nA Cm-2 Research Articles

Planar Cation Passivation on Colloidal Quantum Dots Enables High-Performance 0.35-1.8µm Broadband TFT Imager.

Solution-processed colloidal quantum dots (CQDs) are promising candidates for broadband photodetectors from visible light to shortwave infrared (SWIR). However, large-size PbS CQDs sensitive to longer SWIR are mainly exposed with nonpolar (100) facets on the surface, which lack robust passivation strategies. Herein, an innovative passivation strategy that employs planar cation, is introduced to enable face-to-face coupling on (100) facets and strengthen halide passivation on (111) facets. The defect density of CQDs film (Eg ≈ 0.74eV) is reduced from 2.74×1015 to 1.04×1015 cm-3 , coupled with 0.1eV reduction in the activation energy of defects. The resultant CQDs photodiodes exhibit a low dark current density of 14 nA cm-2 with a high external quantum efficiency (EQE) of 62%, achieving a linear dynamic range of 98dB, a -3dB bandwidth of 103kHz and a detectivity of 4.7×1011 Jones. The comprehensive performance of the CQDs photodiodes outperforms previously reported CQDs photodiodes operating at >1.6µm. By monolithically integrated with thin-film transistor (TFT) readout circuit, the broadband CQDs imager covering 0.35-1.8µm realizes the functions including silicon wafer perspectivity and material discrimination, showing its potential for wide range of applications.

Enhanced Photoelectric Properties of CsPbBr3 by SiO2 and TiO2 Bilayer Heterostructures.

CsPbBr3/SiO2 heterostructures were synthesized by the hydrolysis reaction of a mixture of CsPbBr3 nanocrystals (NCs) and (3-aminopropyl)triethoxysilane (APTS) in air. Compared with CsPbBr3 NCs, the CsPbBr3/SiO2 heterostructures exhibit stronger photoluminescence (PL) intensity, longer lifetime of PL (∼40.5 ns), and higher PL-quantum yield (PLQY, ∼86%). The carrier dynamics of CsPbBr3/SiO2 was detected by the transient absorption (TA) spectrum. The experimental results show that SiO2 passivates the surface traps of CsPbBr3 NCs and enhances the PL intensity. However, photoelectrochemical impedance spectra (PEIS) demonstrate that the impedance of CsPbBr3/SiO2 is higher than that of CsPbBr3 NCs, which reduces carrier transport and extraction. Because the application of CsPbBr3/SiO2 in optoelectronics is limited, CsPbBr3/SiO2/TiO2 heterostructures were synthesized by the further reaction of tetrabutyl titanate (TBT). The TiO2 coating can reduce the impedance of the CsPbBr3/SiO2. Importantly, ∼68% of the PL intensity of CsPbBr3/SiO2 is retained. Compared with CsPbBr3/SiO2 and CsPbBr3 NCs, the CsPbBr3/SiO2/TiO2 demonstrates faster carrier transport (κct = 2.4 × 109 s-1) and higher photocurrent density (J = 76 nA cm-2). In addition, CsPbBr3/SiO2/TiO2 shows good stability under (ultraviolet) UV irradiation, along with water stability and thermal stability. Therefore, the double protection approach can enhance the stability of CsPbBr3 NCs and tune the optoelectronic properties of CsPbBr3 NCs.

(C6H15N3)1.3(NH4)1.5H1.5In3SnS8: a layered metal sulfide based on supertetrahedral T2 clusters with photoelectric response and ion exchange properties.

A new layered metal sulfide, namely (C6H15N3)1.3(NH4)1.5H1.5In3SnS8 (1, C6H15N3 = N-(2-aminoethyl) piperazine), has been solvothermally synthesized and characterized. Compound 1 crystallizes in the monoclinic space group C2/c. Its structure features a two-dimensional layer of {In3SnS8}n3n- with the (4,4) topology net, which is formed by interlinking supertetrahedral T2 clusters as secondary building units. Band structure calculations revealed that 1 had a band gap of 2.7 eV. The photoelectric response of 1 showed steady and reversible on/off cycles with an "on" state of 121.13 nA cm-2. Moreover, the activation of 1 by replacing the sluggish organic cations with harder K+ ions endowed the material with improved adsorption performances for Sr2+ ions from aqueous solutions.

