Probing the Critical Role of Interfaces for Superior Performance in PbS Quantum Dot/Graphene Nanohybrid Broadband Photodetectors.

Colloidal quantum dots/graphene (QD/Gr) nanohybrids have been studied intensively for photodetection in a broadband spectrum including ultraviolet, visible, near-infrared, and shortwave infrared (UV-vis-NIR-SWIR). Since the optoelectronic process in the QD/Gr nanohybrid relies on the photogenerated charge carrier transfer from QDs to graphene, understanding the role of the QD-QD and QD-Gr interfaces is imperative to the QD/Gr nanohybrid photodetection. Herein, a systematic study is carried out to probe the effect of these interfaces on the noise, photoresponse, and specific detectivity in the UV-vis-NIR-SWIR spectrum. Interestingly, the photoresponse has been found to be negligible without a 3-mercaptopropionic acid (MPA) ligand exchange, moderate with a single ligand exchange after all QD layers are deposited on graphene, and maximum if it is performed after each QD layer deposition up to five layers of total QD thickness of 260-280 nm. Furthermore, exposure of graphene to C-band UV (UVC) for a short period of 4-5 min before QD deposition leads to improved photoresponse via removal of polar molecules at the QD/Gr interface. With the combination of the MPA ligand exchange and UVC exposure, optimal optoelectronic properties can be obtained on the PbS QD/Gr nanohybrids with high specific detectivity up to 2.6 × 1011, 1.5 × 1011, 5 × 1010, and 1.9 × 109 Jones at 400, 550, 1000, and 1700 nm, respectively, making the nanohybrids promising for broadband photodetection.

Agricultural land management and rural financial development: coupling and coordinated relationship and temporal-spatial disparities in China.

The integrated development of agricultural land and finance not only promotes rural financial innovation and breaks the bottleneck of agricultural financing but also facilitates agricultural land transfer and scaled operations. This leads to the advancement of the effective growth of contemporary agriculture. The reform of the 'separation of three rights' in agricultural land promotes land circulation, which, in turn, offers an institutional guarantee for the tandem development of rural finance and agricultural land management. This paper measures the comprehensive development index of agricultural land management and rural finance in 30 provinces of China from 2005 to 2020. In light of this, it calculates the degree of coupling and coordination between China's agricultural land management and rural financial development. The Dagum Gini coefficient, kernel density, and the Moran index were used to analyze regional differences and patterns of agglomeration. The study found that the degree of coupling coordination between China's agricultural land management and rural finance is increasing annually. However, there remains a significant gap in achieving high-quality coupling. Notably, the growth rate of rural financial development exceeds that of agricultural land management, and hypervariable density is a major source of regional variation. There is polarization in the coupled development of farmland management and rural finance. Provinces in the eastern and central regions tend to be located in the high-high agglomeration (H-H) in terms of the level of development of agricultural land and financial integration, while the western region tends to fall in low-low aggregation (L-L).

Digital inclusive finance & the high-quality agricultural development: Prevalence of regional heterogeneity in rural China.

Developing digital inclusive finance is one of the most effective ways to alleviate financial exclusion in the agriculture sector. For empirical investigation, data from 30 provinces of Rural China is collected from the period 2011 to 2020. The study constructs five dimensions and 22 indicators in total to critically conduct the impact of digital inclusive finance on high-quality agricultural development. The level of agricultural development is measured by entropy weight TOPSIS, and the impact of digital inclusive finance on its high-quality development is empirically tested. The results show that digital inclusive finance has significantly improved the agricultural sector and, particularly, the Eastern region of China has the greatest impact. Three dimensions of digital inclusion finance have regional heterogeneity in terms of impact on agricultural development in Rural China. Data does not show the simple linear relationship between digital inclusion finance and agricultural development quality. The impact of the former on the latter is characterized by the double thresholds. The digital inclusive finance index is the weakest when it is lower than the first threshold that is 4.7704, and the impact of the second threshold that is 5.3186 on high-quality agricultural development is gradually enhanced. After crossing the second threshold, the impact of digital inclusive finance on high-quality agricultural development in Rural China is significantly enhanced. The development of digital inclusive finance should be strengthened in the Central and Western regions to compensate for regional financial imbalances and promote synergy in the high-quality development of agriculture across the country.

