Abstract Discovery of new materials with enhanced optical properties in the visible and UV‐C range can impact applications in lasers, nonlinear optics, and quantum optics. Here, the optical floating zone growth of a family of rare earth borates,RBa3(B3O6)3(R= Nd, Sm, Tb, Dy, and Er), with promising linear and nonlinear optical (NLO) properties is reported. Although previously identified to be centrosymmetric, the X‐ray analysis combined with optical second harmonic generation (SHG) assigns the noncentrosymmetricPspace group to these crystals. Characterization of linear optical properties reveals a direct bandgap of ≈5.61–5.72 eV and strong photoluminescence in both the visible and mid‐IR regions. Anisotropic linear and nonlinear optical characterization reveals both Type‐I and Type‐II SHG phase matchability, with the highest effective phase‐matched SHG coefficient of 1.2 pm V−1at 800‐nm fundamental wavelength (for DyBa3(B3O6)3), comparable to β‐BaB2O4(phase‐matchedd22≈ 1.9 pm V−1). Laser‐induced surface damage threshold for these environmentally stable crystals is 650–900 GW cm−2, which is four to five times higher than that of β‐BaB2O4, thus providing an opportunity to pump with significantly higher power to generate about six to seven times stronger SHG light. Since the SHG arises from disorder on the Ba‐site, significantly larger SHG coefficients may be realized by “poling” the crystals to align the Ba displacements. These properties motivate further development of this crystal family for laser and wide bandgap NLO applications.
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High Entropy Wide‐Bandgap Borates with Broadband Luminescence and Large Nonlinear Optical properties
ABSTRACT We report the first successful synthesis and characterization of a new family of high‐entropy rare earth borate (RnBBO) single crystals with compositionsR5Ba3(B3O6)3andR6Ba3(B3O6)3(R= Nd, Tb, Sm, Dy, Gd, Yb, Er). Using configurational entropy as a tuning knob, these systems have been grown as large, highly crystalline boules that exhibit a bandgap of ≈5 eV and significantly enhanced optical transparency (20–50%) over singlecomponent systems. The presence of multiple rare‐earth elements results in broadband photoluminescence in both the visible and the near‐infrared wavelength ranges, with co‐existing emission bands at 605, 705, 813, 910, and 1030 nm. Further, broken inversion symmetry enables optical second‐harmonic generation (SHG) with potential for both type‐I and type‐II phase matching. Our highest observed effective phase‐matched SHG coefficient of ≈ 2.1 pm V−1at 800–400 nm wavelength conversion is 20% better than the commercial β‐BaB2O4(BBO), while its laser‐induced surface damage threshold is 5‐6 × larger for 100 fs 800 nm pulse, enabling potentially an order of magnitude improvement in the frequency conversion efficiency. This work illuminates the promise of high‐entropy synthesis strategy for designing next‐generation optoelectronic materials that combine increased transparency, strong broadband luminescence, and enhanced nonlinear response in a single platform.
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- Award ID(s):
- 2011839
- PAR ID:
- 10683390
- Publisher / Repository:
- Wiley Advanced
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 36
- Issue:
- 35
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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