Conspectus With nearly 20% of global electricity consumed by lighting, more efficient illumination sources can enable massive energy savings. However, effectively creating the high-quality white ...light required for indoor illumination remains a challenge. To accurately represent color, the illumination source must provide photons with all the energies visible to our eye. Such a broad emission is difficult to achieve from a single material. In commercial white-light sources, one or more light-emitting diodes, coated by one or more phosphors, yield a combined emission that appears white. However, combining emitters leads to changes in the emission color over time due to the unequal degradation rates of the emitters and efficiency losses due to overlapping absorption and emission energies of the different components. A single material that emits broadband white light (a continuous emission spanning 400–700 nm) would obviate these problems. In 2014, we described broadband white-light emission upon near-UV excitation from three new layered perovskites. To date, nine white-light-emitting perovskites have been reported by us and others, making this a burgeoning field of study. This Account outlines our work on understanding how a bulk material, with no obvious emissive sites, can emit every color of the visible spectrum. Although the initial discoveries were fortuitous, our understanding of the emission mechanism and identification of structural parameters that correlate with the broad emission have now positioned us to design white-light emitters. Layered hybrid halide perovskites feature anionic layers of corner-sharing metal-halide octahedra partitioned by organic cations. The narrow, room-temperature photoluminescence of lead-halide perovskites has been studied for several decades, and attributed to the radiative recombination of free excitons (excited electron–hole pairs). We proposed that the broad white emission we observed primarily stems from exciton self-trapping. Here, the exciton couples strongly to the lattice, creating transient elastic lattice distortions that can be viewed as “excited-state defects”. These deformations stabilize the exciton affording a broad emission with a large Stokes shift. Although material defects very likely contribute to the emission width, our mechanistic studies suggest that the emission mostly arises from the bulk material. Ultrafast spectroscopic measurements support self-trapping, with new, transient, electronic states appearing upon photoexcitation. Importantly, the broad emission appears common to layered Pb–Br and Pb–Cl perovskites, albeit with a strong temperature dependence. Although the emission is attributed to light-induced defects, it still reflects changes in the crystal structure. We find that greater out-of-plane octahedral tilting increases the propensity for the broad emission, enabling synthetic control over the broad emission. Many of these perovskites have color rendering abilities that exceed commercial requirements and mixing halides affords both “warm” and “cold” white light. The most efficient white-light-emitting perovskite has a quantum efficiency of 9%. Improving this value will make these phosphors attractive for solid-state lighting, particularly as large-area coatings that can be deposited inexpensively. The emission mechanism can also be extended to other low-dimensional systems. We hope this Account aids in expanding the phase space of white-light emitters and controlling their exciton dynamics by the synthetic, spectroscopic, theoretical, and engineering communities.
Self-Assembly of Broadband White-Light Emitters Dohner, Emma R; Hoke, Eric T; Karunadasa, Hemamala I
Journal of the American Chemical Society,
02/2014, Letnik:
136, Številka:
5
Journal Article
Recenzirano
We use organic cations to template the solution-state assembly of corrugated lead halide layers in bulk crystalline materials. These layered hybrids emit radiation across the entire visible spectrum ...upon ultraviolet excitation. They are promising as single-source white-light phosphors for use with ultraviolet light-emitting diodes in solid-state lighting devices. The broadband emission provides high color rendition and the chromaticity coordinates of the emission can be tuned through halide substitution. We have isolated materials that emit the “warm” white light sought for many indoor lighting applications as well as “cold” white light that approximates the visible region of the solar spectrum. Material syntheses are inexpensive and scalable and binding agents are not required for film deposition, eliminating problems of binder photodegradation. These well-defined and tunable structures provide a flexible platform for studying the rare phenomenon of intrinsic broadband emission from bulk materials.
Layered halide perovskites offer a versatile platform for manipulating light through synthetic design. Although most layered perovskites absorb strongly in the ultraviolet (UV) or near-UV region, ...their emission can range from the UV to the infrared region of the electromagnetic spectrum. This emission can be very narrow, displaying high color purity, or it can be extremely broad, spanning the entire visible spectrum and providing high color rendition (or accurately reproducing illuminated colors). The origin of the photoluminescence can vary enormously. Strongly correlated electron–hole pairs, permanent lattice defects, transient light-induced defects, and ligand-field transitions in the inorganic layers and molecular chromophores in the organic layers can be involved in the emission mechanism. In this review, we highlight the different types of photoluminescence that may be attained from layered halide perovskites, with an emphasis on how the emission may be systematically tuned through changes to the bulk crystalline lattice: changes in composition, structure, and dimensionality.