Localized Surface Plasmon Resonance Enhanced Light Absorption in AuCu/CsPbCl3 Core/Shell Nanocrystals.

Localized surface plasmon resonance (LSPR) is shown to be effective in trapping light for enhanced light absorption and hence performance in photonic and optoelectronic devices. Implementation of LSPR in all-inorganic perovskite nanocrystals (PNCs) is particularly important considering their unique advantages in optoelectronics. Motivated by this, the first success in colloidal synthesis of AuCu/CsPbCl3 core/shell PNCs and observation of enhanced light absorption by the perovskite CsPbCl3 shell of thickness in the range of 2-4 nm, enabled by the LSPR AuCu core of an average diameter of 7.1 nm, is reported. This enhanced light absorption leads to a remarkably enhanced photoresponse in PNCs/graphene nanohybrid photodetectors using the AuCu/CsPbCl3 core/shell PNCs, by more than 30 times as compared to the counterparts with CsPbCl3 PNCs only (8-12 nm in dimension). This result illustrates the feasibility in implementation of LSPR light trapping directly in core/shell PNCs for high-performance optoelectronics.

Plasmonic WS2 Nanodiscs/Graphene van der Waals Heterostructure Photodetectors.

Two-dimensional material van der Waals (vdW) heterostructures provide an excellent platform for design of novel optoelectronics. In this work, transition-metal dichalcogenide WS2 nanodiscs (WS2-NDs) of lateral dimension of 200-400 nm and layer number of 4-7 were synthesized on graphene using a layer-by-layer, transfer-free chemical vapor deposition. On this WS2-NDs/graphene vdW heterostructures, localized surface plasmonic resonance (LSPR) was achieved, resulting in remarkably enhanced light absorption as compared to the counterpart devices with a continuous WS2 layer (WS2-CL/graphene). Remarkably, the photoresponsivity of 6.4 A/W on the WS2-NDs/graphene photodetectors is seven times higher than that (0.91 A/W) of the WS2-CL/graphene vdW heterostructures at an incident 550 nm light intensity of 10 µW/cm2. Furthermore, the WS2-NDs/graphene photodetectors exhibit higher sensitivity to lower lights. Under 550 nm light illumination of 3 µW/cm2, which is beyond the sensitivity limit of the WS2-CL/graphene photodetectors, high photoresponsivity of 8.05 A/W and detectivity of 2.8 × 1010 Jones are achieved at Vsd = 5 V. This result demonstrates that the LSPR WS2-NDs/graphene vdW heterostructure is promising for scalable high-performance optoelectronics applications.

Using Silver Nanoparticles-Embedded Silica Metafilms as Substrates to Enhance the Performance of Perovskite Photodetectors.

Plasmonic metal nanostructures provide a promising strategy for light trapping and therefore can dramatically enhance photocurrent in optoelectronics only if the trapped light can be coupled effectively from plasmons to excitons, whereas the reverse transfer of energy, charge, and heat from excitons to plasmons can be suppressed. Motivated by this, this work develops a scheme to implement a metafilm with Ag nanoparticles (NPs) embedded in 10 nm thick silica (Ag NPs-silica metafilm) to the active device channel of a hybrid perovskite film/graphene photodetector. Remarkably, an enhancement factor of 7.45 in photoresponsivity, the highest so far among all the reports adopting plasmonic metal NPs in perovskite photodetectors, has been achieved on the photodetectors with the Ag NPs-silica metafilms. Considering that the synthesis of the Ag NPs-silica metafilms can be readily scaled up to coat both rigid and flexible substrates, this result provides a low-cost metaplatform for a variety of high-performance optoelectronic device applications.

Controllable Synthesis of Monodispersed Fe1- xS2 Nanocrystals for High-Performance Optoelectronic Devices.

