Sputtering onto liquids: a critical review

Sputter deposition of atoms onto liquid substrates aims at producing colloidal dispersions of small monodisperse ultrapure nanoparticles (NPs). Since sputtering onto liquids combines the advantages of the physical vapor deposition technique and classical colloidal synthesis, the review contains chapters explaining the basics of (magnetron) sputter deposition and the formation of NPs in solution. This review article covers more than 132 papers published on this topic from 1996 to September 2021 and aims at providing a critical analysis of most of the reported data; we will address the influence of the sputtering parameters (sputter power, current, voltage, sputter time, working gas pressure, and the type of sputtering plasma) and host liquid properties (composition, temperature, viscosity, and surface tension) on the NP formation as well as a detailed overview of the properties and applications of the produced NPs.

Heat-Up Colloidal Synthesis of Shape-Controlled Cu-Se-S Nanostructures—Role of Precursor and Surfactant Reactivity and Performance in N2 Electroreduction

Copper selenide-sulfide nanostructures were synthesized using metal-organic chemical routes in the presence of Cu- and Se-precursors as well as S-containing compounds. Our goal was first to examine if the initial Cu/Se 1:1 molar proportion in the starting reagents would always lead to equiatomic composition in the final product, depending on other synthesis parameters which affect the reagents reactivity. Such reaction conditions were the types of precursors, surfactants and other reagents, as well as the synthesis temperature. The use of ‘hot-injection’ processes was avoided, focusing on ‘non-injection’ ones; that is, only heat-up protocols were employed, which have the advantage of simple operation and scalability. All reagents were mixed at room temperature followed by further heating to a selected high temperature. It was found that for samples with particles of bigger size and anisotropic shape the CuSe composition was favored, whereas particles with smaller size and spherical shape possessed a Cu2−xSe phase, especially when no sulfur was present. Apart from elemental Se, Al2Se3 was used as an efficient selenium source for the first time for the acquisition of copper selenide nanostructures. The use of dodecanethiol in the presence of trioctylphosphine and elemental Se promoted the incorporation of sulfur in the materials crystal lattice, leading to Cu-Se-S compositions. A variety of techniques were used to characterize the formed nanomaterials such as XRD, TEM, HRTEM, STEM-EDX, AFM and UV-Vis-NIR. Promising results, especially for thin anisotropic nanoplates for use as electrocatalysts in nitrogen reduction reaction (NRR), were obtained.

Device Applications of Solution Processed MIR Semiconductor Nanocrystal Thin Films

<p>Colloidal semiconductor nanocrystals (NCs) with bandgaps less than 1 eV allow the development of mid wave infrared (MIR) sensitive detectors that exploit the benefits of colloidal materials, primarily bandgap selection and solution deposition. Additionally, the electrical behaviour of these films can be examined for characteristics that can increase the functionality of NC based detectors. The production of devices that are designed to be competitive as ultra-low-cost, room temperature MIR detectors, operating with photonic, rather than thermal detection is detailed. The evolution of the colloidal synthesis, spray deposition methods, substrate materials and post deposition treatments used here lead to highly robust and high performing devices. These devices demonstrate a “colour” sensitivity down to 300 nm in the MIR (≈10 % of scale), with superior responsivities for this class of device, up to 0.9 AW⁻¹, and competitive specific detectivity up to 8 × 10⁹ Jones at 200 Hz and 300 K. Furthermore, these devices utilise a cheap and robust substrate material that allows operation after deformation up to 45 ° without degradation over many cycles. These devices offer a template for ultra-low-cost MIR detectors with performance that rivals microbolometers but with better measurement speed and spectral sensitivity. As such these devices showcase the key advantages of using colloidal NCs in MIR applications. Planar and fully air processed thin film devices that demonstrate photo-induced memristive behaviour and can be used as a transistors, photode-tectors or memory devices are investigated. Following long term (60 h) air exposure, unpackaged NC films develop reliable memristive characteristics in tandem with temperature, gate and photoresponse. On/off ratios of more than 50 are achieved and the devices show long term stability, producing repeatable metrics over days of measurement. The on/off behaviour is shown to be dependent on previous charge flow and carrier density, implying memristive rather than switching behaviour. These observations are described within a long term trap filling model. This work represents an advance in the integration of NC films into electronic devices, which may lead to the development of multi-functional electronic components. Building on the previous work the steps taken to move from a planar device, that works well in controlled conditions, to a multi-pixel sensor that can demonstrate MIR video imaging at room temperature in a noisy environment are shown. This is achieved with a 15 pixel detector that consists only of a polymer substrate and solution patterned NC pixels. This device can detect a 373 K object with the device at 298 K in a noisy environment. This performance is enabled by photogain at 5 V bias that reaches a maximum External Quantum Efficiency (EQE) of 1940 ± 290 % for a pixel with a 3.3 µm bandgap. Through the use of four separate bandgaps it is shown that “multicolour” thermal imaging systems can deliver another layer of information, on top of intensity, to the user. The behaviour of the system is examined under use and it is shown that the photoconductive device behaves as expected with regards to bias, and that trap enabled gain is sensitive to total incident flux, more than the spectral energy distribution of the target. Finally, it is shown that solution patterned QD fabrication methods can deliver electrical reproducibility between pixels that is sufficient to allow an imaging plane of multiple pixels. The somewhat neglected tin chalcogenide semiconductor nanocrystals are investigated and inverse MIR detection at room temperature is demonstrated with planar, solution and airprocessed PbSnTe and SnTe QD devices. The detection mechanism is shown to be mediated by an interaction between MIR radiation and the vibrational stretches of adsorbed hydroxyl species at the oxdised NC surface. Devices are shown to possess mAW⁻¹ responsivity via a reduction in film conductance due to MIR radiation and, unlike classic MIR photoconductors, are unaffected by visible wavelengths. As such these devices offer the possibility of MIR thermal imaging that has an intrinsic solution to the blinding caused by higher energy light sources. In summary, it is shown that semiconductor NCs with an all ambient fully solution processed deposition and ligand exchange procedure can be used to create simple, robust and cheap devices that are beginning to demonstrate metrics on par with current commercial thermal detector systems. It is also shown that these devices can under certain circumstances demonstrate novel behaviours that offer the prospects of enhanced or novel functionality.</p>

