Influence of the density of states on the open-circuit voltage in small-molecule solar cells

Open-circuit voltages are strongly dependent on the density-of-states in solar cells based on disordered semiconductors. In this work, organic solar cells based on tetraphenyldibenzoperiflanthene and fullerene C₇₀ with a bilayer structure were fabricated to investigate the variation in the density-of-states with the substrate temperature during deposition of the donor. The maximum open circuit voltage was reached at a substrate temperature of 60 °C. Organic thin-film transistors were also fabricated to study their electrical properties, such as the mobility and the density-of-states. Finally, an organic solar cell with p–i–n structure was fabricated at the optimized substrate temperature, and a power conversion efficiency of almost 4% was obtained.     

Phenoxazine-based organic dyes with different chromophores for dye-sensitized solar cells

A series of organic dyes (POZ-2, POZ-3, POZ-4 and POZ-5) involving phenoxazine were synthesized as sensitizers for application in dye-sensitized solar cells (DSSCs). For comparison, three different electron donors namely 10-phenyl-10H-phe-nothiazine, 10-phenyl-10H-phenoxazine and triphenylamine were separately appended onto the 7-position of the model dye (POZ-2). The obtained four dyes exhibit considerably high values of conversion efficiencies of 6.6%, 7.8%, 7.1% and 6.4%, respectively, under the simulated AM1.5G conditions. The geometries of the dyes were optimized to gain insight into the molecular structure and electron distribution, and then the charge extraction and transient photovoltage decay measurements were further performed to understand the influence of electron donors on the photovoltaic behaviors.     

Exciton-induced degradation of organic/electrode interfaces in ultraviolet organic photodetectors

We study the degradation mechanisms of ultraviolet (UV) organic photodetectors (OPDs). Contrary to expectations, we determine that the bulk of the organic layers in UV OPDs is stable under prolonged UV irradiation, showing no detectable changes in photophysical characteristics such as photoluminescence yield and exciton lifetime and thus not contributing to the observed degradation behavior of UV OPDs. However, the results show that the organic/electrode interfaces in UV OPDs, including indium tin oxide (ITO)/organic and organic/metal ones, are susceptible to UV irradiation, leading to a deterioration in both charge injection and extraction across the interfaces. The degradation of the organic/electrode interfaces in UV OPDs is essentially induced by UV-generated excitons in their vicinity and may be responsible for nearly 100% of the photo-current loss of UV OPDs. Approaches for improving the photo-stability of organic/electrode interfaces, and thus the lifetime of UV OPDs, are also investigated. We demonstrate that the use of thin (∼0.5 nm) interfacial layers such as lithium acetylacetonate at organic/metal interfaces can significantly reduce the interfacial degradation, and the use of appropriate hole transport materials such as N,N′-bis (naphthalen-1-yl)-N,N′-bis(phenyl) benzidine at ITO/organic interfaces can greatly improve the interfacial photo-stability.     

Improved photovoltaic characteristics of organic cells with heterointerface layer as a hole-extraction layer inserted between ITO anode and donor layer

We have fabricated an improved organic photovoltaic (OPV) cell in which organic heterointerface layer is inserted between indium-tin-oxide (ITO) anode and copper-phthalocyanine (CuPc) donor layer in the conventional OPV cell of ITO/CuPc/fullerene (C₆₀)/bathophenanthroline (Bphen)/Al to enhance the power conversion efficiency (PCE) and fill factor (FF). The inserted ITO-buffer layer consists of electron-transporting layer (ETL) and hole-transporting layer (HTL). We have changed the ETL and HTL materials variously and also changed their layer thickness variously. It is confirmed that ETL materials with higher LUMO level than the work function of ITO give low PCE and FF. All the double layer buffers give higher PCE than a single layer buffer of TAPC. The highest PCE of 1.67% and FF of 0.57% are obtained from an ITO buffer consisted of 3 nm thick ETL of hexadecafkluoro-copper-phthalocyanine (F₁₆CuPc) and 3 nm thick HTL of 1,1-bis-(4-methyl-phenyl)-aminophenylcyclohexane (TAPC). This PCE is 1.64 times higher than PCE of the cell without ITO buffer and 2.98 times higher than PCE of the cell with single layer ITO buffer of TAPC. PCE is found to increase with increasing energy difference (ΔE) between the HOMO level of HTL and LUMO level of F₁₆CuPc in a range of ΔE < 0.6 eV. From the ΔE dependence of PCE, it is suggested that electrons moved from ITO to the LUMO level of the electron-transporting F₁₆CuPc are recombined, at the F₁₆CuPc/HTL-interface, with holes transported from CuPc to the HOMO level of HTL in the double layer ITO buffer ETL, leading to efficient extraction of holes photo-generated in CuPc donor layer.     

