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The growing need for wearable electronics and self-powered electronic devices has driven the successful development of self-powered two-dimensional (2D) photodetectors using the photovoltaic effect of Schottky and p-n junctions. However, there is an urgent need to develop multifunctional photodetectors capable of harvesting energy from different sources to overcome their limitations in efficiency and cost. While the pyro-phototronic effect has been shown to effectively influence optoelectronic processes in heterojunctions, the number of reported two-dimensional heterojunctions exhibiting interfacial pyroelectricity is still limited, and the responsivity and detectivity based on such heterojunctions tend to be low. In this study, a photodetector based on an Au/WSe2/Ta2NiS5/Au heterojunction was designed and fabricated. By harnessing the interfacial pyro-phototronic effect arising from the built-in electric fields at the Au/WSe2 Schottky junction and WSe2/Ta2NiS5 heterojunction, the photodetector exhibits a broadband response range of 405-1064 nm, with approximately 12 times enhancement in output current compared to solely relying on the photovoltaic effect. Under 660 nm light irradiation, the self-powered photodetector exhibits a responsivity of 121 mA/W, an external quantum efficiency of 22.64%, and a specific detectivity of 2 × 1012 Jones. Notably, its pyroelectric coefficient exceeds 8 × 103 µC·m-2·K-1. These findings pave the way for effectively detecting weak light and temperature variation while presenting a new strategy for developing high-performance photodetectors utilizing the interfacial pyro-phototronic effect.
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Photopyroelectric-based circularly polarized light (CPL) detection, coupling the pyro-phototronic effect and chiroptical phenomena, has provided a promising platform for high-performance CPL detectors. However, as a novel detection strategy, photopyroelectric-based CPL detection is currently restricted by the short-wave optical response, underscoring the urgent need to extend its response range. Herein, visible-to-near-infrared CPL detection induced by the pyro-phototronic effect is first realized in chiral-polar perovskites. Specifically, chiral-polar multilayered perovskites (S-BPEA)2FAPb2I7 (1-S, S-BPEA = (S)-1-4-Bromophenylethylammonium, FA = formamidinium) with spontaneous polarization shows intrinsic pyroelectric and photopyroelectric performance. Strikingly, combining its merits of the pyro-phototronic effect and intrinsic wide-spectrum spin-selective effect, chiral multilayered 1-S presents efficient photopyroelectric-based broadband CPL detection performance spanning 405-785 nm. This research first realizes photopyroelectric-based infrared CPL detection and also sheds light on developing high-performance broadband CPL detectors based on the pyro-phototronic effect in the fields of optics, optoelectronics, and spintronics.
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Photocatalysis offers a direct, yet robust, approach to eradicate pathogenic bacteria. However, the practical implementation of photocatalytic disinfection faces a significant challenge due to low-efficiency photogenerated carrier separation and transfer. Here, we present an effective approach to improve photocatalytic disinfection performance by exploiting the pyro-phototronic effect through a synergistic combination of pyroelectric properties and photocatalytic processes. A set of comprehensive studies reveals that the temperature fluctuation-induced pyroelectric field promotes photoexcited carrier separation and transfer and thus facilitates the generation of reactive oxygen species and ultimately enhances photocatalytic disinfection performance. It is worth highlighting that the constructed film demonstrated an exceptional antibacterial efficiency exceeding 95% against pathogenic bacteria under temperature fluctuations and light irradiation. Moreover, the versatile modulation role of the pyro-phototronic effect in boosting photocatalytic disinfection was corroborated. This work paves the way for improving photocatalytic disinfection efficiency by harnessing the synergistic potential of various inherent material properties.
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A novel property existing in the stain-etching technique that eliminates the need for expensive etchant masks in the texturization process of silicon wafers was identified. Through the combination of grayscale lithography and stain-etching methodologies, selective patterning of silicon with AR-P 3510 T, a positive-photoresist mask, was carried out. The etch area ratio was varied in nine different patterns of various feature sizes ranging from 400 to 1500 µm. The optical characteristics of the patterned substrates were determined from diffuse reflectance spectroscopy analysis, and the results were supported with finite-difference time-domain simulations. Complimenting the improvement in optical properties, the electrical losses in microwell-patterned photodetector devices have been reduced with an electro-optic optimum value of the surface enhancement factor, γ. The photodetecting efficiency of a selectively patterned microwell photodetector device exceeded the planar and black silicon photodetector devices with a considerable improvement in the pyro-phototronic effect. This work suggests an alternative for black silicon optoelectronic devices providing a new route to fabricate selectively patterned substrates with an achieved detectivity 16- and 20-fold higher than black and planar silicon photodetector devices, respectively.
