Driving Triplet State Population in Benzothioxanthene Imide Dyes: Let's twist!

Controlling the formation of photoexcited triplet states is critical for many (photo)chemical and physical applications. Here, we demonstrate that a permanent out-of-plane distortion of the benzothioxanthene imide (BTI) dye promotes intersystem crossing by increasing spin-orbit coupling. This manipulation was achieved through a subtle chemical modification, specifically the bay-area methylation. Consequently, this simple yet efficient approach expands the catalog of known molecular engineering strategies for synthesizing heavy atom-free, dual redox-active, yet still emissive and synthetically accessible photosensitizers.

A new G-quadruplex-specific photosensitizer inducing genome instability in cancer cells by triggering oxidative DNA damage and impeding replication fork progression.

Photodynamic therapy (PDT) ideally relies on the administration, selective accumulation and photoactivation of a photosensitizer (PS) into diseased tissues. In this context, we report a new heavy-atom-free fluorescent G-quadruplex (G4) DNA-binding PS, named DBI. We reveal by fluorescence microscopy that DBI preferentially localizes in intraluminal vesicles (ILVs), precursors of exosomes, which are key components of cancer cell proliferation. Moreover, purified exosomal DNA was recognized by a G4-specific antibody, thus highlighting the presence of such G4-forming sequences in the vesicles. Despite the absence of fluorescence signal from DBI in nuclei, light-irradiated DBI-treated cells generated reactive oxygen species (ROS), triggering a 3-fold increase of nuclear G4 foci, slowing fork progression and elevated levels of both DNA base damage, 8-oxoguanine, and double-stranded DNA breaks. Consequently, DBI was found to exert significant phototoxic effects (at nanomolar scale) toward cancer cell lines and tumor organoids. Furthermore, in vivo testing reveals that photoactivation of DBI induces not only G4 formation and DNA damage but also apoptosis in zebrafish, specifically in the area where DBI had accumulated. Collectively, this approach shows significant promise for image-guided PDT.

Stable ZnS Electron Transport Layer for High-Performance Inverted Cadmium-Free Quantum Dot Light-Emitting Diodes.

We report high-efficiency and long-lifetime inverted green cadmium-free (InP-based) quantum dot light-emitting diodes (QLEDs) using a stable ZnO/ZnS cascaded electron transport layer (ETL). We have successfully developed a strategy to spin-coat stable ZnS ETLs with a relatively higher conduction band minimum (CBM) and lower electron mobility than that of ZnO, which leads to balanced carrier injection and an improved device lifetime. Analysis shows that by using the ZnO/ZnS cascaded ETL, electron injection is reduced, resulting in an improved charge balance in the QD layer and suppressed exciton quenching, which preserves the emission properties of QDs. Optimized devices with ZnO/ZnS cascaded ETLs show a maximum external quantum efficiency of 10.8% and a maximum current efficiency of 37.5 cd/A; these efficiency values are an almost 2.2-fold improvement compared to those of reference devices without ZnS. The QLED devices also showed a remarkably long lifetime (LT70) of 265 h at an initial luminance of 1000 cd/m2. The predicted half-lifetime (LT50) at 100 cd/m2 is 60,255 h, which, to our knowledge, is currently the longest lifetime yet reported for InP-based green QLEDs.

Synthesis of fluorescent organic nano-dots and their application as efficient color conversion layers.

