Sulfonate-Containing Polyelectrolytes for Perovskite Modification: Chemical Configuration, Property, and Performance.

Three sulfonate-containing polyelectrolytes are elaborately designed and used to passivate perovskite film with the anti-solvent method. Under the influence of the secondary monomer, three copolymers present various chemical configurations and deliver different modification effects. Fluorene-thiophene copolymer STF has linear and highly-conjugated chain. STF-perovskite film presents large crystal grains. Fluorene-carbazole copolymer SCF has flexible chain and easily enters into grain boundary areas. SCF-perovskite film is homogenous and continuous. Fluorene-fluorene copolymer SPF agglomerates on the surface and is not applicable to the anti-solvent method. The full investigation demonstrates that STF and SCF not only conduct surface defect passivation, but also improve the film quality by being involved in the perovskite's crystallization process. Compared with the control device, the devices with STF and SCF deliver high efficiency and excellent stability. The unencapsulated devices with STF and SCT maintain ≈80% of the initial power conversion efficiency (PCE) after 40 days of storage under 30-40% relative humidity. SCF performs better and the device maintains 60% of the initial PCE after 20 days of storage under 60-80% relative humidity.

Increasing Stability of SnO2-Based Perovskite Solar Cells by Introducing an Anionic Conjugated Polyelectrolyte for Interfacial Adjustment.

Despite the fact that power conversion efficiency (PCE) has been greatly improved in recent years, perovskite solar cells (PSCs) need to overcome some challenges, like stability, for the commercial application. Herein, an anionic conjugated polyelectrolyte, sulfonic-containing polyfluorene (abbreviated to SPF), has been developed to modify the interface between the electron-transporting layer (ETL) SnO2 and the optoelectronic active layer MAPbI3 in the n-i-p cells. After 40 days of storage in atmospheric environment in the dark with exposure to a controlled humidity of about 10%, PCE of the SPF-modified cells with the structure of ITO/SnO2/SPF/MAPbI3/spiro-OMeTAD/Au still remained 94% of the initial value. In contrast, the control cell without SPF only remained 31.1% of its initial efficiency after 29 days. The main reason for the stability enhancement is the adjustment of interfacial energy level, the crystallinity enhancement, and the removal of the interfacial defect of the perovskite layer by introducing the hydrophobic and smooth SPF interfacial layer. Deep electrical study on the PSCs discloses that the cell has low carrier transfer resistance, low leakage current density, and minor interfacial charge accumulation. What's more, the short-circuit current density is improved, and PCE of 20.47% is achieved.

1,8-Substituted Pyrene Derivatives for High-Performance Organic Field-Effect Transistors.

There have been many reports on the application of pyrene derivatives as organic semiconductors, but 1,8-subsituted pyrene semiconductors are less well-developed. Two p-type 1,8-substituted pyrene derivatives were synthesized that were composed of a pyrene core, thiophene or bithiophene arms, and end-capped octyl chains. These structures were not completely symmetrical and the dihedral angles between the pyrene core and the adjacent thiophene units had a difference of approximately two degrees. The field-effect performance of these materials was tested on a variety of dielectric surfaces. The performance of both materials with a spin-coated polystyrene layer on SiO2 (PS-treated SiO2 ) was better than that with an octadecyltrichlorosilane self-assembled monolayer on SiO2 (OTS-treated SiO2 ), which was mainly attributed to the presence of large grains on the low-leakage and high-capacitance PS films. The thiophene-contained compound presented a hole mobility of up to 0.18 cm2 V-1 s-1 on PS-treated SiO2 , which was 45 times that of the bithiophene-contained compound, owing to less steric hindrance, high crystallinity, and large grain size.

Charge-Storage Aromatic Amino Compounds for Nonvolatile Organic Transistor Memory Devices.

