The smallest PbS nanocrystals pervasively show decreased brightness, linked to surface-mediated decay on the average particle
Bibliographic record
Abstract
PbS semiconductor nanocrystals (NCs) have been heavily explored for infrared optoelectronics but can exhibit visible-wavelength quantum-confined optical gaps when sufficiently small (⌀ = 1.8-2.7 nm). However, small PbS NCs traditionally exhibited very broad ensemble absorption linewidths, attributed to poor size-heterogeneity. Here, harnessing recent synthetic advances, we report photophysical measurements on PbS ensembles that span this underexplored size range. We observe that the smallest PbS NCs pervasively exhibit lower brightness and anomalously accelerated photoluminescence decays-relative to the idealized photophysical models that successfully describe larger NCs. We find that effects of residual ensemble size-heterogeneity are insufficient to explain our observations, so we explore plausible processes that are intrinsic to individual nanocrystals. Notably, the anomalous decay kinetics unfold, surprisingly, over hundreds-of-nanosecond timescales. These are poorly matched to effects of direct carrier trapping or fine-structure thermalization but are consistent with non-radiative recombination linked to a dynamic surface. Thus, the progressive enhancement of anomalous decay in the smallest particles supports predictions that the surface plays an outsized role in exciton-phonon coupling. We corroborate this claim by showing that the anomalous decay is significantly remedied by the installation of a rigidifying shell. Intriguingly, our measurements show that the anomalous aspect of these kinetics is insensitive to temperature between T = 298 and 77 K, offering important experimental constraint on possible mechanisms involving structural fluctuations. Thus, our findings identify and map the anomalous photoluminescence kinetics that become pervasive in the smallest PbS NCs and call for targeted experiments and theory to disentangle their origin.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".