Single-step fabrication of quantum funnels via centrifugal colloidal casting of nanoparticle films.
ABSTRACT: Centrifugal casting of composites and ceramics has been widely employed to improve the mechanical and thermal properties of functional materials. This powerful method has yet to be deployed in the context of nanoparticles--yet size-effect tuning of quantum dots is among their most distinctive and application-relevant features. Here we report the first gradient nanoparticle films to be constructed in a single step. By creating a stable colloid of nanoparticles that are capped with electronic-conduction-compatible ligands we were able to leverage centrifugal casting for thin-films devices. This new method, termed centrifugal colloidal casting, is demonstrated to form films in a bandgap-ordered manner with efficient carrier funnelling towards the lowest energy layer. We constructed the first quantum-gradient photodiode to be formed in a single deposition step and, as a result of the gradient-enhanced electric field, experimentally measured the highest normalized detectivity of any colloidal quantum dot photodetector.
Project description:Biodegradable polyhydroxybutyrate (PHB) films were fabricated using acetic acid as an alternative to common solvents such as chloroform. The PHB films were prepared using a solvent casting process at temperatures ranging from 80 °C to 160 °C. The crystallinity, mechanical properties and surface morphology of the films cast at different temperatures were characterized and compared to PHB films cast using chloroform as a solvent. Results revealed that the properties of the PHB film varied considerably with solvent casting temperature. In general, samples processed with acetic acid at low temperatures had comparable mechanical properties to PHB cast using chloroform. This acetic acid based method is environmentally friendly, cost efficient and allows more flexible processing conditions and broader ranges of polymer properties than traditional methods.
Project description:Small-area metal-halide perovskite solar cells (PSCs) having power-conversion efficiencies (PCEs) of greater than 25% can be prepared by using a spin-coated perovskite layer, but this technique is not readily transferrable to large-scale manufacturing. Drop-casting is a simple alternative method for film formation that is more closely aligned to industry-relevant coating processes. In the present work, drop-casting was used to prepare films for screening two-dimensional Ruddlesden-Popper (2DRP) metal-halide perovskite formulations for potential utility in PSCs, without additional processing steps such as inert-gas blowing or application of antisolvent. The composition of the 2DRP formulation used for drop-casting was found to have a profound effect on optical, spectroscopic, morphological, and phase-distribution properties of the films as well as the photovoltaic performance of related PSC devices. This facile method for screening film quality greatly assists in speeding up the identification of perovskite formulations of interest. The optimal 2DRP perovskite formulation identified from screening was utilized for industry-relevant one-step roll-to-roll slot-die coating on a flexible plastic substrate, producing PSCs having PCEs of up to 8.8%. A mechanism describing film formation and phase distribution in the films is also proposed.
Project description:In situ wide-angle X-ray scattering (WAXS) has been measured during the spin coating process used to make the precursor films required for the formation of thin films of perovskite. A customized hollow axis spin coater was developed to permit the scattered X-rays to be collected in transmission geometry during the deposition process. Spin coating is the technique most commonly used in laboratories to make thin perovskite films. The dynamics of spin-casting MAPbI3-x Cl x and FAPbI3-x Cl x films have been investigated and compared to investigate the differences between the dynamics of MAPbI3-x Cl x and FAPbI3-x Cl x film formation. In particular, we focus on the crystallization dynamics of the precursor film formation. When casting MAPbI3-x Cl x , we observed relatively fast 1D crystallization of the intermediate product MA2PbI3Cl. There was an absence of the desired perovskite phase formed directly; it only appeared after an annealing step that converted the MA2PbI3Cl to MAPbI3. In contrast, slower crystallization via a 3D precursor was observed for FAPbI3-x Cl x film formation compared to MAPbI3-x Cl x . Another important finding was that some FAPbI3-x Cl x perovskite was generated directly during spin-casting before annealing. These findings indicate that there are significant differences between the crystallization pathways for these two perovskite materials. These are likely to explain the differences in the lifetimes of the resulting perovskite solar cell devices produced using FA and MA cations.
Project description:We present results on the photothermal (PT) and heat conductive properties of nanogranular silicon (Si) films synthesized by evaporation of colloidal droplets (drop-casting) of 100 ± 50 nm-sized crystalline Si nanoparticles (NP) deposited on glass substrates. Simulations of the absorbed light intensity and photo-induced temperature distribution across the Si NP films were carried out by using the Finite difference time domain (FDTD) and finite element mesh (FEM) modeling and the obtained data were compared with the local temperatures measured by micro-Raman spectroscopy and then was used for determining the heat conductivities k in the films of various thicknesses. The cubic-to-hexagonal phase transition in Si NP films caused by laser-induced heating was found to be heavily influenced by the film thickness and heat-conductive properties of glass substrate, on which the films were deposited. The k values in drop-casted Si nanogranular films were found to be in the range of lowest k of other types of nanostructurely voided Si films due to enhanced phonon scattering across inherently voided topology, weak NP-NP and NP-substrate interface bonding within nanogranular Si films.
Project description:Self-assembly of colloidal particles into colloidal films has many actual and potential applications. While various strategies have been developed to direct the assembly of colloidal particles, fabrication of crack-free and transferrable colloidal film with controllable crystal structures still remains a major challenge. Here we show a centrifugation-assisted assembly of colloidal silica spheres into free-standing colloidal film by using the liquid/liquid interfaces of three immiscible phases. Through independent control of centrifugal force and interparticle electrostatic repulsion, polycrystalline, single-crystalline and quasi-amorphous structures can be readily obtained. More importantly, by dehydration of silica particles during centrifugation, the spontaneous formation of capillary water bridges between particles enables the binding and pre-shrinkage of the assembled array at the fluid interface. Thus the assembled colloidal films are not only crack-free, but also robust and flexible enough to be easily transferred on various planar and curved substrates.
