Boron-Doped Engineering for Carbon Quantum Dots-Based Memristors with Controllable Memristance Stability.

Carbon quantum dots-based memristors (CQDMs) have emerged as a rising star in data storage and computing. The key constraint to their commercialization is memristance variability, which mainly arises from the disordered conductive paths. Doping methodology can optimize electron and ion transport to help construct a stable conductive mode. Herein, based on boron (B)-doped engineering strategy, three kinds of comparable quantum dots are synthesized, including carbon quantum dots (CQDs), a series of boron-doped CQDs (BCQDs) with different B contents, and boron quantum dots. The corresponding device performances highlight the superiority of BCQDs-based memristors, exhibiting a ternary flash-type memory behavior with longer retention time and more controllable memristance stability. The comprehensive analysis results, including device performance, functional layer morphology, and material simulated calculation, illustrate that the doped B elements can directionally guide the migration of aluminum ions by enhancing the capture of free electrons, resulting in ordered conductive filaments and stable ternary memory behavior. Finally, the conceptual applications of logic display and logic gate are discussed, indicating a bright prospect for BCQDs-based memristors. This work proves that modest B doping can optimize memristance property, establishing a theoretical foundation and template scheme for developing effective and stable CQDMs.

Thermal-Induced Performance Decay of the State-of-the-Art Polymer: Non-Fullerene Solar Cells and the Method of Suppression.

Improving thermal stability is of great importance for the industrialization of polymer solar cells (PSC). In this paper, we systematically investigated the high-temperature thermal annealing effect on the device performance of the state-of-the-art polymer:non-fullerene (PM6:Y6) solar cells with an inverted structure. Results revealed that the overall performance decay (19% decrease) was mainly due to the fast open-circuit voltage (VOC, 10% decrease) and fill factor (FF, 10% decrease) decays whereas short circuit current (JSC) was relatively stable upon annealing at 150 °C (0.5% decrease). Pre-annealing on the ZnO/PM6:Y6 at 150 °C before the completion of cell fabrication resulted in a 1.7% performance decrease, while annealing on the ZnO/PM6:Y6/MoO3 films led to a 10.5% performance decay, indicating that the degradation at the PM6:Y6/MoO3 interface is the main reason for the overall performance decay. The increased ideality factor and reduced built-in potential confirmed by dark J - V curve analysis further confirmed the increased interfacial charge recombination after thermal annealing. The interaction of PM6:Y6 and MoO3 was proved by UV-Vis absorption and XPS measurements. Such deep chemical doping of PM6:Y6 led to unfavorable band alignment at the interface, which led to increased surface charge recombination and reduced built-in potential of the cells after thermal annealing. Inserting a thin C60 layer between the PM6:Y6 and MoO3 significantly improved the cells' thermal stability, and less than 2% decay was measured for the optimized cell with 3 nm C60.

One-Step Synthesis of White-Light-Emitting Carbon Dots for White LEDs with a High Color Rendering Index of 97.

White-light-emitting carbon dots (WCDs) show innate advantages as phosphors in white light-emitting diodes (WLEDs). For WLEDs, the color rendering index (CRI) is the most important metric to evaluate its performance. Herein, WCDs are prepared by a facile one-step solvothermal reaction of trimellitic acid and o-phenylenediamine. It consists of four CDs identified by column chromatography as blue, green, yellow, red, and thus white light is a superposition of these four types of light. The mixture of the four CDs undergoes Förster resonance energy transfer to induce the generation of white light. The photoluminescence of WCDs originates from the synergistic effect of carbon core and surface states. Thereinto, the carbon core states dominate in RCDs, and the increase of amide contents and degree of conjugation promote the redshift of the emission spectra, which is further confirmed by theoretical calculations. In addition, a high CRI of 97 is achieved when the WCDs are used as phosphors to fabricate WLEDs, which is almost the highest value up to now. The multicolor LEDs can also be fabricated by using the four multicolor CDs as phosphors, respectively. This work provides a novel approach to explore the rapid preparation of low-cost, high-performance WCDs and CDs-based WLEDs.

Recent research progress in CDs@MOFs composites: fabrication, property modulation, and application.