Rational ligand design for enhanced carrier mobility in self-powered SWIR photodiodes based on colloidal InSb quantum dots.

Solution-processed colloidal III-V semiconductor quantum dot photodiodes (QPDs) have potential applications in short-wavelength infrared (SWIR) imaging due to their tunable spectral response range, possible multiple-exciton generation, operation at 0-V bias voltage and low-cost fabrication and are also expected to replace lead- and mercury-based counterparts that are hampered by reliance on restricted elements (RoHS). However, the use of III-V CQDs as photoactive layers in SWIR optoelectronic applications is still a challenge because of underdeveloped ligand engineering for improving the in-plane conductivity of the QD assembled films. Here, we report on ligand engineering of InSb CQDs to enhance the optical response performance of self-powered SWIR QPDs. Specifically, by replacing the conventional ligand (i.e., oleylamine) with sulfide, the interparticle distance between the CQDs was shortened from 5.0 ± 0.5 nm to 1.5 ± 0.5 nm, leading to improved carrier mobility for high photoresponse speed to SWIR light. Furthermore, the use of sulfide ligands resulted in a low dark current density (∼nA cm-2) with an improved EQE of 18.5%, suggesting their potential use in toxic-based infrared image sensors.

The impact of mechanical post-treatment on the tribological and corrosion behavior of CrN/CrAlN coatings applied using the CAE-PVD technique

This study examined how wet microblasting affects the tribological and electrochemical properties of CrN/CrAlN nanolayered coatings. The coatings were applied to 430 stainless steel substrates using cathodic arc evaporation (CAE), a physical vapor deposition (PVD) technique. The microblasting was performed at three different pressures (2, 4, and 6 bar) after the deposition process. Field emission SEM and X-ray diffraction techniques were employed to characterize the microstructure and morphology of the samples. The nanoscale indentation method was utilized to evaluate the indentation properties of the coatings. The tribological properties of the samples were investigated by means of a ball-on-disk tester. The coatings’ corrosion behavior was tested by EIS and PDP in a NaCl solution (3.5 wt.%). The wear results indicated that the friction coefficient decreased from 0.3 for the non-treated coating to 0.27, 0.23, and 0.5 for the coatings microblasted at 2, 4, and 6 bar, respectively. The wear resistance increased by 10 % and 23 % for the coatings microblasted at 2 and 4 bar due to the higher compressive residual stress and resistance against plastic deformation (H/E value). The EIS results revealed that the coating microblasted at 2 bar had the highest RP (2425 × 103 W cm2) and the lowest corrosion rate after 24 h of immersion in a 3.5 wt.% salt solution. The results showed that the corrosion resistance at 2 bar pressure improved approximately 16 times. The Potentiodynamic polarization (PDP) diagrams also showed that the coating microblasted at 2 bar had the lowest current density (6.3 nA cm2), indicating the highest corrosion resistance. Therefore, the optimal microblasting pressure for tribological and electrochemical applications was 4 and 2 bar, respectively.

An A2 B2 O7 -Type High-Entropy Oxide for Efficient Photoelectrochemical Photodetector with Excellent Long-Term Stability.

