Colloidal Nanocrystal Films Research Articles

Nanoimaging of Water Bending and Carboxylate Stretching Modes in Colloidal Nanocrystal Films

Nanoimaging of Water Bending and Carboxylate Stretching Modes in Colloidal Nanocrystal Films

Achieving direct electrophoretically deposited highly stable polymer induced CsPbBr3 colloidal nanocrystal films for high-performance optoelectronics

Synthesizing colloidal nanocrystals (NCs) with long-term stable under ambient conditions via appropriate ligands capping is highly challenging. Herein, the rapid synthesis of CsPbBr3 colloidal NCs at room temperature using polyvinylpyrrolidone as the primary ligand is demonstrated. The addition of ethylene glycol stabilizes the colloidal NCs and enhance their photoluminescence by ∼ 5-fold. Colloidal NCs have a net negative surface charge, which enables the direct electrophoretic deposition of a polymer-induced all-inorganic CsPbBr3 NC film with ultra-high stability under ambient conditions at relative humidity of 55% for 240 days. As an example of the application of the CsPbBr3 NC film in an optoelectronic device, a hybrid MoS2/CsPbBr3 field-effect phototransistor is fabricated, which exhibits a detectivity of 9 × 1012 Jones and an ultra-high responsivity of 1.2 × 107 A W−1 under the illumination of 450-nm laser at 4.4 pW. The noble and practical methods applied in our CsPbBr3 NC films could be extended to produce various types of uniform NC films over a large geometrical area with outstanding long-term environmental stability, holding significant promise for use in a broad range of advanced optoelectronic devices.

Ink-Lithography for Property Engineering and Patterning of Nanocrystal Thin Films.

Next-generation devices and systems require the development and integration of advanced materials, the realization of which inevitably requires two separate processes: property engineering and patterning. Here, we report a one-step, ink-lithography technique to pattern and engineer the properties of thin films of colloidal nanocrystals that exploits their chemically addressable surface. Colloidal nanocrystals are deposited by solution-based methods to form thin films and a local chemical treatment is applied using an ink-printing technique to simultaneously modify (i) the chemical nature of the nanocrystal surface to allow thin-film patterning and (ii) the physical electronic, optical, thermal, and mechanical properties of the nanocrystal thin films. The ink-lithography technique is applied to the library of colloidal nanocrystals to engineer thin films of metals, semiconductors, and insulators on both rigid and flexible substrates and demonstrate their application in high-resolution image replications, anticounterfeit devices, multicolor filters, thin-film transistors and circuits, photoconductors, and wearable multisensors.

Nanoscale Patterning of Colloidal Nanocrystal Films for Nanophotonic Applications Using Direct Write Electron Beam Lithography.

The small size of colloidal nanocrystal quantum dots (QDs) leads to a variety of unique optical properties that are well-suited to nanophotonics, including bright, tunable photoluminescence (PL). However, exploring the properties of solid QD assemblies at the nanoscale has proven challenging because of the limitations in the nanoscale QD patterning methods. Generally, the precise placement of QD solids is difficult to achieve, especially for tall structures with multiple QD layers, and when it is achieved the patterns often cannot withstand the further processing steps required for final device construction. Direct electron beam lithography of QDs has emerged as a straightforward patterning process that does not require ligand exchange and results in structures that retain bright PL. Here, we demonstrate that direct patterning QD films on substrates treated with a self-assembled monolayer of octadecyltrichlorosilane allows us to create feature sizes as thin as 30 nm with heights of multiple layers and characterize the pattern resolution, robustness, and placement accuracy. These structures withstand sonication in a variety of solvents, and the structures are placed within 20 nm of their intended location nearly 100% of the time. We further show how this patterning method can be applied to nanophotonics by measuring the complex refractive index of the QD materials to model the absorption and scattering cross sections of QD structures of various sizes and shapes. These simulations reveal that edge effects arising from the finite shape of the QD nanostructure lead to substantial absorption enhancement when compared to an equivalent volume region taken from a continuous QD film. Finally, we explore more complex structures by patterning QD arrays, multilayer QD structures, and QD disks inside plasmonic resonators.

On the kinetics of the removal of ligands from films of colloidal nanocrystals by plasmas.