The optical properties of stoichiometric iron pyrite (FeS2) nanocrystals (NCs) are characterized by strong UV-Visible (UV-Vis) absorption within the cutoff while negligible absorption beyond the cutoff in near-infrared and longer wavelengths. Herein, we show this bandgap limitation can be broken through controllable synthesis of nonstoichiometric Fe1- xS2 NCs ( x = 0.01-0.107) to induce localized surface plasmonic resonance (LSPR) absorption beyond the cutoff to short-wave infrared spectrum (SWIR, 1-3 µm) with remarkably enhanced broadband absorption across UV-Vis-SWIR spectra. To illustrate the benefit of the broadband absorption, colloidal LSPR Fe1- xS2 NCs were printed on graphene to form LSPR Fe1- xS2 NCs/graphene heterostructure photodetectors. Extraordinary photoresponsivity in exceeding 4.32 × 106 A/W and figure-of-merit detectivity D* > 7.50 × 1012 Jones have been demonstrated in the broadband of UV-Vis-SWIR at room temperature. These Fe1- xS2 NCs/graphene heterostructures are printable and flexible and therefore promising for practical optical and optoelectronic applications.

Surface plasmon assisted laser ablation of stainless steel.

Colloidal Au nanoparticles (NPs) were decorated on stainless steel for surface plasmon enhanced laser ablation. A comparative study of the laser ablation efficiency was carried out on stainless steel samples with and without the Au NPs decoration at a variable pulsed laser fluence and laser pulse number. Higher ablation efficiency was clearly demonstrated in the former as illustrated from the larger diameter, maximum depth and the cross-sectional area of the crater generated by the laser ablation under the same conditions. Additionally, both the maximum depth and efficiency enhancement were found to depend on the laser fluence and pulse number. The maximum enhanced ablation efficiency of 36% based on the cross-sectional area of the crater was obtained at 1 pulse number of laser fluence 1.53 J cm-2. The efficiency enhancement of laser ablation is attributed to the highly enhanced surface plasmon field at the interface between Au NPs and stainless steel.

High-Performance All-Inorganic CsPbCl3 Perovskite Nanocrystal Photodetectors with Superior Stability.

All-inorganic perovskites nanostructures, such as CsPbCl3 nanocrystals (NCs), are promising in many applications including light-emitting diodes, photovoltaics, and photodetectors. Despite the impressive performance that was demonstrated, a critical issue remains due to the instability of the perovskites in ambient. Herein, we report a method of passivating crystalline CsPbCl3 NC surfaces with 3-mercaptopropionic acid (MPA), and superior ambient stability is achieved. The printing of these colloidal NCs on the channel of graphene field-effect transistors (GFETs) on solid Si/SiO2 and flexible polyethylene terephthalate substrates was carried out to obtain CsPbCl3 NCs/GFET heterojunction photodetectors for flexible and visible-blind ultraviolet detection at wavelength below 400 nm. Besides ambient stability, the additional benefits of passivating surface charge trapping by the defects on CsPbCl3 NCs and facilitating high-efficiency charge transfer between the CsPbCl3 NCs and graphene were provided by MPA. Extraordinary optoelectronic performance was obtained on the CsPbCl3 NCs/graphene devices including a high ultraviolet responsivity exceeding 106 A/W, a high detectivity of 2 × 1013 Jones, a fast photoresponse time of 0.3 s, and ambient stability with less than 10% degradation of photoresponse after 2400 h. This result demonstrates the crucial importance of the perovskite NC surface passivation not only to the performance but also to the stability of the perovskite optoelectronic devices.

Inkjet-Printed Imbedded Graphene Nanoplatelet/Zinc Oxide Bulk Heterojunctions Nanocomposite Films for Ultraviolet Photodetection.