Here, charge-storage nonvolatile organic field-effect transistor (OFET) memory devices based on interfacial self-assembled molecules are proposed. The functional molecules contain various aromatic amino moieties (N-phenyl-N-pyridyl amino- (PyPN), N-phenyl amino- (PN), and N,N-diphenyl amino- (DPN)) which are linked by a propyl chain to a triethoxysilyl anchor group and act as the interface modifiers and the charge-storage elements. The PyPN-containing pentacene-based memory device (denoted as PyPN device) presents the memory window of 48.43 V, while PN and DPN devices show the memory windows of 24.88 and 8.34 V, respectively. The memory characteristic of the PyPN device can remain stable along with 150 continuous write-read-erase-read cycles. The morphology analysis confirms that three interfacial layers show aggregation due to the N atomic self-catalysis and hydrogen bonding effects. The large aggregate-covered PyPN layer has the full contact area with the pentacene molecules, leading to the high memory performance. In addition, the energy level matching between PyPN molecules and pentacene creates the smallest tunneling barrier and facilitates the injection of the hole carriers from pentacene to the PyPN layer. The experimental memory characteristics are well in agreement with the computational calculation.

Large Planar π-Conjugated Porphyrin for Interfacial Engineering in p-i-n Perovskite Solar Cells.

In hybrid organic-inorganic perovskite solar cells (PSCs), interfacial engineering can efficiently improve the photovoltaic performance. In this work, the planar π-conjugated porphyrin, zinc(II) 5,10,15,20-tetrakis[5-(p-acetylthiopentyloxy)phenyl]porphyrin, was developed to modify the interface between poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) and perovskite. The modified devices increased their highest power conversion efficiency (PCE) to 14.05% relative to 11.35% for the reference devices without modification. Such enhancement in efficiency is mainly attributed to the improved open-circuit voltage (Voc) and fill factor (FF), which benefit from fast hole-extraction and low charge recombination after the employment of well-aligned interlayer.

Efficient and reproducible CH3NH3PbI(3-x)(SCN)x perovskite based planar solar cells.

We report the addition of a small amount of Pb(SCN)2 into PbI2 in a two-step solution method. The resulting CH3NH3PbI(3-x)(SCN)x perovskite films present larger-sized crystals and fewer traps than CH3NH3PbI3. Their planar solar cells exhibit a maximum power conversion efficiency of 11.07% with remarkably high reproducibility and good stability.

Organic dipole layers for ultralow work function electrodes.

The alignment of the electrode Fermi level with the valence or conduction bands of organic semiconductors is a key parameter controlling the efficiency of organic light-emitting diodes, solar cells, and printed circuits. Here, we introduce a class of organic molecules that form highly robust dipole layers, capable of shifting the work function of noble metals (Au and Ag) down to 3.1 eV, that is, ∼1 eV lower than previously reported self-assembled monolayers. The physics behind the considerable interface dipole is elucidated by means of photoemission spectroscopy and density functional theory calculations, and a polymer diode exclusively based on the surface modification of a single electrode in a symmetric, two-terminal Au/poly(3-hexylthiophene)/Au junction is presented. The diode exhibits the remarkable rectification ratio of ∼2·10(3), showing high reproducibility, durability (>3 years), and excellent electrical stability. With this evidence, noble metal electrodes with work function values comparable to that of standard cathode materials used in optoelectronic applications are demonstrated.

Conductance modulation in tetraaniline monolayers by HCl-doping and by field-enhanced dissociation of H2O.

Oligoanilines are interesting candidates for organic electronics, as their conductivity can be varied by several orders of magnitude upon protonic doping. Here we demonstrate that tetraaniline self-assembled monolayers exhibit an unprecedented conductance on/off ratio of ∼710 (at +1 V) upon doping of the layers from the emeraldine base to the emeraldine salt form. Furthermore, a pronounced asymmetry in the current-voltage characteristics indicates dynamic doping of the tetraaniline layer by protons generated through field-enhanced dissociation of water molecules, a phenomenon known as the second Wien effect. These results point toward oligoanilines as promising substitutes for polyaniline layers in next-generation thin film devices.

Fabrication of asymmetric molecular junctions by the oriented assembly of dithiocarbamate rectifiers.

The oriented assembly of molecules on metals is a requirement for rectification in planar metal-molecule-metal junctions. Here, we demonstrate how the difference in adsorption kinetics between dithiocarbamate and thioacetate anchor groups can be utilized to form oriented assemblies of asymmetric molecules that are bound to Au through the dithiocarbamate moiety. The free thioactate group is then used as a ligand to bind Au nanoparticles and to form the desired metal-molecule-metal junction. Besides allowing an asymmetric coupling to the electrodes, the molecules exhibit an asymmetric molecular backbone where the length of the alkyl chains separating the electrodes from a central, para-substituted phenyl ring differs by two methylene units. Throughout the junction fabrication, the layers were characterized by photoelectron spectroscopy, infrared spectroscopy, and scanning tunneling microscopy. Large area junctions using a conducting polymer interlayer between a mercury-drop electrode and the self-assembled monolayer prove the relationship between electrical data and molecular structure.

