Blue emitting Sn-based lead-free halide perovskite nanocrystals (NCs) are considered to be a promising material in lighting and displays. However, industrialised fabrication of blue-emitting NCs still remains a significant challenge due to the use of toxic solvents and optical instability, not mentioning in large-scale synthesis. In this work, a green-route synthesis of blue-emitting lead-free halide perovskite Cs 2 SnCl 6 powders is developed, in which deionized water with a small amount of inorganic acid is used as the solvent and the synthesis of the Cs 2 SnCl 6 powders is achieved on a microfluidic platform. Using the Cs 2 SnCl 6 powders, we prepare Cs 2 SnCl 6 NCs via an ultrasonication process. Changing the volume ratio of the ligands (oleic acid to oleylamine) can alter the photoluminescence (PL) characteristics of the prepared NCs, including the PL-peak wavelength, PL-peak intensity and quantum yield. The highest photoluminescence quantum yield (PLQY) of 13.4% is achieved by the Cs 2 SnCl 6 NCs prepared with the volume ratio of oleic acid to oleylamine of 40 μL to 10 μL. A long-term PL stability test demonstrates that the as-synthesized Cs 2 SnCl 6 NCs can retain a stable PLQY over a period of 60 days. This work opens up a new path for a large-scale green-route synthesis of blue-emitting Sn-based lead-free NCs, such as Cs 2 SnX 6 (Cl, Br and I), towards their applications in optoelectronics.
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High-efficiency blue photoluminescence in the Cs 2 NaInCl 6 :Sb 3+ double perovskite phosphor
In this paper, the photoluminescent properties of a lead-free double perovskite Cs 2 NaInCl 6 doped with Sb 3+ are explored. The host crystal structure is a cubic double perovskite with Fm 3̄ m symmetry, a = 10.53344(4) Å, and rock salt ordering of Na + and In 3+ . It is a wide bandgap compound ( E g ≈ 5.1 eV), and substitution with Sb 3+ leads to strong absorption in the UV due to localized 5s 2 → 5s 1 5p 1 transitions on Sb 3+ centers. Radiative relaxation back to the 5s 2 ground state, via a 3 P 1 → 1 S 0 transition, leads to intense blue luminescence, centered at 445 nm, with a photoluminescent quantum yield of 79%. The Stokes shift of 0.94 eV is roughly 33% smaller than it is in the related vacancy ordered double perovskite Cs 2 SnCl 6 . The reduction in Stokes shift is likely due to a change in coordination number of Sb 3+ from 6-coordinate in Cs 2 NaInCl 6 to 5-coordinate in Cs 2 SnCl 6 . In addition to the high quantum yield, Cs 2 NaInCl 6 :Sb 3+ exhibits excellent air/moisture stability and can be prepared from solution; these characteristics make it a promising blue phosphor for applications involving near-UV excitation.
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- NSF-PAR ID:
- 10206138
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- Volume:
- 8
- Issue:
- 20
- ISSN:
- 2050-7526
- Page Range / eLocation ID:
- 6797 to 6803
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Broadband near infrared (NIR) emission materials are of interest for various applications including non-destructive biomedical imaging. In this work, ytterbium ions (Yb 3+ ) were successfully doped into Cs 2 AgInCl 6 :Cr 3+ (CAIC:Cr 3+ ) double perovskite single crystals (DPSCs) by a facile hydrothermal method. Under 365 nm excitation, the co-doped CAIC:Cr 3+ ,Yb 3+ DPSCs showed broad NIR emission ranging from 800 to 1400 nm, which spanned the NIR-I (700–900 nm) and NIR-II (1000–1700 nm) bio-windows, with an emission band at 1000 nm and a full-width at half maximum (FWHM) of 188 nm. It is found that Yb 3+ ion doping could effectively improve the photoluminescence (PL) performance of CAIC:Cr 3+ DPSCs. Compared to the photoluminescence quantum yield (PLQY) of 22.5% for the single doped CAIC:Cr 3+ , the co-doped CAIC:Cr 3+ ,Yb 3+ DPSCs show a higher PLQY of ∼45%, which is attributed to the synergistic effect of reduced non-radiative recombination due to defect passivation and increase in crystallinity, and energy transfer (ET) of self-trapped excitons (STEs) to Cr 3+ . As a demonstration of applications, NIR pc-LEDs were fabricated by combining the as-synthesized NIR-emitting phosphor CAIC:Cr 3+ ,Yb 3+ with InGaN UV chips ( λ em = 365 nm) and used to image veins in a palm and for night vision using a NIR camera. The results suggest that the synthesized CAIC:Cr 3+ ,Yb 3+ DPSCs have great potential in biological applications.more » « less
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Abstract A few unit cells of thick colloidal CsPbBr3nanoplatelets (NPLs) exhibit strong quantum confinement. However, due to the increased surface‐to‐volume ratio, they show poor photoluminescence quantum yield (PLQY) resulting from surface traps. Here, a unique, quantum‐confined core/crown perovskite is reported for the first time, where the CsPbBr3NPL surface is passivated by laterally grown thin FAPbBr3crown layers. Unlike regular core/shells, the FAPbBr3is coated around the core NPLs resulting in blue emission. Careful control of the growth kinetics while monitoring growth using in situ PL led to the formation of core/crown perovskites with nearly two times improvement in thin film PLQYs. HR‐TEM analyses show that the interplanar distances of the core match with CsPbBr3and the crown match with FAPbBr3. The XRD and TEM analyses revealed that their thickness remains the same even if Cs+to FA+ratios are varied, indicating lateral growth of FAPbBr3around the CsPbBr3core. Further, FA+ions in the crown lattice are confirmed by FTIR and1HNMR. Finally, considering their high PLQYs and narrow linewidths, the core/crown NPLs are employed as blue emitters in light‐emitting diodes, and a maximum external quantum efficiency of 0.4% at 2.71 eV (457 nm) with a luminance of 513 cd m−2is achieved.
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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 All‐inorganic lead halide perovskite nanocrystals (NCs) have great optoelectronic properties with promising applications in light‐emitting diodes (LEDs), lasers, photodetectors, solar cells, and photocatalysis. However, the intrinsic toxicity of Pb and instability of the NCs impede their broad applications. Shell‐coating is an effective method for enhanced environmental stability while reducing toxicity by choosing non‐toxic shell materials such as metal oxides, polymers, silica, etc. However, multiple perovskite NCs can be encapsulated within the shell material and a uniform epitaxial‐type shell growth of well‐isolated NCs is still challenging. In this work, lead‐free vacancy‐ordered double perovskite Cs2SnX6(X = Cl, Br, and I) shells are epitaxially grown on the surface of CsPbX3NCs by a hot‐injection method. The effectiveness of the non‐toxic double perovskite shell protection is demonstrated by the enhanced environmental and phase stability against UV illumination and water. In addition, the photoluminescence quantum yields (PL QYs) increase for the CsPbCl3and CsPbBr3NCs after shelling because of the type I band alignment of the core/shell materials, while enhanced charge transport properties obtained from CsPbI3/Cs2SnI6core/shell NCs are due to the efficient charge separation in the type II core/shell band alignment.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0TC01037E