A ZnO sol-gel precursor (ZnOPr) and graphene nanoplatelets (GnPs) are mixed into a composite ink for inkjet printing photodetectors with bulk heterojunctions of ZnO/GnP on a heated SiO2/Si substrate. Heating of the SiO2/Si wafers at ∼50 °C was found optimal to prevent segregated droplets on the hydrophobic surface of the SiO2/Si substrate during printing. After printing the ZnO/GnP channels, thermal annealing at 350 °C for 2 h was performed for crystallization of ZnO and formation of the ZnO/GnP heterojunctions. The GnP concentration was varied from 0, 5, 20, and 30 mM to evaluate optimal formation of the ZnO/GnP bulk heterojunction nanocomposites based on ultraviolet photoresponse performance. The best performance was observed at the 20 mM GnP concentration with the photoresponsivity reaching 2.2 A/W at an incident ultraviolet power of 2.2 µW and a 5 V bias. This photoresponsivity is an order of magnitude better than the previously reported counterparts, including 0.13 mA/W for dropcasted ZnO-graphite composites and much higher than 0.5 A/W for aerosol printed ZnO. The improved performance is attributed to the ZnO/GnP bulk heterojunctions with improved interfaces that enable efficient exciton dissociation and the charge transport. The developed inkjet printing of sol-gel composite inks approach can be scalable and low cost for practical applications.

Magnetic field-directed hybrid anisotropic nanocomposites.

A facile bottom-up approach is developed to grow magnetic metallic Cu/FeCo (core/shell) nanowires, where their distribution and orientation can be controlled by magnetic field. The nanocomposites consisting of a ferroelectric polymer matrix and magnetic nanowire arrays exhibit the orientation-controlled anisotropy and interfacial magnetoelectric coupling effect.

High-Sensitivity Light Detection via Gate Tuning of Organometallic Perovskite/PCBM Bulk Heterojunctions on Ferroelectric Pb0.92La0.08Zr0.52Ti0.48O3 Gated Graphene Field Effect Transistors.

Organometallic perovskite (OMP) CH3NH3PbI3 doped with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has been shown to form bulk heterojunction (OMP-PCBM BHJ) for improved charge separation. In this work, the OMP-PCBM BHJ photosensitizer is combined with graphene field effect transistors (GFETs) with a ferroelectric Pb0.92La0.08Zr0.52Ti0.48O3 gate of high gating efficiency. A remarkable gate tunability via shifting the Fermi energy of graphene with respect to the valence band maximum and conduction band minimum of the OMP was observed, which is critical for facilitating efficient charge transfer across the OMP-PCBM BHJ/GFET interface. The combination of the high-efficiency charge separation by BHJ and charge transfer by high gate tunability leads to achievement of high photoresponsivity up to 7 × 106 A/W and detectivity exceeding 7 × 1012 Jones at 550 nm at a small gate voltage of 1.0 V. These results represent almost 2 orders of magnitude improvement over that without a gate tuning under the similar experimental condition, illustrating the importance of the interface electronic structure in optimizing the optoelectronic performance of the OMP-PCBM BHJ/GFET devices.

Printable Nanocomposite FeS2-PbS Nanocrystals/Graphene Heterojunction Photodetectors for Broadband Photodetection.

Colloidal nanocrystals are attractive materials for optoelectronics applications because they offer a compelling combination of low-cost solution processing, printability, and spectral tunability through the quantum dot size effect. Here we explore a novel nanocomposite photosensitizer consisting of colloidal nanocrystals of FeS2 and PbS with complementary optical and microstructural properties for broadband photodetection. Using a newly developed ligand exchange to achieve high-efficiency charge transfer across the nanocomposite FeS2-PbS sensitizer and graphene on the FeS2-PbS/graphene photoconductors, an extraordinary photoresponsivity in exceeding ∼106 A/W was obtained in an ultrabroad spectrum of ultraviolet (UV)-visible-near-infrared (NIR). This is in contrast to the nearly 3 orders of magnitude reduction of the photoresponsivity from ∼106 A/W at UV to 103 A/W at NIR on their counterpart of FeS2/graphene detectors. This illustrates the combined advantages of the nanocomposite sensitizers and the high charge mobility in FeS2-PbS/graphene van der Waals heterostructures for nanohybrid optoelectronics with high performance, low cost, and scalability for commercialization.