We report on the second family of layered perovskite white-light emitters with improved photoluminescence quantum efficiencies (PLQEs). Upon near-ultraviolet excitation, two new Pb–Cl and Pb–Br ...perovskites emit broadband “cold” and “warm” white light, respectively, with high color rendition. Emission from large, single crystals indicates an origin from the bulk material and not surface defect sites. The Pb–Br perovskite has a PLQE of 9%, which is undiminished after 3 months of continuous irradiation. Our mechanistic studies indicate that the emission has contributions from strong electron–phonon coupling in a deformable lattice and from a distribution of intrinsic trap states. These hybrids provide a tunable platform for combining the facile processability of organic materials with the structural definition of crystalline, inorganic solids.
Despite the remarkable rise in efficiencies of solar cells containing the lead-halide perovskite absorbers RPbX3 (R = organic cation; X = Br– or I–), the toxicity of lead remains a concern for the ...large-scale implementation of this technology. This has spurred the search for lead-free materials with similar optoelectronic properties. Here, we use the double-perovskite structure to incorporate nontoxic Bi3+ into the perovskite lattice in Cs2AgBiBr6 (1). The solid shows a long room-temperature fundamental photoluminescence (PL) lifetime of ca. 660 ns, which is very encouraging for photovoltaic applications. Comparison between single-crystal and powder PL decay curves of 1 suggests inherently high defect tolerance. The material has an indirect bandgap of 1.95 eV, suited for a tandem solar cell. Furthermore, 1 is significantly more heat and moisture stable compared to (MA)PbI3. The extremely promising optical and physical properties of 1 shown here motivate further exploration of both inorganic and hybrid halide double perovskites for photovoltaics and other optoelectronics.
Abstract
Functional CsPbI
3
perovskite phases are not stable at ambient conditions and spontaneously convert to a non-perovskite δ phase, limiting their applications as solar cell materials. We ...demonstrate the preservation of a black CsPbI
3
perovskite structure to room temperature by subjecting the δ phase to pressures of 0.1 – 0.6 GPa followed by heating and rapid cooling. Synchrotron X-ray diffraction and Raman spectroscopy indicate that this perovskite phase is consistent with orthorhombic γ-CsPbI
3
. Once formed, γ-CsPbI
3
could be then retained after releasing pressure to ambient conditions and shows substantial stability at 35% relative humidity. First-principles density functional theory calculations indicate that compression directs the out-of-phase and in-phase tilt between the PbI
6
4−
octahedra which in turn tune the energy difference between δ- and γ-CsPbI
3
, leading to the preservation of γ-CsPbI
3
. Here, we present a high-pressure strategy for manipulating the (meta)stability of halide perovskites for the synthesis of desirable phases with enhanced materials functionality.
Through structural and optical studies of a series of two-dimensional hybrid perovskites, we show that broadband emission upon near-ultraviolet excitation is common to (001) lead-bromide perovskites. ...Importantly, we find that the relative intensity of the broad emission correlates with increasing out-of-plane distortion of the Pb-(μ-Br)-Pb angle in the inorganic sheets. Temperature- and power-dependent photoluminescence data obtained on a representative (001) perovskite support an intrinsic origin to the broad emission from the bulk material, where photogenerated carriers cause excited-state lattice distortions mediated through electron-lattice coupling. In contrast, most inorganic phosphors contain extrinsic emissive dopants or emissive surface sites. The design rules established here could allow us to systematically optimize white-light emission from layered hybrid perovskites by fine-tuning the bulk crystal structure.
In the few short years since the inception of single-junction perovskite solar cells, their efficiencies have skyrocketed. Perovskite absorbers have at least as much to offer tandem solar cells as ...they do for single-junction cells due in large part to their tunable band gaps. However, modifying the perovskite band structure via halide substitution, the method that has been most effective at tuning band gaps, leads to instabilities in the material for some compositions. Here, we discuss the thermodynamic origin and consequences of light-induced phase segregation observed in mixed-halide perovskites. We propose that, as the phase segregation is rooted in halide migration and possibly affected by lattice strain, modifying the perovskite composition and lattice structure, increasing compositional uniformity, and reducing defect concentrations could significantly improve stability.
We report on reversible, light-induced transformations in (CH
NH
)Pb(Br
I
)
. Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity ...under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics.
We report the metallization of the hybrid perovskite semiconductor (MA)PbI3 (MA = CH3NH3 +) with no apparent structural transition. We tracked its bandgap evolution during compression in ...diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study of metallic properties in oxide perovskites has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.
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