Fu Chiao Wu

Effects of solvents and vacancies on the electrical hysteresis characteristics in regioregular poly(3-hexylthiophene) organic thin-film transistors

The role of residual solvents and vacancies within poly(3-hexylthiophene) (P3HT) active layers, which are made from different boiling point (bp) solvents, on the electrical hysteresis characteristics of P3HT-based transistors was investigated. The improved electrical performance and reduced hysteresis of P3HT films, which are spin coated by high bp solvents, can be interpreted by superior crystalline quality and homogeneity and low vacancies. The hysteresis is dominated by the vacancy-related charge traps in the semiconductor created during film solidification and subsequence solvent evaporation. Furthermore, residual solvents, which initially occupied the vacancies, can contribute to conductivity of regioregular P3HT, thus altering electrical properties and smaller hysteresis.

Electron transport properties in fluorinated copper–phthalocyanine films: importance of vibrational reorganization energy and molecular microstructure

Electron transport (ET) properties of a series of fluorinated copper-phthalocyanine (F(16)CuPc) thin films, which were deposited at different substrate temperatures (T(sub)) ranging from 30 to 150 degrees C, have been investigated by quantum mechanical calculations of the reorganization energy (lambda(reorg)), X-ray diffraction (XRD), atomic force microscopy (AFM), and microRaman spectroscopy. Density functional theory calculations were used to predict the vibrational frequencies, normal mode displacement vectors, and electron-vibrational lambda(reorg) for the F(16)CuPc molecule. The electron mobilities (mu(e)) of F(16)CuPc thin films are strongly dependent on the T(sub), and the value of mu(e) increases with increasing T(sub) from 30 to 120 degrees C, at which point it reaches its maximum value. The importance of electron-vibrational coupling and molecular microstructures for ET properties in F(16)CuPc thin films are discussed on the basis of theoretical vibrational lambda(reorg) calculations and experimental observations of resonance Raman spectra. We observed a good correlation between mu(e) and the full-width-at-half-maximum of the vibrational bands, which greatly contributed to lambda(reorg) and/or which reflects the molecular microstructural quality of the active channel. In contrast, the crystal size analysis by XRD and surface grain morphology by AFM did not reveal a clear correlation with the ET behaviours for these different F(16)CuPc thin films. Therefore, we suggest that for organic films with weak intermolecular interactions, such as F(16)CuPc, optimized microscopic molecular-scale parameters are highly important for efficient long-range charge transport in the macroscopic devices.

Spontaneous Formation of an Ideal-Like Field-Effect Channel for Decay-Free Polymeric Thin-Film Transistors by Multiple-Scale Phase Separation

We demonstrate semiconducting polymer-based thin-film transistors (PTFTs) with fast switching performance and an uncommon nondecaying feature. These PTFTs based on widely studied poly(3-hexylthiophene) are developed by incorporating the insulating polymer into the active channel and subjecting the compound to specific, spontaneous multiple-scale phase separation (MSPS). An in-depth study is conducted on the interfacial and phase-separated microstructure of the semiconducting/insulating blending active layer and its effect on the electrical characteristics of PTFTs. The polyblends exhibit a confined crystallization behavior with continuously semiconducting crystalline domains between scattered insulator-rich domains. The insulator-rich domains can block leakage current and strengthen the gate control of the channel. A small amount of the insulating polymer penetrates the bottom of the active channel, resulting in effective interface modification. We show specific MSPS morphology of the present blending films to reduce charge trapping effects, enhance charge accumulation, and create a high-seed switching channel. The findings enable us to develop the required morphological conceptual model of the ideal-like field-effect-modulated polymer-based active channel. The polyblend-based PTFTs with MSPS morphology also have promising sensing functions. This study offers an effective approach for overcoming the major drawbacks (instability and poor switching) of PTFTs, thus allowing such transistors to have potential applications.

Reformation of conjugated polymer chains toward maximum effective conjugation lengths by quasi-swelling and recrystallization approach

A combined quasi-swelling and recrystallization (QSRC) approach is developed to alter distorted segments of conjugated polymer into highly ordered crystalline domains with super-long effective conjugation lengths (>100mer). These highly extended conjugated chains, at their maximum, are expected to have important implications for photonic and electronic applications and theoretical studies.

Synergistic Effects of Binary-Solvent Annealing for Efficient Polymer-Fullerene Bulk Heterojunction Solar Cells.

Conjugated polymer-fullerene-based bulk-heterojunction (BHJ) organic solar cells (OSCs) have attracted tremendous attention over the past two decades because of their potential to develop low-cost and easy methods to produce energy from light. The complicated microstructure and morphology with randomly organized architecture of these polymer-fullerene-based active layers (ALs) is a key factor that limits photovoltaic performance. In this study, a binary-solvent annealing (BSA) approach was established to improve the poly(3-hexylthiophene):indene-C60 bisadduct-based AL for efficient BHJ-type OSCs by varying the second solvents with different boiling points (BP). Thus, we were able to change the evaporation behavior of cosolvents and consequently obtain the various microstructural properties of the AL. An in-depth study was conducted on the solvent-evaporation driven morphology of the active layer under various cosolvent conditions and its effect on the photovoltaic parameters of OSCs. Under the BSA processes, we found that the specimens with low-BP second solvents allows us to observe a more ideal AL for increasing photon absorption and efficient charge transport and collection at the respective electrodes, resulting in enhanced PCE of the corresponding OSCs. By contrast, the specimens with high-BP second solvents exhibit random microstructures, which are detrimental to charge transport and collection and lead to diminished PCE of the corresponding OSCs. By appropriately selecting the composition of a binary solvent, BSA can be employed as an easy method for the effective manipulation of the microstructures of ALs. BSA is a promising technique for the performance enhancement of not only OSCs but also other organic/polymeric-based electronic devices.

