Halide Perovskite Nanocrystals Research Articles

Role of Passivation Ligand in Exciton Diffusion and Emission Mechanism of Metal Halide Perovskite Nanocrystal Solid

Shorter-ligand passivated metal halide perovskite nanocrystal (PNC) solids possess smaller inter-NC edge distance which can potentially activate shorter-range nonradiative routes of energy transfer. However, these PNCs are prone to develop surface defects due to ligand detachment and the photogenerated excitons also have high probability to undergo dissociation. It remains unclear how these factors influence the exciton diffusion and emission mechanism of PNC solids. Herein, we prepare two PNC solids passivated with alkylamine and alkylacid ligands of different chain lengths and investigate the exciton diffusion and emission properties by combining time-resolved photoluminescence (PL) and low temperature PL spectroscopy. Our results show that due to the easy ligand detachment and rich surface defects, no prominent exciton transfer occurs in PNC solid passivated with short ligands, despite of the shorter distance between adjacent PNCs. In comparison, the PNC solid passivated with long ligands shows significant occurrence of exciton diffusion from high energy sites towards low energy sites. Accordingly, the PL spectra of thick PNC solid passivated with different ligands show a strikingly different evolution trend with decreasing temperature: in short ligand passivated PNC solid, an intrinsic emission is observed along with a defect-related emission arising from carrier trapping and subsequent radiative recombination, and both emissions are enhanced at lower temperature; in long ligand passivated PNC solid, high energy emission quenches while low energy emission is strengthened due to enhanced exciton transfer at lower temperature. This work reveals that the exciton diffusion and emission properties of PNC solid is strongly mediated by the passivation ligands, providing important insights for their applications in optoelectronic devices.

Evolution of structural dynamics in cesium lead halide perovskite colloidal nanocrystals from temperature-controlled synthesis.

Halide perovskite nanocrystals are at the forefront of materials research due to their remarkable optoelectronic properties and versatile applications. While their lattice structure and optical properties have been extensively investigated for the structure-property correlation, their lattice dynamics, the physical link between the lattice structure and optoelectronic properties, has been much less visited. We report the evolution of structural dynamics of a series of cesium lead halide perovskite nanocrystals whose size and morphology are systematically varied by synthesis temperature. Low-frequency Raman spectroscopy uncovers the nanocrystals' structural dynamics, including a relaxational spectral continuum from ligand librations and a phonon spectrum evolving with nanocrystal size. As the size of nanocrystals increases, their phonon spectrum becomes more intense, and their spectral weights redistribute with new first- and second-order modes being activated. The linewidth of the observed phonon modes generally broadens as the nanocrystal grows larger, an interesting deviation from the established phonon confinement model. We suggest that strong confinement and truncation of the lattice and ligands anchoring on the surface might lead to pinning of the lattice dynamics at nanoscale. These findings offer new insights into the bulk-nano-transition in halide perovskite soft semiconductors.

Recent Developments in Halide Perovskite Nanocrystals for Indirect X‐ray Detection

AbstractMetal halide perovskites are revolutionizing X‐ray detection through a combination of low cost, solution processing, favorable optoelectronic properties, and high stopping power for high‐energy ionizing radiation. While perovskite single crystals and polycrystalline wafers are considered direct X‐ray converters, most medical X‐ray applications are based on scintillators that shift high‐energy radiation into the visible. Several materials are on the market, but demonstrations based on CsPbBr3 nanocrystals, possibly embedded in a matrix material or combined with organic molecules as luminescent species, highlight their competitiveness with established scintillators in terms of radioluminescence yield and transient behavior. Major hurdles that perovskite nanocrystal scintillators must overcome are environmental stability and toxicity. While there are still few examples of high‐performance lead‐free perovskite nanocrystal scintillators, microcrystalline perovskites are emerging with promising properties, reduced toxicity, and significant Stokes shifts to avoid reabsorption of emission in thick films. Thus, the near future of perovskite nanocrystal scintillator materials will primarily be the adoption of recipes for materials with proven properties in microcrystalline form. The nanocrystal colloidal solutions will facilitate the large‐scale printing of homogeneous and scattering‐free films to obtain high contrast and spatial resolution X‐ray images by scintillation.

Aluminum Carboxylate Modification Enabled Efficient and Stable Perovskite-Polystyrene Thin Films for Light-Emitting Applications.