Efficient conversion of light from short wavelengths to longer wavelengths using color conversion layers (CCLs) underpins the successful operation of numerous contemporary display and lighting technologies. Inorganic quantum dots, based on CdSe or InP, for example, have received much attention in this context, however, suffer from instability and toxic cadmium or phosphine chemistry. Organic nanoparticles (NPs), though less often studied, are capable of very competitive performance, including outstanding stability and water-processability. Surfactants, which are critical in stabilizing many types of nano-structures, have not yet been used extensively in organic NPs. Here we show the utility of surfactants in the synthesis and processing of organic NPs by thoroughly characterizing the effect of ionic and non-ionic surfactants on the properties of fluorescent organic NPs. Using this information, we identify surfactant processing conditions that result in nearly 100 % conversion of organic fluorophores into sub-micrometer particles, or nano-dots, with outstanding performance as CCLs. Such water dispersions are environmentally benign and efficiently convert light. They can be used for a range of fluorophores covering a full spectral gamut, with excellent color purity, including full-width at half-maximum (FWHM) values as low as 21 nm. Compared to inorganic (InP) reference CCLs, the organic nano-dot based CCLs show superior color conversion efficiency and substantially improved long-term stability.

Lithium Polystyrene Sulfonate as a Hole Transport Material in Inverted Perovskite Solar Cells.

Despite the exceptional efficiency of perovskite solar cells (PSCs), further improvements can be made to bring their power conversion efficiencies (PCE) closer to the Shockley-Queisser limit, while the development of cost-effective strategies to produce high-performance devices are needed for them to reach their potential as a widespread energy source. In this context, there is a need to improve existing charge transport layers (CTLs) or introduce new CTLs. In this contribution, we introduced a new polyelectrolyte (lithium poly(styrene sulfonate (PSS))) (Li:PSS) polyelectrolyte as an HTL in inverted PSCs, where Li+ can act as a counter ion for the PSS backbone. The negative charge on the PSS backbone can stabilize the presence of p-type carriers and p-doping at the anode. Simple Li:PSS performed poorly due to poor surface coverage and voids existence in perovskite film as well as low conductivity. PEDOT:PSS was added to increase the conductivity to the simple Li:PSS solution before its use which also resulted in lower performance. Furthermore, a bilayer of PEDOT:PSS and Li:PSS was employed, which outperformed simple PEDOT:PSS due to high quality of perovskite film with large grain size also the large electron injection barrier (ϕe ) impeded back diffusion of electrons towards anode. As a consequence, devices employing PEDOT:PSS / Li:PSS bilayers gave the highest PCE of 18.64%.

Pseudo-halide anion engineering for α-FAPbI3 perovskite solar cells.

Metal halide perovskites of the general formula ABX3-where A is a monovalent cation such as caesium, methylammonium or formamidinium; B is divalent lead, tin or germanium; and X is a halide anion-have shown great potential as light harvesters for thin-film photovoltaics1-5. Among a large number of compositions investigated, the cubic α-phase of formamidinium lead triiodide (FAPbI3) has emerged as the most promising semiconductor for highly efficient and stable perovskite solar cells6-9, and maximizing the performance of this material in such devices is of vital importance for the perovskite research community. Here we introduce an anion engineering concept that uses the pseudo-halide anion formate (HCOO-) to suppress anion-vacancy defects that are present at grain boundaries and at the surface of the perovskite films and to augment the crystallinity of the films. The resulting solar cell devices attain a power conversion efficiency of 25.6 per cent (certified 25.2 per cent), have long-term operational stability (450 hours) and show intense electroluminescence with external quantum efficiencies of more than 10 per cent. Our findings provide a direct route to eliminate the most abundant and deleterious lattice defects present in metal halide perovskites, providing a facile access to solution-processable films with improved optoelectronic performance.

Light-Emitting Transistors with High Color Purity Using Perovskite Quantum Dot Emitters.

The class of organic-inorganic lead halides with perovskite crystal structures has recently emerged as promising materials for a variety of practical optoelectronic applications. In particular, hybrid halide perovskite quantum dots possess excellent intrinsic optoelectronic properties such as high color purity (full width at half-maximum of 24.59 nm) and photoluminescence quantum yields (92.7%). In this work, we demonstrate the use of perovskite quantum dot materials as an emissive layer of hybrid light-emitting transistors. To investigate the working mechanism of perovskite quantum dots in light-emitting transistors, we investigated the electrical and optical characteristics under both p-channel and n-channel operation. Using these materials, we have achieved perovskite quantum dot light-emitting transistors with high electron mobilities of up to 12.06 cm2·V-1 s-1, high brightness of up to 1.41 × 104 cd m-2, and enhanced external quantum efficiencies of up to 1.79% operating at a source-drain potential of 40 V.

