Near-unity Photoluminescence Quantum Yield Research Articles

Ultrafast dynamics of a highly-emissive zero-dimensional organic tin bromide perovskite

A zero-dimensional (0D) yellow emissive tin bromide perovskite with near-unity photoluminescence quantum yield (PLQY) was synthesized. The ultrafast excited-state dynamics of the yellow emissive perovskite was investigated by using femtosecond transient absorption spectroscopy. Two ultrafast dynamics processes, intersystem crossing (ISC) from a dark singlet self-trapped exciton (STE) state to a triplet STE state with time constant of 571 fs, and a cooling of a hot triplet STE state with time constant of 28.6 ps were unveiled. A clear mechanism depicting the growth and decay pathways of STEs in the 0D assembly was provided.

Size-tunable and stable cesium lead-bromide perovskite nanocubes with near-unity photoluminescence quantum yield.

Stable cesium lead bromide perovskite nanocrystals (NCs) showing a near-unity photoluminescence quantum yield (PLQY), narrow emission profile, and tunable fluorescence peak in the green region can be considered the ideal class of nanomaterials for optoelectronic applications. However, a general route for ensuring the desired features of the perovskite NCs is still missing. In this paper, we propose a synthetic protocol for obtaining near-unity PLQY perovskite nanocubes, ensuring their size control and, consequently, a narrow and intense emission through the modification of the reaction temperature and the suitable combination ratio of the perovskite constituting elements. The peculiarity of this protocol is represented by the dissolution of the lead precursor (PbBr2) as a consequence of the exclusive complexation with the bromide anions released by the in situ SN2 reaction between oleylamine (the only surfactant introduced in the reaction mixture) and 1-bromohexane. The obtained CsPbBr3 nanocubes exhibit variable size (ranging from 6.7 ± 0.7 nm to 15.2 ± 1.2 nm), PL maxima between 505 and 517 nm, and near-unity PLQY with a narrow emission profile (fwhm of 17–19 nm). Additionally, the NCs synthesized with this approach preserve their high PLQYs even after 90 days of storage under ambient conditions, thus displaying a remarkable optical stability. Through the rationalization of the obtained results, the proposed synthetic protocol provides a new ground for the direct preparation of differently structured perovskite NCs without resorting to any additional post-synthetic treatment for improving their emission efficiency and stability.

Poly(vinylidene fluoride)-passivated CsPbBr3 perovskite quantum dots with near-unity photoluminescence quantum yield and superior stability

A passivation strategy was demonstrated for CsPbBr3 QDs with an α-PVDF ligand, which could suppress phase transformation and enhance optical performance.

Pushing the Band Gap Envelope of Quasi-Type II Heterostructured Nanocrystals to Blue: ZnSe/ZnSe 1- X Te X /ZnSe Spherical Quantum Wells

Quasi-type II heterostructured nanocrystals (NCs) have been of particular interest due to their great potential for controlling the interplay of charge carriers. However, the lack of material choices for quasi-type II NCs restricts the accessible emission wavelength from red to near-infrared (NIR), which hinders their use in light-emitting applications that demand a wide range of visible colors. Herein, we demonstrate a new class of quasi-type II nanoemitters formulated in ZnSe/ZnSe 1- X Te X /ZnSe seed/spherical quantum well/shell heterostructures (SQWs) whose emission wavelength ranges from blue to orange. In a given geometry, ZnSe 1- X Te X emissive layers grown between the ZnSe seed and the shell layer are strained to fit into the surrounding media, and thus, the lattice mismatch between ZnSe 1- X Te X and ZnSe is effectively alleviated. In addition, composition of the ZnSe 1- X Te X emissive layer and the dimension of the ZnSe shell layer are engineered to tailor the distribution and energy of electron and hole wave functions. Benefitting from the capabilities to tune the charge carriers on demand and to form defect-free heterojunctions, ZnSe/ZnSe 1- X Te X /ZnSe/ZnS NCs show near-unity photoluminescence quantum yield ( PL QY > 90 % ) in a broad range of emission wavelengths (peak PL from 450 nm to 600 nm). Finally, we exemplify dichromatic white NC-based light-emitting diodes (NC-LEDs) employing the mixed layer of blue- and yellow-emitting ZnSe/ZnSe 1- X Te X /ZnSe/ZnS SQW NCs.

