Pseudohalogen Ammonium Salt-Assisted Syntheses of Large-Sized Indium Phosphide Quantum Dots with Near-Infrared Photoluminescence.

The development of indium phosphide (InP)-based quantum dots (QDs) with a near-infrared (NIR) emission area still lags behind the visible wavelength region and remains problematic. This study describes a one-step in situ pseudohalogen ammonium salt-assisted approach to generate NIR-emitted InP-based QDs with high photoluminescence quantum yields (PLQYs). The coexistence of NH4+ and PF6- ions from NH4PF6 may in situ synchronously etch and passivate the surface oxides and impede the creation of traps under the whole growth process of InP QDs. Experimental findings demonstrated that the in situ pseudohalogen ammonium salt-assisted syntheses technique may feature emission at a full width at half-maximum (fwhm) peak as fine as ∼45 nm and broaden the emission range to around ∼780 nm. A two-step approach for ZnS shells was developed to further improve the PLQY of NIR-emitted InP QDs. Furthermore, the constructed high-power intrinsically stretchable NIR color-conversion film employing the InP-based QDs/polymer composites presented excellent luminescence conversion ability and stretchability.

Surface Passivation toward Multiple Inherent Dangling Bonds in Indium Phosphide Quantum Dots.

Indium phosphide (InP) quantum dots (QDs) have become the most recognized prospect to be less-toxic surrogates for Cd-based optoelectronic systems. Due to the particularly dangling bonds (DBs) and the undesirable oxides, the photoluminescence performance and stability of InP QDs remain to be improved. Previous investigations largely focus on eliminating P-DBs and resultant surface oxidation states; however, little attention has been paid to the adverse effects of the surface In-DBs on InP QDs. This work demonstrates a facile one-step surface peeling and passivation treatment method for both In- and P-DBs for InP QDs. Meanwhile, the surface treatment may also effectively support the encapsulation of the ZnSe shell. Finally, the generated InP/ZnSe QDs display a narrower full width at half-maximum (fwhm) of ∼48 nm, higher photoluminescence quantum yields (PLQYs) of ∼70%, and superior stability. This work enlarges the surface chemistry engineering consideration of InP QDs and considerably promotes the development of efficient and stable optoelectronic devices.

Non-destructive prediction of TVB-N using color-texture features of UV-induced fluorescence image for freeze-thaw treated frozen-whole-round tilapia.

BACKGROUND: The investigation of UV-induced fluorescence imaging coupled with machine learning was conducted to non-destructively detect the total volatile basic nitrogen (TVB-N) of frozen-whole-round tilapia (FWRT) during freezing and thawing. The UV-induced fluorescence images of FWRT at the wavelength of 365 nm were acquired by self-developed fluorescence image acquisition system. In total, 169 color and texture features based on RGB, hue-saturation-intensity and L*a*b* color spaces and gray level co-occurrence matrix were extracted, respectively. Successive projections algorithm (SPA) was employed to select the optimal 16 features to achieve feature dimension reduction modeling. With full and extracted features as input, the models of partial least squares regression (PLSR), least-squares support vector machine (LSSVM) and convolutional neural network (CNN) were established for TVB-N prediction. RESULTS: Results indicated that the full features-based CNN performed better than SPA based prediction models (SPA-PLSR and SPA-LSSVM). The CNN model was determined to be the optimal with an RP2 value of 0.9779, RMSEP value of 1.1502 × 10-2 g N kg-1 and RPD value of 6.721 for TVB-N content predictiin. CONCLUSION: The CNN method based on UV fluorescence imaging technology has potential for quality and safety detection of FWRT. © 2023 Society of Chemical Industry.

Multiple underlying images tuned by Mn-doped Zn-Cu-In-S quantum dots.

In this study, ZnS capped Cu-In-S (ZCIS) quantum dots doped with Mn ions are synthesized by a thermal injection method, with luminescence covering almost the entire visible area. The large Stokes shift effectively inhibits the self-absorption effect under luminescence, and the quantum yield of ZCIS quantum dots increased from 38% to 50% after ZnS capping and further to 69% after doping with Mn. First, red-, yellow-, and blue-emitting quantum dots were synthesized and then, polychromatic ensembles were obtained by mixing the trichromatic quantum dots in a different ratio. Using the home-built inkjet printer, multilayered and multicolor mixed patterns were obtained for information pattern storage and multilayer pattern recognition and reading.