Lead halide perovskite nanocrystals (PNCs) have demonstrated great potential in emerging display technologies. However, the practical application of PNCs is hindered by the inherent instability of their ionic surface. Here, we proposed a surface modification approach to enhance the stability of CsPbBr3 PNCs by postsynthetic treatment with aluminum phenylbutyrate (Al(PA)3). Our study reveals that Al(PA)3 displaces ammonium ligands and binds tightly on surface halide, providing excellent air and moisture resistance while preserving a high quantum efficiency of 81.6%. The modified PNCs maintain a constant photoluminescence intensity under continuous UV light illumination for 500 h. Additionally, the Al(PA)3 ligand is compatible with styrene, enabling homogeneous dispersion of PNCs in polystyrene matrices to form bright and uniform PNC-PS thin films. We demonstrated the application of the composite films for display backlighting, which exhibits a wide color gamut of 125% NTSC. The result highlights the potential of AlPA-modified PNCs in light-emitting and other optoelectronic devices.

One‐step Synthesis of UV‐Curable CsPbX3 (X = Cl, Br, and I) Nanocrystal Inks for Printing

AbstractMetal halide perovskite nanocrystals (NCs) have garnered significant attention due to their captivating optoelectronic properties. One promising application for these materials is their use as color‐conversion layers (CCLs) in blue micro‐LED technology, enabling the realization of full‐color displays. Nonetheless, a pivotal challenge revolves around producing efficient luminescent perovskite inks and subsequently employing them for inkjet printing finely patterned CCLs. In this study, a straightforward single‐step hot‐injection method is introduced for synthesizing inks comprising CsPbX3 NCs, where X represents Cl, Br, and I, or mixed halide systems such as Cl/Br and Br/I. Through precise composition control, the emission spectra can be effortlessly adjusted across the entire visible spectrum, spanning from 410 to 710 nm. The resulting CsPbX3 NCs exhibit narrow emission line‐widths, ranging from 21 to 39 nm, an expansive color gamut encompassing up to 130% of the National Television Standards Committee color standard, and exceptional quantum yields reaching up to 100%. With their superb optical performance, facile synthesis procedure, and robust stability, these CsPbX3 NCs emerge as highly suitable candidates for their use as CCLs with blue light‐emitting devices deployed as backlights.

Organic A‐Site Cations Improve the Resilience of Inorganic Lead‐Halide Perovskite Nanocrystals to Surface Defect Formation

AbstractLead halide perovskite nanocrystals (LHP NCs) are generally prone to surface defect formation during the purification process, resulting in a reduced photoluminescence (PL) quantum yield. The purification of LHP NCs using antisolvents leads to the detachment of surface atoms and ligandsin the form of alkylammonium‐halides or A‐carboxylates (A: Cs, methylammonium, MA, or formamidinium, FA. Currently, intense research is being carried out to improve the surface stability of LHP NCs using various long‐chain organic ligands that strongly bind to the surface of NCs. Herein, the findings on the higher surface stability of hybrid (MAPbBr3 and FAPbBr3) LHP NCs compared to that of inorganic CsPbBr3 NCs against purification with polar antisolvents are reported. It is discovered that the CsPbBr3 NC surface stability can be enhanced (reaching that of hybrid perovskite NCs) by the incorporation of a small amount of MA or FA A‐site organic cations into their lattice, corroborated by the evidence that the PL quantum yield of mixed A‐cation CsxFA1‐xPbBr3 and CsxMA1‐xPbBr3 NCs remains unaffected after several purification cycles. It is hypothesized that this is attributed to hydrogen bonding between the organic A‐site cations and the neighboring halides on the surface. These findings are not only fundamentally important but are also expected to have wide implications in the field of metal‐halide perovskite optoelectronics.

Perovskite Nanocrystals In Situ Encapsulated in TiO2 Microspheres for Stable CO2 Photoreduction in Water.

