Ultra-small PbS nanocrystals as sensitizers for red-to-blue triplet-fusion upconversion
Bibliographic record
Abstract
Photon upconversion is a strategy to generate high-energy excitations from low-energy photon input, enabling advanced architectures for imaging and photochemistry. Here, we show that ultra-small PbS nanocrystals can sensitize red-to-blue triplet-fusion upconversion with a large anti-Stokes shift (ΔE=1.04 eV), and achieve max-efficiency upconversion at near-solar fluences (Ith=220 mW/cm2) despite endothermic triplet sensitization. This system facilitates the photo-initiated polymerization of methylmethacrylate using only long-wavelength light (λ: 637 nm); a demonstration of nanocrystal-sensitized upconversion photochemistry. Time-resolved spectroscopy and kinetic modelling clarify key loss channels, highlighting the benefit of long-lifetime nanocrystal sensitizers, but revealing that many (48%) excitons that reach triplet-extracting carboxyphenylanthracene ligands decay before they can transfer to free-floating acceptors—emphasizing the need to address the reduced lifetimes that we determine for molecular triplets near the nanocrystal surface. Finally, we find that the inferred thermodynamics of triplet sensitization from these ultra-small PbS quantum dots are surprisingly favourable—completing an advantageous suite of properties for upconversion photochemistry—and do not vary significantly across the ensemble, which indicates minimal effects from nanocrystal heterogeneity. Together, our demonstration and study of red-to-blue upconversion using ultra-small PbS nanocrystals in a quasi-equilibrium sensitization scheme offer design rules to advance implementations of triplet fusion, especially where large anti-Stokes wavelength shifts are sought.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.001 | 0.000 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.000 |
| 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 teacher head, 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".