MOF-derived CuxS double-faced-decorated carbon nanosheets as high-performance and stable counter electrodes for quantum dots solar cells.

The development of highly-catalytic counter electrode (CE) materials is vital to the construction of quantum dot-sensitized solar cells (QDSCs) but is still challenging. Here, a novel self-assembly double-faced decorated carbon nanosheets with MOF-derived CuxS nanospheres (DF-CuxS/C NSs) were prepared as high-performance hybrid CEs for improving the catalytic activity towards polysulfide electrolytes and enhancing the performance of QDSCs. It is shown that the MOF-derived CuxS nanospheres disperse well on the surface of the carbon NSs in the obtained DF-CuxS/C NSs hybrids. Electrochemical characterization demonstrated that the DF-CuxS/C NSs with moderate mass ratio exhibited enhanced electrocatalytic activity towards the reduction of the polysulfide redox couple (Sn2-/S2-) and decreased charge transfer resistance at the interface of the CE/electrolyte. Benefitting from the merits of this novel hybrid CE, the power conversion efficiency (PCE) of the CdSeTe QDs-based QDSCs is increased to 9.39%, which is higher than the pristine carrageenan (CA)-derived CEs (5.84%) and Cu-BTC-derived CEs (7.74%). With the further optimization of the substrate, the highest PCE of 11.36% was achieved based on the Ti mesh substrate supported hybrid CE.

Enhancing Efficiency of Nonfullerene Organic Solar Cells via Using Polyelectrolyte-Coated Plasmonic Gold Nanorods as Rear Interfacial Modifiers.

Sufficient sunlight absorption and exciton generation are critical for developing efficient nonfullerene organic solar cells (OSCs). In this work, polyelectrolyte polystyrenesulfonate (PSS)-coated plasmonic gold nanorods (GNRs@PSS) were incorporated, for the first time, into the inverted nonfullerene OSCs as rear interfacial modifiers to improve sunlight absorption and charge generation via the near-field plasmonic and backscattering effects. The plasmonic GNRs effectively improved the sunlight absorption and enhanced the charge generation. Meanwhile, the negatively charged PSS shell ensured the uniform dispersion of the GNRs on the surface of the photoactive layer, optimized the interfacial contact, and further promoted the hole transport to the electrode. These concerted synergistic effects augmented the efficiency (10.11%) by nearly 20% relative to the control device (8.47%). Remarkably, the ultrathin (∼2.2 nm) organic layer on the surface of GNRs was closely examined by acquiring the carbon contrast image through energy-filtered transmission electron microscopy (EF-TEM), which clearly confirmed the coating uniformity from the side to end-cap of GNRs. The surface plasmon resonance (SPR) effect of the GNRs@PSS on the surface of the photoactive layer was unprecedentedly mapped by photoinduced force microscopy (PiFM) under the illumination of a tunable wavelength supercontinuum laser mimicking sunlight. Furthermore, investigations into the effect of size, surface coverage, and incorporation location of GNRs@PSS on the performance of OSCs revealed that the appropriate design and incorporation of the plasmonic nanostructures are crucial, otherwise the performance can be decreased, as evidenced in the case of front interface integration.

Novel Cuboid-like Crystalline Complexes (CLCCs), Photon Emission, Fluorescent Fibers, and Bright Red Fabrics of Eu3+ Complexes Adjusted by Amphiphilic Molecules.