This paper describes the kinetic limitations of etching ligands from colloidal nanocrystal assemblies (CNAs) by plasma processing. We measured the etching kinetics of ligands from a CNA model system (spherical ZrO2 nanocrystals, 2.5-3.5 nm diameter, capped with trioctylphosphine oxide) with inductively coupled plasmas (He and O2 feed gases, powers ranging from 7 to 30 W, at pressures ranging from 100 to 2000 mTorr and exposure times ranging between 6 and 168 h). The etching rate slows down by about one order of magnitude in the first minutes of etching, after which the rate of carbon removal becomes proportional to the third power of the carbon concentration in the CNA. Pressure oscillations in the plasma chamber significantly accelerate the overall rate of etching. These results indicate that the rate of etching is mostly affected by two main factors: (i) the crosslinking of the ligands in the first stage of plasma exposure, and (ii) the formation of a boundary layer at the surface of the CNA. Optimized conditions of plasma processing allow for a 60-fold improvement in etching rates compared to the previous state of the art and make the timeframes of plasma processing comparable to those of calcination.

Colloidal Nanocrystal Films Reveal the Mechanism for Intermediate Temperature Proton Conductivity in Porous Ceramics

Over the past few years, the observation of unexpected but significant proton conductivity in porous, nanocrystalline ceramics has generated substantial scientific interest mirroring the excitement...

Microstructure Evolution and Crystal Growth in Cu2ZnSnS4 Thin Films Formed By Annealing Colloidal Nanocrystal Coatings

A potentially low-cost approach for making copper zinc tin sulfide (CZTS) solar cells relies on annealing colloidal nanocrystal films cast on suitable substrates in a sulfur-containing environment to form thin films with micrometer-sized grains. The film microstructure and grain size affects the solar cell performance. We conducted a systematic study of the factors controlling crystal growth and microstructure development during annealing of films cast from colloidal dispersions of CZTS nanocrystals. The film microstructure is controlled by concurrent normal and abnormal grain growth. At 600 to 800 °C and low sulfur pressures (50 Torr), abnormal CZTS grains up to 10 μm in size grow on the surface of the CZTS nanocrystal film via transport of material from the nanocrystals to the abnormal grains. Meanwhile, the nanocrystals coarsen, sinter, and undergo normal grain growth. The driving force for abnormal grain growth is the reduction in total energy associated with the high surface area nanocrystals. The ev...

Nanocrystal Film Patterning by Inhibiting Cation Exchange via Electron-Beam or X-ray Lithography

In this Letter we report patterning of colloidal nanocrystal films that combines direct e-beam (electron beam) writing with cation exchange. The e-beam irradiation causes cross-linking of the ligand molecules present at the nanocrystal surface, and the cross-linked molecules act as a mask for further processing. Consequently, in the following step of cation exchange, which is performed by directly dipping the substrate in a solution containing the new cations, the regions that have not been exposed to the electron beam are chemically transformed, while the exposed ones remain unchanged. This selective protection allows the design of patterns that are formed by chemically different nanocrystals, yet in a homogeneous nanocrystal film. Spatially resolved compositional analysis by energy-dispersive X-ray spectroscopy (EDS) corroborates that the selective exchange occurs only in the nonirradiated regions. We demonstrate the utility of this lithography approach by fabricating conductive wires and luminescent patterns in CdSe/CdS nanocrystal films by converting nonirradiated regions to Cu2-xSe/Cu2-xS. Furthermore, we show that X-ray irradiation too can lead to protection from cation exchange.

Atomic Ligand Passivation of Colloidal Nanocrystal Films via their Reaction with Propyltrichlorosilane

Colloidal nanocrystal films of different materials (semiconductors, metals) and shapes (spheres and rods) were dipped in solutions of propyltrichlorosilane (PTCS) in acetonitrile. This process remo...

