Single-electron charging in quantum dots with large dielectric mismatch A. Orlandi, M. Rontani, G. Goldoni, F. Manghi, and E. Molinari Istituto Nazionale per la Fisica della Materia (INFM) and Dipartimento di Fisica, Universita ` di Modena e Reggio Emilia, Via Campi 213/A, I-41100 Modena, Italy Received 13 September 2000; published 8 January 2001 Semiconductor quantum dots characterized by a strong dielectric mismatch with their environment are studied theoretically through direct diagonalization of the many-body Hamiltonian. The enhancement of the electron-electron Coulomb interaction, arising from polarization effects, is found to induce a strong increase in addition energies with increasing dielectric mismatch. For large dielectric mismatch, the excited many-body states can undergo reconstructions as the dot is filled with carriers even in the absence of external magnetic fields. DOI: 10.1103/PhysRevB.63.045310 PACS numbers: 73.61.-r, 85.35.Be, 85.35.Gv I. INTRODUCTION Semiconductor quantum dots QD’sare structures where carrier confinement at the nanometer scale is achieved in all spatial directions; the energy spectrum is therefore discrete, as in natural atoms, and the Coulomb interaction among electrons is enhanced owing to the large spatial overlap of their wave functions. In recent years, a large experimental and theoretical effort has lead to the demonstration of QD devices where the strong Coulomb interaction is exploited to allow control of charge injection at the single-electron level: 1–3 Single-electron transistors SET’sare a fascinating manifestation of many-body physics at work. A reason for the importance of SET’s is in the extremely low power re- quired for their operation of the order of nanowatts. This opens the way to their possible integration in bioenviron- ments, which is generally incompatible with the large power dissipation of current microelectronic transistors at least six orders of magnitude larger. A specific characteristic of organic environments is their huge dielectric mismatch with typical inorganic- semiconductor QD structures. Quantum dots with a large di- electric mismatch to the surrounding medium have been pre- pared and studied by different techniques in recent years. They comprise QD’s embedded in glasses 4 and organic ma- terials, including those fabricated by colloidal techniques 5–8 or inserted in biological environments. 9 In most of these sys- tems, photons have been the primary probe for investigating or modifying the electronic properties of the dots. More re- cently, it was shown that spherical nanocrystals in low- dielectric-constant matrices can be built into a single- electron device, and that capacitance or tunneling spectroscopies can be used to obtain their addition spectra. 6–8,10 The effects of the large dielectric mismatch have been, however, overlooked in the interpretation of single-electron charging phenomena in these dots. In this article we present a theoretical calculation of these effects, based on the direct solution of the exact few-particle Hamiltonian for the dots. For large electron numbers, where the dimension of the Hilbert space becomes excidingly big, we also make use of a Hubbard-like approximation to the full Hamiltonian. 11 We show that the enhancement of the electron-electron Coulomb interaction, arising from the buildup of large polarization charges at the interfaces, pro- duces new features in the addition spectra, namely: ia strong increase in the absolute values of addition energies, and iithe possible occurrence of ‘‘reconstructions’’ of the electronic configurations as the dot is filled with electrons. The operation of single-electron devices in organic environ- ments is therefore expected to involve phenomena that modify the relevant energy scale and charge distribution with respect to conventional QD devices embedded in inorganic semiconductor matrices. These phenomena may be relevant for applications of SET’s as sensors of dielectric properties at the nanoscale. II. THEORETICAL APPROACH The key quantities that are used to characterize these sys- tems experimentally are the addition energies E add ( N ) the variation of the energy required to add an electron to a QD containing N electrons, analogous to the differences between electron affinities in natural atoms. These are defined as differences between the QD chemical potentials, , as one electron is added to the dot: E add ( N ) =( N +1) -( N ). In turn, the chemical potential of the QD with N electrons is ( N ) =E 0 ( N ) -E 0 ( N -1), where E 0 ( N ) are the ground- state energies in the dot. To calculate E 0 ( N ) we need to know the ground-state configuration of the many-electron system. The full many- body Hamiltonian is H ˆ = a a c ˆ a c ˆ a + 1 2 abcd ' V abcd c ˆ a , c ˆ b ' c ˆ c ' c ˆ d , 1 where c ˆ a ( c ˆ a ) is the fermionic creation destructionop- erator in the eigenstate | a of the single-particle Hamil- tonian a stands for the set of orbital quantum numbers, for spin; a are the single-particle energies; V abcd are the inter- action integrals V abcd =  a *r b *r' V r, r' c r' d rd r d r' 2 where a ( r) are the single-particle envelope functions. 12 PHYSICAL REVIEW B, VOLUME 63, 045310 0163-1829/2001/634/0453106/$15.00 ©2001 The American Physical Society 63 045310-1