With the growing needs for flexible fluorescence emission materials, emission fibers and related wearable fabrics with bright emission properties have become key factors for wearable applications. In this article, novel cuboid-like crystals of Eu3+ complexes were generated. Except for light-energy-harvesting ligands of thenoyltrifluoroacetone (TTA) and 1,10-phenanthroline hydrate (Phen), the crystal structures were adjusted by other functional amphiphilic molecules. Not only does ETPC-SA, adjusted by stearic acid, have a regular cuboid-like crystal with a size of about 2 µm size, but it also generates the best photon emission property, with a fluorescence quantum yield of 98.4% fluorescence quantum yield in this report. Furthermore, we succeeded in producing novel fluorescent fibers by mini-twin-screw extrusion, and it was easy to form bright red fabrics, which are equipped with strong fluorescence intensity, flexibility, and a smooth hand feeling, with the normal fabricating method in our work. It is worth noting that ETPC-HQ fibers, which carry a crystal complex adjusted by hydroquinone, possess the lowest quantum yield but have the longest average fluorescence lifetime of 1259 µs. This result means that a low-density polyethylene (LDPE) matrix could make excited electrons stand in the excited state for a relatively long time when adjusted by hydroquinone, so as to increase the afterglow property of fluorescent fibers.

An Efficient Cyan Emission from Copper (II) Complexes with Mixed Organic Conjugate Ligands.

Copper (II) complexes containing mixed ligands were synthesized in dimethyl formamide (DMF). The intense cyan emission at an ambient temperature is observed for solid copper (II) complexes with salicylic acid and a 12% quantum yield with a fluorescent lifetime of approximately 10 ms. Hence, copper (II) complexes with salicylic acid are excellent candidates for photoactive materials. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) reveal that the divalent copper metal centers coordinate with the nitrogen and oxygen lone pairs of conjugate ligands. XPS binding energy trends for core electrons in lower-lying orbitals are similar for all three copper (II) complexes: nitrogen 1s and oxygen 1s binding energies increase relative to those for undiluted ligands, and copper 2p3/2 binding energies decrease relative to that for CuCl2. The thermal behavior of these copper complexes reveals that the thermal stability is characterized by the following pattern: Cu(1,10-phenanthroline)(salicylic acid) > Cu(1,10-phenanthroline)(2,2'-bipyridine) > Cu(1,10-phenanthroline)(1-benzylimidazole)2.

An Effective Strategy to Design a Large Bandgap Conjugated Polymer by Tuning the Molecular Backbone Curvature.

With the significant progress of low bandgap non-fullerene acceptors, the development of wide bandgap (WBG) donors possessing ideal complementary absorption is of crucial importance to further enhance the photovoltaic performance of organic solar cells. An ideal strategy to design WBG donors is to down-shift the highest occupied molecular orbital (HOMO) and up-shift the lowest unoccupied molecular orbital (LUMO). A properly low-lying HOMO of the donor is favorable to obtaining a high open-circuit voltage, and a properly high-lying LUMO of the donor is conductive to efficient exciton dissociation. This work provides a new strategy to enlarge the bandgap of a polymer with simultaneously decreased HOMO and increased LUMO by increasing the polymer backbone curvature. The polymer PIDT-fDTBT with a large molecular backbone curvature shows a decreased HOMO of -5.38 eV and a prominently increased LUMO of -3.35 eV relative to the linear polymer PIDT-DTBT (EHOMO = -5.30 eV, ELUMO = -3.55 eV). The optical bandgap of PIDT-fDTBT is obviously broadened from 1.75 to 2.03 eV. This work demonstrates that increasing the polymer backbone curvature can effectively broaden the bandgap by simultaneously decreasing HOMO and increasing LUMO, which may guide the design of WBG conjugated materials.

Recent advances, challenges and prospects in ternary organic solar cells.

The past decade has seen a tremendous development of organic solar cells (OSCs). To date, high-performance OSCs have boosted power conversion efficiencies (PCEs) over 17%, showing bright prospects toward commercial applications. Compared with binary OSCs, ternary OSCs, by introducing a third component as a second donor or acceptor into the active layer, have great potential in realizing outstanding photovoltaic performance. Herein, a comprehensive review of the recent advances of ternary solar cells is presented. According to the chemical components of active layer materials, we classify the ternary systems into four categories, including polymer/small molecule/small molecule, polymer/polymer/small molecule, all-polymer and all-small-molecule types. The relationships among the photovoltaic materials structure and weight ratio, active layer morphology and photovoltaic performance are systematically analyzed and summarized. The features and design strategies of each category are also discussed and summarized. Key issues and challenges faced in ternary OSCs are pointed out, and potential strategies and solutions are proposed. This review may provide guidance for the field of ternary OSCs.