Optoelectronics with excellent long-term stability is meaningful for practical applications. Herein, for the first time, an A2 B2 O7 type high-entropy oxide of (La0.2 Ce0.2 Nd0.2 Gd0.2 Bi0.2 )2 Ti2 O7 (ATO) is synthesized and applied for photoelectrochemical photodetection. The lattice distortion, highly dispersed metal composition, and exposed active sites of ATO are beneficial for the fast separation and transmission of photogenerated electron/hole pairs, endowing ATO-based devices with good photodetection performance. Both the density functional theory calculations and the nondegenerate transient absorption spectroscopy demonstrate the good optoelectronic properties of ATO. The systematic experimental studies reveal the tunable photodetection capability of ATO-based photodetector (PD) in the visible region. A photocurrent of 772.00 nA cm-2 and a responsivity of 4.02µA W-1 can be achieved as the PD in 1.0m KOH with the bias potential of 0.6V. Importantly, the robust and reproducible ON/OFF signals of the PD can be verified and there is only ≈5.00% attenuation in photocurrent even after 6 months, revealing the great potential of high- entropy oxides for practical applications.

Molecular surface programming of rectifying junctions between InAs colloidal quantum dot solids

Heavy-metal-free III-V colloidal quantum dots (CQDs) show promise in optoelectronics: Recent advancements in the synthesis of large-diameter indium arsenide (InAs) CQDs provide access to short-wave infrared (IR) wavelengths for three-dimensional ranging and imaging. In early studies, however, we were unable to achieve a rectifying photodiode using CQDs and molybdenum oxide/polymer hole transport layers, as the shallow valence bandedge (5.0 eV) was misaligned with the ionization potentials of the widely used transport layers. This occurred when increasing CQD diameter to decrease the bandgap below 1.1 eV. Here, we develop a rectifying junction among InAs CQD layers, where we use molecular surface modifiers to tune the energy levels of InAs CQDs electrostatically. Previously developed bifunctional dithiol ligands, established for II-VI and IV-VI CQDs, exhibit slow reaction kinetics with III-V surfaces, causing the exchange to fail. We study carboxylate and thiolate binding groups, united with electron-donating free end groups, that shift upward the valence bandedge of InAs CQDs, producing valence band energies as shallow as 4.8 eV. Photophysical studies combined with density functional theory show that carboxylate-based passivants participate in strong bidentate bridging with both In and As on the CQD surface. The tuned CQD layer incorporated into a photodiode structure achieves improved performance with EQE (external quantum efficiency) of 35% (>1 μm) and dark current density < 400 nA cm-2, a >25% increase in EQE and >90% reduced dark current density compared to the reference device. This work represents an advance over previous III-V CQD short-wavelength IR photodetectors (EQE < 5%, dark current > 10,000 nA cm-2).

Suppressing Interfacial Side Reactions of Anode-Free Lithium Batteries by an Organic Salt Monolayer.

Anode-free lithium (Li) batteries are attractive owing to their high energy density. However, Li loss by forming solid-electrolyte interphase (SEI) during cell activation leads to a ≈25% capacity decrease, and the capacity constantly fades upon cycling due to the side reactions on the copper (Cu) current collector. This paper reports high-initial-efficiency, long-cycle-life, and long-calendar-life anode-free Li batteries by using an organic Li salt monolayer bonded on Cu. The functional salt, namely lithium ((4-carbamoylphenyl)sulfonyl)(fluorosulfonyl)imide, electrochemically decomposes and passivates the Cu surface, which reduces Li sacrifice by SEI formation and suppresses galvanic Li corrosion and Li-electrolyte reactions during cycling. This work records a LiF-rich interphase on Cu and guided Li nucleation and growth. A 93.6% initial Li deposition efficiency is realized in a regular carbonate electrolyte, and the galvanic current is decreased to ≈40 nA cm-2 , merely one-tenth of bare Cu. After cell activation, 95.2% capacity is retained for a Cu|LiNi0.8 Mn0.1 Co0.1 pouch cell with a theoretical capacity of 200 mAh, and the cell is operated over 600 cycles. Calendar aging showed no damage to cell performance.

High-Performance and Stable Colloidal Quantum Dots Imager via Energy Band Engineering.

