Geometrical and crystal structures,optical absorption and device characterization of N-(5-{[antipyrinyl-hydrazono]-cyanomethyl}-[1,3,4]thiadiazol-2-yl)-benzamide

The molecular structure of the N-(5-{[antipyrinyl-hydrazono]-cyanomethyl}-[1,3,4]thiadiazol-2-yl)-benzamide (ACTB) is optimized theoretically in which the energies of highest occupied molecular orbital and lowest unoccupied molecular orbital are calculated. ACTB crystalizes in triclinic structure with a space group, P2. ACTB thin films were prepared by using thermal evaporation technique onto quartz and n-Si single crystal substrates. The optical properties of the films are investigated in terms of the spectrophotometric measurements of the transmittance and reflectance. The current–voltage (I–V) characteristics of the fabricated In/ACTB/n-Si/Au diode are studied in temperature range 298–398 K. The device showed rectification behavior. At low forward voltage, the thermionic theory is applied for determining the ideality factor and barrier height as a function of temperature. The series resistance of the device is found to decrease with increasing temperature. At relatively high forward voltage, the space charge limited current dominated by exponential distribution of traps is found to be the operating mechanism in which the trapping parameters and charge carriers mobility are estimated.     

Development of a new class of hole-transporting and emitting vinyl polymers and their application in organic electroluminescent devices

A new class of hole-transporting vinyl polymers, poly{4-vinyl-4^′-[bis(4^′-tert-butylbiphenyl-4-yl)amino]biphenyl} (PVBAB) and poly{4-vinyl-4^′-[N,N-bis(9,9-dimethylfluoren-2-yl)amino]biphenyl} (PVFAB), and a new emitting vinyl polymer, poly(2-{4-[4-vinylphenyl(4-methylphenyl)amino]phenyl}-5-dimesitylborylthiophene) (PVPhAMB-1T), were designed and synthesized. These new vinyl polymers form smooth amorphous films with high glass-transition temperatures of ca. 200 °C. PVBAB and PVFAB possess electron-donating properties, and PVPhAMB-1T possesses bipolar character with both electron-donating and accepting properties, exhibiting strong fluorescence in solution and as films. Organic electroluminescent devices using PVBAB or PVFAB as a hole-transport layer and N,N^′-dimethylquinacridone-doped tris(8-quinolinolato)aluminum as an emitting layer were thermally stable and exhibited very high performance. The use of PVPhAMB-1T as an emitting material also permitted the fabrication of a high-performance, green-emitting organic EL device.     

Molecular order,charge injection efficiency and the role of intramolecular polar bonds at organic/organic heterointerfaces

The effect of orientational changes in thin films of the non-crystalline hole transport material α-N-N′-diphenyl N-N″-bis(1 naphthayl)-1,1′-biphenyl-4,4′-diamine (α-NPD) on the energy level alignment and the film electronic structure has been investigated by angle-resolved ultraviolet photoelectron spectroscopy and related to the transport characteristics of hole-only devices. Changes in the anisotropic α-sexithiophene (α-6T) substrate from a “standing” to a “flat” molecular orientation induced by mechanical rubbing lead to molecular order and a preferential orientation in subsequently deposited thin α-NPD films and cause a reduction of the charge injection barrier at the organic/organic interface. The results show that the height of this barrier is determined by the surface dipoles of the individual organic films that relate to the orientation of intramolecular polar bonds at the interface.     

Utilizing intermixing of conjugated polymer and fullerene from sequential solution processing for efficient polymer solar cells

Efficient polymer solar cells based on poly[2, 6-(4, 4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-fluorobenzothiadiazole)] (PCPDTFBT) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) are successfully fabricated by a sequential processing (SqP). With appropriate orthogonal solvent and thermal treatment, the SqP film can form an inter-diffused layer, and the SqP devices show efficient photovoltaic performance in both conventional and inverted layouts. The SqP inverted device was firstly demonstrated and the highest power conversion efficiency (PCE) of 5.84% with the enhanced J_sc of 16.4 mA cm⁻² was able to be achieved with the high internal quantum efficiency (IQE). Photoluminescence quenching shows the SqP films can provide efficient exciton quenching. X-ray photoemission spectroscopy (XPS) and ellipsometry analysis shows a polymer-rich surface in SqP films after thermal annealing. The charge mobilities in the SqP films were significantly enhanced as measured by space-charge-limited-current (SCLC) method. All these contribute to the improved photovoltaic performance in the inverted SqP device. We believe that these results inspire a new way of forming the active layer with controllable morphology, efficient charge separation and collection in polymer solar cells.     

