Charge transport properties and microstructure of polythiophene/polyfluorene blends

We present a combined charge transport and X-ray diffraction study of blends based on regioregular poly(3-hexylthiophene) (P3HT) and the polyfluorene co-polymer poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2′,2′′-diyl) (F8TBT) that are used in efficient all-polymer solar cells. Hole mobility is observed to increase by nearly two orders of magnitude from less than 10^?7 cm² V^?1 s^?1 for as spin-coated blends to 6 × 10^?6 cm² V^?1 s^?1 for blends annealed at 453 K at a field of 2.7 × 10⁵ V/cm, but still significantly below the time-of-flight mobility of unblended P3HT of 1.7 × 10^?4 cm² V^?1 s^?1. The hole mobility of the blends also show a strong negative electric-field dependence, compared with a relatively flat electric-field dependence of unblended P3HT, suggestive of increased spatial disorder in the blends. X-ray diffraction measurements reveal that P3HT/F8TBT blends show a phase separation of the two components with a crystalline part attributed to P3HT and an amorphous part attributed to F8TBT. In as-spun and mildly annealed blends, the measured d-values and relative intensities of the 100, 200 and 300 P3HT peaks are noticeably different to unblended P3HT indicating an incorporation of F8TBT in P3HT crystallites that distorts the crystal structure. At higher anneal temperatures the blend d-values approach that of unblended P3HT suggesting a well separated blend with pure P3HT crystallites. P3HT crystallite size in the blend is also observed to increase with annealing from 3.3 to 6.1 nm, however similar changes in crystallite size are observed in unblended P3HT films with annealing. The lower mobility of P3HT/F8TBT blends is attributed not only to increased P3HT structural disorder in the blend, but also due to the blend morphology (increased spatial disorder). Changes in hole mobility with annealing are interpreted in terms of the need to form percolation networks of P3HT crystallites within an F8TBT matrix, with a possible contribution due to the intercalation of F8TBT in P3HT crystallites acting as defects in the as-prepared state.     

Polymer solar cells incorporating one-dimensional polyaniline nanotubes

We have fabricated polymer solar cell devices based on poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) and incorporating one-dimensional nanostructured acid-doped polyaniline nanotubes (a-PANINs) as an interfacial layer. The power conversion efficiency of an annealed device incorporating the a-PANIN layer reached 4.26% under AM 1.5 G (100 mW/cm²) illumination, an increase of ca. 26% relative to that of the annealed device lacking an a-PANIN interfacial layer. The incorporation of the a-PANINs in the solution-processed polymer solar cells was reproducible; the high conductivity, controlled tubular nanoscale morphologies, and mobility of the annealed a-PANIN layer led to efficient extraction of photogenerated holes to the buffer layer and suppression of exciton recombination, thereby improving the photovoltaic performance.     

Enhancement of the field-effect mobility of poly(3-hexylthiophene)/functionalized carbon nanotube hybrid transistors

With the aim of enhancing the field-effect mobility of poly(3-hexylthiophene) (P3HT) field-effect transistors (FETs), we added functionalized multiwalled carbon nanotubes (CNTs) to the P3HT solution prior to film formation. The nanotubes were found to be homogeneously dispersed in the P3HT films because of their functional groups. We found that at the appropriate CNT concentration (up to 10 wt% CNT), the P3HT FETs have a high field-effect mobility of 0.04 cm² V⁻¹ s⁻¹, which is an improvement by a factor of more than 10. This remarkable increase in the field-effect mobility over that of the pristine P3HT film is due to the high conductivity of the CNTs which act as conducting bridges between the crystalline regions of the P3HT film, and the reduction in the hole-injection barrier due to the low work function of CNTs, which results in more efficient carrier injection.     