Highly luminescent CH3NH3PbBr3 quantum dots with 96.5% photoluminescence quantum yield achieved by synergistic combination of single-crystal precursor and capping ligand optimization

Inorganic–organic lead halide perovskite quantum dots (PQDs) are promising for application in a wide range of optoelectronic devices due to their high photoluminescence quantum yield (PLQY), tunable band gap, and narrow emission width. Despite intense research effort being devoted to the synthesis of highly luminescent PQDs, the achievement of defect-mediated low PLQY is still challenging. For PQDs processed by the well-known ligand-assisted reprecipitation technique, defects are inevitably formed on the surface, possibly due to the highly ionic precursor solution containing disordered elemental ions. To overcome this problem, in this work, CH3NH3PbBr3 single crystals with low defect densities were prepared using the inverse temperature crystallization method and were applied as sources for PQDs. Furthermore, capping ligands with different alkyl chain lengths were utilized to reprecipitate uniform and stable PQDs. Through the synergistic effect achieved by the use of the single-crystalline precursor and capping ligand optimization, we achieved a near-unity PLQY of 96.5% and a strong green emission. In addition, the obtained highly luminescent PQDs displayed few metallic Pb surface defects and reduced Stokes shifts that will be beneficial for future device applications.

Ni2+-doped CsPbI3 perovskite nanocrystals with near-unity photoluminescence quantum yield and superior structure stability for red light-emitting devices

Room temperature phase instability of cubic CsPbI3 perovskite nanocrystals is one of the notorious limitations for practical applications in optoelectronic fields. Herein, the incorporation of Ni2+ ions into CsPbI3 lattice was successfully achieved by a modified hot-injection method using nickel acetate as doping precursor. The as-prepared Ni2+ (3.3 mol%): CsPbI3 nanocrystals exhibited an improved, near-unity (95%~100%) photoluminescence quantum yield owing to the enhanced radiative decay rate and the decreased non-radiative decay rate. Additionally, Ni-doping was demonstrated to stabilize CsPbI3 lattice and the Ni2+: CsPbI3 film and colloidal solution can retain their red luminescence up to 15 days and 7 months in atmosphere, respectively. First-principle calculations verified that the significantly improved optical performance and stability of Ni2+: CsPbI3 nanocrystals arose primarily from the increased formation energy due to the successful doping of Ni2+ in CsPbI3. Benefiting from such an effective doping strategy, the as-prepared Ni2+-doped CsPbI3 perovskite nanocrystals can function well as efficient red-light emitter toward the fabrication of high-performance perovskite LED with a peak external quantum efficiency of ~7%.

Highly efficient and air-stable Eu(II)-containing azacryptates ready for organic light-emitting diodes

Divalent europium 5d-4f transition has aroused great attention in many fields, in a way of doping Eu2+ ions into inorganic solids. However, molecular Eu2+ complexes with 5d-4f transition are thought to be too air-unstable to explore their applications. In this work, we synthesized four Eu2+-containing azacryptates EuX2-Nn (X = Br, I, n = 4, 8) and systematically studied the photophysical properties in crystalline samples and solutions. Intriguingly, the EuX2-N8 complexes exhibit near-unity photoluminescence quantum yield, good air-/thermal-stability and mechanochromic property (X = I). Furthermore, we proved the application of Eu2+ complexes in organic light-emitting diodes (OLEDs) with high efficiency and luminance. The optimized device employing EuI2-N8 as emitter has the best performance as the maximum luminance, current efficiency, and external quantum efficiency up to 25470 cd m−2, 62.4 cd A−1, and 17.7%, respectively. Our work deepens the understanding of structure-property relationship in molecular Eu2+ complexes and could inspire further research on application in OLEDs.