Oriented Electrophoretic Deposition of GdOCl Nanoplatelets

Electrophoretic deposition has emerged as a versatile and precisely tunable approach for the rapid deposition of conformal thin films of colloidal nanocrystals. The electrophoretic deposition of phosphor particles has assumed special significance in recent years as a commercially viable means toward the fabrication of large-area, ultrathin high-resolution emissive display screens. Here, we demonstrate that the anisotropic shape of colloidal ligand-passivated GdOCl nanoplatelets enables their assembly with remarkable substrate alignment and a high packing density upon electrophoretic deposition. GdOCl nanocrystals are promising candidates for phosphor applications given their low maximum phonon cutoff energy, robust chemical stability over prolonged periods of operation, and ability to promote efficacious phonon energy transfer to dopant ions. Potentiostatic deposition of GdOCl nanoplatelets from cyclohexane dispersions allows the deposition of individual nanoplatelets with their basal planes parallel to the electrode surface. Tuning the applied voltage and solution concentration allows control of film thickness, ranging up to several tens of micrometers. The high degree of particle alignment is attributed to anisotropic charge distribution and entrainment within electroosmotic flows established in the vicinity of the electrode surface. The oriented high-particle-density GdOCl nanoplatelet thin films are possible candidates for phosphor applications, which is illustrated by the green emission from a Tb-doped GdOCl thin film on indium tin oxide (ITO)-coated glass.

Diffusion-limited aggregation in dry nanocrystal films

ABSTRACTWe demonstrate that drop cast films of colloidal nanocrystals containing excess surfactants develop aggregation over several weeks after solvent evaporation. Fingered structures, typical of diffusion-limited aggregation, are created because of the residual mobility that nanocrystals retain in the film. We are able to control the aggregation through the concentration of surfactant molecules and the drying temperature of the films.

Pulsed Laser Annealing of Thin Films of Self-Assembled Nanocrystals

We investigated how pulsed laser annealing can be applied to process thin films of colloidal nanocrystals (NCs) into interconnected nanostructures. We illustrate the relationship between incident laser fluence and changes in morphology of PbSe NC films relative to bulk-like PbSe films. We found that laser pulse fluences in the range of 30 to 200 mJ/cm(2) create a processing window of opportunity where the NC film morphology goes through interesting transformations without large-scale coalescence of the NCs. NC coalescence can be mitigated by depositing a thin film of amorphous silicon (a-Si) on the NC film. Remarkably, pulsed laser annealing of the a-Si/PbSe NC films crystallized the silicon while NC morphology and translational order of the NC film are preserved.

Charge transport in mixed CdSe and CdTe colloidal nanocrystal films

We report the influence of trap states on charge transport through films of mixed CdTe and CdSe nanocrystals (NCs) between lateral electrodes, through layered films of CdTe and CdSe NCs in a layered geometry, and through films of CdTe/CdSe nanobarbells in a layered geometry. We find that an electron trapping state on the surface of the CdTe NCs dominates the conduction in all devices studied. X-ray photoelectron spectroscopy and thermal activation studies implicate unpassivated or oxidized Te as the electron-trapping site.

Structural, Optical, and Electrical Properties of PbSe Nanocrystal Solids Treated Thermally or with Simple Amines

We describe the structural, optical, and electrical properties of films of spin-cast, oleate-capped PbSe nanocrystals that are treated thermally or chemically in solutions of hydrazine, methylamine, or pyridine to produce electronically coupled nanocrystal solids. Postdeposition heat treatments trigger nanocrystal sintering at approximately 200 degrees C, before a substantial fraction of the oleate capping group evaporates or pyrolyzes. The sintered nanocrystal films have a large hole density and are highly conductive. Most of the amine treatments preserve the size of the nanocrystals and remove much of the oleate, decreasing the separation between nanocrystals and yielding conductive films. X-ray scattering, X-ray photoelectron and optical spectroscopy, electron microscopy, and field-effect transistor electrical measurements are used to compare the impact of these chemical treatments. We find that the concentration of amines adsorbed to the NC films is very low in all cases. Treatments in hydrazine in acetonitrile remove only 2-7% of the oleate yet result in high-mobility n-type transistors. In contrast, ethanol-based hydrazine treatments remove 85-90% of the original oleate load. Treatments in pure ethanol strip 20% of the oleate and create conductive p-type transistors. Methylamine- and pyridine-treated films are also p-type. These chemically treated films oxidize rapidly in air to yield, after short air exposures, highly conductive p-type nanocrystal solids. Our results aid in the rational development of solar cells based on colloidal nanocrystal films.

Viscoplastic and Granular Behavior in Films of Colloidal Nanocrystals

Nanoindentation measurements of electrophoretically deposited films of colloidal CdSe nanocrystals, capped by organic ligands, show the films have an elastic stiffness modulus of approximately 10 GPa and exhibit viscoplasticity. This mechanical response suggests polymeric features that are attributable to the ligands. After particle cross-linking and partial ligand removal, the films exhibit more features of granularity.