Hybrid Lead-Halide Polyelectrolytes as Interfacial Electron Extraction Layers in Inverted Organic Solar Cells.

A series of lead-halide based hybrid polyelectrolytes was prepared and used as interfacial layers in organic solar cells (OSCs) to explore their effect on the energy band structures and performance of OSCs. Nonconjugated polyelectrolytes based on ethoxylated polyethylenimine (PEIE) complexed with PbX2 (I, Br, and Cl) were prepared as polymeric analogs of the perovskite semiconductors CH3NH3PbX3. The organic/inorganic hybrid composites were deposited onto Indium tin oxide (ITO) substrates by solution processing, and ultraviolet photoelectron spectroscopy (UPS) measurements confirmed that the polyelectrolytes allowed the work function of the substrates to be controlled. In addition, X-ray photoelectron spectroscopy (XPS) results showed that Pb(II) halide complexes were present in the thin film and that the Pb halide species did not bond covalently with the cationic polymer and confirmed the absence of additional chemical bonds. The composite ratio of organic and inorganic materials was optimized to improve the performance of OSCs. When PbBr2 was complexed with the PEIE material, the efficiency increased up to 3.567% via improvements in open circuit voltage and fill factor from the control device (0.3%). These results demonstrate that lead-halide based polyelectrolytes constitute hybrid interfacial layers which provide a novel route to control device characteristics via variation of the lead halide composition.

Tungsten-Doped Zinc Oxide and Indium-Zinc Oxide Films as High-Performance Electron-Transport Layers in N-I-P Perovskite Solar Cells.

Perovskite solar cells (PSCs) have attracted tremendous research attention due to their potential as a next-generation photovoltaic cell. Transition metal oxides in N-I-P structures have been widely used as electron-transporting materials but the need for a high-temperature sintering step is incompatible with flexible substrate materials and perovskite materials which cannot withstand elevated temperatures. In this work, novel metal oxides prepared by sputtering deposition were investigated as electron-transport layers in planar PSCs with the N-I-P structure. The incorporation of tungsten in the oxide layer led to a power conversion efficiency (PCE) increase from 8.23% to 16.05% due to the enhanced electron transfer and reduced back-recombination. Scanning electron microscope (SEM) images reveal that relatively large grain sizes in the perovskite phase with small grain boundaries were formed when the perovskite was deposited on tungsten-doped films. This study demonstrates that novel metal oxides can be used as in perovskite devices as electron transfer layers to improve the efficiency.

Depth-dependent electronic band structure at the Au/CH3NH3PbI3-xClx junction.

The electronic properties of the interface between Au and organometallic triiodide perovskite (CH3NH3PbI3-xClx) were investigated by ultraviolet photoelectron spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS). CH3NH3PbI3-xClx films were prepared on Au surfaces by spin casting with various concentrations to control the film thickness. Their morphology was examined by atomic force microscopy (AFM). CH3NH3PbI3-xClx films exhibited a maximum valence band edge of 5.91 eV. The energy levels shifted downward by 0.26 eV with a perovskite coverage of 116.3 nm, indicating that band bending occurs at the interface. The observed energy level shift indicates an interface dipole at the Au/CH3NH3PbI3-xClx junction. These findings contribute to the understanding of how perovskite materials function in electronic devices and aid in the design of new perovskite materials.

Pseudohalides in Lead-Based Perovskite Semiconductors.