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Recently, perovskite photodetectors (PDs) are risen to prominence due to substantial research interest. Beyond merely tweaking the composition of materials, a cutting-edge advancement lies in leveraging the innate piezoelectric polarization properties of perovskites themselves. Here, the investigation shows utilizing Ti3C2Tx, a typical MXene, as an intermediate layer for significantly boosting the piezoelectric property of MAPbI3 thin films. This improvement is primarily attributed to the enhanced polarization of the methylammonium (MA+) groups within MAPbI3, induced by the OH groups present in Ti3C2Tx. A flexible PD based on the MAPbI3/MXene heterostructure is then fabricated. The new device is sensitive to a wide range of wavelengths, displays greatly enhanced performance owing to the piezo-phototronic coupling. Moreover, the device is endowed with a greatly reduced response time, down to millisecond level, through the pyro-phototronic effect. The characterization shows applying a -1.2% compressive strain on the PD leads to a remarkable 102% increase in the common photocurrent, and a 76% increase in the pyro-phototronic current. The present work reveals how the emerging piezo-phototronic and pyro-phototronic effects can be employed to design high-performance flexible perovskite PDs.
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The interfacial pyro-phototronic effect (IPPE) presents a novel approach for improving the performance of self-powered photodetectors (PDs) based on metal halide perovskites (MHPs). The interfacial contact conditions within the Schottky junctions are crucial in facilitating the IPPE phenomenon. However, the fabrication of an ideal Schottky junction utilizing MHPs is a challenging endeavor. In this study, we present a surface passivation method aimed at enhancing the performance of self-powered photodetectors based on inverted planar perovskite structures in micro- and nanoscale metal-halide perovskite SCs. Our findings demonstrate that the incorporation of a lead halide salt with a benzene ring moiety for surface passivation leads to a substantial improvement in photoresponses by means of the IPPE. Conversely, the inclusion of an alkane chain in the salt impedes the IPPE. The underlying mechanism can be elucidated through an examination of the band structure, particularly the work function (WF) modulated by surface passivation. Consequently, this alteration affects the band bending and the built-in field (VBi) at the interface. This strategy presents a feasible and effective method for producing interfacial pyroelectricity in MHPs, thus facilitating its potential application in practical contexts such as energy conversion and infrared sensors.
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Ferroelectric perovskites, where ferroelectricity is embedded in the structure, are being considered for different device applications. In this study, we introduce Cs2PbI2Cl2, an all-inorganic 2D Ruddlesden-Popper (RP) halide perovskite, as a ferroelectric material suitable for pyro-phototronic applications. Thin-films of the all-inorganic perovskite are successfully cast, and they demonstrate ferroelectric properties. Unlike hybrid materials, the ferroelectricity in Cs2PbI2Cl2 does not rely on the organic moiety possessing an electric dipole moment. Instead, the 2D-layer-forming octahedra are twisted and tilted due to a distortion in the bond lengths, leading to the emergence of spontaneous electric polarization. Based on the properties, we fabricate p-i-n heterojunctions by integrating the perovskite with carrier-transport layers. To determine the band-energies of the materials, scanning tunneling spectroscopy and Kelvin probe force microscopy are employed. The band-edges evidence a type-II band-alignment at both interfaces, enabling the material to exhibit both photovoltaic and pyroelectric behaviors when subjected to pulsed illumination. The devices based on the all-inorganic RP perovskite developed in this study exhibit pyro-phototronic effects and serve as self-powered photodetectors without any need for an external bias.