Efficient electronic coupling and improved stability with dithiocarbamate-based molecular junctions.

Molecular electronic devices require stable and highly conductive contacts between the metal electrodes and molecules. Thiols and amines are widely used to attach molecules to metals, but they form poor electrical contacts and lack the robustness required for device applications. Here, we demonstrate that dithiocarbamates provide superior electrical contact and thermal stability when compared to thiols on metals. Ultraviolet photoelectron spectroscopy and density functional theory show the presence of electronic states at 0.6 eV below the Fermi level of Au, which effectively reduce the charge injection barrier across the metal-molecule interface. Charge transport measurements across oligophenylene monolayers reveal that the conductance of terphenyl-dithiocarbamate junctions is two orders of magnitude higher than that of terphenyl-thiolate junctions. The stability and low contact resistance of dithiocarbamate-based molecular junctions represent a significant step towards the development of robust, organic-based electronic circuits.

[Synthesis, characterization and photoluminescence properties of (EuxRE1-x)(beta-NTA)3phen complexes].

Two series of solid complexes of EuxRE1-x(beta-NTA)3 phen (RE = Y3+ and Tb3+, x = 0.10, 0.30, 0.50, 0.70, 0.90) were synthesized in alcohol. They were characterized by elemental analysis, IR spectra, molar conductivity, 1H NMR spectra and TG-DTA. The molar conductivity indicated that all the complexes were nonelectrolyte; and 1H NMR spectra and IR spectra showed that the ligand coordinates(double-tooth) with RE3+ ions through the oxygen negative ion of enolic form of beta-NTA and the two nitrogen atoms of phen. The fluorescence properties of these complexes were studied, the results indicated that the chemical bonds have formed by the rare earth ions with the two ligands energy can be transferred from the ligand to the RE3+, and the excited spectra was very wide showing that energy transfer was efficient, the fluorescence emission intensity of 5 D0-->7 F2 transitions in the strongest according to the emission spectra of the complexes. So the authors choose this energy transition as the research object and the results showed that the emission intensity of Eu3+ ion can be enhanced if a part of Eu3+ ions were substituted by Y3+ or Tb3+ ions. But the concentration of the Y3+ or Tb3+ ions can influence the fluorescence emission intensity of the rare earth complexes. The authors changed the concentration of Y3+ and Tb3+ in order to find the proper proportion Finally the authors found that if the x < 0.3 for the complexes EuxY1-x (beta-NTA)3 phen can get higher fluorescence intensity than pure Eu3+ system, but compared with the concentration of Y3+, the proportion of Tb3+ is different. The result showed that if x < 0.5 the authors can get higher fluorescence intensity. In all, at a proper proportion of the doping ions (Y3+ or Tb3+) the authors can get higher fluorescence intensity. This doping method not only decreases the cost of materials, but also enhances the fluorescence intensity, so it has a bright future in practical application.

Diphenyloligothiophene-based dichromophoric macrocycles and their ability to form donor/acceptor complexes.

A series of four dichromophoric rigid macrocycles 6a-6d, two with diphenyloligothiophene chromophores, the other two with more electron-rich diphenyl-EDOT or diphenyl-bis-EDOT chromophores, have been synthesized. The absorption spectrum of the diphenyl-bis-EDOT based macrocycle 6d displayed the most pronounced vibronic resolution with a well-resolved 0-0 transition, indicating a fully planarized geometry of the diphenyl-bis-EDOT chromophores. The (1)H NMR spectra of the macrocycles displayed weak to moderate chemical shifts of characteristic signals upon addition of pi-conjugated oligonitro-9-fluorenone acceptors. X-ray single-crystal analysis showed that columnar pi-stacked donor/acceptor complexes are formed with the stacks composed of alternating donor and acceptor molecules. The stoichiometry of the crystalline, dark-colored complexes was found to be 1:1 by elemental analysis and integration of the (1)H NMR peaks. The complex formation is accompanied by remarkably large Stern-Volmer constants of fluorescence quenching.