PL spectroscopy of single CdSe nanocrystalline quantum dots Empedocles et al., Phys. Rev. Lett.

77, 3873 (1996) Two kinds of CdSe nanocrystals were used: "Standard" (crystal structure: wurtzite, slightly prolate, 3 different sizes: 3.9, 4.5 and 5.0 nm) and "overcoated" (ZnS capping layer, size=4.3 nm, higher QYield ~ 50%) NCs dispersed in 50 nm PMMA film, lateral dispersion <1 QD/m2 Epifluorescence microscopy Excitation volume

Radius of the focused spot (I = Imaxe), w = 1.27 f nD

A) PL Image of single 4.5 nm NCs at 10 K. White dotted lines represent the center of the entrance slit. Note that all NCs are not equally bright. B) Spectra of a few NCs collected after closing the entrance slit to 0.125 mm. Only those particles lying between the dotted lines in (A) were measured. Note that the general nature of the spectra (one main peak, and a vibronic side band) is same, but not their position.

(B) (C) (D) are comparison of single particle and ensemble spectra for 3 differently sized NCs. Note that vibronic sidebands cannot be seen in ensemble spectrum. (A) Comparison of a single NC spectrum with that of fluorescence line narrowed spectrum. Single NC spectrum is an order of magnitude narrower. (B) The histogram of PL peak positions for 513 individual NC reproduces the ensemble Pl spectra, suggesting that ensemble spectrum is inhomogeneously broadened.

Power dependence of Linewidth

314 W/cm2, t = 60s 150 W/cm2, t = 60s 65 W/cm2, t = 60s

PL linewidth broadens with increasing excitation power/intensity, and eventually saturates.

t = 30s

Averaged over 34 core-shell 56.5 NCs Saturation is best seen when not averaged over several particles.

Acquisition time dependence of Linewidth

200 W/cm2 t = 0.1 s

85 W/cm2 0.48 meV

t = 10 s 2 meV

Same sample!! Averaged over 40 NCs PL linewidth broadening with increasing integration (exposure) time. Once again saturation is observed at higher time scales.

t = 30 s

85 W/cm2

Linewidth saturation at higher energy densities!!

40 K

PL linewidths of single core-shell dots were studied at 514 nm and 573 nm excitations. Integration time, temp., and number of excitations were kept constant. For 126 dots studied, 573 nm (lower energy) excitation resulted in 25% decrease in average linewidth

10 K

What is changing: NC or its surroundings?

Surface charge : unsaturated dangling bonds, distortions of ionic lattice. Net charge setup a local electric field that can induce Stark shift of emission energies. It is a fluid situation that can change as excess excitation energy is dumped onto it. The amount of excess excitation energy released as the exciton relaxes to its emitting state (internal conversion). Could be energy released following a single excitation (excitation energy dependence) OR cumulative release over several excitation events (time and power dependence). Cannot be non-radiative contribution (0.25 eV vs. 2.4 eV) Cannot even be a local heating effect. Heat dissipation happens over 10-12 s. At high energy densities, the charges can effectively sample all possible trap sites leading to a saturation of linewidth.

Single charge in a double well trap potential

In absence of excess excitation energy, i.e, lower powers and/or small exposure times, the charge is localized in a particular trap site. Correspondingly the field it creates is not time dependent. Depending on which site traps the charge, one gets either spectrum (B) or (D). With excess excitation energy, the charge can move between traps and the resultant spectrum is a linear combination of (B) and (D). With poor spectral resolution, this will be seen as an effective broadening. But with high spectral resolution it is possible to see individual peaks.

Higher resolution spectra (0-0 line), for t = 60 s

Linewidth in the limit of vanishing energy density

25 dots Electrical and physical screening of local electric field in core-shell NCs

34 dots

Large spectral diffusion

Spectral shifts happening over 10s of meV and on timescales from sec to minutes

80 meV shifts over 16 min. Decreased PL intensity and increased vibronic (phonon) coupling in red shifted spectra. Similarity with single NC Stark spectroscopy

4 nm core-only NC, tinteg = 60s, 2.5 kW/cm2

Stark spectroscopy
Why should a NC PL spectrum respond to external electric field? Charge traps at the surface, very localized, dipole character : Linear stark effect Electron and hole wavefunctions, delocalized and therefore polarizable : Quadratic 7.9 nm core-shell NC, 25 W/cm2 Red shift associated with decreased PL intensity and increased phonon coupling

Both linear and quadratic responses

Linear and Quadratic Stark responses

Stark response from 4 different 5.8 nm single NC particles Response averaged over for 54 single NC particles is all quadratic! Stark shift observed in ensemble measurement is also quadratic Average dipolar contribution in an ensemble goes to 0 Is this dipole related to transition dipole moment?

Polarizable wavefunctions and Frolich coupling

External electric field can separate electron and hole wavefunctions: quantum confined stark effect (QCSE) Red shift is a result of apparent reduction in quantum confinement due to e- and h+ wavefunctions pulled apart. Reduced PL intensity is a result of reduced e- and h+ wavefunction overlap. What sort of electric field produces large spectral diffusion? ~ an electron on the surface of the NC Type II nanocrystals are another way Will you expect identical phonon coupling across different NC particles?

on-overlapping

This is a good comparison!

Spectral diffusion Stark shifts

Correlation of phonon coupling and spectral shift are identical in Stark spectroscopy and spectral diffusion experiments. This suggests that a local field is responsible for the observed spectral diffusion. What is the source of local field? Spectral Jitter (Gaussian) slowly varying surface charge density Spectral Jump (Lorentzian) rapidly occurring polarization change due to a reversible expulsion of a charge carrier (Auger photoionization)

No effect on the transition dipole moment (orientation)

Effect of spectral diffusion on Stark shift

tinteg = 30 s

Before the shift: = 80 D, = 3.3105 3 After the shift: = 33 D, = 3.5105 3

References
1. For epifluorescence and confocal microscopy, refer Methods of single-molecule fluorescence spectroscopy and microscopy, Moerner and Fromm, Rev. Sci. Intrum. 74, 3597 (2003). 2. Empedocles et al., Photoluminescence spectroscopy of single CdSe nanocrystallite quantum dots, Phys. Rev. Lett. 77, 3783 (1996). 3. Empedocles et al., Spectroscopy of single CdSe nanocrystallites, Acc. Chem. Res. 32, 389 (1999). 4. Empedocles et al., Photoluminescence from single semiconductor nanostructures, Adv. Mater. 11, 1243 (1999). Section 5 onwards 5. Empedocles et al., Influence of spectral diffusion on the lineshapes of single CdSe nanocrystallite quantum dots, J. Phys. Chem. B 103, 1826 (1999). ** Ref. 3 and 4 are reviews based mainly on results reported in Ref. 2 and 5. 6. Neuhauser et al., Correlation between fluorescence intermittency and spectral diffusion in single semiconductor q-dots, Phys. Rev. Lett. 85, 3301 (2000).