Photoreduction of carbon dioxide (CO2) into fuels presents a promising approach to mitigate global warming and energy crises. Halide perovskite nanocrystals (NCs) with prominent optoelectronic properties have triggered substantial attention as photocatalysts but are limited by the charge recombination and instability. Here, we develop stable CsPbBr3/titania microspheres (TMs) by in situ growth of CsPbBr3 NCs inside mesoporous TMs through solid-state sintering, which significantly improves the stability of perovskite NCs, making them applicable in water with efficient CO2 photoreduction performance. Notably, the CsPbBr3/TMs demonstrates a 6.73- and 9.23-fold increase in the rate of CH4 production compared to TMs and CsPbBr3, respectively. The internal electric field facilitates S-scheme charge transfer, enhancing the separation of electron-hole pairs, as evidenced by X-ray photoelectron spectroscopy and electron paramagnetic resonance analysis, which is pivotal for the selective photoreduction of CO2. These insights pave the way for the design of CsPbBr3-based photocatalysts with superior efficiency and stability.

Synthesis and Properties of Halide Perovskites Nanocrystals Toward Solar Cells Application

Halide perovskite nanocrystals (HP NCs) based perovskite solar cells (PSCs) have attracted serious attention along with relatively unstable bulk HP‐based thin‐film solar cells aiming to make more efficient and stable PSCs. HP NCs have still limited employment in PSCs despite their inherent unique properties such as strong absorption and photoluminescence, controlled transport and charge‐carrier mobility, low defect density, solution processability, and compatibility with large‐scale deposition techniques suitable for PSCs. Nanostructuring of the perovskites offers other unique characteristics such as confinement effects. These exciting characteristics together with the exceptional tunability in their shape, composition, and functionalities make HP NCs promising for PVs applications. In order to develop efficient HP NCs PSCs, major focus lies on discussing the various synthesis approaches, optoelectrical behaviors of HP NCs, and optimized device architectures. In this context, this review article deals with various approaches to HP NCs synthesis, properties, current challenges, and factors affecting the performance of the NC‐based PSCs. Based on these discussions, perspectives on promising directions for effective utilization of HP NCs toward the improvement and commercialization of the exciting promising material‐based stable and efficient PSCs in the near future are provided.

Near‐unity broadband emissive hybrid manganese bromides as highly‐efficient radiation scintillators

Near‐unity broadband emissive hybrid manganese bromides as highly‐efficient radiation scintillators

Growth of CsPbX3 nanocrystals using sol–gel SiO2 solid powders as reactors without capping agents towards anomalous stable emission membranes

To overcome the poor stability of metal halide perovskite nanocrystals (NCs) prepared in organic solvents, a solid reaction method at high temperature was developed using sol–gel porous SiO2 as a reactor. Sol-gel SiO2 powders were used to encapsulate CsPbX3 NCs at high temperatures (600–800 °C) in air to get SiO2/CsPbX3 glass by dispersing growth cites in advance and no ligands added. After NaOH etching, a thin dense SiO2 shell was remained on the surface of CsPbX3 NCs (named as CsPbX3@SiO2).The photoluminescence (PL) quantum yield of the CsPbX3@SiO2 was 86.7 %, in which their PL peak wavelengths were adjusted from 410-707 nm by changing halogen components. The dense SiO2 shell on CsPbX3 NCs blocked the connection of CsPbX3 cores with water and oxygen in the external environment, resulting in CsPbX3@SiO2 revealed extraordinary high stability. After immersing in water for half year, the PL intensity of CsPbX3@SiO2 composites was remained unchanged and the composites still revealed bright PL after heat-treating in boiling water for 14 h. These highly stable composites were used to fabricate a white light-emitting diode, in which the color coordinates are located at (0.36, 0.33), and the color temperature reaches 5169 K which belongs to the warm white light range.

Synergistically enhanced water-resistive perovskite nanocrystals for cell nucleus imaging and acid phosphatase detection

Despite the impressive success of metal halide perovskite nanocrystals (NCs) in diverse fields, such as solar cells, light-emitting diodes, photodetectors, and so forth, their intrinsic sensitivity to water limits the extending applications in aqueous systems. Herein, enhanced water stability is achieved for NH2-PEG-COOH capped Mn2+-doped CsPbCl3/CsPb2Cl5 core/shell NCs through the synergistic effect of ion doping, core/shell construction and polymer encapsulation. The NH2-PEG-COOH encapsulation is validated crucial for the formation of CsPbCl3/CsPb2Cl5 core/shell structure, since it retains contact for CsPbCl3 NCs with trace water, and guarantees a slow water-etching process, triggering the CsPbCl3 to CsPb2Cl5 transformation. Thanks to the high formation energy induced by Mn2+ doping, CsPbCl3/CsPb2Cl5 hetero core/shell construction and NH2-PEG-COOH protective barrier, the obtained NCs exhibit unattenuated photoluminescence quantum yield after dipped in water for 15 days. Based on the robust water stability, the NH2-PEG-COOH capped Mn2+-doped CsPbCl3/CsPb2Cl5 NCs work well in cell nucleus imaging and acid phosphatase detection. This work not only produces a novel perovskite fluorescence probe in aqueous systems but also provides a general and effective combination strategy to enhance the water stability of perovskite materials.