Quantum Dots-Facilitated Printing of ZnO Nanostructure Photodetectors with Improved Performance.

A nanocomposite ink composed of zinc oxide precursor (ZnOPr) and crystalline ZnO quantum dots (ZnOPrQDs) has been explored for printing high-performance ultraviolet (UV) photodetectors. The performance of the devices has been compared with their counterparts' printed from ZnOPr ink without ZnO QDs. Remarkably, higher UV photoresponsivity of 383.6 A/W and the on/off ratio of 2470 are observed in the former, which are significantly better than 14.7 A/W and 949 in the latter. The improved performance is attributed to the increased viscosity in the nanocomposite ink to enable a nanoporous structure with improved crystallinity and surface-to-volume ratio. This is key to enhanced surface electron-depletion effect for higher UV responsivity and on/off ratio. In addition, the QD-assisted printing provides a simple and robust method for printing high-performance optoelectronics and sensors.

Designing the Interface of Carbon Nanotube/Biomaterials for High-Performance Ultra-Broadband Photodetection.

Inorganic/biomolecule nanohybrids can combine superior electronic and optical properties of inorganic nanostructures and biomolecules for optoelectronics with performance far surpassing that achievable in conventional materials. The key toward a high-performance inorganic/biomolecule nanohybrid is to design their interface based on the electronic structures of the constituents. A major challenge is the lack of knowledge of most biomolecules due to their complex structures and composition. Here, we first calculated the electronic structure and optical properties of one of the cytochrome c (Cyt c) macromolecules (PDB ID: 1HRC ) using ab initio OLCAO method, which was followed by experimental confirmation using ultraviolet photoemission spectroscopy. For the first time, the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of Cyt c, a well-known electron transport chain in biological systems, were obtained. On the basis of the result, pairing the Cyt c with semiconductor single-wall carbon nanotubes (s-SWCNT) was predicted to have a favorable band alignment and built-in electrical field for exciton dissociation and charge transfer across the s-SWCNT/Cyt c heterojunction interface. Excitingly, photodetectors based on the s-SWCNT/Cyt c heterojunction nanohybrids demonstrated extraordinary ultra-broadband (visible light to infrared) responsivity (46-188 A W-1) and figure-of-merit detectivity D* (1-6 × 1010 cm Hz1/2 W-1). Moreover, these devices can be fabricated on transparent flexible substrates by a low-lost nonvacuum method and are stable in air. These results suggest that the s-SWCNT/biomolecule nanohybrids may be promising for the development of CNT-based ultra-broadband photodetectors.

Printable Transfer-Free and Wafer-Size MoS2/Graphene van der Waals Heterostructures for High-Performance Photodetection.

Two-dimensional (2D) MoS2/graphene van der Waals heterostructures integrate the superior light-solid interaction in MoS2 and charge mobility in graphene for high-performance optoelectronic devices. Key to the device performance lies in a clean MoS2/graphene interface to facilitate efficient transfer of photogenerated charges. Here, we report a printable and transfer-free process for fabrication of wafer-size MoS2/graphene van der Waals heterostructures obtained using a metal-free-grown graphene, followed by low-temperature growth of MoS2 from the printed thin film of ammonium thiomolybdate on graphene. The photodetectors based on the transfer-free MoS2/graphene heterostructures exhibit extraordinary short photoresponse rise/decay times of 20/30 ms, which are significantly faster than those of the previously reported MoS2/transferred-graphene photodetectors (0.28-1.5 s). In addition, a high photoresponsivity of up to 835 mA/W was observed in the visible spectrum on such transfer-free MoS2/graphene heterostructures, which is much higher than that of the reported photodetectors based on the exfoliated layered MoS2 (0.42 mA/W), the graphene (6.1 mA/W), and transfer-free MoS2/graphene/SiC heterostructures (∼40 mA/W). The enhanced performance is attributed to the clean interface on the transfer-free MoS2/graphene heterostructures. This printable and transfer-free process paves the way for large-scale commercial applications of the emerging 2D heterostructures in optoelectronics and sensors.