Dependence of charge carrier mobility of 4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine on doping concentration of tetrafluoro-tetracyano-quinodimethane

Electrical transport of pure and tetrafluoro-tetracyano-quinodimethane doped 4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA) films have been studied at various temperatures and doping concentrations. Pure films show space charge limited conduction with field and temperature dependent mobility. The J-V characteristics of doped m-MTDATA were ohmic at low voltages due to thermally released carriers from dopant states. At higher voltages the current density increases nonlinearly due to field dependent mobility and carrier concentration thereby filling of tail states of HOMO of the host. The conductivity of doped films were analysed using the Unified Gaussian Disorder Model (UGDM). The carrier concentration obtained from the fitting show a non-linear dependence on doping concentration which may be due to a combined effect of thermally activated carrier generation and increased carrier mobility.     

Enhancing the performance of porphyrin based solar cells by the Bipy coordination

Solution processed organic solar cells (OSCs) often suffer from low charge mobilities partially due to the disordered non-crystalline or amorphous morphology of their films. In this study, 4,4′-bipyridyl (Bipy) is introduced to coordinate a zinc(II) porphyrin to form porphyrin complexes. A significant enhanced hole mobility and solar cell device performance are attained when the ratio of Bipy is 0.25 in blend films with [6, 6]-phenyl C₆₁-butyric acid methyl ester (PC₆₁BM). When [6, 6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) was used instead of PC₆₁BM, the PCE is enhanced to 2.83% in the presence of 0.25 equiv Bipy, which is an increase of 53% compared to that without Bipy.     

Efficient co-sensitization of dye-sensitized solar cells by novel porphyrin/triazine dye and tertiary aryl-amine organic dye

A novel porphyrin dye ZnP-triazine-(gly)₂, consisting of a zinc-metallated porphyrin unit covalently linked through its peripheral aryl-amino group with a 1,3,5-triazine group which is functionalized by two carboxylic acid groups of glycine moieties, has been synthesized. Photophysical and electrochemical measurements, as well as theoretical DFT calculations, suggest that the compound exhibits appropriate light absorption characteristics and frontier molecular orbital levels for use as sensitizer in dye-sensitized solar cells (DSSCs). The ZnP-triazine-(gly)₂ based solar cell was found to exhibit a power conversion efficiency (PCE) value of 4.72%. A significant improvement of the overall photovoltaic efficiency of the solar cell was achieved up to 7.34% upon co-sensitization with a tertiary aryl-amine D with two ethynyl-pyridine substituents and cyano-acetic acid anchoring group, which exhibits complementary light absorption characteristics with the porphyrin dye. The higher PCE value of the co-sensitized solar cell is attributed to its enhanced short circuit current (J_sc), which is due to improved light harvesting efficiency, reduced porphyrin aggregation, and faster electron injection and charge collection, as well as its enhanced open circuit voltage (V_oc), which is due to increased electron density in the TiO₂ conduction band of the photoanode. These results are in accordance with electrochemical impedance spectra (EIS) of the solar cells, which revealed higher charge recombination resistance (R_rec), longer electron lifetime (τ_e), and shorter electron transport time (τ_d) for the co-sensitized solar cell.     

Improved polymer light-emitting diodes by the tuning of charge balance

We have prepared polymer-small molecule hybrid electroluminescence devices with improved brightness and efficiency by a doping method. The doping effect on the hole transporter N,N′-diphenyl-N,N′-bis(4′-[N,N-bis(naphth-1-yl)-amino]-biphenyl-4-yl)-benzidine has been investigated in bilayer devices with structure of ITO/MEH-PPV: TPTE/PBD/Al. It was found that the effective hole mobility increases with increasing TPTE content in the blend, which is directly determined by space charge limited current at high voltage. The brightness and EL efficiencies of the doped OLEDs were increased significantly over those obtained for devices based only on MEH-PPV, which is attributed to more balanced electron and hole recombination due to improved hole mobility.     