Carbon dots (CDs) have exhibited a promising application prospect in many fields because of their good fluorescence properties, biocompatibility, low toxicity, and easy functionalization. In order to improve their photoelectricity and stability, metal-organic frameworks (MOFs) can be used as host materials to provide ideal carriers for CDs to realize the multifunctional composites of CDs and MOFs (CDs@MOFs). At present, CDs@MOFs composites have shown tremendous application potential because they have various advantages of both CDs and MOFs. In this review, the synthesis methods of CDs@MOFs composites are firstly introduced. Then, the influence of the synergy between CDs and MOFs on the regulation of their structures and optical properties is highlighted. Furthermore, the recent application researches of CDs@MOFs composites in fluorescent probes, solid-state lighting, and photoelectrocatalysis are generalized. Finally, the critical issues, challenges, and solutions on their structure and property regulation and application are put forward, and their commercialization direction is also prospected.

Robust singlet fission process in strong absorption π-expanded diketopyrrolopyrroles.

Singlet fission (SF) has drawn tremendous attention as a multiexciton generation process that could mitigate the thermal loss and boost the efficiency of solar energy conversion. Although a SF-based solar cell with an EQE above 100% has already been fabricated successfully, the practical efficiency of the corresponding devices is plagued by the limited scope of SF materials. Therefore, it is of great importance to design and develop new SF-capable compounds aiming at practical device application. In the current contribution, via a π-expanded strategy, we presented a new series of robust SF chromophores based on polycyclic DPP derivatives, Ex-DPPs. Compared to conventional DPP molecules, Ex-DPPs feature strong absorption with a fivefold extinction coefficient, good molecular rigidity to effectively restrain non-radiative deactivation, and an expanded π-skeleton which endow them with well-suited intermolecular packing geometries for achieving efficient SF process. These results not only provide a new type of high-efficiency SF chromophore but also address some basic guidelines for the design of potential SF materials targeting practical light harvesting applications.

Carbon dots-based delayed fluorescent materials: Mechanism, structural regulation and application.

Delayed fluorescent (DF) materials have high internal quantum efficiency because of the triplet excitons involved in the radiation transition, and the spin-forbidden transition can effectively improve their luminescent lifetime. Compared with traditional afterglow materials including metal-containing inorganic coordination compounds and organic compounds, the DF materials based on carbon dots (CDs) have drawn extensive attention because of their advantages of low toxicity, environmental friendliness, stable luminescence, easy preparation and low cost. Most CDs-based DF materials can be realized by embedding CDs in matrix with covalent bonds, hydrogen bonds or/and other supramolecular interactions. Recently, matrix-free self-protective CDs-based DF materials are emerging. This review systematically summarizes the DF mechanism and structural regulation strategies of CDs-based DF materials, and the applications of CDs-based DF materials in anti-counterfeiting, information encryption, temperature sensing and other fields are introduced. Finally, the existing problems and future potentials of CDs-based DF materials are proposed and prospected.

Simultaneously Achieving Highly Efficient and Stable Polymer:Non-Fullerene Solar Cells Enabled By Molecular Structure Optimization and Surface Passivation.

Despite the tremendous efforts in developing non-fullerene acceptor (NFA) for polymer solar cells (PSCs), only few researches are done on studying the NFA molecular structure dependent stability of PSCs, and long-term stable PSCs are only reported for the cells with low efficiency. Herein, the authors compare the stability of inverted PM6:NFA solar cells using ITIC, IT-4F, Y6, and N3 as the NFA, and a decay rate order of IT-4F > Y6 ≈ N3 > ITIC is measured. Quantum chemical calculations reveal that fluorine substitution weakens the C═C bond and enhances the interaction between NFA and ZnO, whereas the ß-alkyl chains on the thiophene unit next to the C═C linker blocks the attacking of hydroxyl radicals onto the C═C bonds. Knowing this, the authors choose a bulky alkyl side chain containing molecule (named L8-BO) as the acceptor, which shows slower photo bleaching and performance decay rates. A combination of ZnO surface passivation with phenylethanethiol (PET) yields a high efficiency of 17% and an estimated long T80 and Ts80 of 5140 and 6170 h, respectively. The results indicate functionalization of the ß-position of the thiophene unit is an effective way to improve device stability of the NFA.

Hybrid Hole Extraction Layer Enabled High Efficiency in Polymer Solar Cells.

Charge extraction layers with excellent charge extraction capability are essential for achieving high photovoltaic performance in cells. In this work, a hole extraction layer (HEL) is developed by doping conductive polymer TFB into CuSCN (CuSCN:TFB(X)), which exhibits good light transparency and high affinity for the light absorber. Compared to the reference cell, the CuSCN:TFB(X) HEL-based cells show impressive enhancement owing to the increased exciton dissociation and charge extraction processes and weak recombination losses. Furthermore, matched work function, better interface contact, and appropriate domain size also contribute to the enhanced power conversion efficiency. As a consequence, the highest conversion efficiency of 15.28% is observed in a cell based on the PM6:Y6 blend film and CuSCN:TFB(1.0%) HEL, which is >16% higher than the efficiency of 13.13% in a cell with CuSCN HEL.

