Developing chemically and thermally stable, highly efficient green-emitting inorganic phosphors is a significant challenge in solid-state lighting. One accessible pathway for achieving green emission is by forming a solid solution with superior blue-emitting materials. In this work, we demonstrate that the cyan-emission ( λ em = 481 nm) of the BaScO 2 F:Eu 2+ perovskite can be red-shifted by forming a solid solution following (Ba 1− x Sr x ) 0.98 Eu 0.02 ScO 2 F ( x = 0, 0.075, 0.15, 0.25, 0.33, 0.40). Although green emission is achieved ( λ em = 516 nm) as desired, the thermal quenching (TQ) resistance is reduced, and the photoluminescence quantum yield (PLQY) drops by 65%. Computation reveals the source of these changes. Surprisingly, a basic density functional theory analysis shows the gradual Sr Ba substitution has negligible effects on the band gap ( E g ) energy, suggesting the activation energy barrier for the thermal ionization quenching remains unchanged, while the nearly constant Debye temperature indicates no loss of average structural rigidity to explain the decrease in the PLQY. Instead, temperature-dependent ab initio molecular dynamics (AIMD) simulations show that gradual changes of the Eu 2+ ion's local coordination environment rigidity are responsible for the drop in the observed TQ and PLQY. These results express the need to computationally analyze the local rare-earth environment as a function of temperature to understand the fundamental origin of optical properties in new inorganic phosphors.
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Identifying an efficient, thermally robust inorganic phosphor host via machine learning
Rare-earth substituted inorganic phosphors are critical for solid state lighting. New phosphors are traditionally identified through chemical intuition or trial and error synthesis, inhibiting the discovery of potential high-performance materials. Here, we merge a support vector machine regression model to predict a phosphor host crystal structure’s Debye temperature, which is a proxy for photoluminescent quantum yield, with high-throughput density functional theory calculations to evaluate the band gap. This platform allows the identification of phosphors that may have otherwise been overlooked. Among the compounds with the highest Debye temperature and largest band gap, NaBaB9O15shows outstanding potential. Following its synthesis and structural characterization, the structural rigidity is confirmed to stem from a unique corner sharing [B3O7]5–polyanionic backbone. Substituting this material with Eu2+yields UV excitation bands and a narrow violet emission at 416 nm with a full-width at half-maximum of 34.5 nm. More importantly, NaBaB9O15:Eu2+possesses a quantum yield of 95% and excellent thermal stability.
more » « less- NSF-PAR ID:
- 10154367
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 9
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Unveiling the underlying mechanisms of properties of functional materials, including the luminescence differences among similar pyrochlores A2B2O7, opens new gateways to select proper hosts for various optoelectronic applications by scientists and engineers. For example, although La2Zr2O7(LZO) and La2Hf2O7(LHO) pyrochlores have similar chemical compositional and crystallographic structural features, they demonstrate different luminescence properties both before and after doped with Eu3+ions. Based on our earlier work, LHO‐based nanophosphors display higher photo‐ and radioluminescence intensity, higher quantum efficiency, and longer excited state lifetime compared to LZO‐based nanophosphors. Moreover, under electronic O2−→Zr4+/Hf4+transition excitation at 306 nm, undoped LHO nanoparticles (NPs) have only violet blue emission, whereas LZO NPs show violet blue and red emissions. In this study, we have combined experimental and density functional theory (DFT) based theoretical calculation to explain the observed results. First, we calculated the density of state (DOS) based on DFT and studied the energetics of ionized oxygen vacancies in the band gaps of LZO and LHO theoretically, which explain their underlying luminescence difference. For Eu3+‐doped NPs, we performed emission intensity and lifetime calculations and found that the LHOE NPs have higher host to dopant energy transfer efficiency than the LZOE NPs (59.3% vs 24.6%), which accounts for the optical performance superiority of the former over the latter. Moreover, by corroborating our experimental data with the DFT calculations, we suggest that the Eu3+doping states in LHO present at exact energy position (both in majority and minority spin components) where oxygen defect states are located unlike those in LZO. Lastly, both the NPs show negligible photobleaching highlighting their potential for bioimaging applications. This current report provides a deeper understanding of the advantages of LHO over LZO as an advanced host for phosphors, scintillators, and fluoroimmunoassays.