Thick-shell CdZnSe/ZnSe/ZnS quantum dots for bright white light-emitting diodes

Quantum dots (QDs) have become promising light sources for next-generation lightings and displays. Realizing their applications in optoelectronic devices requires that QDs should retain their superior optical performances in condense QD films. However, most QD systems suffer intense photoluminescence (PL) quenching after film formation. Here, we report device-grade thick-shell CdZnSe/ZnSe/ZnS QDs with near-unity PL quantum yield (QY) in QD solution and 82% PL QY in QD film. We demonstrate that the thick shell functions well in restraining undesired inter-dot energy transfer by separating the emitting cores in condense QD film, and therefore preserving their superior emission properties. White light-emitting diodes (WLEDs) integrated with 5 different CdZnSe/ZnSe/ZnS QDs cover the visible spectrum, delivering a color rendering index (CRI) Ra as high as 91.4, a luminous efficiency (LE) of 68.5 lm/W and a warm bright sun light with correlated color temperature (CCT) of 4138 K. In particular, the champion CdZnSe/ZnSe/ZnS based WLED exhibits a special color index R9 as high as 93.1.

Unraveling the Near-Unity Narrow-Band Green Emission in Zero-Dimensional Mn2+-Based Metal Halides: A Case Study of (C10H16N)2Zn1-xMnxBr4 Solid Solutions.

Zero-dimensional (0D) Mn2+-based metal halides are potential candidates as narrow-band green emitters, and thus it is critical to provide a structural understanding of the photophysical process. Herein, we propose that a sufficiently long Mn-Mn distance in 0D metal halides enables all Mn2+ centers to emit spontaneously, thereby leading to near-unity photoluminescence quantum yield. Taking lead-free (C10H16N)2Zn1-xMnxBr4 (x = 0-1) solid solution as an example, the Zn/Mn alloying inhibits the concentration quenching that is caused by the energy transfer of Mn2+. (C10H16N)2MnBr4 exhibits highly thermal stable luminescence even up to 150 °C with a narrow-band green emission at 518 nm and a full width at half maximum of 46 nm. The fabricated white light-emitting diode device shows a high luminous efficacy of 120 lm/W and a wide color gamut of 104% National Television System Committee standard, suggesting its potential for liquid crystal displays backlighting. These results provide a guidance for designing new narrow-band green emitters in Mn2+-based metal halides.

K2CuX3 (X = Cl, Br): All-Inorganic Lead-Free Blue Emitters with Near-Unity Photoluminescence Quantum Yield

Recently, copper(I) halides have been gaining increased attention as highly luminescent nontoxic alternatives to lead halide perovskites for optoelectronic applications. Here, we report preparation...

Quantum Dots with Highly Efficient, Stable, and Multicolor Electrochemiluminescence.

Outstanding photoluminescence (PL) and electroluminescence properties of quantum dots (QDs) promise possibilities for them to meet challenging expectations of electrochemiluminescence (ECL), which at present relies on inefficient and spectral-irresolvable emitters based on transition-metal complexes (such as Ru(bpy)32+). However, ECL is reported to be extremely sensitive to the surface traps on the QDs likely because of the spatially and temporally separated electrochemical charge injections. Results here reveal that, by engineering the interior inorganic structure (CdSe/CdS/ZnS core/shell/shell structure) and inorganic–organic interface using new synthetic methods, the trap-insensitive QDs with near-unity PL quantum yield and monoexponential PL decay dynamics in water generated narrow band-edge ECL with efficiencies about six orders of magnitude higher than that of the standard Ru(bpy)32+. The band-edge and spectrally resolved ECL from CdSe/CdS/ZnS core/shell/shell QDs demonstrated a new readout scheme using electrochemical potential. Excellent ECL performance of QDs uncovered here offer opportunities to realize the full potential of ECL for biomedical detection and diagnosis.

Preparation of Lead-free Two-Dimensional-Layered (C8H17NH3)2SnBr4 Perovskite Scintillators and Their Application in X-ray Imaging.