Device Applications of Solution Processed MIR Semiconductor Nanocrystal Thin Films

<p>Colloidal semiconductor nanocrystals (NCs) with bandgaps less than 1 eV allow the development of mid wave infrared (MIR) sensitive detectors that exploit the benefits of colloidal materials, primarily bandgap selection and solution deposition. Additionally, the electrical behaviour of these films can be examined for characteristics that can increase the functionality of NC based detectors. The production of devices that are designed to be competitive as ultra-low-cost, room temperature MIR detectors, operating with photonic, rather than thermal detection is detailed. The evolution of the colloidal synthesis, spray deposition methods, substrate materials and post deposition treatments used here lead to highly robust and high performing devices. These devices demonstrate a “colour” sensitivity down to 300 nm in the MIR (≈10 % of scale), with superior responsivities for this class of device, up to 0.9 AW⁻¹, and competitive specific detectivity up to 8 × 10⁹ Jones at 200 Hz and 300 K. Furthermore, these devices utilise a cheap and robust substrate material that allows operation after deformation up to 45 ° without degradation over many cycles. These devices offer a template for ultra-low-cost MIR detectors with performance that rivals microbolometers but with better measurement speed and spectral sensitivity. As such these devices showcase the key advantages of using colloidal NCs in MIR applications. Planar and fully air processed thin film devices that demonstrate photo-induced memristive behaviour and can be used as a transistors, photode-tectors or memory devices are investigated. Following long term (60 h) air exposure, unpackaged NC films develop reliable memristive characteristics in tandem with temperature, gate and photoresponse. On/off ratios of more than 50 are achieved and the devices show long term stability, producing repeatable metrics over days of measurement. The on/off behaviour is shown to be dependent on previous charge flow and carrier density, implying memristive rather than switching behaviour. These observations are described within a long term trap filling model. This work represents an advance in the integration of NC films into electronic devices, which may lead to the development of multi-functional electronic components. Building on the previous work the steps taken to move from a planar device, that works well in controlled conditions, to a multi-pixel sensor that can demonstrate MIR video imaging at room temperature in a noisy environment are shown. This is achieved with a 15 pixel detector that consists only of a polymer substrate and solution patterned NC pixels. This device can detect a 373 K object with the device at 298 K in a noisy environment. This performance is enabled by photogain at 5 V bias that reaches a maximum External Quantum Efficiency (EQE) of 1940 ± 290 % for a pixel with a 3.3 µm bandgap. Through the use of four separate bandgaps it is shown that “multicolour” thermal imaging systems can deliver another layer of information, on top of intensity, to the user. The behaviour of the system is examined under use and it is shown that the photoconductive device behaves as expected with regards to bias, and that trap enabled gain is sensitive to total incident flux, more than the spectral energy distribution of the target. Finally, it is shown that solution patterned QD fabrication methods can deliver electrical reproducibility between pixels that is sufficient to allow an imaging plane of multiple pixels. The somewhat neglected tin chalcogenide semiconductor nanocrystals are investigated and inverse MIR detection at room temperature is demonstrated with planar, solution and airprocessed PbSnTe and SnTe QD devices. The detection mechanism is shown to be mediated by an interaction between MIR radiation and the vibrational stretches of adsorbed hydroxyl species at the oxdised NC surface. Devices are shown to possess mAW⁻¹ responsivity via a reduction in film conductance due to MIR radiation and, unlike classic MIR photoconductors, are unaffected by visible wavelengths. As such these devices offer the possibility of MIR thermal imaging that has an intrinsic solution to the blinding caused by higher energy light sources. In summary, it is shown that semiconductor NCs with an all ambient fully solution processed deposition and ligand exchange procedure can be used to create simple, robust and cheap devices that are beginning to demonstrate metrics on par with current commercial thermal detector systems. It is also shown that these devices can under certain circumstances demonstrate novel behaviours that offer the prospects of enhanced or novel functionality.</p>

