Engineering colloidal semiconductor nanocrystals for quantum information processing.

Quantum information processing-which relies on spin defects or single-photon emission-has shown quantum advantage in proof-of-principle experiments including microscopic imaging of electromagnetic fields, strain and temperature in applications ranging from battery research to neuroscience. However, critical gaps remain on the path to wider applications, including a need for improved functionalization, deterministic placement, size homogeneity and greater programmability of multifunctional properties. Colloidal semiconductor nanocrystals can close these gaps in numerous application areas, following years of rapid advances in synthesis and functionalization. In this Review, we specifically focus on three key topics: optical interfaces to long-lived spin states, deterministic placement and delivery for sensing beyond the standard quantum limit, and extensions to multifunctional colloidal quantum circuits.

Rigid Conjugated Diamine Templates for Stable Dion-Jacobson-Type Two-Dimensional Perovskites.

Hybrid organic-inorganic perovskites (HOIPs) have garnered widespread interest, yet stability remains a critical issue that limits their further application. Compared to their three-dimensional (3D) counterparts, two-dimensional (2D)-HOIPs exhibit improved stability. 2D-HOIPs are also appealing because their structural and optical properties can be tuned according to the choice of organic ligand, with monovalent or divalent ligands forming Ruddlesden-Popper (RP) or Dion-Jacobson (DJ)-type 2D perovskites, respectively. Unlike RP-type 2D perovskites, DJ-type 2D perovskites do not contain a van der Waals gap between the 2D layers, leading to improved stability. However, bifunctional organic ligands currently used to develop DJ-type 2D perovskites are limited to commercially available aliphatic and single-ring aromatic ammonium cations. Large conjugated organic ligands are in demand for their semiconducting properties and their potential to improve materials stability further. In this manuscript, we report the design and synthesis of a new set of larger conjugated diamine ligands and their incorporation into DJ-type 2D perovskites. Compared with analogous RP-type 2D perovskites, DJ 2D perovskites reported here show blue-shifted, narrower emissions and significantly improved stability. By changing the structure of rings (benzene vs thiophene) and substituents, we develop structure-property relationships, finding that fluorine substitution enhances crystallinity. Single-crystal structure analysis and density functional theory calculations indicate that these changes are due to strong electrostatic interactions between the organic templates and inorganic layers as well as the rigid backbone and strong π-π interaction between the organic ligands themselves. These results illustrate that targeted engineering of the diamine ligands can enhance the stability of DJ-type 2D perovskites.

Bound State in the Continuum in Nanoantenna-Coupled Slab Waveguide Enables Low-Threshold Quantum-Dot Lasing.

Colloidal quantum dots (CQDs) are a promising gain material for solution-processed, wavelength-tunable lasers, with potential application in displays, communications, and biomedical devices. In this work, we combine a CQD film with an array of nanoantennas, made of titanium dioxide cylinders, to achieve lasing via bound states in the continuum (BICs). Here, the BICs are symmetry-protected cavity modes with giant quality factors, arising from slab waveguide modes in the planar CQD film, coupled to the periodic nanoantenna array. We engineer the thickness of the CQD film and size of the nanoantennas to achieve a BIC with good spatial and spectral overlap with the CQDs, based on a second-order transverse-electric (TE)-polarized waveguide mode. We obtain room-temperature lasing with a low threshold of approximately 11 kW/cm2 (peak intensity) under 5-ns-pulsed optical excitation. This work sheds light on the optical modes in solution-processed, distributed-feedback lasers and highlights BICs as effective, versatile, surface-emitting lasing modes.

Pentacene-Bridge Interactions in an Axially Chiral Binaphthyl Pentacene Dimer.