Scintillators, as spectral and energy transformers, are essential for X-ray imaging applications. However, their current disadvantages, including high-temperature sintering and generation of agglomerated powders or large bulk crystals, may not meet the increasing demands of low cost, nontoxicity, and flexible radiation detection. Thus, improved perovskite scintillators are developed in this research. A hybrid perovskite ((C8H17NH3)2SnBr4), which is nontoxic, lead-free, and organic-inorganic, is developed as a scintillator with good emission performance and radioluminescence intensity. These perovskite scintillators are synthesized at low temperatures in an aqueous acid solution, through which they generate a near-unity photoluminescence quantum yield of 98% with the excitation of ultraviolet light. As far as we know, this work is the first to show that the two-dimensional (2D) (C8H17NH3)2SnBr4 perovskite scintillator films prepared by coating a polymer layer can be applied to an X-ray imaging system. The results demonstrate that the low cost X-ray imaging device with good resolution and performance benefits dramatically from this lead-free organic-inorganic hybrid perovskite film. Therefore, this 2D-layered (C8H17NH3)2SnBr4 perovskite scintillator may be a high potential candidate for scintillating material for X-ray imaging techniques.

Thermodynamic Control in the Synthesis of Quantum-Confined Blue-Emitting CsPbBr3 Perovskite Nanostrips.

Size control is critical in the synthesis of quantum-confined semiconductor nanocrystals, otherwise known as quantum dots. The achievement of size-uniformity and narrow spectral line-width in quantum dots conventionally relies on a very precise kinetic control of the reactions, where reaction time plays a significant role in defining the final crystal sizes and distribution. Here, we show that synthesis of quantum-confined perovskite nanostrips could be achieved through a thermodynamically controlled reaction, using a low-temperature and ligand-rich approach. The nanostrip growth proceeds through an initial one-dimensional (1D) nanorod stage, followed by the lateral widening of the rod to form a two-dimensional (2D) nanostrip. The spectral characteristics of the final product remain unchanged after prolonged reaction, indicating no signs of crystal ripening and confirming the thermodynamic nature of this reaction. The CsPbBr3 perovskite nanostrips were highly uniform and emit at a deep-blue wavelength of 462 nm with a remarkably narrow line-width of 13 nm. This corresponds to color coordinates of (0.136, 0.049) on the CIE 1931 color space, which fulfils the stringent Rec. 2020 standard for next-generation color displays. The well-passivated nanostrips also possess negligible defects and provide a near-unity photoluminescence quantum yield at 94%. Crucially, the achievement of blue emission through a pure-halide perovskite circumvents the problems of spectral instability that are frequently experienced in mixed-halide perovskite systems. The convenience and scalability of our thermodynamic approach, coupled with the excellent optical attributes, would likely enable these quantum-confined perovskite systems to be the preferred method toward color control in trichromatic display applications.

All-Inorganic Copper Halide as a Stable and Self-Absorption-Free X-ray Scintillator.

Lead halide perovskites have recently shown great potential as X-ray scintillators; however, the toxicity of the lead element seriously restricts their applications. Herein we report a new lead-free and self-absorption-free scintillator based on Rb2CuCl3 metal halide. The Rb2CuCl3 exhibits a near-unity photoluminescence quantum yield (99.4%) as well as a long photoluminescence lifetime (11.3 μs). Furthermore, Rb2CuCl3 demonstrates an appreciable light yield of 16 600 photons per megaelectronvolt and a large scintillation response with a linear range from 48.6 nGyair s-1 to 15.7 μGyair s-1. Notably, the detection limit is as low as 88.5 nGyair s-1, enabling a reduced radiation dose to the human body when a medical and security check is conducted. In addition, Rb2CuCl3 exhibits good stability against the atmosphere, continuous ultraviolet light, as well as X-ray irradiation. The combination of the decent scintillation performance, low toxicity and good stability suggests the Rb2CuCl3 could be a possible promising X-ray scintillator.

Near-unity photoluminescence quantum yield in inorganic perovskite nanocrystals by metal-ion doping.

