness is presumably due to the different surface morphologies and energies of the substrates. As

indicated by the results shown in Supplementary Fig. S12, a thinner perovskite layer can lead to a faster photoresponse. Therefore, the faster response of the flexible device compared with

the device prepared on the SiO2/Si substrate can be attributed to the thinner perovskite layer of the former. CONCLUSIONS In summary, we have demonstrated ultrasensitive broadband

phototransistors with vertical heterojunctions based on CH3NH3PbI3-_x_Cl_x_/PEDOT:PSS for the first time. Because of the high light absorption coefficient, long carrier lifetime and high

dielectric constant of the perovskite, a high density of photo-generated electrons can accumulate in the perovskite layer and induce a pronounced photogating effect on the channel through

the following processes. Strong light absorption in the perovskite leads to the creation of excitons or electron–hole pairs. Holes tend to diffuse into the PEDOT:PSS layer because it is

energetically favorable for them to do so, leaving electrons trapped in the perovskite layer. The holes will transfer and recirculate many times in the PEDOT:PSS channel throughout their

long lifetimes, giving rise to an ultrahigh gain. The devices exhibit an unprecedented responsivity of as high as ~2 × 109 A W−1, a gain of 4.0 × 109 and a high specific detectivity of up to

~1.7 × 1014 Jones under visible light at an operating voltage of only 0.5 V. This responsivity is several orders of magnitude higher than those achieved in previously reported perovskite

photodetectors. Although the perovskite material shows weak light absorption above the absorption edge of ~800 nm, the devices still can exhibit high responsivities of close to 109 A W−1

under NIR light at wavelengths of up to 1.1 μm because of their extremely high gain. Moreover, high-performance devices that exhibit excellent bending stability can be assembled on flexible

plastic substrates. This work opens up the possibility of the application of organolead halide perovskites in highly sensitive, low-cost and flexible photodetectors for broadband detection.

AUTHOR CONTRIBUTIONS FY, LL and CX conceived of the experiments. CX fabricated and characterized the devices. PY and ZL assisted with experiments on device fabrication. The manuscript was

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financially supported by the Research Grants Council (RGC) of Hong Kong, China (Project No. C4030-14G), and the Hong Kong Polytechnic University (Project No. G-YBB7, 1-BBA3, 1-ZVK1 and

1-ZVGH). AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong 999077, China Chao Xie, Peng You, Zhike Liu & Feng

Yan * Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hong Kong 999077, China Li Li Authors * Chao Xie View author publications You can also search for this author

inPubMed Google Scholar * Peng You View author publications You can also search for this author inPubMed Google Scholar * Zhike Liu View author publications You can also search for this

author inPubMed Google Scholar * Li Li View author publications You can also search for this author inPubMed Google Scholar * Feng Yan View author publications You can also search for this

author inPubMed Google Scholar CORRESPONDING AUTHOR Correspondence to Feng Yan. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no conflict of interest. ADDITIONAL INFORMATION

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THIS ARTICLE CITE THIS ARTICLE Xie, C., You, P., Liu, Z. _et al._ Ultrasensitive broadband phototransistors based on perovskite/organic-semiconductor vertical heterojunctions. _Light Sci

Appl_ 6, e17023 (2017). https://doi.org/10.1038/lsa.2017.23 Download citation * Received: 11 August 2016 * Revised: 08 February 2017 * Accepted: 13 February 2017 * Published: 22 February

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organic semiconductor * perovskite * photodetector