Near-IR Photoinduced Electrochemiluminescence Imaging with Structured Silicon Photoanodes.

Infrared (IR) imaging devices that convert IR irradiation (invisible to the human eye) to a visible signal are based on solid-state components. Here, we introduce an alternative concept based on light-addressable electrochemistry (i.e., electrochemistry spatially confined under the action of a light stimulus) that involves the use of a liquid electrolyte. In this method, the projection of a near-IR image (λexc = 850 or 840 nm) onto a photoactive Si-based photoanode, immersed into a liquid phase, triggers locally the photoinduced electrochemiluminescence (PECL) of the efficient [Ru(bpy)3]2+-TPrA system. This leads to the local conversion of near-IR light to visible (λPECL = 632 nm) light. We demonstrate that compared to planar Si photoanodes, the use of a micropillar Si array leads to a large enhancement of local light generation and considerably improves the resolution of the PECL image by preventing photogenerated minority carriers from diffusing laterally. These results are important for the design of original light conversion devices and can lead to important applications in photothermal imaging and analytical chemistry.

Nanoparticle Imprint Lithography: From Nanoscale Metrology to Printable Metallic Grids.

Large scale and low-cost nanopatterning of materials is of tremendous interest for optoelectronic devices. Nanoimprint lithography has emerged in recent years as a nanofabrication strategy that is high-throughput and has a resolution comparable to that of electron-beam lithography (EBL). It is enabled by pattern replication of an EBL master into polydimethylsiloxane (PDMS), that is then used to pattern a resist for further processing, or a sol-gel that could be calcinated into a solid material. Although the sol-gel chemistry offers a wide spectrum of material compositions, metals are still difficult to achieve. This gap could be bridged by using colloidal nanoparticles as resist, but deep understanding of the key parameters is still lacking. Here, we use supported metallic nanocubes as a model resist to gain fundamental insights into nanoparticle imprinting. We uncover the major role played by the surfactant layer trapped between nanocubes and substrate, and measure its thickness with subnanometer resolution by using gap plasmon spectroscopy as a metrology platform. This enables us to quantify the van der Waals (VDW) interactions responsible for the friction opposing the nanocube motion, and we find that these are almost in quantitative agreement with the Stokes drag acting on the nanocubes during nanoimprint, that is estimated with a simplified fluid mechanics model. These results reveal that a minimum thickness of surfactant is required, acting as a spacer layer mitigating van der Waals forces between nanocubes and the substrate. In the light of these findings we propose a general method for resist preparation to achieve optimal nanoparticle mobility and show the assembly of printable Ag and Au nanocube grids, that could enable the fabrication of low-cost transparent electrodes of high material quality upon nanocube epitaxy.

Metal-Insulator-Semiconductor Anodes for Ultrastable and Site-Selective Upconversion Photoinduced Electrochemiluminescence.

Photoinduced electrochemiluminescence (PECL) allows the electrochemically assisted conversion of low-energy photons into high-energy photons at an electrode surface. This concept is expected to have important implications, however, it is dramatically limited by the stability of the surface, impeding future developments. Here, a series of metal-insulator-semiconductor (MIS) junctions, using photoactive n-type Si (n-Si) as a light absorber covered by a few-nanometer-thick protective SiOx /metal (SiOx /M, with M=Ru, Pt, and Ir) overlayers are investigated for upconversion PECL of the model co-reactant system involving the simultaneous oxidation of tris(bipyridine)ruthenium(II) and tri-n-propylamine. We show that n-Si/SiOx /Pt and n-Si/SiOx /Ir exhibit high photovoltages and record stabilities in operation (35 h for n-Si/SiOx /Ir) for the generation of intense PECL with an anti-Stokes shift of 218 nm. We also demonstrate that these surfaces can be employed for spatially localized PECL. These unprecedented performances are extremely promising for future applications of PECL.

Ordered SnO2 nanotube arrays of tuneable geometry as a lithium ion battery material with high longevity.