All-Printable ZnO Quantum Dots/Graphene van der Waals Heterostructures for Ultrasensitive Detection of Ultraviolet Light.

In ZnO quantum dot/graphene heterojunction photodetectors, fabricated by printing quantum dots (QDs) directly on the graphene field-effect transistor (GFET) channel, the combination of the strong quantum confinement in ZnO QDs and the high charge mobility in graphene allows extraordinary quantum efficiency (or photoconductive gain) in visible-blind ultraviolet (UV) detection. Key to the high performance is a clean van der Waals interface to facilitate an efficient charge transfer from ZnO QDs to graphene upon UV illumination. Here, we report a robust ZnO QD surface activation process and demonstrate that a transition from zero to extraordinarily high photoresponsivity of 9.9 × 108 A/W and a photoconductive gain of 3.6 × 109 can be obtained in ZnO QDs/GFET heterojunction photodetectors, as the ZnO QDs surface is systematically engineered using this process. The high figure-of-merit UV detectivity D* in exceeding 1 × 1014 Jones represents more than 1 order of magnitude improvement over the best reported previously on ZnO nanostructure-based UV detectors. This result not only sheds light on the critical role of the van der Waals interface in affecting the optoelectronic process in ZnO QDs/GFET heterojunction photodetectors but also demonstrates the viability of printing quantum devices of high performance and low cost.

Colorful Hydrophobic Poly(Vinyl Butyral)/Cationic Dye Fibrous Membranes via a Colored Solution Electrospinning Process.

Colorful nanofibrous membranes have attracted much attention for their visual varieties and various functionalities. In this article, a colored solution electrospinning process was used to fabricate colorful hydrophobic poly(vinyl butyral) (PVB)/cationic dye nanofibrous membranes (NFMs) successfully. The color and morphology of these as-spun nanofibrous membranes have been analyzed by colorimetry, spectroscopy, and scanning electron microscopy (SEM). It is shown that the as-spun colorful PVB-based membranes exhibit excellent level-dyeing property and color stability. Furthermore, the doping of cationic dye and the increase of dye concentration can decrease the diameter of the as-spun colored fibers, which results in better level-dyeing property and higher water contact angle more than 140°. The stained PVB fibrous membranes with excellent level-dyeing property and hydrophobicity are promising in some applications such as textiles, wallpapers, and anticorrosive coating/painting.

Fabrication of Continuous Microfibers Containing Magnetic Nanoparticles by a Facile Magneto-Mechanical Drawing.

A facile method termed magneto-mechanical drawing is used to produce polymer composite microfibers. Compared with electrospinning and other fiber spinning methods, magneto-mechanical drawing uses magnetic force generated by a permanent magnet to draw droplets of polymer/magnetic nanoparticle suspensions, leading to fabrication of composite microfibers. In addition, because of the rotating collector, it is easy to control the fiber assembly such as fibrous array in parallel or crossed fibrous structure. The general applicability of this method has also been proved by spinning different polymers and magnetic nanoparticles. The resultant fibers exhibit good superparamagnetic behavior at room temperature and ultrahigh stretchability (~443.8 %). The results indicate that magneto-mechanical drawing is a promising technique to fabricate magnetic and stretchable microfibers and devices.

Magnetic dipolar interaction induced cobalt nanowires.

The dipolar interaction of magnetic nanoparticles is of intense interest to engineer material self-assembly for anisotropic functional nanostructures. Here we report the solution synthesis of cobalt nanowires, where the one-dimensional nanowire formation is ultimately dependent on the magnetic dipolar interaction to realize in situ assembly of cobalt nanoparticles. The morphology transition of cobalt nanostructures is well controlled via the ligand-free synthesis and thermal decomposition of zero-valent cobalt precursor. This study provides a self-assembly approach to the development of anisotropic cobalt nanostructures and a better understanding of nucleation parameters, which are demonstrated to correlate strongly with the size and morphology of final cobalt nanowires. This approach may be extended to other magnetic materials for the control of their nanostructure and magnetic performance.