Molecular chirality can be exploited as a sensitive reporter of the nature of intra- and interchromophore interactions in π-conjugated systems. In this report, we designed an intramolecular singlet fission (iSF)-based pentacene dimer with an axially chiral binaphthyl bridge (2,2'-(2,2'-dimethoxy-[1,1'-binaphthalene]-3,3'-diyl) n-octyl-di-isopropyl silylethynyl dipentacene, BNBP) to utilize its chiroptical response as a marker of iSF chromophore-bridge-chromophore (SFC-ß-SFC) interactions. The axial chirality of the bridge enforces significant one-handed excitonic coupling of the pentacene monomer units; as such, BNBP exhibits significant chiroptical response in the ground and excited states. We analyzed the chiroptical response of BNBP using the exciton coupling method and quadratic response density functional theory calculations to reveal that higher energy singlet transitions in BNBP involve significant delocalization of the electronic density on the bridging binaphthyl group. Our results highlight the promising application of chiroptical techniques to investigate the nature of SFC-ß-SFC interactions that impact singlet fission dynamics.

Magnetic optical rotary dispersion and magnetic circular dichroism in methylammonium lead halide perovskites.

Large magnetic optical rotary dispersion (Faraday rotation) has been demonstrated recently in methylammonium lead bromide. Here, we investigate the prospect of extending the active spectral range by altering the halogen. We also investigate the origins of large Faraday rotation in these diamagnetic materials using magnetic circular dichroism (MCD) spectroscopy and the Kramers-Kronig relations. We find that, while MAPbCl3 (MA = methylammonium) single crystals exhibit a large Verdet constant in the blue, no appreciable Faraday rotation is observed in the red/near infra-red for MAPbI3 single crystals. However, in all film samples, we find clear evidence of large MCD resulting from the Zeeman splitting of the highly resonant 1s exciton state. Our Kramers-Kronig calculations of Faraday rotation based on MCD data matches well with the dispersion of our experimental data for MAPbCl3 and MAPbBr3 , with some deviation in magnitude-demonstrating the excitonic nature of Faraday rotation in these materials. However, our calculations predict significant Faraday rotation in MAPbI3 , contrary to our experimental results, indicating a potential discrepancy between the properties of the thin film and single crystal.

Solution-Processed Faraday Rotators Using Single Crystal Lead Halide Perovskites.

Lead halide perovskites (LHPs) have become a promising alternative for a wide range of optoelectronic devices, thanks to their solution-processability and impressive optical and electrical properties. More recently, LHPs have been investigated in magneto-optic studies and have exhibited spin-polarized emission, photoinduced magnetization, and long spin lifetimes. Here, the viability of methylammonium lead bromide (MAPbBr3) single crystals as solution-processed Faraday rotators is demonstrated. Compared to terbium gallium garnet, the industry standard in the visible, it is found that MAPbBr3 exhibits Verdet constants (i.e., strength of Faraday effect) of similar or greater magnitude (up to 2.5x higher), with lower temperature dependence. Due to its low trap absorption, it is calculated that an optical isolator made from MAPbBr3, with appropriate antireflection coatings, should reach ≈95% transmission and achieve 40 dB isolation for incoming powers of over 2 W. It is also shown that the Verdet constant of MAPbBr3 can be calculated accurately from its dispersion in refractive index, allowing the possibility to predict similar effects in other perovskite materials.

Temperature-Induced Self-Compensating Defect Traps and Gain Thresholds in Colloidal Quantum Dots.

Continuous-wave (CW) lasing was recently achieved in colloidal quantum dots (CQDs) by lowering the threshold through the introduction of biaxial strain. However, the CW laser threshold is still much higher than the femtosecond threshold. This must be addressed before electrically injected lasing can be realized. Here we investigate the relationship between threshold and temperature and find a subpicosecond recombination process that proceeds very efficiently at temperatures reached during CW excitation. We combine density functional theory and molecular dynamics simulations to explore potential candidates for such a process, and find that crystal defects having thermally vibrating energy levels can become electronic traps-i.e., they can protrude into the bandgap-when they are sufficiently distorted at higher temperatures. We find that biaxially strained CQDs, which have a lower femtosecond laser threshold than traditional CQDs, result in less heat for a given transparency/gain level and thus undergo this trapping to a lower extent. We also propose methods to tailor CQDs to avoid self-compensating defect traps.

Picosecond Charge Transfer and Long Carrier Diffusion Lengths in Colloidal Quantum Dot Solids.