The luminescence and charge transport properties of inorganic CsPbX3 perovskite nanocrystals (NCs) make them attractive candidates for various optoelectronic applications, such as lasing, X-ray imaging, light communication, and light-emitting diodes (LEDs). However, to realize cutting-edge device performance, high-quality NCs with high photoluminescence quantum yields (PLQYs) are essential. Therefore, substantial efforts and progress have been made to attain superior design/engineering and optimization of the inorganic NCs with a focus on surface quality, reduced nonradiative charge carrier recombination centers, and improved colloidal stabilities. Metal-ion doping has been proven to have a robust influence on the electronic band structure, PL behavior, and charge carrier recombination dynamics. Thus, in this perspective, we summarize the recent progress of the significant impact of metal cation doping on the optical properties, including the PL enhancement of CsPbCl3, CsPbBr3, and CsPbI3 perovskite NCs. Moreover, we shed light on the mechanism behind such improved properties. We conclude by recommending possible aspects and strategies to be further explored and considered for better utilization of these doped NCs in thin-film optoelectronic and energy conversion devices.

Cation exchange assisted synthesis of ZnCdSe/ZnSe quantum dots with narrow emission line widths and near-unity photoluminescence quantum yields.

Quantum dots with narrow emission line width have persistently received attention for their applications in biological imaging, lasers and next-generation displays. We herein report a cation exchange assisted shelling approach changing the starting CdSe emitting cores into new ZnCdSe alloy emitting cores and finally ZnCdSe/ZnSe core/shell QDs. The resulting ZnCdSe/ZnSe QDs exhibit an emission line width as narrow as 17.1 nm with a near-unity photoluminescence quantum yield and a single emission channel. We anticipate that our study on a cation exchange assisted synthetic route for controlling the emission line widths of the QDs could be extended to high-quality green and blue ones beyond currently achieved.

A new route for the shape differentiation of cesium lead bromide perovskite nanocrystals with near-unity photoluminescence quantum yield.

The ongoing interest in all-inorganic cesium lead bromide perovskite nanocrystals (CsPbBr3 NCs) is mainly due to their optical properties, in particular their high photoluminescence quantum yields (PLQYs). Three-precursor synthetic methods, in which the sources of the three elements (cesium, lead and bromine) constituting the perovskite scaffold are chemically independent, often succeed in the achievement of near-unity PLQY perovskite NCs. However, this class of synthetic approaches precludes the accessibility to crystal morphologies different from the traditional cuboidal ones. In order to upgrade three-precursor synthetic schemes to obtain more sophisticated morphologies - such as rods - we propose a conceptually original synthetic methodology, in which a potentially controllable stage of the reaction anticipates the fast crystallization promoted by cesium injection. To this purpose, lead oxide, 1-bromohexane (at different molar ratios with respect to lead) and the ligands (oleic acid and a suitable amine) in 1-octadecene are reacted at 160 °C for an incubation period of 30 min before cesium injection. During this stage and at high C6H13Br/PbO molar ratios, the bromide release from reactions between the ligands and 1-bromohexane promotes the evolution of [PbBr(2+n)]n- species as well as of two-dimensional [(RNH3)2(PbBr4)]n structures with a rod-like shape (aspect ratios ∼10). These structures act as the templating agents for the subsequent crystallization promoted by cesium injection, ensuring the formation of near-unity PLQY nanorods in the presence of decylamine. Conversely, the pronounced decomposition of the preformed [(RNH3)2(PbBr4)]n structures preludes to the formation of near-unity PLQY nanocubes in the presence of hexylamine. The amine choice exerts also an important role in the emission stability of the corresponding NCs, since the nanocubes prepared in the presence of hexylamine maintain their near-unity PLQYs up to 90 days under ambient conditions. In addition to the long-term PLQY stability, the nanorods prepared with decylamine also exhibit a remarkable resistance to the presence of water, due to the compact and hydrophobic organic shell passivating the NC surface. These findings can contribute to the development of innovative synthetic methodologies for controlling the shape and stability of near-unity PLQY perovskite NCs.