High field-effect mobility from poly(3-hexylthiophene) thin-film transistors by solvent–vapor-induced reflow

Room-temperature exposure of spin-coated poly(3-hexylthiophene) (P3HT) films to ortho-dichlorobenzene vapor increases the field-effect mobility of the P3HT organic thin-film transistors (OTFTs). The mobility increases moderately with unsaturated vapor exposure, owing to increased crystallinity of the P3HT films; on the other hand, the mobility increases abruptly with saturated vapor exposure, to 0.11 cm²/V s. The saturated vapor exposure causes the P3HT films to reflow, leaving in the active area approximately 2–3 P3HT monolayers whose molecular ordering is enhanced by the flow-generated shear against the gate dielectric. Although the reflowed OTFTs degrade in air much faster than do the non-reflowed OTFTs due to the susceptibility of the ultra-thin reflowed films, they become highly stable when encapsulated, obtaining a lifetime of more than 3000 h.     

Using d-limonene as the non-aromatic and non-chlorinated solvent for the fabrications of high performance polymer light-emitting diodes and field-effect transistors

Aiming to environment protection, green solvents are crucial for commercialization of solution-processed optoelectronic devices. In this work, d-limonene, a natural product, was introduced as the non-aromatic and non-chlorinated solvent for processing of polymer light-emitting diodes (PLEDs) and organic field effect transistors (OFETs). It was found that d-limonene could be a good solvent for a blue-emitting polyfluorene-based random copolymer for PLEDs and an alternating copolymer FBT-Th₄(1,4) with high hole mobility (μ_h) for OFETs. In comparisons to routine solvent-casted films of the two conjugated polymers, the resulting d-limonene-deposited films could show comparable film qualities, based on UV–vis absorption spectra and observations by atomic force microscopy (AFM). With d-limonene as the processing solvent, efficient blue PLEDs with CIE coordinates of (0.16, 0.16), maximum external quantum efficiency of 3.57%, and luminous efficiency of 3.66 cd/A, and OFETs with outstanding μ_h of 1.06 cm² (V s)⁻¹ were demonstrated. Our results suggest that d-limonene would be a promising non-aromatic and non-chlorinated solvent for solution processing of conjugated polymers and molecules for optoelectronic device applications.     

Enhancement in electrical performance of indium gallium zinc oxide-based thin film transistors by low temperature thermal annealing

We have studied the characteristics of transparent bottom-gate thin film transistors (TFTs) using In–Ga–Zn–O (IGZO) as an active channel material. IGZO films were deposited on SiO₂/Si substrates by DC sputtering techniques. Thereafter, the bottom-gate TFT devices were fabricated by depositing Ti/Au metal pads on IGZO films, where the channel length and width were defined to be 200 and 1000 μm, respectively. Post-metallization thermal annealing of the devices was carried out at 260, 280 and 300 °C in nitrogen ambient for 1 h. The devices annealed at 280 °C have shown better characteristics with enhanced field-effect mobility and high on–off current ratio. The compositional variation of IGZO films was also observed with different annealing temperatures.     

Patterning effects on poly (3-hexylthiophene) organic thin film transistors using photolithographic processes

We explore the effects of conventional photo lithographic patterning of the active layer of poly (3-hexylthiophene) (P3HT) organic thin film transistors (OTFT) on device performance. The performance of the devices was monitored in each step of the patterning process. We successfully developed a patterning process which is compatible with plastic substrates and P3HT as the organic semiconductor. In this process, parylene and atomic layer deposition (ALD) Al₂O₃ were used as capping layers. Al₂O₃ and parylene/P3HT were etched using Al etchant and O₂ plasma reactive ion etching (RIE), respectively. The degradation occurred primarily during the ALD Al₂O₃ deposition and capping layer etching. There was a 30% degradation in mobility, a 1–2× reduction in drive current, and an increase in threshold voltage after the ALD Al₂O₃ deposition. In the capping layer etching, a near 50% degradation in mobility was observed. The patterned devices have a mobility of 0.02 cm²/V s, which is 1000× better than photo lithographically patterned P3HT OTFTs previously reported in the literature, and comparable to un-patterned P3HT devices.     