Providing a Review of HC Relaxation Dynamics and Strategies of HC Extraction in Perovskites Nanocrystals

Metal halide perovskite (MHPs) nanocrystals (NCs) have recently emerged as promising materials for optoelectronic applications due to their exceptional photophysical properties. A comprehensive understanding of the underlying principles and key challenges associated with controlling the hot carrier (HCs) cooling dynamics in MHPs is pivotal for the design of efficient perovskite‐based optoelectronic applications. This review highlights the general carrier cooling mechanism and identifies crucial controlling parameters influencing carrier dynamics. The discussion includes strategies for manipulating HC cooling dynamics through carrier‐phonon and carrier‐carrier interactions. Notably, recent advancements in HC extraction with suitable acceptors are explored, as efficient HC extraction is imperative for the advancement of optoelectronic applications. The objective of this review is to outline potential pathways for strategically modifying carrier cooling processes to align with specific optoelectronic applications. A profound comprehension of charge carrier dynamics in MHPs NCs will pave the way for the development of highly efficient optoelectronic applications.

Gram-scale microwave-assisted synthesis of high-quality CsPbBr3 nanocrystals for optoelectronic applications

Fully inorganic halide perovskite nanocrystals (NCs) are promising candidates for optoelectronic applications due to their beneficial properties such as their amenability to solution processing, high absorption coefficients, and high quantum yields. Various methods have been developed to prepare perovskite CsPbX3 (X = Cl, Br, and I) NCs; however, large-scale synthesis with high-quality CsPbX3 NCs remains challenging. In the study, we report an advanced method for the gram-scale synthesis of all-inorganic perovskite NCs via specially designed microwave-assisted synthesis, which offers uniform reaction energy transfer, excellent reproducibility, and flexible parameter tuning. The composition, size and uniformity of the CsPbBr3 NCs have been optimized by controlling the surfactant ratio, precursor ratio, and reaction time. This systematic optimization leads to the production of gram-scale (> 0.165 g per a 100 ml reaction mixture for a single synthesis cycle) high-quality, phase-pure CsPbBr3 NCs with a uniform size of ∼ 10 nm. These optimized NCs exhibit a sharp photoluminescence peak centered at 515 nm with a photoluminescence quantum yield of 94 % and produce excellent radioluminescence under X-ray irradiation. To test the feasibility of these NCs for use in real optoelectronic devices, a photodetector consisting of CsPbBr3 NCs and monolayer MoS2 was fabricated, demonstrating enhanced photosensitivity and a faster response time compared with a pure MoS2-based photodetector. The proposed gram-scale microwave-assisted synthesis method thus has the potential to promote the commercialization of metal halide perovskite NCs through cost-effective mass production for use in many optoelectronic applications.

Luminescent Perovskite-Cross-Linked Polymer with Low Shrinkage and Excellent Stability.

When organic cross-linked polymers are combined with metal halide perovskite nanocrystals (PNCs) for realizing luminescent perovskite-polymer display materials, the stability of PNCs is enhanced and their shrinkage is suppressed. This work presents a feasible strategy for preparing CsPbBr3 nanocrystals (NCs) within a polydicyclopentadiene (PDCPD) thermosetting cross-linked resin matrix simultaneously via a one-step reaction. The obtained PDCPD@PNCs composite exhibits narrow peak half-widths (15-20 nm), high light transmittance (80%), low curing volume shrinkage (1.4%), tunable tensile properties, excellent stability, and a photoluminescence quantum yield (PLQY) of 44.3%. The composite material exhibits long-term stability in water, acid, and base solutions for over 90 days, with the PL intensity being maintained at over 90%. Furthermore, the composite is highly resistant to polar organic solvents owing to the insolubility imparted by cross-linking. White LEDs (WLED) fabricated using the as-prepared composite demonstrate excellent potential as light sources in optical devices.