Solution-processed colloidal quantum dot (CQD) photodiodes are compatible for monolithic integration with silicon-based readout circuitry, enabling ultrahigh resolution and ultralow cost infrared imagers. However, top-illuminated CQD photodiodes for longer infrared imaging suffer from mismatched energy band alignment between narrow-bandgap CQDs and the electron transport layer. In this work, we designed a new top-illuminated structure by replacing the sputtered ZnO layer with a SnO2 layer by atomic layer deposition. Benefiting from matched energy band alignment and improved heterogeneous interface, our top-illuminated CQD photodiodes achieve a broad-band response up to 1650 nm. At 220 K, these SnO2-based devices exhibit an ultralow dark current density of 3.5 nA cm-2 at -10 mV, reaching the noise limit for passive night vision. The detectivity is 4.1 × 1012 Jones at 1530 nm. These SnO2-based devices also demonstrate exceptional operation stability. By integrating with silicon-based readout circuitry, our CQD imager realizes water/oil discrimination and see-through smoke imaging.

Metal seeding growth of three-dimensional perovskite nanowire forests for high-performance stretchable photodetectors

Metal halide perovskites have been ubiquitously utilized in both rigid and flexible optoelectronics with high performance. However, developing perovskites-based stretchable optoelectronics is highly challenging because perovskites are intrinsically not stretchable unlike some organic semiconductors. Here, for the first time, we devised a novel metal seeding growth method to obtain three-dimensional (3D) perovskite nanowire forests (NWFs) with excellent mechanical stretchability, akin to the seeding growth of grass in nature. Benefiting from their intrinsic stretchability, perovskite NWFs-based stretchable photodetectors have been demonstrated with excellent photodetection performance. Under 0% strain, the device dark current is as low as 0.18 nA cm-2 at − 2 V bias, contributing to an ultrahigh light-to-dark current ratio (Ilight/Idark) of 1.1 × 105 under 5.5 mW cm-2 illumination. The device also exhibits a high responsivity of 455.3 mA W-1 and specific detectivity of 8.69 × 1012 Jones. Meanwhile, under 80% strain conditions, the device have shown negligible performance drop, especially in the aspect of Ilight/Idark. Our work reports a novel growth process that leads to intriguing 3D perovskite nanostructures with unique mechanical flexibility and stretchability, in addition to high optoelectronic sensing performance. These appealing properties can find applications in high-performance stretchable and wearable optoelectronics in the future.

Novel cells integrated biosensor based on superoxide dismutase on electrospun fiber scaffolds for the electrochemical screening of cellular stress

A novel electrochemical biosensor was developed to monitor fibroblast cells stress levels for the first time in situ under external stimuli based on the recognition of superoxide anion released upon cell damage. The biosensor comprised metallized polycaprolactone electrospun fibers covered with zinc oxide for improved cell adhesion and signal transduction, whilst stable bioconjugates of mercaptobenzoic acid-functionalized gold nanoparticles/superoxide dismutase were employed as recognition bioelements. Biosensors were first tested and optimized for in situ generated superoxide detection by fixed potential amperometry at +0.3 V, with minimal interferences from electroactive species in cell culture media. L929 fibroblast cells were then implanted on the optimized biosensor surface and the biosensor morphologically characterized by scanning electron microscopy (SEM) and fluorescence microscopy, which illustrated the network-type pattern of fibroblasts adjacent to the fiber scaffold. Fibroblast stress was induced by zymosan and monitored at the cells integrated biosensor using fixed potential amperometry (CA) with a sensitivity of 26 nA cm-2 μg mL-1 zymosan and electrochemical impedance spectroscopy (EIS), with similar sensitivity of the biosensor considering the Rs and Z’ parameters of around 0.13 Ω cm2 μg-1 mL and high correlation factors R2 of 0.9994. The obtained results underline the applicability of the here developed biosensor for the electrochemical screening of the fibroblast cells stress. The concept in using low-cost biocompatible polymeric fibers as versatile scaffolds for both enzyme immobilization and cell adhesion, opens a new path in developing biosensors for the in-situ investigation of a variety of cellular events.