The emerging class of lead halide perovskite (LHP) semiconductors offers a surprising combination of low cost, ease of preparation, outstanding material properties, and performance in optoelectronic devices that has not yet been observed in any other class of material. Considering their general ABX3 formula, the halide (X) composition in LHP compositions has proven to be one of the best handles to control the material characteristics such as bandgap, morphology, and electronic properties. However, compared to the amount of effort that has been expended to discover new A cations and B cations, relatively few reports have dealt with the subject of discovering new X anions outside of the series of halides (Cl- , Br- , I- ). In principal, a much wider range of anions with a -1 charge (pseudohalides) may form the ABX3 stoichiometry with Pb2+ , yet the general ability of polyatomic pseudohalides to form semiconducting perovskite crystal phases with Pb2+ remains an open question. Herein, the prospect of using polyatomic pseudohalide anions in LHP semiconductors is addressed.

Morphology-Dependent Hole Transfer under Negligible HOMO Difference in Non-Fullerene Acceptor-Based Ternary Polymer Solar Cells.

In the field of organic solar cells, it has been generally accepted until recently that a difference in band energies of at least 0.3 eV between the highest occupied molecular orbital (HOMO) level of the donor and the HOMO of the acceptor is required to provide adequate driving force for efficient photoinduced hole transfer due to the large binding energy of excitons in organic materials. In this work, we investigate polymeric donor:non-fullerene acceptor junctions in binary and ternary blend polymer solar cells, which exhibit efficient photoinduced hole transfer despite negligible HOMO offset and demonstrate that hole transfer in this system is dependent on morphology. The morphology of the organic blend was gradually tuned by controlling the amount of ITIC and PC70BM. High external quantum efficiency was achieved at long wavelengths, despite ITIC-to-PC70BM ratio of 1:9, which indicates efficient photoinduced hole transfer from ITIC to the donor despite an undesirable HOMO energy offset. Transient absorption spectra further confirm that hole transfer from ITIC to the donor becomes more efficient upon optimizing the morphology of the ternary blend compared to that of donor:ITIC binary blend.

Effect of counter-ions on the properties and performance of non-conjugated polyelectrolyte interlayers in solar cell and transistor devices.

We have investigated a series of non-conjugated polyelectrolytes (NPEs) which are based on a polyethylenimine (PEI) backbone with various counterions, such as Br- I- and BIm4 -, as interfacial layers at the electrodes of solar cells and transistor devices to improve the power conversion efficiency (PCE) and device performance. This new series of NPEs with different counterions are capable of forming electric dipoles at NPE/metal electrode interfaces; as a consequence tuning of the energy levels, and work function (WF) of the electrodes is possible. Using this approach, the PCE of organic solar cells could be improved from 1.05% (without NPEs) to 6.77% (with NPEs) while the charge carrier mobility and on/off ratio of FET devices could be improved, showing the broad utility of this type of material. This study provides a novel approach towards investigating the influence of ions on interfacial dipoles and electrode WFs in solution-processed semiconducting devices.

Nanoparticle-Enhanced Silver-Nanowire Plasmonic Electrodes for High-Performance Organic Optoelectronic Devices.

Improved performance in plasmonic organic solar cells (OSCs) and organic light-emitting diodes (OLEDs) via strong plasmon-coupling effects generated by aligned silver nanowire (AgNW) transparent electrodes decorated with core-shell silver-silica nanoparticles (Ag@SiO2 NPs) is demonstrated. NP-enhanced plasmonic AgNW (Ag@SiO2 NP-AgNW) electrodes enable substantially enhanced radiative emission and light absorption efficiency due to strong hybridized plasmon coupling between localized surface plasmons (LSPs) and propagating surface plasmon polaritons (SPPs) modes, which leads to improved device performance in organic optoelectronic devices (OODs). The discrete dipole approximation (DDA) calculation of the electric field verifies a strongly enhanced plasmon-coupling effect caused by decorating core-shell Ag@SiO2 NPs onto the AgNWs. Notably, an electroluminescence efficiency of 25.33 cd A-1 (at 3.2 V) and a power efficiency of 25.14 lm W-1 (3.0 V) in OLEDs, as well as a power conversion efficiency (PCE) value of 9.19% in OSCs are achieved using hybrid Ag@SiO2 NP-AgNW films. These are the highest values reported to date for optoelectronic devices based on AgNW electrodes. This work provides a new design platform to fabricate high-performance OODs, which can be further explored in various plasmonic and optoelectronic devices.