PHOTOLUMINESCENCE OF NANOCRYSTALLINE CdTe, INTRODUCED INTO POROUS SILICON

A method of colloidal synthesis of monodisperse nanocrystals (NC) with high stability, narrow bands of photoluminescence (PL) and high quantum yield has been developed. The process of colloidal synthesis took place at room temperature and for the passivation of NC used a variety of surfactants. The surface of NC CdTe was modified by introducing them into a matrix, organic or crystalline. In our case, the matrix was porous Silicon (PS), that is a composite structure was formed on the basis of the matrix and NC semiconductor. Nanocomposite structures of PS – NC CdTe were obtained by introducing colloidal solutions of NC CdTe into the solid matrix of PS and subsequent processing at a certain temperature regime. The photoluminescent properties of a composite system in which the matrix is microcrystalline PS and the second component is NC CdTe deposited from a colloidal solution of NC CdTe have been studied. The peculiarity of this system is that both components have PL of different intensities.The large difference in PL intensities and different positions of the radiation bands allowed, comparing the PL spectra of the colloidal solution of NC CdTe, PS and NC CdTe – PS at different stages of introduction of CdTe nanoparticles into the porous Silicon surface, to identify the interaction and mutual influence of the two constituent materials. The main disadvantages of the method are its relative novelty, which leads to the need for empirical selection of some parameters of the synthesis. The planned change of properties of PS and colloidal solutions of NC CdTe by variation of technological methods of synthesis and processing methods will allow to control the physical properties of this composite system and use it to develop new principles of design and creation of new generation sensor devices.

Nanostructured Inorganic Metal Halide Perovskites for Optoelectronic Applications

<p>Semiconductor quantumdots have proven to be promising materials for optoelectronic devices, such as light emitting devices (LEDs) and solar cells, due to their thin linewidth of emission, high photoluminescence quantum yield and high absorption coefficient. Over the last decade, perovskite crystals have gained significant attention due to their extraordinary optoelectronic properties. Therefore, perovskite nanocrystals combine the advantage of both crystalline perovskite and quantum dots. Here, we synthesised high quantum yield (50 - 80 %) monodispersed CsPbX₃ (X= Cl, Br, I) quantum dots, with tuneable emission spectra over the entire visible region, by a colloidal synthesis method. We have then successfully processed them to produce thin films as the emitting layer in an organic LED-type device architecture. Most importantly, we demonstrated field induced halide separation in mixed halide CsPb(Br/I)₃ NCs which is the reason color instability in these LEDs. Perovskite nanocrystal LEDs were found to have low external quantum efficiency (EQE) due to their bulky ligands. As a result, Ruddlesden-Popper (RP) phase layered perovskite was investigated to increase the EQE over perovskite QD LEDs. As a result, we constructed RP perovskite phase CsPbX₃ LEDs with emission through the entire visible spectrum (460-700 nm). Colour tuning was achieved by taking advantage of both quantum confinement effect and halide mixing. The EQE of these LEDs outperformed the literature values in the blue and blue-green spectral regions, with relatively long life time. We also invented a novel perovskite nanocrystals made from thalliumlead halide by replacing caesium with thallium. These materials are potential candidates for various optoelectronic applications. Size-, shape-, and composition- tuning in these nanocrystals were performed by varying the reaction conditions andmixing the halide composition. A weak confinementwas observed in these NCs. Additionally, we have shown the application of TlPbI₃ nanowires as photoconductors. Collectively, this thesis includes the synthesis of various types of inorganic metal halide perovskite nanostructures followed by their implementation into working optoelectronic devices, specifically LEDs.</p>