Nanocrystals or quantum dots of the IV−VI semiconductors PbS, PbSe, and PbTe provide unique properties for investigating the effects of strong confinement on electrons and phonons. The degree of confinement of charge carriers can be many times stronger than in most II−VI and III−V semiconductors, and lead salt nanostructures may be the only materials in which the electronic energies are determined primarily by quantum confinement. This Account briefly reviews recent research on lead salt quantum dots.

Lead Salt Quantum Dots: the Limit of Strong Quantum Confinement

We analyze theoretically the optical properties of ideal semiconductor crystallites so small that they show quantum confinement in all three dimensions [quantum dots (QD's)]. In the limit of a QD much smaller than the bulk exciton size, the linear spectrum will be a series of lines, and we consider the phonon broadening of these lines. The lowest interband transition will saturate like a two-level system, without exchange and Coulomb screening. Depending on the broadening, the absorption and the changes in absorption and refractive index resulting from saturation can become very large, and the local-field effects can become so strong as to give optical bistability without external feedback. The small QD limit is more readily achieved with narrow-band-gap semiconductors.

Theory of the linear and nonlinear optical properties of semiconductor microcrystallites

PbSe nanocrystal colloids exhibit a well-defined excitonic structure with the lowest energy exciton tuning from 0.5 to 1 eV, as a function of size. Band-edge fluorescence is observed from 1.2 to 2 μm with a small Stokes shift, sub-μs lifetime, and near-unity quantum yield. Upon pumping at 1.064 μm, the first exciton decay is consistent with radiative relaxation at low pump intensity and with Auger recombination at higher pump intensities. Optically induced absorption is observed at approximately midgap. These transitions exhibit strengths similar to the interband exciton and are size-tunable. They are assigned to the 1Se,h−1Pe,h and 1Pe,h−1De,h intraband excitations. Intraband pump−probe measurements of the 1Se,h−1Pe,h transition reveal a short lifetime and the absence of the phonon bottleneck.

Interband and Intraband Optical Studies of PbSe Colloidal Quantum Dots

Recently, inorganic and hybrid light absorbers such as quantum dots and organometal halide perovskites have been studied and applied in fabricating thin-film photovoltaic devices because of their low-cost and potential for high efficiency. Further boosting the performance of solution processed thin-film solar cells without detrimentally increasing the complexity of the device architecture is critically important for commercialization. Here, we demonstrate photocurrent and efficiency enhancement in meso-superstructured organometal halide perovskite solar cells incorporating core-shell Au@SiO2 nanoparticles (NPs) delivering a device efficiency of up to 11.4%. We attribute the origin of enhanced photocurrent to a previously unobserved and unexpected mechanism of reduced exciton binding energy with the incorporation of the metal nanoparticles, rather than enhanced light absorption. Our findings represent a new aspect and lever for the application of metal nanoparticles in photovoltaics and could lead to facile tuning of exciton binding energies in perovskite semiconductors.

http://pubs.acs.org/doi/pdf/10.1021/nl4024287

Enhancement of perovskite-based solar cells employing core-shell metal nanoparticles.

Inductively coupled plasma mass spectrometry (ICP-MS) was combined with UV–vis−NIR spectrophotometry and transmission electron microscopy to determine the nanocrystal composition and molar extinction coefficient ϵ of colloidal PbSe quantum dot (Q-PbSe) suspensions. The ICP-MS results show a nonstoichiometric Pb/Se ratio, with a systematic excess of lead for all samples studied. The observed ratio is consistent with a faceted spherical Q-PbSe model, composed of a quasi stoichiometric Q-PbSe core terminated by a Pb surface shell. At high photon energies, we find that ϵ scales with the nanocrystal volume, irrespective of the Q-PbSe size. From ϵ, we calculated a size-independent absorption coefficient. Its value is in good agreement with the theoretical value for bulk PbSe. At the band gap, ϵ is size-dependent. The resulting absorption coefficient increases quadratically with decreasing Q-PbSe size. Calculations of the oscillator strength of the first optical transition are in good agreement with theoretical ...

Composition and size-dependent extinction coefficient of colloidal PbSe quantum dots

We observe that the temperature coefficients of electron-hole pair energies $(dE/dT)$ in PbS and PbSe quantum dots depend strongly on the size of the quantum dot. With decreasing size the temperature coefficient of the lowest electron-hole pair energy ${\mathrm{dE}}_{g}/dT$ decreases by more than an order of magnitude from the bulk value. The weak temperature dependence found in the strong-confinement limit is expected for atomiclike levels, but has not been observed previously in a semiconductor.

Size-Dependent Temperature Variation of the Energy Gap in Lead-Salt Quantum Dots

The controlled synthesis of PbSe nanocrystal quantum dots with narrow size distributions was achieved through phase decomposition of the PbSe solid solution in a phosphate glass host. Structural characterization by electron microscopy and x-ray diffraction shows that the dots have mean diameters between 2 and 15 nm. The exciton Bohr radius aB=46 nm in PbSe, so these quantum dots provide unusual and perhaps unique access to the regime of strong quantum confinement. The optical absorption spectra are compared to the predictions of a theoretical treatment of the electronic structure. The theory agrees well with experiment for dots larger than ∼7 nm, but for smaller dots there is some deviation from the theoretical predictions.

http://staff.chess.cornell.edu/~shen/Articles_published/APL97_PbSe.pdf

Synthesis and characterization of PbSe quantum dots in phosphate glass

Cubic PbS crystallites with diameter from 2.5 up to 15 nm were grown within a P2O5-Na2O-ZnO-AlF3-Ga2O3 glass matrix. Optical absorption spectra of the quantum dots exhibit structure reflecting distinct quantum transitions and narrow (5–7%) size distributions of the crystallites. The variation of the optical spectra depends on the size of the quantum dot.

A. Olkhovets

Papers

Size-Dependent Temperature Variation of the Energy Gap in Lead-Salt Quantum Dots

Synthesis and characterization of PbSe quantum dots in phosphate glass

Synthesis of monodisperse PbS quantum dots in phosphate glass