Alkoxybenzothiadiazole-Based Fullerene and Nonfullerene Polymer Solar Cells with High Shunt Resistance for Indoor Photovoltaic Applications.

We synthesized three semicrystalline polymers (PTTBTBO, PDTBTBO, and P2FDTBTBO) by modulating the intra- and intermolecular noncovalent Coulombic interactions and investigated their photovoltaic characteristics under various light intensities. Low series (Rs) and high shunt (Rsh) resistances are essential prerequisites for good device properties under standard illumination (100 mW cm-2). Considering these factors, among three polymers, PDTBTBO polymer solar cells (PSCs) exhibited the most desirable characteristics, with peak power conversion efficiencies (PCE) of 7.52 and 9.60% by being blended with PC71BM under standard and dim light (2.5 mW cm-2), respectively. P2FDTBTBO PSCs exhibited a low PCE of 3.69% under standard light due to significant charge recombination with high Rs (9.42 Ω cm2). However, the PCE was remarkably improved by 2.3 times (8.33% PCE) under dim light, showing negligible decrease in open-circuit voltage and remarkable increase in fill factor, which is due to an exceptionally high Rsh of over 1000 kΩ cm2. Rs is less significant under dim light because the generated current is too small to cause noticeable Rs-induced voltage losses. Instead, high Rsh becomes more important to avoid leakage currents. This work provides important tips to further optimize PSCs for indoor applications with low-power electronic devices such as Internet of things sensors.

Formamidinium-based planar heterojunction perovskite solar cells with alkali carbonate-doped zinc oxide layer.

We herein demonstrate n-i-p-type planar heterojunction perovskite solar cells employing spin-coated ZnO nanoparticles modified with various alkali metal carbonates including Li2CO3, Na2CO3, K2CO3 and Cs2CO3, which can tune the energy band structure of ZnO ETLs. Since these metal carbonates doped on ZnO ETLs lead to deeper conduction bands in the ZnO ETLs, electrons are easily transported from the perovskite active layer to the cathode electrode. The power conversion efficiency of about 27% is improved due to the incorporation of alkali carbonates in ETLs. As alternatives to TiO2 and n-type metal oxides, electron transport materials consisting of doped ZnO nanoparticles are viable ETLs for efficient n-i-p planar heterojunction solar cells, and they can be used on flexible substrates via roll-to-roll processing.

Non-halogenated diphenyl-chalcogenide solvent processing additives for high-performance polymer bulk-heterojunction solar cells.

The ability to control the morphologies of active layers is a critical factor in the successful development of polymer solar cells (PSCs), and solvent processing additives offer a simple and effective way to accomplish this. In particular, diphenyl ether (DPE) is one of the most effective solvent additives but analogous additives based on this structure have not yet been extensively investigated. In this work, we have fabricated PSCs and investigated photovoltaic device characteristics using the series of non-halogenated, diphenyl-chalcogen solvent additives; DPE, diphenyl sulfide (DPS) and diphenyl selenide (DPSe). DPS devices showed optimal power conversion efficiencies (PCEs) of up to 9.08%, and DPE devices also showed similarly high PCEs of up to 8.85%. In contrast, DPSe devices showed relatively low PCEs (5.45% at best) which we attribute to significant surface recombination and high series resistance, which led to limited open-circuit voltage (V OC). In the case of DPS, fast, field-independent photocurrent saturation with negligible bimolecular recombination led to efficient charge separation and collection, which resulted in the highest PCEs. Additionally, using 1,2,4-trimethylbenzene and DPS as an entirely non-halogenated solvent/additive system, we successfully demonstrated device fabrication with comparably high PCEs of up to 8.4%. This work elucidates the effects of diphenyl-based solvent additives in PSCs and suggests a great potential of DPS as an effective non-halogenated solvent additive.