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CdS, with a noncentrosymmetric structure, is thought as an important electron transport layer (ETL) in perovskite-based devices, but its pyroelectric effect, which can efficiently modulate the optoelectronic processes, is not well explored. In this work, a MAPbI3 heterojunction of CdS/MAPbI3/Spiro-OMeTAD with a c-axis preferred oxygen-doped CdS ETL is developed as a high-performance photodetector (PD). This PD exhibits a stable self-powered property in the spectral range of â¼360-780 nm due to its excellent photovoltaic effect. Moreover, the light-induced pyroelectric potential in the CdS ETL is demonstrated to be an efficient approach for improving the photoresponses, and different effects are observed for different laser irradiations, which can be well understood from their working mechanisms. Upon 450 nm laser irradiation, the photovoltage responsivity (R) is greatly improved from 596.9 to 6383.6 V/W with an increment of 1069.54%. In addition, the response spectrum is also extended outside the bandgap restriction of the MAPbI3 to 1550 nm due to both the pyroelectric and photothermoelectric effects, which is a big breakthrough for the perovskite heterojunction PD. Through turning the external bias voltage and ambient temperature, the coupling mechanisms of the pyroelectric and photovoltaic effects are further analyzed. This work provides an important understanding of designing the CdS ETL-based perovskite heterojunction for broadband high-performance photoelectric devices by introducing the pyroelectric effect.
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Self-powered photodetectors (PDs) have the advantages of no external power requirement, wireless operation, and long life. Spontaneous ferroelectric polarizations can significantly increase built-in electric field intensity, showing great potential in self-powered photodetection. Moreover, ferroelectrics possess pyroelectric and piezoelectric properties, beneficial for enhancing self-powered PDs. 2D metal halide perovskites (MHPs), which have ferroelectric properties, are suitable for fabricating high-performance self-powered PDs. However, the research on 2D metal halide perovskites ferroelectrics focuses on growing bulk crystals. Herein, 2D ferroelectric perovskite films with mixed spacer cations for self-powered PDs are demonstrated by mixing Ruddlesden-Popper (RP)-type and Dion-Jacobson (DJ)-type perovskite. The (BDA0.7 (BA2 )0.3 )(EA)2 Pb3 Br10 film possesses, overall, the best film qualities with the best crystalline quality, lowest trap density, good phase purity, and obvious ferroelectricity. Based on the ferro-pyro-phototronic effect, the PD at 360 nm exhibits excellent photoelectric properties, with an ultrahigh peak responsivity greater than 93 A W-1 and a detectivity of 2.5 × 1015 Jones, together with excellent reproducibility and stability. The maximum responsivities can be modulated by piezo-phototronic effect with an effective enhancement ratio of 480%. This work will open up a new route of designing MHP ferroelectric films for high-performance PDs and offers the opportunity to utilize it for various optoelectronics applications.
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Self-powered photodetectors (PD) based on ferroelectric materials have gained huge attention because of the spontaneous polarization and unique photovoltaic effect. However, the low photocurrent values and switch ratio of the ferroelectric materials limit their further practical applications in a wide temperature range. In this study, the self-powered ZnO nanofiber array/BaTiO3 (ZnO-NFA/BTO) PD was fabricated by high-ordered ZnO-NFA via electrospinning method deposited on a 300 nm BTO film synthesized using sol-gel method. The electrospinning can prepare ZnO-NFAs with a controllable diameter (100 nm) and orientation and is directly deposited on the quartz at a large scale, which simplifies the fabrication process. This device possesses a greater on/off ratio of 2357 at zero bias than that of BTO PD (3.33) and the ZnO-NFA PD (125) at 0.2 V. The highest responsivity and specific detectivity are 1.41 mA W-1 and 1.48 × 109 Jones at 368 nm under 0 V bias, respectively, which is enhanced about three magnitudes than the pristine BTO PD (1.21 µA W-1 and 1.02 × 109 Jones). The photocurrent of the ZnO-NFA/BTO PD strongly depends on the temperature. After the cooling system and prepolarization processing are both introduced, the largest light current (475 nA) and photovoltaic plateaus (585 nA) are enhanced by about 4417 and 4278% under 368 nm at a power intensity of 4.46 mW cm-2 at 0 °C, respectively. The enhancement of photocurrent is associated with a ferro-pyro-phototronic effect, evidenced by enhanced ferroelectric polarization. The ZnO-NFA/BTO PD can detect weak signals at low power intensity with a wide temperature range of 0-100 °C under 0 V bias. The self-powered ZnO-NFA/BTO PD provides a new and promising way to fabricate high-performance and low-cost photodetectors from inorganic perovskite materials.