Dual-Band, Efficient Self-Powered Organic Photodetectors with Isotype Subphthalocyanine-Based Heterojunctions toward Secure Optical Communications

High-performance heterojunction organic photodetectors (OPDs) are of great significance in optical detecting technology due to their tailorable optoelectronic properties. Herein, we designed and synthesized three n-type subphthalocyanine (SubPc) derivatives PhO-BSubPcF12, CHO-PhO-BSubPcF12, and NO2-PhO-BSubPcF12 via axial nonhalogen substitution on fluorinated SubPc. These SubPc derivatives exhibit improved intramolecular charge transfer, high electron mobilities, optimized energy levels, and good thermal stability. The novel isotype p-n SubPc heterojunctions are evaluated as photosensitive layers in OPDs, which show a UV-visible dual-band response and self-powered effect. The optimal OPD with Br-BSubPc/NO2-PhO-BSubPcF12 presents stable and superior performances with a high responsivity (R) of 0.14 A W-1, a peak external quantum efficiency (EQE) of 30.6%, and an extremely low dark current of 0.92 nA cm-2 under a 570-595 nm illumination without a bias voltage. It has outperformed most of the reported SubPc-based OPDs. The better interfacial contact of p-n SubPc derivatives leads to a large depletion region with decreased trap densities as well as a low carrier recombination rate, which is conducive to the photoinduced carriers' separation and well-balanced transport, resulting in high device performances. Moreover, a secure communication strategy is successfully demonstrated by dual-band optimal OPD. This work is expected to provide some guidance for molecular engineering and device performance toward multifunctional electronics.

Interlayer-Assisted Growth of Si-Based All-Inorganic Perovskite Films via Chemical Vapor Deposition for Sensitive and Stable X-ray Detection.

All-inorganic perovskites are considered as preferred materials for next-generation X-ray detectors. However, preparing high-quality thick films by traditional solution-based methods remains challenging due to the low solubility of the precursors. In this work, chemical vapor deposition technology is employed to grow Si-based all-inorganic cesium-lead-bromide perovskite thick films. By introducing a SnO2 nanocrystal interlayer onto the Si substrate to facilitate the heterogeneous nucleation of the perovskite, we are able to grow high-quality films with a smooth surface and compact grains at a relatively low substrate temperature of 260 °C. The resultant X-ray detectors exhibit a decent sensitivity of 2930 μC Gyair-1 cm-2, a small dark current density of 1.5 nA cm-2, and a low detection limit of 120 nGyair s-1. Moreover, the devices show excellent biasing stability with a record small baseline drift of 4.6 × 10-9 nA cm-1 s-1 V-1 under a large electric field of 1100 V/cm among all perovskite polycrystalline film-based detectors ever reported.

Photosystem II in bio-photovoltaic devices

Hybrid photoelectrodes containing biological pigment-protein complexes can be used for environmentally friendly solar energy conversion, herbicide detection, and other applications. The total number of scientific publications on hybrid bio-based devices has grown rapidly over the past decades. Particular attention is paid to the integration of the complexes of PSII into photoelectrochemical devices. A notable feature of these complexes from a practical point of view is their ability to obtain electrons from abundant water. The utilization or imitation of the PSII functionality seems promising for all of the following: generating photoelectricity, photo-producing hydrogen, and detecting herbicides. This review summarizes recent advances in the development of hybrid devices based on PSII. In a brief historical review, we also highlighted the use of quinone-type bacterial reaction centers in hybrid devices. These proteins are the first from which the photoelectricity signal was detected. The photocurrent in these first systems, developed in the 70s-80s, was about 1 nA cm-2. In the latest work, by GĂźzel et al. (2020), a stable current of about 888 &mu;A cm-2 as achieved in a PSII-based solar cell. The present review is inspired by this impressive progress. The advantages, disadvantages, and future endeavors of PSII-inspired bio-photovoltaic devices are also presented.

Unprecedented Self-Powered Visible-Infrared Dual-Modal Photodetection Induced by a Bulk Photovoltaic Effect in a Polar Perovskite.

