# Fixed Number and Quantum Size Effects in Nanoscale Superconductors

## Abstract

In recent experiments on nanoscale Al particles, whose electron number was fixed by charging effects, a “negative gap” was observed in particles with an odd number of electrons. This observation has called into question the use of a grand canonical ensemble in describing superconductivity in such ultrasmall particles.

We have studied the effects of fixed electron number and finite size in nanoscale superconductors, by applying the canonical BCS theory for the attractive Hubbard model. The ground state energy and the energy gap are compared with the conventional and parity-projected grand canonical BCS results, and in one dimension also with the exact solutions by the Bethe ansatz. The crossover from the bulk to quantum limit is studied for various regimes of electron density and coupling strength. The effects of boundary conditions and different lattice structures are also examined.

A “negative gap” for odd electron number emerges most naturally in the canonical scheme. For even electron number, the gap is particularly large for “magic numbers” of electrons for a given system size or of atoms for a fixed electron density. These features are in accordance with the exact solutions, but are essentially missed in the grand canonical results.

The ability to fabricate ultrasmall superconducting particles in a reasonably controlled way  allows us to revive old questions . The question we focus on here is the validity (and usefulness) of the grand canonical ensemble vs a canonical one for a description of very small superconducting particles.

The canonical and parity-projected BCS formalisms have been described elsewhere . Figure 1 shows a comparison of even and odd canonical (CBCS) and grand canonical (GCBCS) ground state energies, along with exact ones, for the attractive Hubbard model (AHM) in 1 D, for coupling strength (scaled by the kinetic energy parameter $`t`$) $`|U|/t=4`$ and 10. Odd-even effects are clearly discernible.

Figure 2 shows the (even) GCBCS result for the gap ($`\mathrm{\Delta }_{}`$) vs. electron density $`n`$, along with the smoothed density of states (DOS) as a function of single-electron energy $`ϵ_k`$. The structure visible in the gap requires painstaking numerical work, and reflects the underlying discrete density of states (as seen in Fig. 3 below). In Fig. 3 we show a smaller system, with both CBCS and (even) GCBCS results as a function of electron density. Quite a few anomalously high gaps occur, at various values of $`n`$, as revealed by the CBCS result ($`\mathrm{\Delta }_{N_e}`$).

Finally, in Fig. 4 we examine the CBCS gap (normalized by the bulk value) as a function of system size $`N`$, for systems with an even number of electrons. There are two distinct curves which approach the bulk limit (solid circles), corresponding to $`N_e=4m`$ or $`N_e=4m+2`$, with $`m`$ an integer, the so-called ‘super-even’ effect . Clearly, the transition to the bulk is smooth.