MOF-Derived Co,N Codoped Carbon/Ti Mesh Counter Electrode for High-Efficiency Quantum Dot Sensitized Solar Cells.

Carbon supported on titanium mesh electrodes has been recognized as the best performing counter electrodes (CEs) in quantum dot sensitized solar cells (QDSCs). Herein, layered double hydroxides (LDHs) are applied as a scaffold template for the growth of cobalt-zeolite-imidazole framework (ZIF-67) crystals, and micrometer-sized Co,N codoped porous carbon materials (Co,N-C) are obtained through a carbonization process. The as-prepared Co,N-C exhibits favorable features for electrocatalytic reduction of polysulfide, including a high surface area of 491.36 m2/g, highly effective active sites, and a hierarchical micro/mesoporous structure. Due to the large particle size, the obtained Co,N-C can couple with a Ti mesh substrate for the fabrication of high-performance Co,N-C/Ti CEs for QDSCs. As a result, the corresponding QDSCs exhibit an average efficiency of 13.55% (Jsc = 25.93 mA/cm2, Voc = 0.778 V, FF = 0.672), which is a 10.5% enhancement compared to the previous best result from the N-doped mesoporous carbon counterpart.

Solar Paint from TiO2 Particles Supported Quantum Dots for Photoanodes in Quantum Dot-Sensitized Solar Cells.

The preparation of quantum dot (QD)-sensitized photoanodes, especially the deposition of QDs on TiO2 matrix, is usually a time-extensive and performance-determinant step in the construction of QD-sensitized solar cells (QDSCs). Herein, a transformative approach for immobilizing QD on the TiO2 matrix was developed by simply mixing the as-prepared oil-soluble QDs with TiO2 P25 particles suspension for a period as short as half a minute. The solar paint was prepared by adding the TiO2/QD composite in a binder solution under ultrasonication. The QD-sensitized photoanodes were then obtained by simply brushing the solar paint on a fluorine-doped tin oxide substrate followed by a low-temperature annealing at ambient atmosphere. Sandwich-structured complete QDSCs were assembled with the use of Cu2S/brass as counter electrode and polysulfide redox couple as an electrolyte. The photovoltaic performance of the resulting Zn-Cu-In-Se (ZCISe) QDSCs was evaluated after primary optimization of the QD/TiO2 ratio as well as the thicknesses of photoanode films. In this proof of concept with a simple solar paint approach for photoanode films, an average power conversion efficiency of 4.13% (J sc = 11.11 mA/cm2, V oc = 0.590 V, fill factor = 0.631) was obtained under standard irradiation condition. This facile solar paint approach offers a simple and convenient approach for QD-sensitized photoanodes in the construction of QDSCs.

Alloying Strategy in Cu-In-Ga-Se Quantum Dots for High Efficiency Quantum Dot Sensitized Solar Cells.

I-III-VI2 group "green" quantum dots (QDs) are attracting increasing attention in photoelectronic conversion applications. Herein, on the basis of the "simultaneous nucleation and growth" approach, Cu-In-Ga-Se (CIGSe) QDs with light harvesting range of about 1000 nm were synthesized and used as sensitizer to construct quantum dot sensitized solar cells (QDSCs). Inductively coupled plasma atomic emission spectrometry (ICP-AES), wild-angle X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses demonstrate that the Ga element was alloyed in the Cu-In-Se (CISe) host. Ultraviolet photoelectron spectroscopy (UPS) and femtosecond (fs) resolution transient absorption (TA) measurement results indicate that the alloying strategy could optimize the electronic structure in the obtained CIGSe QD material, thus matching well with TiO2 substrate and favoring the photogenerated electron extraction. Open circuit voltage decay (OCVD) and impedance spectroscopy (IS) tests indicate that the intrinsic recombination in CIGSe QDSCs was well suppressed relative to that in CISe QDSCs. As a result, CIGSe based QDSCs with use of titanium mesh supported mesoporous carbon counter electrode exhibited a champion efficiency of 11.49% (Jsc = 25.01 mA/cm2, Voc = 0.740 V, FF = 0.621) under the irradiation of full one sun in comparison with 9.46% for CISe QDSCs.