Visible-infrared dual-modal light harvesting is crucial for various optoelectronic devices, particularly for solar cells and photodetectors. Hybrid metal-halide perovskites are recently emerging for visible-infrared dual-modal photodetection owing to their prominent multiphoton absorption and carrier transport performances. However, they work relying on an applied external power source or complicated heterostructures. It is still a difficult task to realize visible-infrared dual-modal self-powered photoresponse induced by a bulk photovoltaic effect (BPVE) in a single material. In this work, we constructed a polar multilayered perovskite, (Br-BA)2(EA)2Pb3Br10 (BEP; EA+ = ethylammonium, and Br-BA+ = 4-brombutylammonium). Notably, the polar feature endows BEP with a BPVE. In addition, BEP presents a distinctive two-photon activity arising from the layered quantum-well structure. Benefitting from these striking characteristics, self-powered visible-infrared dual-modal photodetection is realized, and a direct self-powered detection of 800 nm light with a photocurrent of 2.1 nA cm-2 is achieved. This work will inspire the design of desired photoelectric materials with a BPVE for high-performance self-powered visible-infrared dual-modal photodetection.

0D structured Cs4PbI6 single crystals for highly performance UV photodetection

In this work, a high-performance and stable UV photodetector is reported that is based on solution-processed lead bulk Cs4PbI6 single crystals. The Cs4PbI6 single crystals are demonstrated with unique 0D structural and high visible transparent with the wide optical bandgap at 3.46 eV. The crystals exhibit excellent electrical properties with a large μτ value of 9.5 × 10-4 cm2 V-1 and a low trap density of 1.7 × 1010 cm-3. Further, a symmetrical Au-semiconductor-Au structured ultraviolet photodetector based on Cs4PbI6 single crystals has been achieved. The device has been demonstrated with good UV detection performances at 1 V bias: low dark current density of 63.6 nA cm-2, the ratio of the photocurrent to the dark current was about 728 times, fast time profile (response time and recovery time are 11.65 and 12.80 μs, respectively), high UV response (responsivity of 5.07 mA W-1). In addition, the device has good environmental stability under the temperature from 303 K to 404 K and air. This work proves that Cs4PbI6 is a competitive candidate for ultraviolet photon detectors with high detection performance and strong environmental stability.

Energy-Level Manipulation in Novel Indacenodithiophene-Based Donor–Acceptor Polymers for Near-Infrared Organic Photodetectors

Organic photodetectors (OPDs) are promising candidates for next-generation digital imaging and wearable sensors due to their low cost, tuneable optoelectrical properties combined with high-level performance, and solution-processed fabrication techniques. However, OPD detection is often limited to shorter wavelengths, whereas photodetection in the near-infrared (NIR) region is increasingly being required for wearable electronics and medical device applications. NIR sensing suffers from low responsivity and high dark currents. A common approach to enhance NIR photon detection is lowering the optical band gap via donor-acceptor (D-A) molecular engineering. Herein, we present the synthesis of two novel indacenodithiophene (IDT)-based D-A conjugated polymers, namely, PDPPy-IT and PSNT-IT via palladium-catalyzed Stille coupling reactions. These novel polymers exhibit optical band gaps of 1.81 and 1.27 eV for PDPPy-IT and PSNT-IT, respectively, with highly desirable visible and NIR light detection through energy-level manipulation. Moreover, excellent materials' solubility and thin-film processability allow easy incorporation of these polymers as an active layer into OPDs for light detection. In the case of PSNT-IT devices, a photodetection up to 1000 nm is demonstrated with a peak sensitivity centered at 875 nm, whereas PDPPy-IT devices are efficient in detecting the visible spectrum with the highest sensitivity at 660 nm. Overall, both OPDs exhibit spectral responsivities up to 0.11 A W-1 and dark currents in the nA cm-2 range. With linear dynamic ranges exceeding 140 dB and fast response times recorded below 100 μs, the use of novel IDT-based polymers in OPDs shows great potential for wearable optoelectronics.