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Desirable phosphors for lighting, scintillation and composite films must have good light absorption properties, high concentration quenching, high quantum efficiency, a narrow color emission, and so forth. In this work, we first show that undoped yttrium hafnate Y 2 Hf 2 O 7 (YHO) nanoparticles (NPs) display dual blue and red bands after excitation using 330 nm light. Based on density functional theory (DFT) calculations, these two emission bands are correlated with the defect states arising in the band-gap region of YHO owing to the presence of neutral and charged oxygen defects. Once doped with Eu 3+ ions (YHOE), the YHO NPs show a bright red emission, a long excited state lifetime and stable color coordinates upon near-UV and X-ray excitation. Concentration quenching is active when Eu 3+ doping reaches 10 mol% with a critical distance of ∼4.43 Å. This phenomenon indicates a high Eu 3+ solubility within the YHO host and the absence of Eu 3+ clusters. More importantly, the optical performance of the YHOE NPs has been further improved by lithium co-doping. The origin of the emission, structural stability, and role of Li + -co-doping are explored both experimentally and theoretically. DFT calculation results demonstrate that Li + -co-doping increases the covalent character of the Eu 3+ –O 2− bonding in the EuO 8 polyhedra. Furthermore, the YHOE NPs have been dispersed into polyvinyl alcohol (PVA) to make transparent nanocomposite films, which show strong red emission under excitation at 270 and 393 nm. Overall, we demonstrate that the YHO NPs with Eu 3+ and (Eu 3+ /Li + ) doping have a high emission intensity and quantum efficiency under UV and X-ray excitation, which makes them suitable for use as phosphors, scintillators and transparent films for lighting, imaging and detection applications.more » « less
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Resonant tunneling diodes (RTDs) have come full-circle in the past 10 years after their demonstration in the early 1990s as the fastest room-temperature semiconductor oscillator, displaying experimental results up to 712 GHz and fmax values exceeding 1.0 THz [1]. Now the RTD is once again the preeminent electronic oscillator above 1.0 THz and is being implemented as a coherent source [2] and a self-oscillating mixer [3], amongst other applications. This paper concerns RTD electroluminescence – an effect that has been studied very little in the past 30+ years of RTD development, and not at room temperature. We present experiments and modeling of an n-type In0.53Ga0.47As/AlAs double-barrier RTD operating as a cross-gap light emitter at ~300K. The MBE-growth stack is shown in Fig. 1(a). A 15-μm-diam-mesa device was defined by standard planar processing including a top annular ohmic contact with a 5-μm-diam pinhole in the center to couple out enough of the internal emission for accurate free-space power measurements [4]. The emission spectra have the behavior displayed in Fig. 1(b), parameterized by bias voltage (VB). The long wavelength emission edge is at = 1684 nm - close to the In0.53Ga0.47As bandgap energy of Ug ≈ 0.75 eV at 300 K. The spectral peaks for VB = 2.8 and 3.0 V both occur around = 1550 nm (h = 0.75 eV), so blue-shifted relative to the peak of the “ideal”, bulk InGaAs emission spectrum shown in Fig. 1(b) [5]. These results are consistent with the model displayed in Fig. 1(c), whereby the broad emission peak is attributed to the radiative recombination between electrons accumulated on the emitter side, and holes generated on the emitter side by interband tunneling with current density Jinter. The blue-shifted main peak is attributed to the quantum-size effect on the emitter side, which creates a radiative recombination rate RN,2 comparable to the band-edge cross-gap rate RN,1. Further support for this model is provided by the shorter wavelength and weaker emission peak shown in Fig. 1(b) around = 1148 nm. Our quantum mechanical calculations attribute this to radiative recombination RR,3 in the RTD quantum well between the electron ground-state level E1,e, and the hole level E1,h. To further test the model and estimate quantum efficiencies, we conducted optical power measurements using a large-area Ge photodiode located ≈3 mm away from the RTD pinhole, and having spectral response between 800 and 1800 nm with a peak responsivity of ≈0.85 A/W at =1550 nm. Simultaneous I-V and L-V plots were obtained and are plotted in Fig. 2(a) with positive bias on the top contact (emitter on the bottom). The I-V curve displays a pronounced NDR region having a current peak-to-valley current ratio of 10.7 (typical for In0.53Ga0.47As RTDs). The external quantum efficiency (EQE) was calculated from EQE = e∙IP/(∙IE∙h) where IP is the photodiode dc current and IE the RTD current. The plot of EQE is shown in Fig. 2(b) where we see a very rapid rise with VB, but a maximum value (at VB= 3.0 V) of only ≈2×10-5. To extract the internal quantum efficiency (IQE), we use the expression EQE= c ∙i ∙r ≡ c∙IQE where ci, and r are the optical-coupling, electrical-injection, and radiative recombination efficiencies, respectively [6]. Our separate optical calculations yield c≈3.4×10-4 (limited primarily by the small pinhole) from which we obtain the curve of IQE plotted in Fig. 2(b) (right-hand scale). The maximum value of IQE (again at VB = 3.0 V) is 6.0%. From the implicit definition of IQE in terms of i and r given above, and the fact that the recombination efficiency in In0.53Ga0.47As is likely limited by