Bimetallic cyclometalated iridium complexes bridged by a BODIPY linker.

Presented here is a new class of supramolecular cyclometalated Ir(iii) complexes. The 2 : 1 assemblies include two phosphorescent cyclometalated Ir(iii) centers spanned by a BODIPY bridge with pyridine substituents at the β-pyrrole positions. The three complexes, which vary with respect to the cyclometalating ligand on iridium, are prepared via a simple one-pot procedure, with the target complexes isolated in 31-75% yield. The photophysics of these new compounds are described in detail. All complexes are strongly photoluminescent, with fluorescence from BODIPY being the dominant emission pathway. One member of the series has a near-unity photoluminescence quantum yield, significantly enhanced relative to the free BODIPY. The cyclometalating ligand on iridium controls the energy of the Ir-centered triplet excited state, but in all cases energy transfer from the Ir centers to the BODIPY quenches almost all phosphorescence. This work outlines a new, simple synthetic method for accessing supramolecular complexes.

Record High External Quantum Efficiency of 19.2% Achieved in Light-Emitting Diodes of Colloidal Quantum Wells Enabled by Hot-Injection Shell Growth.

Colloidal quantum wells (CQWs) are regarded as a highly promising class of optoelectronic materials, thanks to their unique excitonic characteristics of high extinction coefficients and ultranarrow emission bandwidths. Although the exploration of CQWs in light-emitting diodes (LEDs) is impressive, the performance of CQW-LEDs lags far behind other types of soft-material LEDs (e.g., organic LEDs, colloidal-quantum-dot LEDs, and perovskite LEDs). Herein, high-efficiency CQW-LEDs reaching close to the theoretical limit are reported. A key factor for this high performance is the exploitation of hot-injection shell (HIS) growth of CQWs, which enables a near-unity photoluminescence quantum yield (PLQY), reduces nonradiative channels, ensures smooth films, and enhances the stability. Remarkably, the PLQY remains 95% in solution and 87% in film despite rigorous cleaning. Through systematically understanding their shape-, composition-, and device-engineering, the CQW-LEDs using CdSe/Cd0.25 Zn0.75 S core/HIS CQWs exhibit a maximum external quantum efficiency of 19.2%. Additionally, a high luminance of 23 490 cd m-2 , extremely saturated red color with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.715, 0.283), and stable emission are obtained. The findings indicate that HIS-grown CQWs enable high-performance solution-processed LEDs, which may pave the path for future CQW-based display and lighting technologies.

Effects of Surface Chemistry on the Photophysics of Colloidal InP Nanocrystals.

Indium phosphide (InP) semiconductor nanocrystals (NCs) provide a promising alternative to traditional heavy-metal-based luminescent materials for lighting and display technologies, and implementation of InP NCs in consumer products is rapidly increasing. As-synthesized InP NCs typically have very low photoluminescence quantum yields (PLQY), however. Although empirical methods have led to NCs with near-unity PLQYs, a fundamental understanding of how specific synthetic and post-synthetic protocols can alter the electronic landscape of InP NCs is still lacking. Here, we have studied a series of homologous InP NCs prepared from InP clusters using a combination of room-temperature and low-temperature time-resolved spectroscopies to elucidate how specific charge-carrier trapping processes are affected when various surface modifications are performed. The data allow identification of large PLQY increases that occur specifically through elimination of surface electron traps and provide a rationale for understanding the microscopic origins of this trap suppression in terms of elimination of undercoordinated surface In3+ ions. Despite essentially complete elimination of surface electron trapping when surface In3+ is addressed, hole trapping still exists. This hole trapping is shown to be partially suppressed by even very thin shell growth, attributable to elimination of undercoordinated surface phosphides. We also observe signatures of bright-dark excitonic splitting in InP NCs with only submonolayer surface coverage of select additives (divalent Lewis acids or fluoride anions)-signatures that have only been previously observed in thick-shelled InP NCs. Together, these synthetic and spectroscopic results improve our understanding of relationships between specific InP NC surface chemistries and the resulting NC photophysics.