Raman spectroscopic study of In2S3 films prepared by spray pyrolysis

Indium sulfide (In₂S₃) thin films are of interest as buffer layers in chalcopyrite absorber based solar cells; and as media providing two-photon absorption for intermediate-band solar cells. We investigated the suitability of chemical spray pyrolysis (CSP) for growing In₂S₃ thin films in a structural order where indium atoms are preferentially in the octahedral sites. We sprayed aqueous or alcoholic solutions of indium chloride (InCl₃) and thiourea (SC(NH₂)₂) precursors onto a substrate with surface temperatures (T_S) of 205, 230, 275 and 320 °C. The as-deposited films grown from aqueous solutions were annealed in 5% H₂S containing atmosphere at 500 °C. We used Raman spectroscopy, X-ray diffraction and Energy Dispersive X-ray spectroscopy to evaluate the effect of growth temperature and the effect of annealing on the film structure and stoichiometry. The use of alcoholic solvent instead of aqueous allows us to use much lower T_S while preserving the quality of the β-In₂S₃ films obtained. Similarly, films with increased stoichiometry and quality are present at a higher T_S; and when annealed. The annealing of the films grown at T_S of 205 °C results in a much higher gain of the crystal quality compared to the gain when annealing the films grown at T_S of 320 °C, although the quality remain higher when deposited at T_S of 320 °C. Simultaneously with the increase of the film quality, there is a sign of increased quality of the crystal ordering with indium in the octahedral sites. Such a crystal ordering favor the use of CSP deposited In₂S₃ films in the intermediate band solar cells.     

Channel width effect for organic thin film transistors using TIPS-pentacene employed as a dopant of poly-triarylamine

The effects of the physical channel width on the characteristics of organic thin film transistors (OTFTs), made with 6,13-bis(triisopropyl-silylethynyl)-pentacene (TIPS-pentacene) embedded into poly-triarylamine (PTAA, hole conductor within an active channel), have been examined in this paper. The devices are estimated by measuring the drain-source current (I_DS) for different contact metals such as Au and Ag, at fixed gate and drain voltages. The results show that the threshold voltage (V_T) and I_DS increase with increasing channel width. Furthermore, it has been observed that the field effect mobility is dependent on V_T, which is influenced by the channel width. The OTFTs, produced using Au and Ag contacts, exhibited the highest values of mobility in the saturation regime, namely 5.44 × 10^?2 and 1.33 × 10^?2 cm²/Vs, respectively.     

On the stability of the electrical and photoelectrical properties of P3HT and P3HT:PCBM blends thin films

New photoelectrical properties of poly(3-hexylthiophene-2,5-diyl), highly regioregular (P3HT): Methanofullerene Phenyl-C₆₁-Butyric-Acid-Methyl-Ester [60] PCBM films were putted in evidence. For the first time the electrical conductivity dependencies on temperature in dark and under different illuminations were studied for the P3HT and P3HT:PCBM blend films. These dependencies shows reversible processes and a high sensitivity of the P3HT and P3HT:PCBM to light. The decrease of the resistivity at the exposure to light is of 18% for P3HT films and of 20% for P3HT:PCBM blend films, for a irradiation under 0.5 W/m² white light at room temperature. By adding the fullerene molecules, in the 1:0.8 polymer:fullerene ratio, the electrical resistivity at room temperature of the blend films decrease compared to the polymer film by 40% in dark, and by 68% under 250 W/m² white light irradiance.The decrease of the resistivity with the temperature is more pronounced in the presence of light indicating a photon activated process.The existence of the open circuit voltage was evidenced even for planar geometry photodiodes and the values of the open circuit voltage under 1000 W/m² solar light illumination are coherent with the difference between the work functions of the electrodes.     

TiSiOx gate dielectrics produced by reactive sputtering for high performance InGaZnO thin film transistors

High dielectric constant TiSiOx thin films are produced by reactive sputtering under different oxygen partial pressure ratio (P_O2) from 15% to 30%. All the TiSiOx films show an excellent transmittance value of almost 95%. The TiSiOx film has a low leakage current density by optimizing oxygen partial pressure, and the leakage current density of TiSiOx film under P_O2 of 20% is 4.88×10⁻⁷ A/cm² at electrical field strength of 2 MV/cm. Meanwhile, their associated InGaZnO thin-film transistors (IGZO-TFTs) with different P_O2 TiSiOx thin films as gate insulators are fabricated. IGZO-TFTs under P_O2 of 20% shows an optimized electrical performance, and the threshold voltage, sub-threshold swing, field effect mobility and I_on/I_off ratio of this device are 2.22 V, 0.33 V/decade, 29.3 cm²/V s and 5.03×10⁷, respectively. Moreover, the density of states (DOS) is calculated by temperature-dependent field-effect measurement. The enhancements of electrical performance and temperature stability are attributed to better active/insulator interface and smaller DOS.     