Quantum dots (QDs) are promising candidates for solution-processed thin-film optoelectronic devices. Both the diffusion length and the mobility of photoexcited charge carriers in QD solids are critical determinants of solar cell performance; yet various techniques offer diverse values of these key parameters even in notionally similar films. Here we report diffusion lengths and interdot charge transfer rates using a 3D donor/acceptor technique that directly monitors the rate at which photoexcitations reach small-bandgap dot inclusions having a known spacing within a larger-bandgap QD matrix. Instead of relying on photoluminescence (which can be weak in strongly coupled QD solids), we use ultrafast transient absorption spectroscopy, a method where sensitivity is undiminished by exciton dissociation. We measure record diffusion lengths of ∼300 nm in metal halide exchanged PbS QD solids that have led to power conversion efficiencies of 12%, and determine 8 ps interdot hopping of carriers following photoexcitation, among the fastest rates reported for PbS QD solids. We also find that QD solids composed of smaller QDs ( d = ∼3.2 nm) exhibit 5 times faster interdot charge transfer rates and 10 times lower trap state densities compared to larger ( d = ∼5.5 nm) QDs.

Perovskites for Light Emission.

Next-generation displays require efficient light sources that combine high brightness, color purity, stability, compatibility with flexible substrates, and transparency. Metal halide perovskites are a promising platform for these applications, especially in light of their excellent charge transport and bandgap tunability. Low-dimensional perovskites, which possess perovskite domains spatially confined at the nanoscale, have further extended the degree of tunability and functionality of this materials platform. Herein, the advances in perovskite materials for light-emission applications are reviewed. Connections among materials properties, photophysical and electrooptic spectroscopic properties, and device performance are established. It is discussed how incompletely solved problems in these materials can be tackled, including the need for increased stability, efficient blue emission, and efficient infrared emission. In conclusion, an outlook on the technologies that can be realized using this material platform is presented.

Small-Band-Offset Perovskite Shells Increase Auger Lifetime in Quantum Dot Solids.

Colloidal quantum dots (CQDs) enable low-cost, high-performance optoelectronic devices including photovoltaics, photodetectors, LEDs, and lasers. Continuous-wave lasing in the near-infrared remains to be realized based on such materials, yet a solution-processed NIR laser would be of use in communications and interconnects. In infrared quantum dots, long-lived gain is hampered by a high rate of Auger recombination. Here, we report the use of perovskite shells, grown on cores of IR-emitting PbS CQDs, and we thus reduce the rate of Auger recombination by up to 1 order of magnitude. We employ ultrafast transient absorption spectroscopy to isolate distinct Auger recombination phenomena and study the effect of bandstructure and passivation on Auger recombination. We corroborate the experimental findings with model-based investigations of Auger recombination in various CQD core-shell structures. We explain how the band alignment provided by perovskite shells comes close to the optimal required to suppress the Auger rate. These results provide a step along the path toward solution-processed near-infrared lasers.

Continuous-wave lasing in colloidal quantum dot solids enabled by facet-selective epitaxy.

Colloidal quantum dots (CQDs) feature a low degeneracy of electronic states at the band edges compared with the corresponding bulk material, as well as a narrow emission linewidth. Unfortunately for potential laser applications, this degeneracy is incompletely lifted in the valence band, spreading the hole population among several states at room temperature. This leads to increased optical gain thresholds, demanding high photoexcitation levels to achieve population inversion (more electrons in excited states than in ground states-the condition for optical gain). This, in turn, increases Auger recombination losses, limiting the gain lifetime to sub-nanoseconds and preventing steady laser action. State degeneracy also broadens the photoluminescence linewidth at the single-particle level. Here we demonstrate a way to decrease the band-edge degeneracy and single-dot photoluminescence linewidth in CQDs by means of uniform biaxial strain. We have developed a synthetic strategy that we term facet-selective epitaxy: we first switch off, and then switch on, shell growth on the (0001) facet of wurtzite CdSe cores, producing asymmetric compressive shells that create built-in biaxial strain, while still maintaining excellent surface passivation (preventing defect formation, which otherwise would cause non-radiative recombination losses). Our synthesis spreads the excitonic fine structure uniformly and sufficiently broadly that it prevents valence-band-edge states from being thermally depopulated. We thereby reduce the optical gain threshold and demonstrate continuous-wave lasing from CQD solids, expanding the library of solution-processed materials that may be capable of continuous-wave lasing. The individual CQDs exhibit an ultra-narrow single-dot linewidth, and we successfully propagate this into the ensemble of CQDs.