Environmental effects on the electrical behavior of pentacene thin-film transistors with a poly(methyl methacrylate) gate insulator

The electrical properties of top-contact pentacene thin-film transistors (TFTs) with a poly(methyl methacrylate) (PMMA) gate dielectric were analyzed in air and vacuum environments. Compared to the vacuum case, the pentacene TFT in air exhibited lower drain currents and more pronounced shifts in the threshold voltage upon reversal of the gate voltage sweep direction, together with a decrease in the field-effect mobility. These characteristic variations were explained in terms of two distinctive actions of polar H₂O molecules in pentacene TFT. H₂O molecules were suggested to diffuse under the source and drain contacts and interrupt the charge injection into the pentacene film, whereas those that permeate at the pentacene/PMMA interface retard hole depletion in and around the TFT channel. The diffusion process was much slower than the permeation process. The degraded TFT characteristics in air could be recovered mostly by storing the device under vacuum, which suggests that the air instability of TFTs is due mainly to the physical adsorption of H₂O molecules within the pentacene film.     

Work function difference of naphthyl end-capped oligothiophene in different crystal alignments studied by Kelvin probe force microscopy

The performance of organic semiconductor devices is strongly affected by the interface energetics at the junctions between the constituent materials. A large group of organic semiconductors consists of rodlike small molecules that crystallize upon deposition with a molecular orientation dependent on the specifics of the molecule–molecule and molecule–substrate interactions. By means of Kelvin probe force microscopy (KPFM), this work studies naphthyl end-capped oligothiophene, 5,50-bis(naphth-2-yl)-2,20-bithiophene (NaT2), deposited on samples of pristine ${\text{SiO}}_2$ and samples of graphene-covered ${\text{SiO}}_2$. The crystal molecular orientation of NaT2 is dependent on the substrate on which it is deposited. On ${\text{SiO}}_2$, the NaT2 molecules are predominately upright standing, forming crystallites with distinct terrace heights of $2.0\pm 0.1\text{nm}$. Measurements indicate formation of an initial wetting layer in the NaT2-${\text{SiO}}_2$ system for the upright standing molecules. When deposited on graphene, the molecules additionally form fibrous structures with heights of $10-115\text{nm}$ consisting of molecules lying down (face-on orientation). Using KPFM, a difference in the local contact potential difference (CPD) of upright standing NaT2 and face-on oriented structures on graphene is measured to be $-0.16\pm 0.04\text{V}$, indicating a work function difference between the two system configurations, which is confirmed through Density Functional Theory calculations.     

Organic field-effect transistor circuits using atomic layer deposited gate dielectrics patterned by reverse stamping

We report on a reverse stamping method to produce via-holes in circuits comprising acene-based top-gate organic field-effect transistors (OFETs) having a CYTOP/Al₂O₃ (by atomic layer deposition) bilayer gate dielectric. This method relies on the weak adhesive force that exists between a small molecule acene film and a polymer to enable easy delamination of the bilayer gate dielectric by using a PDMS stamp. We demonstrate the effectiveness of this method by fabricating simple circuits using top-gate triisopropylsilylethynyl pentacene (TIPS-pentacene)/poly (triarylamine) (PTAA) OFETs.     