Electrical properties of low-dielectric-constant films prepared by PECVD in O2/CH4/HMDSO

Low-dielectric constant (low-k) films have been prepared by plasma-enhanced chemical vapor deposition (PECVD) from hexamethyldisiloxane (HMDSO) mixed with oxygen or methane. The films are analyzed by ellipsometry, infrared absorption spectroscopy while their electrical properties are deduced from C–V, I–V and R–f measurements performed on Al/insulator/Si structures. For an oxygen and methane fraction equal to 50% and 22%, respectively, the dielectric constant and losses are decreased compared with those of the film prepared in a pure HMDSO plasma. The effect of adding 22% of CH₄ in HMDSO plasma increases the Si–CH₃ bonds containing in the polymer film and as the constant of methyl groups in the film increased the dielectric constant of the film decreases. For this film, the dielectric constant is 2.8, the dielectric losses at 1 kHz are equal to 2×10⁻³, the leakage current density measured for an electric field of 1 MV/cm is 3×10⁻⁹ A/cm² and the breakdown field is close to 5 MV/cm.     

Structural and electrical properties of radio frequency magnetron sputtered tantalum oxide films: Influence of post-deposition annealing

The as-deposited and annealed radio frequency reactive magnetron sputtered tantalum oxide (Ta₂O₅) films were characterized by studying the chemical binding configuration, structural and electrical properties. X-ray photoelectron spectroscopy and X-ray diffraction analysis of the films elucidate that the film annealed at 673 K was stoichiometric with orthorhombic β-phase Ta₂O₅. The dielectric constant values of the tantalum oxide capacitors with the sandwich structure of Al/Ta₂O₅/Si were in the range from 14 to 26 depending on the post-deposition annealing temperature. The leakage current density was <20 nA cm^?2 at the gate bias voltage of 0.04 MV/cm for the annealed films. The electrical conduction mechanism observed in the films was Poole–Frenkel.     

Influence of annealing temperature on the phase composition and optical properties of CuInS2 films

We studied the growth of CuInS₂ thin films by single-source evaporation of CuInS₂ powder in a high-vacuum system with a base pressure of 10^?3 Pa. After evaporation, the films were annealed in a sulfur atmosphere at temperatures from 200 to 500 °C for 1 h. XRD curves and Raman spectra of the films demonstrated that chalcopyrite CuInS₂ was the major crystalline phase. The morphology of Cu_xS exhibited a star-like structure, which we report for the first time. The phase composition and optical properties of our polycrystalline thin films were effectively modified by annealing in S. For films annealed at 200 and 350 °C, a secondary CuIn₁₁S₁₇ phase appeared, which may be related to solid-state reaction in the S atmosphere. This secondary CuIn₁₁S₁₇ phase has not been widely reported in previous studies. After annealing at 500 °C, only a chalcopyrite phase was detected, with bandgap energy of 1.46 eV, which is nearly identical to the optimal bandgap energy (1.5 eV) of single-crystal CuInS₂. This indicates that the composition of the CuInS₂ film annealed at 500 °C was nearly stoichiometric. The bandgap of the samples first increased and then decreased with increasing annealing temperature, which may be attributed to an increase in grain size, the secondary CuIn₁₁S₁₇ phase, and deviation from stoichiometry.     

Aggregation,crystallization, and resistance properties of poly(3-hexylthiophene-2,5-diyl) solid films gel-cast from CHCl3/p-xylene mixed solvents