Auger scattering, this result for IQE suggests that i might be significantly high. To estimate i, we have used the experimental total current of Fig. 2(a), the Kane two-band model of interband tunneling [7] computed in conjunction with a solution to Poisson’s equation across the entire structure, and a rate-equation model of Auger recombination on the emitter side [6] assuming a free-electron density of 2×1018 cm3. We focus on the high-bias regime above VB = 2.5 V of Fig. 2(a) where most of the interband tunneling should occur in the depletion region on the collector side [Jinter,2 in Fig. 1(c)]. And because of the high-quality of the InGaAs/AlAs heterostructure (very few traps or deep levels), most of the holes should reach the emitter side by some combination of drift, diffusion, and tunneling through the valence-band double barriers (Type-I offset) between InGaAs and AlAs. The computed interband current density Jinter is shown in Fig. 3(a) along with the total current density Jtot. At the maximum Jinter (at VB=3.0 V) of 7.4×102 A/cm2, we get i = Jinter/Jtot = 0.18, which is surprisingly high considering there is no p-type doping in the device. When combined with the Auger-limited r of 0.41 and c ≈ 3.4×10-4, we find a model value of IQE = 7.4% in good agreement with experiment. This leads to the model values for EQE plotted in Fig. 2(b) - also in good agreement with experiment. Finally, we address the high Jinter and consider a possible universal nature of the light-emission mechanism. Fig. 3(b) shows the tunneling probability T according to the Kane two-band model in the three materials, In0.53Ga0.47As, GaAs, and GaN, following our observation of a similar electroluminescence mechanism in GaN/AlN RTDs (due to strong polarization field of wurtzite structures) [8]. The expression is Tinter = (2/9)∙exp[(-2 ∙Ug 2 ∙me)/(2h∙P∙E)], where Ug is the bandgap energy, P is the valence-to-conduction-band momentum matrix element, and E is the electric field. Values for the highest calculated internal E fields for the InGaAs and GaN are also shown, indicating that Tinter in those structures approaches values of ~10-5. As shown, a GaAs RTD would require an internal field of ~6×105 V/cm, which is rarely realized in standard GaAs RTDs, perhaps explaining why there have been few if any reports of room-temperature electroluminescence in the GaAs devices. [1] E.R. Brown,et al., Appl. Phys. Lett., vol. 58, 2291, 1991. [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [2] M. Feiginov et al., Appl. Phys. Lett., 99, 233506, 2011. [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [3] Y. Nishida et al., Nature Sci. Reports, 9, 18125, 2019. [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [4] P. Fakhimi, et al., 2019 DRC Conference Digest. [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018).more » « less
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Abstract Using molten‐salt synthetic techniques, NaNbO3(Space group
Pbcm ; No. 57) was prepared in high purity at a reaction time of 12 hours and a temperature of 900°C. All NaNbO3products were prepared from stoichiometric ratios of Nb2O5and Na2CO3together with the addition of a salt flux introduced at a 10:1 molar ratio of salt to NaNbO3, that is, using the Na2SO4, NaF, NaCl, and NaBr salts. A solid‐state synthesis was performed in the absence of a molten salt to serve as a control. The reaction products were all found to be phase pure through powder X‐ray diffraction, for example, with refined lattice constants ofa = 5.512(5) Å,b = 5.567(3) Å, andc = 15.516(8) Å from the Na2SO4salt reaction. The products were characterized using UV‐Vis diffuse reflectance spectroscopy to have a bandgap size of ~3.5 eV. The particles sizes were analyzed by scanning electron microscopy (SEM) and found to be dependent upon the flux type used, from ~<1 μm to >10 μm in length, with overall surface areas that could be varied from 0.66 m2/g (for NaF) to 1.55 m2/g (for NaBr). Cubic‐shaped particle morphologies were observed for the metal halide salts with the set of exposed (100)/(010)/(001) crystal facets, while a truncated octahedral morphology formed in the sodium sulfate salt reaction with predominantly the set of (110)/(101)/(011) crystal facets. The products were found to be photocatalytically active for hydrogen production under UV‐Vis irradiation, with the aid of a 1 wt% Pt surface cocatalyst. The platinized NaNbO3particles were suspended in an aqueous 20% methanol solution and irradiated by UV‐Vis light (λ > 230 nm). After 6 hours of irradiation, the average total hydrogen production varied with the particle morphologies and sizes, with 753 µmol for Na2SO4, 334 µmol for NaF, 290 µmol for NaCl, 81 µmol for NaBr, and 249 µmol for the solid‐state synthesized NaNbO3. These trends show a clear relationship to particle sizes, with smaller particles showing higher photocatalytic activity in the order of NaF > NaCl > NaBr. Furthermore, the particle morphologies obtained from the Na2SO4flux showed even higher photocatalytic activity, though having a relatively similar overall surface area, owing to the higher activity of the (110) crystal facets. The apparent quantum yield (100 mW/cm2,λ = 230 to 350 nm, pH = 7) was measured to be 3.7% for NaNbO3prepared using the NaF flux, but this was doubled to 6.8% when prepared using the Na2SO4flux. Thus, these results demonstrate the powerful utility of flux synthetic techniques to control particle sizes and to expose higher‐activity crystal facets to boost their photocatalytic activities for molecular hydrogen production.