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Two-dimensional (2D) Ruddlesden-Popper (RP) layered halide perovskite has attracted wide attentions due to its unique structure and excellent optoelectronic properties. With inserting organic cations, inorganic octahedrons are forced to extend in a certain direction, resulting in an asymmetric 2D perovskite crystal structure and causing spontaneous polarization. The pyroelectric effect resulted from spontaneous polarization exhibits a broad prospect in the application of optoelectronic devices. Herein, 2D RP polycrystalline perovskite (BA)2 (MA)3 Pb4 I13 film with excellent crystal orientation is fabricated by hot-casting deposition, and a class of 2D hybrid perovskite photodetectors (PDs) with pyro-phototronic effect is proposed, achieving temperature and light detection with greatly improved performance by coupling multiple energies. Because of the pyro-phototronic effect, the current is ≈35 times to that of the photovoltaic effect current under 0 V bias. The responsivity and detectivity are 12.7 mA W-1 and 1.73 × 1011 Jones, and the on/off ratio can reach 3.97 × 103 . Furthermore, the influences of bias voltage, light power density, and frequency on the pyro-phototronic effect of 2D RP polycrystalline perovskite PDs are explored. The coupling of spontaneous polarization and light facilitates photo-induced carrier dissociation and tunes the carrier transport process, making 2D RP perovskites a competitive candidate for next-generation photonic devices.
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Pyroelectricity was discovered long ago and utilized to convert thermal energy that is tiny and usually wasted in daily life into useful electrical energy. The combination of pyroelectricity and optoelectronic yields a novel research field named as Pyro-Phototronic, where light-induced temperature variation of the pyroelectric material produces pyroelectric polarization charges at the interfaces of semiconductor optoelectronic devices, capable of modulating the device performances. In recent years, the pyro-phototronic effect has been vastly adopted and presents huge potential applications in functional optoelectronic devices. Here, we first introduce the basic concept and working mechanism of the pyro-phototronic effect and next summarize the recent progress of the pyro-phototronic effect in advanced photodetectors and light energy harvesting based on diverse materials with different dimensions. The coupling between the pyro-phototronic effect and the piezo-phototronic effect has also been reviewed. This review provides a comprehensive and conceptual summary of the pyro-phototronic effect and perspectives for pyro-phototronic-effect-based potential applications.
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Self-powered photodetectors (PDs) have been recognized as one of the developing trends of next-generation optoelectronic devices. Herein, it is shown that by introducing a thin layer of SnO film between the Si substrate and the ZnO film, the self-powered photodetector Al/Si/SnO/ZnO/ITO exhibits a stable and uniform violet sensing ability with high photoresponsivity and fast response. The SnO layer introduces a built-in electrostatic field to highly enhance the photocurrent by over 1000%. By analyzing energy diagrams of the p-n junction, the underlying physical mechanism of the self-powered violet PDs is carefully illustrated. A high photo-responsivity (R) of 93 mA W-1 accompanied by a detectivity (D*) of 3.1 × 1010 Jones are observed under self-driven conditions, when the device is exposed to 405 nm excitation laser wavelength, with a laser power density of 36 mW cm-2 and at a chopper frequency of 400 Hz. The Si/SnO/ZnO/ITO device shows an enhancement of 3067% in responsivity when compared to the Al/Si/ZnO/ITO. The photodetector holds an ultra-fast response of ≈ 2 µs, which is among the best self-powered photodetectors reported in the literature based on ZnO.
