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.

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.

Heat-Assisted Inkjet Printing of Tungsten Oxide for High-Performance Ultraviolet Photodetectors.

An ammonium metatungstate precursor (WO3Pr) ink was printed for tungsten oxide (WO3) UV detectors on SiO2/Si wafers with prefabricated Au electrodes. A systematic study was carried out on the printing parameters including substrate temperatures in the range of 22-80 °C, WO3Pr molar concentrations of 0.01, 0.02, and 0.03 M, and printing scan numbers up to 7 to understand their effects on the resulted WO3 film morphology and optoelectronic properties. It has been found that the printing parameters can sensitively affect the WO3 film morphology, which in turn impacts the WO3 photodetector performance. In particular, the printed films experienced a systematic change from discontinuous droplets at below 40 °C to continuous films at 40-60 °C of the substrate temperature. At higher temperatures, the excessive heat from the substrate not only caused drastic evaporation of the printed ink, resulting in highly nonuniform films, but also detrimental heating of the ink in the printer nozzle in proximity of the substrate, preventing continuous printing operation. An optimal printing window of the substrate temperature of 45-55 °C at a molar concentration of 0.02 M of ammonium metatungstate and three printing scans was obtained for the best UV detector performance. A large on/off ratio of 3538 and a high responsivity up to 2.70 A/W at 5 V bias (0.54 A/W·V) represent a significant improvement over the best report of ∼0.28 µA/W·V on WOX photodetectors, which indicates that the printed WO3 films are promising for various applications of optoelectronics and sensors.

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.

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.