Nitrogen-Doped Mesoporous Carbons as Counter Electrodes in Quantum Dot Sensitized Solar Cells with a Conversion Efficiency Exceeding 12.

The exploration of catalyst materials for counter electrodes (CEs) in quantum dot sensitized solar cells (QDSCs) that have both high electrocatalytic activity and low charge transfer resistance is always significant yet challenging. In this work, we report the incorporation of nitrogen heteroatoms into carbon lattices leading to nitrogen-doped mesoporous carbon (N-MC) materials with superior catalytic activity when used as CEs in Zn-Cu-In-Se QDSCs. A series of N-MC materials with different nitrogen contents were synthesized by a colloidal silica nanocasting method. Electrochemical measurements revealed that the N-MC with a nitrogen content of 8.58 wt % exhibited the strongest activity in catalyzing the reduction of a polysulfide redox couple (Sn2-/S2-), and therefore, the corresponding QDSC device showed the best photovoltaic performance with an average power conversion efficiency (PCE) of 12.23% and a certified PCE of 12.07% under one full sun illumination, which is a new PCE record for quantum dot based solar cells.

Carbon Counter-Electrode-Based Quantum-Dot-Sensitized Solar Cells with Certified Efficiency Exceeding 11.

The mean power conversion efficiency (PCE) of quantum-dot-sensitized solar cells (QDSCs) is mainly limited by the low photovoltage and fill factor (FF), which are derived from the high redox potential of polysulfide electrolyte and the poor catalytic activity of the counter electrode (CE), respectively. Herein, we report that this problem is overcome by adopting Ti mesh supported mesoporous carbon (MC/Ti) CE. The confined area in Ti mesh substrate not only offers robust carbon film with submillimeter thickness to ensure high catalytic capacity, but also provides an efficient three-dimension electrical tunnel with better conductivity than state-of-art Cu2S/FTO CE. More importantly, the MC/Ti CE can down shift the redox potential of polysulfide electrolyte to promote high photovoltage. In all, MC/Ti CEs boost PCE of CdSe0.65Te0.35 QDSCs to a certified record of 11.16% (Jsc = 20.68 mA/cm(2), Voc = 0.798 V, FF = 0.677), an improvement of 24% related to previous record. This work thus paves a way for further improvement of performance of QDSCs.

Zn-Cu-In-Se Quantum Dot Solar Cells with a Certified Power Conversion Efficiency of 11.6%.

The enhancement of power conversion efficiency (PCE) and the development of toxic Cd-, Pb-free quantum dots (QDs) are critical for the prosperity of QD-based solar cells. It is known that the properties (such as light harvesting range, band gap alignment, density of trap state defects, etc.) of QD light harvesters play a crucial effect on the photovoltaic performance of QD based solar cells. Herein, high quality ∼4 nm Cd-, Pb-free Zn-Cu-In-Se alloyed QDs with an absorption onset extending to ∼1000 nm were developed as effective light harvesters to construct quantum dot sensitized solar cells (QDSCs). Due to the small particle size, the developed QD sensitizer can be efficiently immobilized on TiO2 film electrode in less than 0.5 h. An average PCE of 11.66% and a certified PCE of 11.61% have been demonstrated in the QDSCs based on these Zn-Cu-In-Se QDs. The remarkably improved photovoltaic performance for Zn-Cu-In-Se QDSCs vs Cu-In-Se QDSCs (11.66% vs 9.54% in PCE) is mainly derived from the higher conduction band edge, which favors the photogenerated electron extraction and results in higher photocurrent, and the alloyed structure of Zn-Cu-In-Se QD light harvester, which benefits the suppression of charge recombination at photoanode/electrolyte interfaces and thus improves the photovoltage.