Surface Engineering of Metal and Semiconductor Nanocrystal Assemblies and Their Optical and Electronic Devices

Abstract

Conspectus Colloidal nanocrystals (NCs) are composed of inorganic cores and organic or inorganic ligand shells and serve as building blocks of NC assemblies. Metal and semiconductor NCs are well known for the size-dependent physical properties of their cores. The large NC surface-to-volume ratio and the space between NCs in assemblies places significant importance on the composition of the NC surface and ligand shell. Nonaqueous colloidal NC syntheses use relatively long organic ligands to control NC size and uniformity during growth and to prepare stable NC dispersions. However, these ligands create large interparticle distances that dilute the metal and semiconductor NC properties of their assemblies. In this Account, we describe postsynthesis chemical treatments to engineer the NC surface and design the optical and electronic properties of NC assemblies. In metal NC assemblies, compact ligand exchange reduces the interparticle distance and drives an insulator-to-metal transition tuning the dc resistivity over a 1010 range and the real part of the optical dielectric function from positive to negative across the visible-to-IR region. Juxtaposing NC and bulk metal thin films in bilayers allows the differential chemical and thermal addressability of the NC surface to be exploited in device fabrication. Ligand exchange and thermal annealing densifies the NC layer, creating interfacial misfit strain that triggers folding of the bilayers and is used to fabricate, with only one lithography step, large-area 3D chiral metamaterials. In semiconductor NC assemblies, chemical treatments such as ligand exchange, doping, and cation exchange control the interparticle distance and composition to add impurities, tailor stoichiometry, or make entirely new compounds. These treatments are employed in longer studied II–VI and IV–VI materials and are being developed as interest in III–V and I–III–VI2 NC materials grows. NC surface engineering is used to design NC assemblies with tailored carrier energy, type, concentration, mobility, and lifetime. Compact ligand exchange increases the coupling between NCs but can introduce intragap states that scatter and reduce the lifetime of carriers. Hybrid ligand exchange with two different chemistries can enhance the mobility-lifetime product. Doping increases carrier concentration, shifts the Fermi energy, and increases carrier mobility, creating n- and p-type building blocks for optoelectronic and electronic devices and circuits. Surface engineering of semiconductor NC assemblies is also important to modify device interfaces to allow the stacking and patterning of NC layers and to realize excellent device performance. It is used to construct NC-integrated circuits, exploiting the library of metal, semiconductor, and insulator NCs, to achieve all-NC, solution-fabricated transistors.

Chemically Driven Sintering of Colloidal Cu Nanocrystals for Multiscale Electronic and Optical Devices

“…Instead of removing ligands through thermal annealing or laser irradiation, the Cu NC thin films are immersed in room temperature, methanolic salt solutions of Na 2 S, NaN 3 , NH 4 SCN, and NH 4 Cl for 2–5 min and then rinsed with pure methanol (MeOH), a process known as solid-state ligand exchange (Scheme ). ,, The salt solutions allow us to screen a series of compact anions often explored as ligands for colloidal NCs. However, S 2– anions convert the Cu NCs into Cu x S NCs, losing their metallic character, similar to the reaction of S 2– with Ag NCs to form Ag 2 S NCs, and N 3 – anions do not substantially remove the organic ligands (Figure S2).…”