The Role of the Hydrogen Bond between Piperazine and Fullerene Molecules in Stabilizing Polymer:Fullerene Solar Cell Performance.

Piperazine has been recently reported as a stabilizer for polymer:fullerene solar cells that can minimize the "burn-in" degradation of the cell. In this paper, the influence of N-substituents on the stabilization effect of piperazine in P3HT:PC61BM cells was investigated. Results confirmed that only piperazine derivatives (PZs) with N-H bonds showed the stabilization effect, whereas the bis-alkyl-substituted piperazine compounds cannot improve the stability. An efficient photon-induced electron transfer (PET) process between PZ and PC61BM was only detected for the N-H-containing PZ:PC61BM blends, corresponding very well to the stabilization effect of the PZs, which indicates that the PET process between PZ and PC61BM stabilizes the cell performance, and the N-H bond plays a critical role ensuring the PET process and the consequent stabilization effect. Both 1H-NMR spectroscopy and theoretical calculations confirmed the formation of N-H···O-C and N-H···π bonds for the PC61BM:piperazine adduct, which was considered as the driving force that promotes the PET process between these two components. In addition, comparison of the calculated electron affinity energy (EA) and excitation energy (EEx) of PC61BM with/without piperazine confirmed that piperazine doping is able to promote the electron transfer (which leads to the formation of PC61BM anions) than the energy transfer (leads to the formation of PC61BM excitons) between P3HT and PC61BM, which is beneficial for the performance and stability improvement.

Efficiency above 12% for 1 cm2 Flexible Organic Solar Cells with Ag/Cu Grid Transparent Conducting Electrode.

With the rapid progress of organic solar cells (OSCs), improvement in the efficiency of large-area flexible OSCs (>1 cm2) is crucial for real applications. However, the development of the large-area flexible OSCs severely lags behind the growth of the small-area OSCs, with the electrical loss due to the large sheet resistance of the electrode being a main reason. Herein, a high conductive and high transparent Ag/Cu composite grid with sheet resistance <1 Ω sq-1 and an average visible light transparency of 84% is produced as the transparent conducting electrode of flexible OSCs. Based on this Ag/Cu composite grid electrode, a high efficiency of 12.26% for 1 cm2 flexible OSCs is achieved. The performances of large-area flexible OSCs also reach 7.79% (4 cm2) and 7.35% (9 cm2), respectively, which are much higher than those of the control devices with conventional flexible indium tin oxide electrodes. Surface planarization using highly conductive PEDOT:PSS and modification of the ZnO buffer layer by zirconium acetylacetonate (ZrAcac) are two necessary steps to achieve high performance. The flexible OSCs employing Ag/Cu grid have excellent mechanical bending resistance, maintaining high performance after bending at a radius of 2 mm.

Synthesis of N,S-Doped Carbon Quantum Dots for Use in Organic Solar Cells as the ZnO Modifier To Eliminate the Light-Soaking Effect.

Zinc oxide (ZnO) is one of the most extensively used electron-transporting layers (ETLs) in organic solar cells. However, owing to numerous surface defects and mismatched energy bands with the photoactive layer, light-soaking process is usually required to achieve a high device performance for the ZnO-based cells. Herein, we reported the synthesis of N,S-doped carbon quantum dots (N,S-CQDs) by a simple hydrothermal treatment using ascorbic acid and ammonium persulfate as reagents. As characterized by high-resolution transmission electron microscopy and X-ray diffraction, the synthesized CQDs were found to be 2-7 nm in dimensions, having a graphite-structured core and amorphous carbon on the shell. Fourier transform infrared and X-ray photoelectron spectroscopy analyses confirmed that these CQDs are highly nitrogen- and sulfur-doped, which leads to efficient (with a quantum yield of 33%) downconversion and excitation-dependent photoluminescence character. Application of these N,S-CQDs as surface modifier for ZnO layer in inverted organic solar cells was investigated. Results indicate that the cells with N,S-CQDs-decorated ZnO ETL showed higher power conversion efficiency without S-shaped kink in the current density-voltage curves. The performance improvement and the elimination of light-soaking effect for ZnO:N,S-CQDs cells are attributed to the ZnO surface defect passivation by N,S-CQDs, as confirmed by fluorescence spectroscopy and scanning Kelvin probe microscopy. The cells with N,S-CQDs-modified ZnO ETL showed a high power conversion efficiency of 9.31%, which is higher than the reference ZnO cells. The current work provides a feasible way to achieve shell element-doped CQDs for specific application in organic electronic devices.