Mitigating Dark Current for High-Performance Near-Infrared Organic Photodiodes via Charge Blocking and Defect Passivation.

Thin-film organic near-infrared (NIR) photodiodes can be essential building blocks in the rapidly emerging fields including the internet of things and wearable electronics. However, the demonstration of NIR organic photodiodes with not only high responsivity but also low dark current density that is comparable to that of inorganic photodiodes, for example, below 1 nA cm-2 for silicon photodiodes, remains a challenge. In this work, we have demonstrated non-fullerene acceptor-based NIR photodiodes with an ultralow dark current density of 0.2 nA cm-2 at -2 V by innovating on charge transport layers to mitigate the reverse charge injection and interfacial defect-induced current generation. The same device also shows a high external quantum efficiency approaching 70% at 850 nm and a specific detectivity of over 1013 Jones at wavelengths up to 940 nm. Furthermore, the versatility of our approach for mitigating dark current is demonstrated using a NIR photodetector utilizing different non-fullerene systems. Finally, the practical application of NIR organic photodiodes is demonstrated with an image sensor integrated on a silicon CMOS readout. This work provides new insight into the device stack design of low-dark current NIR organic photodiodes for weak light detection.

Ionic Liquid-Assisted 3D Printing of Self-Polarized β-PVDF for Flexible Piezoelectric Energy Harvesting.

Three-dimensional (3D) printing technologies have unparalleled advantages in constructing piezoelectric devices with three-dimensional structures, which are conducive to improving the efficiency of energy harvesting. Among them, fused deposition modeling (FDM) is the most widely used thanks to its low cost and wide range of molding materials. However, as the best piezoelectric polymer, a high electroactive β-phase poly(vinylidene fluoride) (PVDF) piezoelectric device cannot be directly obtained by FDM printing because the β-crystal is unstable at the molten state. Herein, we develop for the first time ionic liquid (IL)-assisted FDM for direct printing of β-PVDF piezoelectric devices. An IL can induce and maintain β crystals during melt extrusion and FDM printing, ensuring that the β-crystal in the printed PVDF device is as high as 98.3%, which is the highest in 3D-printed PVDF as far as we know. Furthermore, the shearing force provided by the FDM facilitates the directional arrangement of the dipoles, resulting in the printed PVDF device having self-polarization characteristics without poling. Finally, the piezoelectric output voltage of the 3D-printed PVDF device is 4.7 times that of the flat PVDF device, and its area current density (17.5 nA cm-2) is more than that of the reported 3D-printed PVDF piezoelectric device in the literature by two orders of magnitude. The one-step 3D printing strategy proposed in this paper can realize the rapid preparation of complex-shaped and lightweight self-polarized β-PVDF-based piezoelectric devices for energy harvesting.

Photovoltaic properties in an orthorhombic Fe doped KTN single crystal.

Since the domain wall photovoltaic effect (DW-PVE) is reported in BiFeO3 film, the investigations on photovoltaic properties in ferroelectrics have appealed more and more attention. In this work, we employed two Fe doped KTa1-xNbxO3 (Fe:KTN) single crystals in tetragonal phase and orthorhombic phase, respectively, possessing similar net polarization along [001]C direction, to quantize the contribution on photovoltaic properties from bulk photovoltaic effect (BPVE) and DW-PVE in Fe:KTN. The results show that there are significant enhancements of open-circuit voltages (VOC = -6.0 V, increases over 440%) and short-circuit current density (JSC = 18.5 nA cm-2, increases over 1580%) in orthorhombic Fe:KTN with engineer-domain structure after poled, corresponding to 14.2 mV and 2.2 mV for the single domain wall and bulk region under illumination of 405 nm light (100 mW). It reveals that DW-PVE plays a major role in KTN-based ferroelectrics, indicating an orthorhombic Fe:KTN single crystal is one of the potential photovoltaic materials.