Filling the lowest quantum state of the conduction band of colloidal nanocrystals with a single electron, which is analogous to the filling the lowest unoccupied molecular orbital in a molecule with a single electron, has attracted much attention due to the possibility of harnessing the electron spin for potential spin-based applications. The quantized energy levels of the artificial atom, in principle, make it possible for a nanocrystal to be filled with an electron if the Fermi-energy level is optimally tuned during the nanocrystal growth. Here, we report the singly occupied quantum state (SOQS) and doubly occupied quantum state (DOQS) of a colloidal nanocrystal in steady state under ambient conditions. The number of electrons occupying the lowest quantum state can be controlled to be zero, one (unpaired), and two (paired) depending on the nanocrystal growth time via changing the stoichiometry of the nanocrystal. Electron paramagnetic resonance spectroscopy proved the nanocrystals with single electron to show superparamagnetic behavior, which is a direct evidence of the SOQS, whereas the DOQS of the two- or zero-electron occupied nanocrystals in the 1S exhibit diamagnetic behavior. In combination with the superconducting quantum interference device measurement, it turns out that the SOQS of the HgSe colloidal quantum dots has superparamagnetic property. The appearance and change of the steady-state mid-IR intraband absorption spectrum reflect the sequential occupation of the 1S state with electrons. The magnetic property of the colloidal quantum dot, initially determined by the chemical synthesis, can be tuned from diamagnetic to superparamagnetic and vice versa by varying the number of electrons through postchemical treatment. The switchable magnetic property will be very useful for further applications such as colloidal nanocrystal based spintronics, nonvolatile memory, infrared optoelectronics, catalyst, imaging, and quantum computing.

Electron occupation in the lowest quantized state of the conduction band (1Se) in the colloidal quantum dot leads to the intraband transition in steady-state (1Se-1Pe). The intraband transition, solely originating from the quantum confinement effect, is the unique property of semiconducting nanocrystals. To achieve the electron occupation in 1Se state in the absence of impurity ions, nonthiol ligand passivated HgS colloidal quantum dots are synthesized. The nonthiol ligand passivated HgS quantum dot exhibits strong steady-state intraband transition in ambient condition and enables a versatile ligand replacement to oxide, acid, and halide functional ligands, which was not achievable from conventional HgS or HgSe quantum dots. Surprisingly, the atomic ligand passivation to HgS colloidal quantum dot solution efficiently maintains the electron occupation at 1Se of HgS CQDs in ambient condition. The electron occupation in 1Se of HgS CQD solid film is controlled by surface treatment with charged ions, which is confirmed by the mid-IR intraband absorption (1Se-1Pe) intensity imaged by the FTIR microscope. Furthermore, a novel second intraband transition (1Pe-1De) is observed from the HgS CQD solid. The observation of the second intraband transition (1Pe-De) allows us to utilize the higher quantized states that were hidden for the last three decades. The use of the intraband transition with narrow bandwidth in mid-IR would enable to choose an optimal electronic transition occurring in the nanocrystal for a number of applications: wavelength-selective low-energy consuming electronics, space-communication light source, mid-infrared energy sensitized electrode and catalyst, infrared photodetector, and infrared filter.

Cd x Hg1–x Se alloy nanocrystals are obtained from CdSe semiconductor nanocrystals via cation exchange. By varying the composition during the exchange process, the Cd x Hg1–x Se alloy nanocrystals offer a widely tunable electronic transition from visible to NIR and even to mid-IR range. The visible bandgap transition of the CdSe colloidal quantum dot gradually red-shifts to the near-IR with the addition of the Hg precursor, and then the steady-state intraband (or intersub-band) transition of the Cd x Hg1–x Se alloy nanocrystals appears. Finally, as the electron density is increased by successive addition of metal precursor, localized surface plasmon resonances (LSPRs) appear as a major electronic transition in the mid-IR regime. The shift of the major electronic transition from the bandgap to LSPRs infers that the exciton spatially moves to the surface from the inside of the nanocrystal through the cation change and further crystal growth. The corresponding variance of the nanocrystals’ structural, compositional, optical, electrical, and magnetic properties was carefully monitored by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron-dispersive X-ray (EDS) spectroscopy, time-resolved photoluminescence, photocurrent measurement, and electron paramagnetic resonance (EPR) spectroscopy, respectively. While a shift in only the bandgap has been observed in conventional quantum dots when cation-exchanged, the major oscillating transition transfers from the bandgap to the higher quantum states in Cd x Hg1–x Se alloy nanocrystal formed by the cation-exchange in this report. The compositional change expanding the optical range of nanocrystals from visible to mid-IR regime will provide a useful means of optimally tuning the electronic transition of nanocrystal-based applications along with improved optical selectivity demonstrated by a single intraband or LSPR peak.

Steady-state electron occupation of the lowest quantum state in the conduction band of a colloidal quantum dot gives rise to unique electrical properties. An electron mobility of 1.29 cm2 V−1 s−1 was measured in a mercury sulfide quantum dot FET.