Efficient red electrophosphorescence from a fluorene-based bipolar host material

We have prepared efficient red organic light-emitting diodes (OLEDs) incorporating 2,7-bis(diphenylphosphoryl)-9-[4-(N,N-diphenylamino)phenyl]-9-phenylfluorene (POAPF) as the host material doped with the osmium phosphor Os(fptz)₂(PPh₂Me)₂ (fptz = 3-trifluoromethyl-5-pyridyl-1,2,4-triazole). POAPF, which possesses bipolar functionalities, can facilitate both hole- and electron-injection from the charge transport layers to provide a balanced charge flux within the emission layer. The peak electroluminescence performance of the device reached as high as 19.9% and 34.5 lm/W – the highest values reported to date for a red phosphorescent OLED. In addition, we fabricated a POAPF-based white light OLED – containing red-[doped with Os(fptz)₂(PPh₂Me)₂] and blue-emitting {doped with iridium(III) bis[(4,6-difluorophenyl)pyridinato-N,C^2′] picolinate, FIrpic} layers – that also exhibited satisfactory efficiencies (18.4% and 43.9 lm/W).     

Charge injection and transport studies of poly(2,7-carbazole) copolymer PCDTBT and their relationship to solar cell performance

The charge injection and transport properties of a high performance semiconducting polymer for organic photovoltaic (OPV) applications, poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT), are investigated by time-of-flight (TOF) and dark-injection space-charge-limited current (DI-SCLC) techniques. OPV cells employing PCDTBT are known to possess power conversion efficiency (PCE) exceeding 6% [1], [2]. While TOF probes only the hole mobilities of a thick film, DI-SCLC is shown to be useful down to a sample thickness of ～200 nm, which is comparable to thicknesses used in OPV cells. We show that for pristine PCDTBT, the hole mobilities for both thick used in TOF and thin films for DI-SCLC are essentially the same, and they are in the range of 0.4–3.0 × 10^?4 cm²/Vs at room temperature. Both poly(3,4-ethylene dioxythioplene) doped with poly(strenesulfonate) (PEDOT:PSS) and molybdenum (VI) oxide (MoO₃) form quasi-Ohmic contacts to PCDTBT with better hole injection from MoO₃. Furthermore, the Gaussian Disorder Model (GDM) was employed to analyze the hopping transport of PCDTBT thin films. We show that PCDTBT possesses a relatively large energetic disorder (σ) of ～129 meV, which is significantly higher than the σ of poly(3-hexylthiophene) (P3HT) processed under similar conditions. The correlation between σ and OPV device performance is addressed.     

The internal electric field distribution in bilayer organic light emitting diodes

The internal electric field distribution in a bilayer 4,4^′-bis[N-(1-napthyl)-N-phenylamino]-biphenyl/tris-(8-hydroxyquinoline) aluminium organic light emitting diode has been investigated experimentally using electroabsorption spectroscopy. The experimental results have been compared to those obtained from a drift–diffusion device simulation, further validating the model and highlighting the potential worth of such modelling. With the aid of the simulation, the electric field distribution can be explained in terms of charge carrier accumulation at the interface between the two organic layers, due to the HOMO and LUMO band offsets, and charge injection into the device, demonstrating the influence of contact materials on device behaviour.     

Performance improvement of flash memory using AlN as charge-trapping Layer

Potential of high-k dielectric films for future scaled charge storage non-volatile memory (NVM) device applications is discussed. To overcome the problems of charge loss encountered in conventional flash memories with silicon-nitride (Si₃N₄) films and polysilicon-oxide-nitride-oxide-silicon (SONOS) and nonuniformity issues in nanocrystal memories (NC), such as Si, Ge and metal, it is shown that the use of high-k dielectrics allows more aggressive scaling of the tunnel dielectric, smaller operating voltage, better endurance, and faster program/erase speeds. Charge-trapping characteristics of high-k AlN films with SiO₂ as a blocking oxide in p-Si/SiO₂/AlN/SiO₂/poly-silicon (SOHOS) memory structures have been investigated in detail. The experimental results of program/erase characteristics obtained as the functions of gate bias voltage and pulse width are presented.     