Ordered arrays of straight, parallel SnO2 nanotubes are prepared by atomic layer deposition (ALD) on inert 'anodic' aluminum oxide porous membranes serving as templates. Various thicknesses of the SnO2 tube walls and various tube lengths are characterized in terms of morphology by scanning electron microscopy (SEM), chemical identity by X-ray photoelectron spectroscopy (XPS) and phase composition by X-ray diffraction (XRD). Their performance as negative electrode ('anode') materials for lithium-ion batteries (LIBs) is quantified at different charge and discharge rates in the absence of additives. We find distinct trends and optima for the dependence of initial capacity and long-term stability on the geometric parameters of the nanotube materials. A sample featuring SnO2 tubes of 30 µm length and 10 nm wall thickness achieves after 780 cycles a coulombic efficiency of >99% and a specific capacity of 671 mA h g-1. This value represents 92% of the first-cycle capacity and 86% of the theoretical value.

Boron Nitride as a Novel Support for Highly Stable Palladium Nanocatalysts by Atomic Layer Deposition.

The ability to prepare controllable nanocatalysts is of great interest for many chemical industries. Atomic layer deposition (ALD) is a vapor phase technique enabling the synthesis of conformal thin films and nanoparticles (NPs) on high surface area supports and has become an attractive new route to tailor supported metallic NPs. Virtually all the studies reported, focused on Pd NPs deposited on carbon and oxide surfaces. It is, however, important to focus on emerging catalyst supports such as boron nitride materials, which apart from possessing high thermal and chemical stability, also hold great promises for nanocatalysis applications. Herein, the synthesis of Pd NPs on boron nitride (BN) film substrates is demonstrated entirely by ALD for the first time. X-ray photoelectron spectroscopy indicated that stoichiometric BN formed as the main phase, with a small amount of BNxOy, and that the Pd particles synthesized were metallic. Using extensive transmission electron microscopy analysis, we study the evolution of the highly dispersed NPs as a function of the number of ALD cycles, and the thermal stability of the ALD-prepared Pd/BN catalysts up to 750 °C. The growth and coalescence mechanisms observed are discussed and compared with Pd NPs grown on other surfaces. The results show that the nanostructures of the BN/Pd NPs were relatively stable up to 500 °C. Consequent merging has been observed when annealing the samples at 750 °C, as the NPs' average diameter increased from 8.3 ± 1.2 nm to 31 ± 4 nm. The results presented open up exciting new opportunities in the field of catalysis.

The transformation behaviour of "alucones", deposited by molecular layer deposition, in nanoporous Al2O3 layers.

Nanoporous alumina films can be synthesized from hybrid organic-inorganic "alucone" films deposited by molecular layer deposition (MLD) by wet etching in deionized water or calcination in air at 500 °C. This transformation process was systematically investigated for two alucone chemistries based on ethylene glycol (EG) and glycerol (GL). Ellipsometric porosimetry (EP) was used for the characterization of the porous alumina structures that are formed as a result of the treatments. Etching in deionized water transforms both EG- and GL-alucones into porous alumina with a porosity of about 40%, albeit with a different pore structure: cylindrical pores for EG-alucones and ink-bottle structures for GL-alucones. Calcination in air up to 500 °C only successfully transformed EG-alucones into porous alumina if the chosen heating and cooling rate was lower than 200 °C h-1. Below this ramp rate, a relationship between the resulting porosity and the ramp rate was found. At the lowest investigated ramp rate of 20 °C h-1, the highest porosity of 36% was achieved. For this treatment type, the pore shape was of the ink-bottle type for all investigated ramp rates with narrow 1 nm-sized pores. Infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy revealed that the final chemistry of the porous structures was slightly different for both treatments due to trace amounts of carbon left behind by water etching. This suggests that the internal surface of the porous structure has a different termination depending on the chosen treatment. The precise thickness control and conformal nature inherent to MLD combined with the wet and heat treatments enables the coating of complex 3D structures with a porous alumina film with a well-defined thickness and pore structure.

Protected Light-Trapping Silicon by a Simple Structuring Process for Sunlight-Assisted Water Splitting.