Near-unity quantum yield and long-term emission stability in halide perovskite nanocrystal glass composite

Metal halide perovskites are promising optoelectronic materials due to their outstanding luminescent properties. However, the instability of perovskites has long been the bottleneck to their practical applications. Here Cs4PbBr6 nanocrystals based glass composite (Cs4PbBr6 NCs@glass) are successfully prepared, which displays green emission color (520 nm), narrow bandwidth (23 nm) and a near-unity photoluminescence quantum yield (PLQY). The H2O molecules permeating in the lattice of Cs4PbBr6 were found to be a crucial role in the subband energy emission. The Cs4PbBr6 NCs@glass has excellent emission stability; maintains 93 % of initial PL intensity after ultraviolet light irradiation for over 5000 h. In addition, by adjusting the halogen content, we have achieved tunable emission color from blue (450 nm) to green (520 nm) and red (670 nm) on Cs4PbX6 NCs@glass (X = Cl, Br, I), which covers up to 127 % of the National Television Systems Board (NTSC) standard system. Our finding indicates the commercial applications of perovskite materials in lighting and display.

Ligand engineering for improving the stability and optical properties of CsPbI3 perovskite nanocrystals

Inorganic lead halide perovskite nanocrystals (NCs) have recently become one of the research topics for optoelectronic applications due to their excellent photophysical properties. Despite their notable thermal stability over organic-inorganic halide perovskites, CsPbI3 NCs suffer from the phase instability of α-CsPbI3 phase at room temperature and under ambient conditions. Here, the effects of 4-Hydroxybenzoic acid (4-HBA) as an additive to standard oleic acid – oleylamine pair on the stability and optical properties of CsPbI3 perovskite NCs are discussed. 4-HBA addition into perovskite NC systems causes a compressive strain on perovskite lattice, which leads to the formation of a mixed phase α- and γ-CsPbI3 phases while pristine perovskite has α-CsPbI3 phase. Time-dependent stability of the perovskite NCs was tested under an ethanol (EtOH) medium. After EtOH exposure of the perovskite NCs, CsPbI3 NCs transformed to non-perovskite phase in 1 h while 4-HBA added CsPbI3 NCs still have perovskite phase after 48 h. In addition to the improved optical properties of the perovskite NCs, 4-HBA addition remarkably improves CsPbI3 perovskite stability.

Surface-Engineered Cesium Lead Bromide Perovskite Nanocrystals for Enabling Photoreduction Activity.

In recent years, colloidal lead halide perovskite (LHP) nanocrystals (NCs) have exhibited such intriguing light absorption properties to be contemplated as promising candidates for photocatalytic conversions. However, for effective photocatalysis, the light harvesting system needs to be stable under the reaction conditions propaedeutic to a specific transformation. Unlike photoinduced oxidative reaction pathways, photoreductions with LHP NCs are challenging due to their scarce compatibility with common hole scavengers like amines and alcohols. In this contribution, it is investigated the potential of CsPbBr3 NCs protected by a suitably engineered bidentate ligand for the photoreduction of quinone species. Using an in situ approach for the construction of the passivating agent and a halide excess environment, quantum-confined nanocubes (average edge length = 6.0 ± 0.8 nm) are obtained with a low ligand density (1.73 ligand/nm2) at the NC surface. The bifunctional adhesion of the engineered ligand boosts the colloidal stability of the corresponding NCs, preserving their optical properties also in the presence of an amine excess. Despite their relatively short exciton lifetime (τAV = 3.7 ± 0.2 ns), these NCs show an efficient fluorescence quenching in the presence of the selected electron accepting quinones (1,4-naphthoquinone, 9,10-phenanthrenequinone, and 9,10-anthraquinone). All of these aspects demonstrate the suitability of the NCs for an efficient photoreduction of 1,4-naphthoquinone to 1,4-dihydroxynaphthalene in the presence of triethylamine as a hole scavenger. This chemical transformation is impracticable with conventionally passivated LHP NCs, thereby highlighting the potential of the surface functionalization in this class of nanomaterials for exploring new photoinduced reactivities.

Exceptional Stability against Water, UV Light, and Heat for CsPbBr3@Pb-MOF Composites.