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Dual-polarity response photodetectors (PDs) take full advantage of the directivity of the photocurrent to identify optical information. The dual-polarity signal ratio, a key parameter that represents the equilibrium degree of responses to different lights, is proposed for the first time. The synchronous enhancement of dual-polarity photocurrents and the amelioration of the dual-polarity signal ratio are beneficial to the practical applications. Herein, based on the selective light absorption and energy band structure design, a self-powered CdS/PEDOT:PSS/Au heterojunction PD consisting of a p-n junction and a Schottky junction exhibits unique wavelength-dependent dual-polarity response, where the photocurrent is negative and positive in the short and long wavelength regions, respectively. More importantly, the pyro-phototronic effect inside the CdS layer significantly improves the dual-polarity photocurrents with the maximum enhancement factors of 120%, 343%, 1167%, 1577%, and 1896% at 405, 450, 532, 650, and 808 nm, respectively. Furthermore, the dual-polarity signal ratio tends to 1:1 due to different degrees of the enhancement. This work provides a novel design strategy for dual-polarity response PDs with a simple working principle and improved performance, which can supply a substitution for two traditional PDs in the filterless visible light communication (VLC) system.
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The emergence of nanomaterials has brought about the development of miniature photodetectors into a new stage, and ZnO nanomaterials are currently one of the most popular research objects. Here, the performance of a photodetector consisting of micropyramid structured p-Si/n-ZnO NWs heterojunction constructed by an anisotropic chemical etching and hydrothermal method is optimized by using the pyro-phototronic effect, and the photoresponses of the device to 405 and 648 nm lasers are investigated. The results show that, with the introduction of pyro-phototronic effect, the photoresponsivity Rpyro increases to 208 times that of Rphoto when the wavelength is 405 nm and the optical power density is 0.0693 mW/cm2. Moreover, with the increase of the chopper frequency, the photocurrent increases by more than 3 times, and the photoresponsivity is also increased by a factor of 4.5, making it possible to detect ultrafast pulsed light. In addition, in order to increase the current collection efficiency, a thin film Al layer was deposited as the back electrode on the basis of the device, and the photocurrent and photoresponsivity are significantly improved. Finally, the coupling between the pyro-phototronic effect and the piezo-phototronic effect is analyzed by applying compressive strain to the photodetector. When the compressive strain is -1.02%, the photocurrent decreases by 31.4% and the photoresponsivity decreases by 27.9% due to the opposite direction between laser illumination induced pyroelectric polarization charges and compressive strain induced piezoelectric polarization charges. This work not only demonstrates the great potential of pyro-phototronic effect in enhancing the silicon-based heterojunction photodetectors for high-performance photodetection and ultrafast pulsed light detection but also provides assistance for a better understanding of the coupling mechanism between pyro-phototronic and piezo-phototronic effects.
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The bottom-up preparation of two-dimensional material micro-nano structures at scale facilitates the realisation of integrated applications in optoelectronic devices. Fibrous Phosphorus (FP), an allotrope of black phosphorus (BP), is one of the most promising candidate materials in the field of optoelectronics with its unique crystal structure and properties.[1] However, to date, there are no bottom-up micro-nano structure preparation methods for crystalline phosphorus allotropes.[1c, 2] Herein, we present the bottom-up preparation of fibrous phosphorus micropillar (FP-MP) arrays via a low-pressure gas-phase transport (LP-CVT) method that controls the directional phase transition from amorphous red phosphorus (ARP) to FP. In addition, self-powered photodetectors (PD) of FP-MP arrays with pyro-phototronic effects achieved detection beyond the band gap limit. Our results provide a new approach for bottom-up preparation of other crystalline allotropes of phosphorus.
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Metal halide perovskite ferroelectrics possess various physical characteristics such as piezoelectric and pyroelectric effects, which could broaden the application of perovskite ferroelectrics and enhance the optoelectronic performance. Therefore, it is promising to combine multiple effects to optimize the performance of the self-powered PDs. Herein, patterned 2D ferroelectric perovskite (PMA)2PbCl4 microbelt arrays were demonstrated through a PDMS template-assisted antisolvent crystallization method. The perovskite arrays based flexible photodetectors exhibited fine self-powered photodetection performance under 320 nm illumination and much enhanced reproducibility compared with the randomly distributed single-crystal microbelts-based PDs. Furthermore, by introducing the piezo-phototronic effect, the performance of the flexible PD was greatly enhanced. Under an external tensile strain of 0.71%, the responsivity was enhanced by 185% from 84 to 155.5 mA/W. Our findings offer the advancement of comprehensively utilizing various physical characteristics of the ferroelectrics for novel ferroelectric optoelectronics.