Inserting a Mn-doped TiO2 layer for improving performance of pentacene organic thin-film transistors

Device performance of pentacene organic thin-film transistors (OTFTs) was significantly improved via inserting a Mn-doped TiO₂ layer between pentacene semiconductor and the source–drain electrodes. In comparison with the OTFTs with only-Au electrodes, the introduction of a thin Mn-doped TiO₂ layer leads to saturation current increasing from 31.9 μA to 0.22 mA, effective field-effect mobility improving from 0.24 to 1.13 cm²/V s, and threshold voltage downshifting from −11 to −2 V. These performance enhancements are ascribed to the significant reduction of contact resistance and smoothed surface of pentacene layer. This work may provide an effective approach to improve the performance of the pentacene based OTFTs by inserting a Mn-doped TiO₂ layer.     

Novel organic dye employing dithiafulvenyl-substituted arylamine hybrid donor unit for dye-sensitized solar cells

In order to increase electron-donating ability of the donor part of the organic dye, two dithiafulvenyl (DTF) units were introduced into a triphenylamine unit to form dithiafulvenyl-substituted triphenylamine hybrid donor for dye-sensitized solar cells (DSSCs) for the first time. Novel donor–acceptor organic dye WD-10 containing this hybrid donor and 2-cyanoacetic acid acceptor has been designed, synthesized and applied in DSSCs. The influence of the substituent unit DTF in the dye on the device performance has been investigated. It was found that the dye with dithiafulvenyl-substituted triphenylamine hybrid donor gave higher photocurrent, open-circuit voltage, and efficiency value. The DSSC based on organic dye WD-10 displayed a short-circuit current (J_sc) of 9.58 mA cm^?2, an open-circuit voltage (V_oc) of 648 mV, and a fill factor (ff) of 0.71, corresponding to an overall conversion efficiency of 4.41%. An increase in η of about 79% was obtained from simple triphenylamine dye L0 to WD-10. The different photovoltaic behaviors of the solar cells based on the organic dyes were further elucidated by the electrochemical impedance spectroscopy. This work identifies that the introduction of DTF unit into the simple triphenylamine dye could significant improve the photovoltaic performance.     

A DCM‐Type Red‐Fluorescent Dopant for High‐Performance Organic Electroluminescent Devices

2‐(2‐tert‐Butyl‐6‐((E)‐2‐(2,6,6‐trimethyl‐2,4,5,6‐tetrahydro‐1H‐pyrrolo[3,2,1‐ij]quinolin‐8‐yl)vinyl)‐4H‐pyran‐4‐ylidene)malononitrile (DCQTB) is designed and synthesized in high yield for application as the red‐light‐emitting dopant in organic light‐emitting diodes (OLEDs). Compared with 4‐(dicyanomethylene)‐2‐tert‐butyl‐6‐(1,1,7,7,‐tetramethyljulolidyl‐9‐enyl)‐4H‐pyran (DCJTB), one of the most efficient red‐emitting dopants, DCQTB exhibits red‐shifted fluorescence but blue‐shifted absorption. The unique characteristics of DCQTB with respect to DCJTB are utilized to achieve a red OLED with improved color purity and luminous efficiency. As a result, the device that uses DCQTB as dopant, with the configuration: indium tin oxide (ITO)/N,N′‐bis(1‐naphthyl)‐N,N′‐diphenyl‐1,1′‐biphenyl‐4,4′‐diamine (NPB; 60 nm)/tris(8‐quinolinolato) aluminum (Alq₃):dopant (2.3 wt %) (7 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 12 nm)/Alq₃(45 nm)/LiF(0.3 nm):Al (300 nm), shows a larger maximum luminance (L_max = 6021 cd m^–2 at 17 V), higher maximum efficiency (η_max = 4.41 cd A^–1 at 11.5 V (235.5 cd m^–2)), and better chromaticity coordinates (Commission Internationale de l'Eclairage, CIE, (x,y) = (0.65,0.35)) than a DCJTB‐based device with the same structure (L_max = 3453 cd m^–2 at 15.5 V, η_max = 3.01 cd A^–1 at 10 V (17.69 cd m^–2), and CIE (x,y) = (0.62,0.38)). The possible reasons for the red‐shifted emission but blue‐shifted absorption of DCQTB relative to DCJTB are also discussed.