All-inorganic lead halide perovskite nanocrystals (NCs) have been widely applied in optoelectronic devices owing to their excellent photoluminescence (PL) properties. However, poor stability upon exposure to water, UV light or heat strongly limits their practical application. Herein, CsPbBr3@Pb-MOF composites with exceptional stability against water, UV light, and heat are synthesized by ultrasonic processing the precursors of lead-based MOF (Pb-MOF), oleylammonium bromide (OAmBr) and cesium oleate (Cs-OA) solutions at room temperature. Pb-MOF can not only provide the lead source for the in situ growth of CsPbBr3 NCs, but also the protective layer of perovskites NCs. The formed CsPbBr3@Pb-MOF composites show a considerable PL quantum yield (PLQY) of 67.8%, and can maintain 90% of the initial PL intensity when immersed in water for 2 months. In addition, the outstanding PL stability against UV light and heat is demonstrated with CsPbBr3 NCs synthesized by the conventional method as a comparison. Finally, a green (light-emitting diode) LED is fabricated using green-emitting CsPbBr3@Pb-MOF composites and exhibits excellent stability without packaging when immersed in water for 30 days. This study provides a practical approach to improve the stability in aqueous phase, which may pave the way for future applications for various optoelectronic devices.

Efficiently green-emitting and ultra-stable CsPbBr3@SiO2 nanocomposites for white light-emitting diodes

Inorganic oxide especially SiO2 encapsulation strategy is an effective way to improve the stability of all-inorganic cesium lead halide perovskite (CsPbX3, X = Cl, Br, I) nanocrystals (NCs). However, when CsPbX3 NCs are encapsulated in SiO2 by in situ tetraethyl orthosilicate (TEOS) hydrolysis, the unavoidable by-products (water and ethanol) of TEOS hydrolysis commonly damage the structural and optical properties of the CsPbX3 NCs. Herein, TDPA-CsPbBr3 NCs with the dense tetradecylphosphonic acid (TDPA) passivation were pre-prepared and subsequently encapsulated into SiO2 via in situ TEOS hydrolysis. Benefitting from the dense phosphonic passivation layer capable of resisting the erosion of polar by-products generated by TEOS hydrolysis, the obtained TDPA-CsPbBr3@SiO2 nanocomposites maintain the excellent optical properties of the colloidal CsPbBr3 NCs, showing near-unity photoluminescence quantum yield (PLQY) and ultra-narrow full width at half maximum (FWHM). Furthermore, the TDPA-CsPbBr3@SiO2 nanocomposites exhibit outstanding stability against ethanol, UV light, and heating treatment due to the dual protection of dense phosphonate ligand layers and inorganic SiO2 matrix. The white light-emitting diodes (WLED) device was fabricated by sequentially depositing green-emitting TDPA-CsPbBr3@SiO2 nanocomposites and red-emitting K2SiF6:Mn on blue-emitting GaN LED chip. The obtained WLED exhibits excellent luminous performances with standard white emission of CIE Coordinates (0.33, 0.33), a color gamut 138 % of the NTSC and 103 % of Rec. 2020, respectively. This study demonstrates that TDPA-CsPbBr3@SiO2 nanocomposites have a potential application in solid-state lighting and backlight displays.

Dynamical self-rectifying memristors based on halide perovskite nanocrystals

The integration of rectifying effects with resistance switching in a self-rectifying memristor offers the opportunity to suppress the sneak current in high-density crossbar arrays for energy-efficient neuromorphic computing. Here, we report a new type of two-terminal self-rectifying memristor that gets rid of asymmetric complex structures by using CsPbBr3 perovskite nanocrystals (NCs). The simple metal-insulator-metal (Au/CsPbBr3 NCs/Au) configuration that eases integration exhibits multiple resistance states that can be precisely controlled by the stimulus properties and dynamical rectifying characteristics dependent on both the bias voltage and bias time. We have extended an earlier proposed theory that predicts electric-potential-distribution-controlled rectification to rationalize all the observed rectifying behavior that are regulated by mobile-ion-induced interfacial electrochemical reactions and found excellent agreement between theory and experiments. Our study thus demonstrates the possibility of constructing controllable self-rectifying memristors without involving asymmetric complex structures, paving a new way for resolving the sneak current issue in crossbar arrays of memristors.