Field-emission from quantum-dot-in-perovskite solids.

Quantum dot and well architectures are attractive for infrared optoelectronics, and have led to the realization of compelling light sensors. However, they require well-defined passivated interfaces and rapid charge transport, and this has restricted their efficient implementation to costly vacuum-epitaxially grown semiconductors. Here we report solution-processed, sensitive infrared field-emission photodetectors. Using quantum-dots-in-perovskite, we demonstrate the extraction of photocarriers via field emission, followed by the recirculation of photogenerated carriers. We use in operando ultrafast transient spectroscopy to sense bias-dependent photoemission and recapture in field-emission devices. The resultant photodiodes exploit the superior electronic transport properties of organometal halide perovskites, the quantum-size-tuned absorption of the colloidal quantum dots and their matched interface. These field-emission quantum-dot-in-perovskite photodiodes extend the perovskite response into the short-wavelength infrared and achieve measured specific detectivities that exceed 1012 Jones. The results pave the way towards novel functional photonic devices with applications in photovoltaics and light emission.

A comparative study of the photophysics of phenyl, thienyl, and chalcogen substituted rhodamine dyes.

Although rhodamine dyes have been extensively studied for a variety of applications, many details of their photophysics are not yet fully understood, including the possible presence of a charge separated electronic state lying near the optically active excited singlet state and the role of twisting substituent groups in excited-state quenching. To address this, a large library of rhodamine dyes was studied in which the chalcogen is varied from O, to S and Se and the aryl group is either absent (in the pyronin series) or is a phenyl or thienyl substituent. Through an analysis of steady-state absorption spectroscopy, electrochemistry, X-ray crystallography, and quantum mechanical calculations, we show that the lowest unoccupied molecular orbital (LUMO) energy decreases in the O → S → Se series and when a phenyl or thienyl substituent is added. The reduction of the LUMO energy is larger for thienyl species in which the aromatic group has increased torsional flexibility. Excited state lifetimes and fluorescence quantum yields of these dyes in a high and low polarity solvent reveal dramatically different photophysics between chromophores with phenyl and thienyl substituents, due to a combination of torsional and inductive effects. In the pyronin and phenyl-substituted species, non-radiative decay can occur through an amine-to-xanthylium core charge separated state that is stabilized in a highly polar environment. In the thienyl derivatives, a lower energy excited state, which we term S'1, is accessed from S1via rotation of the aryl group and the excited state population rapidly equilibrates between S1 and S'1 in 6-30 ps. Preliminary photochemical hydrogen production data display the potential application of the thienyl derivatives for conversion of solar energy.

Efficient Bimolecular Mechanism of Photochemical Hydrogen Production Using Halogenated Boron-Dipyrromethene (Bodipy) Dyes and a Bis(dimethylglyoxime) Cobalt(III) Complex.