Macroporous layers are grown onto n-type silicon by successive photoelectrochemical etching in HF-containing solution and chemical etching in KOH. This specific latter treatment gives highly antireflective properties of the Si surface. The duration of the chemical etching is optimized to render the surface as absorbent as possible, and the morphology of the as-grown layer is characterized by scanning electron microscopy. Further functionalization of such structured Si surface is carried out by atomic layer deposition of a thin conformal and homogeneous TiO2 layer that is crystallized by an annealing at 450 °C. This process allows using such surfaces as photoanodes for water oxidation. The 40 nm thick TiO2 film acts indeed as an efficient protective layer against the photocorrosion of the porous Si in KOH, enhances its wettability, and improves the light absorption of the photoelectrode. The macroporous dual-absorber TiO2/Si has a beneficial effect on water oxidation in 1 M KOH and leads to a considerable negative shift of the onset potential of ∼400 mV as well as a 50% increase in photocurrent at 1 V vs SCE.

Atomic Layer Deposition of Pd Nanoparticles on TiO2 Nanotubes for Ethanol Electrooxidation: Synthesis and Electrochemical Properties.

Palladium nanoparticles are grown on TiO2 nanotubes by atomic layer deposition (ALD), and the resulting three-dimensional nanostructured catalysts are studied for ethanol electrooxidation in alkaline media. The morphology, the crystal structure, and the chemical composition of the Pd particles are fully characterized using scanning and transmission electron microscopies, X-ray diffraction, and X-ray photoelectron spectroscopy. The characterization revealed that the deposition proceeds onto the entire surface of the TiO2 nanotubes leading to the formation of well-defined and highly dispersed Pd nanoparticles. The electrooxidation of ethanol on Pd clusters deposited on TiO2 nanotubes shows not only a direct correlation between the catalytic activity and the particle size but also a steep increase of the response due to the enhancement of the metal-support interaction when the crystal structure of the TiO2 nanotubes is modified by annealing at 450 °C in air.

Atomic Layer Deposition from Dissolved Precursors.

We establish a novel thin film deposition technique by transferring the principles of atomic layer deposition (ALD) known with gaseous precursors toward precursors dissolved in a liquid. An established ALD reaction behaves similarly when performed from solutions. "Solution ALD" (sALD) can coat deep pores in a conformal manner. sALD offers novel opportunities by overcoming the need for volatile and thermally robust precursors. We establish a MgO sALD procedure based on the hydrolysis of a Grignard reagent.

3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid.

Three-dimensionally (3D) nanoarchitectured palladium/nickel (Pd/Ni) catalysts, which were prepared by atomic layer deposition (ALD) on high-aspect-ratio nanoporous alumina templates are investigated with regard to the electrooxidation of formic acid in an acidic medium (0.5 M H2SO4). Both deposition processes, Ni and Pd, with various mass content ratios have been continuously monitored by using a quartz crystal microbalance. The morphology of the Pd/Ni systems has been studied by electron microscopy and shows a homogeneous deposition of granularly structured Pd onto the Ni substrate. X-ray diffraction analysis performed on Ni and NiO substrates revealed an amorphous structure, while the Pd coating crystallized into a fcc lattice with a preferential orientation along the [220]-direction. Surface chemistry analysis by X-ray photoelectron spectroscopy showed both metallic and oxide contributions for the Ni and Pd deposits. Cyclic voltammetry of the Pd/Ni nanocatalysts revealed that the electrooxidation of HCOOH proceeds through the direct dehydrogenation mechanism with the formation of active intermediates. High catalytic activities are measured for low masses of Pd coatings that were generated by a low number of ALD cycles, probably because of the cluster size effect, electronic interactions between Pd and Ni, or diffusion effects.

Highly conformal electrodeposition of copolymer electrolytes into titania nanotubes for 3D Li-ion batteries.

The highly conformal electrodeposition of a copolymer electrolyte (PMMA-PEO) into self-organized titania nanotubes (TiO2nt) is reported. The morphological analysis carried out by scanning electron microscopy and transmission electron microscopy evidenced the formation of a 3D nanostructure consisting of a copolymer-embedded TiO2nt. The thickness of the copolymer layer can be accurately controlled by monitoring the electropolymerization parameters. X-ray photoelectron spectroscopy measurements confirmed that bis(trifluoromethanesulfone)imide salt was successfully incorporated into the copolymer electrolyte during the deposition process. These results are crucial to fabricate a 3D Li-ion power source at the micrometer scale using TiO2nt as the negative electrode.