In this study we found that the gelation time and crystallinity of P3HT solid films are adjustable when aging and casting from CHCl₃/p-xylene mixed solvents. After aging for 36 h in pure p-xylene, CHCl₃, or various mixtures of the two as cosolvents, we found that the solid P3HT film gel-cast from 20 vol% CHCl₃ had the highest degree of crystallinity of its main chain (ϕ_m = 0.54), highest melting point of its main chain (T_m = 232.7 °C), fastest gelation time (30 min), largest melting enthalpy of its main chain (ΔH_m = 19.81 J g⁻¹), and lowest resistance (R_P = 0.76 MΩ); the latter value was three orders and one order of magnitude lower than those of the films cast from pure CHCl₃ (ca. 110 MΩ) and pure p-xylene (ca. 4.4 MΩ), respectively. In differential scanning calorimetry scans, we attribute the presence of melting peaks near 75 °C to the solid-to-solid phase transition of the side chain crystallites of P3HT, thereby affecting the aggregation of the P3HT main chain and resulting in the changes in resistance, crystallinity, melting enthalpy, and melting point of the gel-cast P3HT solid films.     

Low-operating-voltage polymeric transistor with solution-processed low-k polymer/high-k metal-oxide bilayer insulators

We have successfully demonstrated a polymeric semiconductor-based transistor with low-k polymer/high-k metal-oxide (TiO₂) bilayer as gate dielectric. The TiO₂ layers are readily processable from solution and cured at low temperature, instead of traditionally sputtering or high temperature sintering process, thus may suitable for a low-cost organic field effect transistors (FETs) manufacture. The low-k polymer capped on TiO₂ layer could further smooth the TiO₂ dielectric surface and suppress the leakage current from grain boundary of TiO₂ films. The resulting unpatented P3HT-OFETs could operate with supply voltage less than 10 V and the mobility and threshold voltage were 0.0140 cm²/V s and 1.14 V, respectively. The on/off ratio was 1.0 × 10³.     

All solution-processed organic single-crystal transistors with high mobility and low-voltage operation

High-mobility organic single-crystal field-effect transistors of 3,11-didecyldinaphtho[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]-dithiophene (C₁₀-DNBDT) operating at low driving voltage are fabricated by an all-solution process. A field-effect mobility as high as 6.9 cm²/V s is achieved at a driving voltage below 5 V, a voltage as low as in battery-operated devices, for example. A low density of trap states is realized at the surface of the solution-processed organic single-crystal films, so that the typical subthreshold swing is less than 0.4 V/decade even on a reasonably thick amorphous polymer gate dielectrics with reliable insulation. The high carrier mobility and low interface trap density at the surface of the C₁₀-DNBDT crystals are both responsible for the development of the high-performance all-solution processed transistors.     

Properties of In2O3 films obtained by thermal oxidation of sprayed In2S3

In₂S₃ thin films were grown by the chemical spray pyrolysis (CSP) method using indium chloride and thiourea as precursors at a molar ratio of S:In=2.5. The deposition was carried out at 350 °C on quartz substrates. The film thickness is about 1 µm. The films were then annealed for 2 h at 550, 600, 650 and 700 °C in oxygen flow. This process allows the transformation of nanocrystal In₂O₃ from In₂S₃ and the reaction is complete at 600 °C. X-ray diffraction spectra show that In₂O₃ films are polycrystalline with a cubic phase and preferentially oriented towards (222). The film grain size increases from 19 to 25 nm and RMS values increase from 9 to 30 nm. In₂O₃ films exhibit transparency over 70–85% in the visible and infrared regions due to the thickness and crystalline properties of the films. The optical band gap is found to vary in the range 3.87–3.95 eV for direct transitions. Hall effect measurements at room temperature show that resistivity is decreased from 117 to 27 Ω cm. A carrier concentration of 1×10¹⁶ cm^?3 and mobility of about 117 cm² V^?1 s^?1 are obtained at 700 °C.     

High-performance n-type organic field-effect transistors fabricated by ink-jet printing using a C60 derivative

We report on the performance of ink-jet-printed n-type organic thin-film transistors (OTFTs) based on a C₆₀ derivative, namely, C₆₀-fused N-methyl-2-(3-hexylthiophen-2-yl)pyrrolidine (C₆₀TH-Hx). The new devices exhibit excellent n-channel performance, with a highest mobility of 2.8 × 10^?2 cm² V^?1 s^?1, an I_On/I_Off ratio of about 1 × 10⁶, and a threshold voltage of 7 V. The C₆₀TH-Hx films show large crystalline domains that result from the influence of an evaporation-induced flow, thus leading to high electron mobility in the ink-jet-printed devices.