| Autor: |
Stecher JT; Department of Chemistry, Duke University, French Family Science Center, 124 Science Drive, Durham, NC 27708, USA. joshua.stecher@duke.edu., Rohlfing AB; Department of Chemistry, Duke University, French Family Science Center, 124 Science Drive, Durham, NC 27708, USA. anne.rohlfing@duke.edu., Therien MJ; Department of Chemistry, Duke University, French Family Science Center, 124 Science Drive, Durham, NC 27708, USA. michael.therien@duke.edu. |
| Abstrakt: |
We report a one-pot solvothermal synthesis of sub-10 nm, dominant ultraviolet (UV) emissive upconverting nanocrystals (UCNCs), based on sodium-codoped LaF₃ and BaLaF₅ (0.5%Tm; 20%Yb) and their corresponding core@shell derivatives. Elemental analysis shows a Na-codopant in these crystal systems of ~20% the total cation content; X-ray diffraction (XRD) data indicate a shift in unit cell dimensions consistent with these small codopant ions. Similarly, X-ray photoelectron spectroscopic (XPS) analysis reveals primarily substitution of Na⁺ for La 3+ ions (97% of total Na⁺ codopant) in the crystal system, and interstitial Na⁺ (3% of detected Na⁺) and La 3+ (3% of detected La 3+ ) present in (Na)LaF₃ and only direct substitution of Na⁺ for Ba 2+ in Ba(Na)LaF₅. In each case, XPS analysis of La 3d lines show a decrease in binding energy (0.08-0.25 eV) indicating a reduction in local crystal field symmetry surrounding rare earth (R.E. 3+ ) ions, permitting otherwise disallowed R.E. UC transitions to be enhanced. Studies that examine the impact of laser excitation power upon luminescence intensity were conducted over 2.5-100 W/cm² range to elucidate UC mechanisms that populate dominant UV emitting states. Low power saturation of Tm 3+ ³F₃ and ³H₄ states was observed and noted as a key initial condition for effective population of the ¹D₂ and ¹I₆ UV emitting states, via Tm-Tm cross-relaxation. |