薄栅介质层可靠性与陷阱统计分析

本文以高电场(＞11.8MV/cm)恒电流TDDB为手段研究了厚度为7.6、10.3、12.5、14.5nm薄氧化层的击穿统计特性.实验分析表明在加速失效实验中测量击穿电量Q_bd的同时,还可以测量击穿时的栅电压增量ΔV_bd.因为ΔV_bd的统计分布反映了栅介质层中带电陷阱的数量及其位置分布,可以表征栅介质层的质量和均匀性.此外由Q_bd和ΔV_bd能够较合理地计算临界陷阱密度N_bd.实验结果表明本征击穿时N_bd与测试条件无关而随工艺和介质层厚度变化.同样厚度时N_bd反映不同工艺生成的介质质量.陷阱生成的随机性使N_bd随栅介质厚度减小而下降.氧化层厚度约10nm时N_bd达到氧化层分子密度的1%发生击穿(10²⁰cm^-3).N_bd的物理意义清楚,不象Q_bd随测试应力条件变化,是薄栅介质层可靠性的较好的定量指标.     

Morphology and local transport characteristics of metalloporphyrin thin films

Organic systems such as porphyrin-based molecules stand as a promising alternative for molecular devices. These systems have important photophysical and electrochemical properties and can be easily prepared by well-established synthesis and deposition techniques. Nevertheless, not very much is known about their electrical properties and charge transport mechanisms. In this work, the local electrical properties of [5,10,15,20-tetra(p-methoxyphenyl)porphyrin]copper(II) (Cu-TMPP) thin films deposited on nickel substrates are investigated. The implementation of current-sensing atomic force microscopy (cs-AFM) allows the detection of local variations of the topographic and transport properties of Cu-TMPP thin films with nanometric spatial resolution. In particular, the electric current mapping approach adopted here allows the quantification of the local charge transfer through the organic structures in a reliable and controlled manner. The formation of organic dendrites with heights between 2 and 5 nm and lengths in the micrometric scale is observed. On thicker organic films, a layered filamentary-like growth is observed. These dendrites behave as a semiconducting matrix structure over a conducting metallic substrate and could be used for tuning transport properties on a device scale by reducing the contact area at the organic film-metal electrode interface. In addition, a detailed investigation of the electrical evolution of the conducting sites in the organic thin films is presented as a function of the thickness and applied electric field. For the majority of the conducting sites (>70–80%), a field dependent transition from a linear-like to an exponential transport regime is identified. We relate the non-homogeneous electrical response to the formation of molecular dendrites and interface defects. This electrical analysis and the understanding of the underlying transport mechanism become important for future implementation of porphyrin-based devices.     

Controlling organization of conjugated polymer films from binary solvent mixtures for high performance organic field-effect transistors

We investigate the effect of a binary solvent blend as a solvent for poly{[N,N′-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} P(NDI2OD-T2) on the characteristics of n-channel organic field-effect transistors (OFETs). To make the binary solvent blend, the low-boiling-point non-solvent propylene glycol methyl ether acetate (PGMEA, b.p ∼146 °C) is added to the high-boiling-point good solvent 1,2-dichlorobenzene (O-DCB, b.p ∼180 °C) at various mixing ratio from 0 to 40 v%. UV–vis spectra of P(NDI2OD-T2) solution dissolved in the binary solvent clearly show the formation of polymer aggregates through a gradual red shift of the intramolecular charge transfer band with the addition of high concentrations of non-solvent PGMEA. Higher edge-on oriented crystallinity is observed for P(NDI2OD-T2) films spin-coated from the binary solvent with 5–10 v% PGMEA by out-of-order x-ray diffraction. P(NDI2OD-T2) films are applied as the active layer in top-gate/bottom-contact OFETs. Improved n-type field-effect mobility of the P(NDI2OD-T2) semiconducting layer up to 0.59 cm²/Vs was achieved for on-center spin coated films compared to 1.03 cm²/Vs for off-center (parallel alignment) spin-coated films respectively employing the binary solvent with 10 v% PGMEA.     