Silane-Capped ZnO Nanoparticles for Use as the Electron Transport Layer in Inverted Organic Solar Cells.

Zinc oxide (ZnO) nanoparticles are widely used as electron- transport layer (ETL) materials in organic solar cells and are considered to be the candidate with the most potential for ETLs in roll-to-roll (R2R)-printed photovoltaics. However, the tendency of the nanoparticles to aggregate reduces the stability of the metal oxide inks and creates many surface defects, which is a major barrier to its printing application. With the aim of improving the stability of metal oxide nanoparticle dispersions and suppressing the formation of surface defects, we prepared 3-aminopropyltrimethoxysilane (APTMS)-capped ZnO (ZnO@APTMS) nanoparticles through surface ligand exchange. The ZnO@APTMS nanoparticles exhibited excellent dispersibility in ethanol, an environmentally friendly solvent, and remained stable in air for at least one year without any aggregation. The capping of the ZnO nanoparticles with APTMS also reduced the number of surface-adsorbed oxygen defects, improved the charge transfer efficiency, and suppressed the light-soaking effect. The thickness of the ZnO@APTMS ETL could reach 100 nm without an obvious decrease in the performance. Large-area APTMS-modified ZnO films were successfully fabricated through roll-to-roll microgravure printing and exhibited good performance in flexible organic solar cells. This work demonstrated the distinct advantages of this ZnO@APTMS ETL as a potential buffer layer for printed organic electronics.

Effect of the π-conjugation length on the properties and photovoltaic performance of A-π-D-π-A type oligothiophenes with a 4,8-bis(thienyl)benzo[1,2-b:4,5-b']dithiophene core.

Benzo[1,2-b:4,5-b']dithiophene (BDT) is an excellent building block for constructing π-conjugated molecules for the use in organic solar cells. In this paper, four 4,8-bis(5-alkyl-2-thienyl)benzo[1,2-b:4,5-b']dithiophene (TBDT)-containing A-π-D-π-A-type small molecules (COOP-nHT-TBDT, n = 1, 2, 3, 4), having 2-cyano-3-octyloxy-3-oxo-1-propenyl (COOP) as terminal group and regioregular oligo(3-hexylthiophene) (nHT) as the π-conjugated bridge unit were synthesized. The optical and electrochemical properties of these compounds were systematically investigated. All these four compounds displayed broad absorption bands over 350-600 nm. The optical band gap becomes narrower (from 1.94 to 1.82 eV) and the HOMO energy levels increased (from -5.68 to -5.34 eV) with the increase of the length of the π-conjugated bridge. Organic solar cells using the synthesized compounds as the electron donor and PC61BM as the electron acceptor were fabricated and tested. Results showed that compounds with longer oligothiophene π-bridges have better power conversion efficiency and higher device stability. The device based on the quaterthiophene-bridged compound 4 gave a highest power conversion efficiency of 5.62% with a VOC of 0.93 V, JSC of 9.60 mA·cm-2, and a FF of 0.63.

Photoluminescent carbon quantum dots as a directly film-forming phosphor towards white LEDs.

Photoluminescent organosilane-functionalized carbon quantum dots (CQDs), 3.0-3.5 nm in diameter, were synthesized via a facile hydrothermal method using citric acid monohydrate as a precursor and N-(3-(trimethoxysilyl) propyl) ethylenediamine as a coordinating and passivation agent. The optical properties of the as-obtained CQDs were investigated in detail. The CQD aqueous solution emits bright blue-white light under ultraviolet (UV) illumination with a quantum yield of 57.3% and high red-green-blue (RGB) spectral composition of 60.1%, and in particular the CQDs exhibit excitation-independent photoluminescence. The CQDs have a narrow size distribution around 3.1 nm and good film-forming ability through simple heat-treatment. By virtue of these excellent optical characteristics and good film-forming ability, a white light-emitting device (LED) was fabricated by combining a UV-LED chip with a single CQD phosphor film, which exhibited cool white light with a CIE coordinate of (0.31, 0.36), a color rendering index of 84 and a correlated color temperature of 6282 K. In addition, the white LED exhibits good optical stability under various working currents and for different working time intervals. Moreover, the interaction between the carbogenic core and surface groups was discussed using the DMol(3) program based on density functional theory. This research suggests the great potential of CQDs for solid-state lighting systems and reveals the effect of the surface state on the photoluminescent mechanism of CQDs.