Asunto(s)
Óxidos , Óxido de Zinc , Reproducibilidad de los Resultados , Compuestos de Calcio , Óxido de Zinc/químicaRESUMEN
Silicon carbide (SiC), one of the third-generation semiconductor materials with excellent electrical and optoelectronic properties, is ideal for high light-sensing performance. Here, a self-powered SiC ultraviolet (UV) photodetector (PD) is constructed with wider applicability and higher commercialization potential. The great performance of the PD is realized by a remarkable photoinduced dynamic Schottky effect derived from the symbiotic modulation of Schottky and Ohmic contact. Using the pyro-phototronic effect that exists in the N-doped 4H-SiC single crystal PDs, a fast pyroelectric response time of 0.27 s is achieved, which is almost ten times shorter than that obtained from the steady-state signal under UV illumination. The maximal transient photoresponsivity reaches 9.12 nA mW-1 , which is ≈20% higher than the conventional photoelectric signal. Moreover, different regions of the 4H-SiC centimeter-scale chip output distinct signals under UV illumination, demonstrating efficient optical imaging and information transmission capabilities of this device. This work not only reveals the fundamental optoelectronic physics lying in this vital third-generation semiconductor, but also sheds light on its potential photosensing applications for large-scale commercialization.
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2D hybrid perovskite ferroelectrics have drawn great attention in the field of photodetection, because the spontaneous polarization-induced built-in electric field can separate electron-hole pairs, and makes self-powered photodetection possible. However, most of the 2D hybrid perovskite-based photodetectors focused on the detection of visible light, and only a few reports realized the self-powered and sensitive ultraviolet (UV) detection using wide bandgap hybrid perovskites. Here, 2D ferroelectric PMA2PbCl4 monocrystalline microbelt (MMB)-based PDs are demonstrated. By using the ferro-pyro-phototronic effect, the self-powered Ag/Bi/2D PMA2PbCl4 MMB/Bi/Ag PDs show a high photoresponsivity up to 9 A/W under 320 nm laser illumination, which is much higher than those of previously reported self-powered UV PDs. Compared with responsivity induced by the photovoltaic effect, the responsivity induced by the ferro-pyro-phototronic effect is 128 times larger. The self-powered PD also shows fast response and recovery speed, with the rise time and fall time of 162 and 226 µs, respectively. More importantly, the 2D PMA2PbCl4 MMB-based PDs with Bi/Ag electrode exhibit significant stability when subjected to high humidity, continuous laser illumination, and thermal conditions. Our findings would shed light on the ferro-pyro-phototronic-effect-based devices, and provide a good method for high-performance UV detection.
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Ferro-pyro-phototronic (FPP) effect is a triple coupling of ferroelectricity, light-induced pyroelectricity, and photo-excitation, which holds a bright promise for next-generation modern optoelectronic devices. However, except for few oxides (e.g., BaTiO3 ), new FPP-active candidates remain extremely scarce due to the knowledge lacking on the underlying role of three coupling components. By tailoring the interlayered spacers, the authors present a series of 2D cesium-based perovskite ferroelectrics, (A')2 CsPb2 Br7 (where A'-site cation is organic spacer), showing remarkable FPP-active properties. As expected, the dynamic ordering and reorientation of spacers along with atomic displacement of Cs+ in the perovskite cavity lead to their ferroelectric polarizations. Particularly, exceptional FPP properties are created through this cooperation; the most FPP-active candidate (n-hexylammonium)2 CsPb2 Br7 endows a giant contrast up to 1500% for photopyroelectric current to photovoltaic signal. This figure-of-merit is far beyond most inorganic oxide counterparts, such as ≈110% for BaTiO3 . Further, the electric switching and controlling of FPP directions confirm a crucial role of ferroelectric polarization to this coupling effect. To the authors' best knowledge, this is the first study on an FPP-active candidate of 2D hybrid perovskites, which affords a new avenue to design ferroelectrics with targeted physical properties and forward their potentials to smart optoelectronic device application.