A series of Boron-dipyrromethene (Bodipy) dyes were used as photosensitizers for photochemical hydrogen production in conjunction with [Co(III)(dmgH)2pyCl] (where dmgH = dimethylglyoximate, py = pyridine) as the catalyst and triethanolamine (TEOA) as the sacrificial electron donor. The Bodipy dyes are fully characterized by electrochemistry, X-ray crystallography, quantum chemistry calculations, femtosecond transient absorption, and time-resolved fluorescence, as well as in long-term hydrogen production assays. Consistent with other recent reports, only systems containing halogenated chromophores were active for hydrogen production, as the long-lived triplet state is necessary for efficient bimolecular electron transfer. Here, it is shown that the photostability of the system improves with Bodipy dyes containing a mesityl group versus a phenyl group, which is attributed to increased electron donating character of the mesityl substituent. Unlike previous reports, the optimal ratio of chromophore to catalyst is established and shown to be 20:1, at which point this bimolecular dye/catalyst system performs 3-4 times better than similar chemically linked systems. We also show that the hydrogen production drops dramatically with excess catalyst concentration. The maximum turnover number of ∼ 700 (with respect to chromophore) is obtained under the following conditions: 1.0 × 10(-4) M [Co(dmgH)2pyCl], 5.0 × 10(-6) M Bodipy dye with iodine and mesityl substituents, 1:1 v:v (10% aqueous TEOA):MeCN (adjusted to pH 7), and irradiation by light with λ > 410 nm for 30 h. This system, containing discrete chromophore and catalyst, is more active than similar linked Bodipy-Co(dmg)2 dyads recently published, which, in conjunction with our other measurements, suggests that the nominal dyads actually function bimolecularly.

Light-driven generation of hydrogen: New chromophore dyads for increased activity based on Bodipy dye and Pt(diimine)(dithiolate) complexes.

New dyads consisting of a strongly absorbing Bodipy (dipyrromethene-BF2) dye and a platinum diimine dithiolate (PtN2S2) charge transfer (CT) chromophore have been synthesized and studied in the context of the light-driven generation of H2 from aqueous protons. In these dyads, the Bodipy dye is bonded directly to the benzenedithiolate ligand of the PtN2S2 CT chromophore. Each of the new dyads contains either a bipyridine (bpy) or phenanthroline (phen) diimine with an attached functional group that is used for binding directly to TiO2 nanoparticles, allowing rapid electron photoinjection into the semiconductor. The absorption spectra and cyclic voltammograms of the dyads show that the spectroscopic and electrochemical properties of the dyads are the sum of the individual chromophores (Bodipy and the PtN2S2 moieties), indicating little electronic coupling between them. Connection to TiO2 nanoparticles is carried out by sonication leading to in situ attachment to TiO2 without prior hydrolysis of the ester linking groups to acids. For H2 generation studies, the TiO2 particles are platinized (Pt-TiO2) so that the light absorber (the dyad), the electron conduit (TiO2), and the catalyst (attached colloidal Pt) are fully integrated. It is found that upon 530 nm irradiation in a H2O solution (pH 4) with ascorbic acid as an electron donor, the dyad linked to Pt-TiO2 via a phosphonate or carboxylate attachment shows excellent light-driven H2 production with substantial longevity, in which one particular dyad [4(bpyP)] exhibits the highest activity, generating ∼ 40,000 turnover numbers of H2 over 12 d (with respect to dye).

Solvation and rotation dynamics in the trihexyl(tetradecyl)phosphonium chloride ionic liquid/methanol cosolvent system.

The interactions and solvent structure in trihexyl(tetradecyl)phosphonium chloride ionic liquid ([P(14,6,6,6)(+)][Cl(-)], "PIL-Cl")/methanol (MeOH) solutions across the entire range of mole fraction PIL-Cl (x(IL) = 0-1) are discussed. Viscosity and conductivity measurements are used to characterize the bulk solvent properties. At x(IL) < 0.1, the log(η) data show a nonlinear dependence on mole fraction in contrast to the data for x(IL) > 0.1 where the data vary linearly with mole fraction. Conductivity data show a maximum at x(IL) = 0.03 in good agreement with conductivity measurements in imidazolium ILs. Steady-state and time-resolved fluorescence spectroscopies were used to measure the equilibrium, lifetime, and rotational response of coumarin 153 (C153) in neat and MeOH cosolvent modified PIL-Cl. The collective set of data depicts the formation of an increasingly aggregated solvent structure that changes in proportion to the amount of PIL-Cl present in MeOH. Average solvation and rotation times are found to scale with solution viscosity. At x(IL) values of 0.02-0.2, the rotation times are at or near the hydrodynamic stick limit, whereas for x(IL) > 0.2 rotation times drop to between 40 and 70% of the stick limit, consistent with the IL literature. In this cosolvent system, the most dramatic changes in solution behavior occur between 0 and 10% PIL-Cl.