Project description:We report a facile method of ordering block copolymer (BCP) morphologies in which the conventional two-step casting and annealing steps are replaced by a single-step process where microphase separation and grain coarsening are seamlessly integrated within the casting protocol. This is achieved by slowing down solvent evaporation during casting by introducing a nonvolatile solvent into the BCP casting solution that effectively prolongs the duration of the grain-growth phase. We demonstrate the utility of this solvent evaporation annealing (SEA) method by producing well-ordered large-molecular-weight BCP thin films in a total processing time shorter than 3 min without resorting to any extra laboratory equipment other than a basic casting device, <i>i.e</i>., spin- or blade-coater. By analyzing the morphologies of the quenched samples, we identify a relatively narrow range of polymer concentration in the wet film, just above the order-disorder concentration, to be critical for obtaining large-grained morphologies. This finding is corroborated by the analysis of the grain-growth kinetics of horizontally oriented cylindrical domains where relatively large growth exponents (1/2) are observed, indicative of a more rapid defect-annihilation mechanism in the concentrated BCP solution than in thermally annealed BCP melts. Furthermore, the analysis of temperature-resolved kinetics data allows us to calculate the Arrhenius activation energy of the grain coarsening in this one-step BCP ordering process.
Project description:We introduce indium arsenide colloidal quantum dot films for photovoltaic devices, fabricated by two-step surface modification. Native ligands and unwanted oxides on the surface are peeled off followed by passivating with incoming atomic or short ligands. The near-infrared-absorbing n-type indium arsenide colloidal quantum dot films can be tuned in energy-level positions up to 0.4?eV depending on the surface chemistry, and consequently, they boost collection efficiency when used in various emerging solar cells. As an example, we demonstrate p-n junction between n-type indium arsenide and p-type lead sulfide colloidal quantum dot layers, which leads to a favorable electronic band alignment and charge extraction from both colloidal quantum dot layers. A certified power conversion efficiency of 7.92% is achieved without additionally supporting carrier transport layers. This study provides richer materials to explore for high-efficiency emerging photovoltaics and will broaden research interest for various optoelectronic applications using the n-type covalent nanocrystal arrays.
Project description:We report on a template-stripping method for the direct surface patterning of colloidal quantum-dot thin films to produce highly luminescent structures with feature sizes less than 100 nm. Through the careful design of high quality bull's-eye gratings we can produce strong directional beaming (10° divergence) with up to 6-fold out-coupling enhancement of spontaneous emission in the surface-normal direction. A transition to narrow single-mode lasing is observed in these same structures at thresholds as low as 120 ?J/cm<sup>2</sup>. In addition, we demonstrate that these structures can be fabricated on flexible substrates. Finally, making use of the size-tunable character of colloidal quantum dots, we demonstrate spectrally selective out-coupling of light from mixed quantum-dot films. Our results provide a straightforward route toward significantly improved optical properties of colloidal quantum-dot assemblies.
Project description:Vacuum-induced surface freezing has been used to produce uni-directional freezing of colloidal aluminum oxide dispersions. It leads to zones of different structure within the resulting sintered monoliths that are highly similar to those known for freeze casting using a cryogen cold source. A more-or-less dense surface layer and a cellular sub-surface region are formed, beneath which is a middle region of aligned lamellae and pores that stretches through most of the depth of the monolith. This is the case even at a volume fraction of dispersed phase as low as 0.032. A more-dense but still porous base layer is formed by accumulation of rejected nanoparticles preceding the freezing front and differs from previous reports in that no ice lenses are observed. X-ray micro-computed tomography reveals a uniform aligned pore structure vertically through the monolith. The pores close to the periphery are oriented radially or as chords, while the center region contains domains of parallel pores/lamellae. The domains are randomly oriented to one another, as already reported for regular freeze casting. This technique for directional freezing is convenient and easy to perform, but requires further refinement in that the temperature gradient and freezing rates remain yet to be measured. Also, control of the temperature gradient by varying chamber vacuum and shelf temperature needs to be evaluated.
Project description:It is crucial to align two-dimensional nanosheets to form a highly compact layered structure for many applications, such as electronics, optoelectronics, thermal management, energy storage, separation membranes, and composites. Here we show that continuous centrifugal casting is a universal, scalable and efficient method to produce highly aligned and compact two-dimensional nanosheets films with record performances. The synthesis mechanism, structure control and property dependence of alignment and compaction of the films are discussed. Significantly, 10-?m-thick graphene oxide films can be synthesized within 1?min, and scalable synthesis of meter-scale films is demonstrated. The reduced graphene oxide films show super-high strength (~660?MPa) and conductivity (~650?S?cm-1). The reduced graphene oxide/carbon nanotube hybrid-film-based all-solid-state flexible supercapacitors exhibit ultrahigh volumetric capacitance (407?F?cm-3) and energy density (~10?mWh?cm-3) comparable to that of thin-film lithium batteries. We also demonstrate the production of highly anisotropic graphene nanocomposites as well as aligned, compact films and vertical heterostructures of various nanosheets.