High performance top-emitting organic light-emitting diodes with copper iodide-doped hole injection layer

Efficient top-emitting organic light-emitting diodes were fabricated using copper iodide (CuI) doped 1,4-bis[N-(1-naphthyl)-N′-phenylamino]-4,4′-diamine (NPB) as a hole injection layer and Ir(ppy)₃ doped CBP as the emitting layer. CuI doped NPB layer functions as an efficient p-doped hole injection layer and significantly improves hole injection from a silver bottom electrode. The top-emitting device shows high current efficiency of 69 cd/A with Lambertian emission pattern. The enhanced hole injection is originated from the formation of the charge transfer complex between CuI and NPB.     

Silicon nitride for the improvement of silicon inversion layer solar cells

It is demonstrated that CVD Si-nitride films as transparent dielectric satisfy all requirements for achieving MIS/IL solar cells with high efficiency and long term stability. Deposited on silicon by the SiH₄/NH₃ reaction at temperatures lower than usual (between 600° and 650°C) fixed positive interface charge densities Q_N/q up to 7 × 10¹² cm^?2 with excellent stability have been obtained. Utilizing the Si-nitride charge storage effect, the highest known Q_N/q values (> 10¹³cm^?2) combined with low values of N_it have been achieved. The charge distribution is discussed and an energy band diagram modified according to new analytical results is presented. MIS/IL solar cells with AM1 efficiencies of 15% (active area) and high UV sensitivity have been obtained.     

Comparison of Charge‐Carrier Transport in Thin Films of Spiro‐Linked Compounds and Their Corresponding Parent Compounds

The charge‐transport properties of the spiro‐linked compounds 2,2′,7,7′‐tetrakis(diphenylamino)‐9,9′‐spirobifluorene, 2,2′,7,7′‐tetrakis(N,N′‐di‐p‐methylphenylamino)‐9,9′‐spirobifluorene, 2,2′,7,7′‐tetra(m‐tolyl‐phenylamino)‐9,9′‐spirobifluorene, and 2,2′,7,7′‐tetra(N‐phenyl‐1‐naphthylamine)‐9,9′‐spirobifluorene, and their corresponding parent compounds, N,N,N′,N′‐tetraphenylbenzidine, N,N,N′,N′‐tetrakis(4‐methylphenyl)benzidine, and N,N′‐bis(3‐methylphenyl)‐(1,1′‐biphenyl)‐4,4′‐diamine, N,N′‐diphenyl‐N,N′‐bis(1‐naphthyl)‐1,1′‐biphenyl‐4,4′‐diamine, are investigated. The field‐effect mobilities of charge carriers in thin films of the parent compounds are slightly higher than those of the spiro‐linked compounds. However, the transistor action of the parent‐compound thin films vanishes because the films crystallize after being stored in ambient atmosphere for a few days. In contrast, the hole mobilities in thin films of the spiro‐linked compounds do not change significantly after the samples are stored in ambient atmosphere for up to nine months. Also discussed is the temperature dependency of the mobilities of charge carriers, which is presented using two models, namely the Arrhenius and the Gaussian disorder models.     

Color stable white organic light-emitting diode based on a novel triazine derivative

A novel red–orange emitting material with a branched molecular structure, 2,4,6-tris[2-(N-ethyl-3-carbazole)carboxethenyl]-1,3,5-s-triazine (TC3), has been synthesized and characterized using UV–visible, photoluminescence (PL) and electroluminescence (EL) spectroscopy. White EL devices were fabricated using TC3 as a red–orange emitter and 8-hydroxyquinolinolato lithium (Liq) as a blue–green emitter. N,N-bis(3-methylphenyl)-N,N-diphenylbenzidine (TPD) as the adjustor for charge carrier mobility was introduced between the two emitting layers to improve the stability of the white emission color on bias voltage. The EL devices of ITO/poly(N-vinylcarbazole) (PVK):TC3 (56 nm)/TPD (5 nm)/Liq (30 nm)/Mg:Ag exhibited good quality white emission. The Commission Internationale De L’Eclairage chromaticity coordinates are (0.34, 0.39) and are stable on the bias voltage.