Fluorine Functionalized Graphene Nano Platelets for Highly Stable Inverted Perovskite Solar Cells.

Edged-selectively fluorine (F) functionalized graphene nanoplatelets (EFGnPs-F) with a p-i-n structure of perovskite solar cells achieved 82% stability relative to initial performance over 30 days of air exposure without encapsulation. The enhanced stability stems from F-substitution on EFGnPs; fluorocarbons such as polytetrafluoroethylene are well-known for their superhydrophobic properties and being impervious to chemical degradation. These hydrophobic moieties tightly protect perovskite layers from air degradation. To directly compare the effect of similar hydrophilic graphene layers, edge-selectively hydrogen functionalized graphene nanoplatelet (EFGnPs-H) treated devices were tested under the same conditions. Like the pristine MAPbI3 perovskite devices, EFGnPs-H treated devices were completely degraded after 10 days. The hydrophobic properties of EFGnPs-F were characterized by contact angle measurement. The test results showed great water repellency compared to pristine perovskite films or EFGnPs-H coated films. This resulted in highly air-stable p-i-n perovskite solar cells.

Effect of Heterocyclic Anchoring Sequence on the Properties of Dithienogermole-Based Solar Cells.

The synthesis and characterization of two new small molecular donor materials, DTGe(ThFBTTh2)2 and DTGe(FBTTh3)2, are presented for application in organic solar cells. These two materials represent structural evolutions of the high-efficiency, dithienogermole (DTGe)-cored small molecule DTGe(FBTTh2)2, in which the conjugation length in the backbone was extended by incorporating additional thiophene units. Using the same molecular framework, we have evaluated how the anchoring sequence of heterocyclic units influences material properties and function in solar cell devices. It was found that incorporating additional thiophene units into the backbone, regardless of the position in the molecular platform, caused a small reduction in band gaps; however, both highest occupied molecular orbitals and lowest unoccupied molecular orbital energy bands were at lower energies when the thiophenes were incorporated near the terminus of the molecule. The film morphologies of both materials could be controlled by either thermal or solvent vapor annealing to yield phase separation on the order of tens of nanometers and improved crystallinity. Peak power-conversion efficiencies of 3.6% and 3.1% were obtained using DTGe(ThFBTTh2)2 and DTGe(FBTTh3)2, after solvent vapor treatment and thermal annealing, respectively. Our study provides a detailed analysis of how the ordering sequence of heterocyclic building blocks influences the properties and function of organic solar cells.

Clean thermal decomposition of tertiary-alkyl metal thiolates to metal sulfides: environmentally-benign, non-polar inks for solution-processed chalcopyrite solar cells.

We report the preparation of Cu2S, In2S3, CuInS2 and Cu(In,Ga)S2 semiconducting films via the spin coating and annealing of soluble tertiary-alkyl thiolate complexes. The thiolate compounds are readily prepared via the reaction of metal bases and tertiary-alkyl thiols. The thiolate complexes are soluble in common organic solvents and can be solution processed by spin coating to yield thin films. Upon thermal annealing in the range of 200-400 °C, the tertiary-alkyl thiolates decompose cleanly to yield volatile dialkyl sulfides and metal sulfide films which are free of organic residue. Analysis of the reaction byproducts strongly suggests that the decomposition proceeds via an SN1 mechanism. The composition of the films can be controlled by adjusting the amount of each metal thiolate used in the precursor solution yielding bandgaps in the range of 1.2 to 3.3 eV. The films form functioning p-n junctions when deposited in contact with CdS films prepared by the same method. Functioning solar cells are observed when such p-n junctions are prepared on transparent conducting substrates and finished by depositing electrodes with appropriate work functions. This method enables the fabrication of metal chalcogenide films on a large scale via a simple and chemically clear process.