A nanocrystal with one semiconducting composition surrounded by another. band offsets, interface quality and shell thickness govern carrier confinement and coupling to external traps. type-I band alignment favors electron and hole localization together; type-II band alignment can separate them. A larger shell band gap does not by itself determine those offsets.
Nanocrystal growth 2026-10-20
Addition or rearrangement of material in a nanocrystal. Solute addition, Ostwald ripening and oriented attachment are distinct mechanisms that can coexist.
The competition between crystallization, exposed surfaces, adhesion and elastic strain can be summarized by
Here measures the bulk driving force from supersaturation, and the values are interfacial free energies. For a free spherical nucleus, gives . A support changes the heterogeneous nucleation barrier through adhesion and geometry.
Precursor activities and supply rate, temperature, time, solvent and ligands control nucleation, attachment, detachment and surface diffusion. Many nuclei divide a fixed solute inventory into smaller particles; continued growth or Ostwald ripening can enlarge them. Substrate defects determine preferred nucleation sites; lattice mismatch and interface bonding constrain orientation and elastic relaxation. Facet-selective adsorption can change both surface energies and growth rates.
Near equilibrium, a free nanocrystal follows a Wulff construction; a supported particle can follow a Winterbottom construction. Under kinetic control, slowly advancing facets remain visible while rapidly growing ones disappear. Equilibrium facet energy and kinetic growth rate are different controls, so a crystal structure does not uniquely determine particle shape.
For standard deviations of position and momentum,
Confinement to a region of size requires a momentum spread of order , hence kinetic energy of order . A sufficiently small semiconducting nanocrystal therefore has discrete energy levels and an optical edge shifted above the bulk band gap.
An illustrative strong-confinement model is
where is a geometry-dependent number of order unity. The positive confinement contribution grows as ; electron-hole Coulomb interaction contributes an attractive term of order . The uncertainty principle motivates the scale, not the exact coefficient or oscillator strength. Strong size dependence occurs near the exciton Bohr radius. Finite barriers, dielectric mismatch and surface states modify this model, while size distributions broaden ensemble spectra.
Three useful growth mechanisms are monomer addition, Ostwald ripening and oriented attachment. They can occur sequentially or compete; they are not necessarily three distinct experimental recipes.
In monomer-addition crystal growth, dissolved atoms, ions or molecular growth units attach to an existing nanocrystal. Supersaturation provides a chemical-potential driving force, approximately for an ideal solution. Transport through solution and incorporation at steps or facets determine the rate. Growth consumes the excess solute without requiring collisions between whole crystals.
In Ostwald ripening, smaller crystals dissolve while larger ones grow through solution. Curvature raises the surface contribution to chemical potential, approximately for a sphere with surface free energy and atomic volume . Dissolved material therefore moves from high-curvature particles to lower-curvature ones, reducing total interfacial free energy.
In oriented attachment, whole crystallites align compatible lattice planes and join. Removing exposed surface and forming a coherent interface lowers free energy; rotation, ligand removal and interface healing can be rate limiting. Misalignment can leave twins or other defects. Simple aggregation without crystallographic registration is related particle attachment, but is not necessarily oriented attachment.
Figure 1.
Solution growth pathways and routes from fcc seeds to anisotropic nanostructures
. Original conceptual diagrams of three growth mechanisms and symmetry-breaking routes to a wire or plate. Shapes and arrows illustrate mechanisms, not copied microscopy data or an asserted unique growth sequence. Details.