A nanoscale study of charge extraction in organic solar cells: The impact of interfacial molecular configurations

In the optimization of organic solar cells (OSCs), a key problem lies in the maximization of charge carriers from the active layer to the electrodes. Hence, this study focused on the interfacial molecular configurations in efficient OSC charge extraction by theoretical investigations and experiments, including small molecule-based bilayer-heterojunction (sm-BLHJ) and polymer-based bulk-heterojunction (p-BHJ) OSCs. We first examined a well-defined sm-BLHJ model system of OSC composed of p-type pentacene, an n-type perylene derivative, and a nanogroove-structured poly(3,4-ethylenedioxythiophene) (NS-PEDOT) hole extraction layer. The OSC with NS-PEDOT shows a 230% increment in the short circuit current density compared with that of the conventional planar PEDOT layer. Our theoretical calculations indicated that small variations in the microscopic intermolecular interaction among these interfacial configurations could induce significant differences in charge extraction efficiency. Experimentally, different interfacial configurations were generated between the photo-active layer and the nanostructured charge extraction layer with periodic nanogroove structures. In addition to pentacene, poly(3-hexylthiophene), the most commonly used electron-donor material system in p-BHJ OSCs was also explored in terms of its possible use as a photo-active layer. Local conductive atomic force microscopy was used to measure the nanoscale charge extraction efficiency at different locations within the nanogroove, thus highlighting the importance of interfacial molecular configurations in efficient charge extraction. This study enriches understanding regarding the optimization of the photovoltaic properties of several types of OSCs by conducting appropriate interfacial engineering based on organic/polymer molecular orientations. The ultimate power conversion efficiency beyond at least 15% is highly expected when the best state-of-the-art p-BHJ OSCs are combined with present arguments.

Charge transfer highways in polymer solar cells embedded with imprinted PEDOT:PSS gratings

This study presents the developed poly(3-hexylthiophene):indene-C60 bisadduct (P3HT:ICBA)-based organic solar cells, where nanoimprinted poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) gratings successfully functioned as charge transport highways and induced an ICBA-rich surface. The embedded nanostructures improved light harvesting and contact area; however, these two factors were not the primary enhancers of solar cell performance. Atomic force microscopy and conductive atomic force microscopy revealed that the imprinted PEDOT:PSS gratings activated hole- and electron-conducting pathways. This result can be attributed to the enhancement of the π–π orbital overlap between P3HT and PEDOT:PSS polymer chains and to the grating-induced ICBA phase separation. These two effects were the primary factors that increased the short-circuit current of the imprinted devices, which resulted in the increase of power conversion efficiency. In-plane and out-of-plane grazing incident X-ray diffraction revealed that the chain orientation of P3HT on the PEDOT:PSS gratings was the same as that on the plane PEDOT:PSS surface. This study proved the feasibility of nanoimprinting for organic solar cells, as well as for organic field-effect transistors.

Open-circuit voltage shifted by the bending effect for flexible organic solar cells

The shift of the open-circuit voltage (Voc) of flexible organic solar cells (OSCs) under bending conditions was investigated by fabricating bi-layer heterojunction and polymer-based OSCs on flexible polyethylene terephthalate (PET) substrates. To realize the performance variations of flexible solar cells characterized by important parameters, Voc was measured when the substrate was bent under various curvatures. The Voc was increased and decreased by using tensile and compressive stresses, respectively. The ratio of increase for Voc is larger than the ratio of reduction, thus indicating that the intermolecular distance of an organic semiconductor is difficult to change because of the strong electrostatic repulsive force. A quantitative analysis of energy levels by the photoluminescence spectrum, UV-visible absorption spectrum, and quantum chemical calculation at various bending states was used to explain the Voc as a function of bending curvature. The peak shifts of UV-visible absorption and photoluminescence spectra provide direct evidence of the variation in energy levels when devices are bent, which causes Voc shifts. For bent organic semiconductor films, the bending curvature-dependent intermolecular distance was studied by Raman spectroscopy by analyzing the intermolecular coupling energy. This study shows that the change of Voc cannot be neglected in the application of flexible OSCs on a flexible loading circuit.

Influences of device structures on microstructure-correlated photovoltaic characteristics of organic solar cells

Photovoltaic characteristics of organic solar cells (OSCs) are correlated with microstructural qualities of active layers (ALs). Numerous efforts focused on improving process conditions of ALs to attain effective microstructures to achieve high-efficiency OSCs. Aside from AL process conditions, layer properties under AL can also influence microstructural qualities of AL. In this study, we adopted poly(3-hexylthiophene) (P3HT):(6,6)-phenyl C61-butyric acid methyl ester (PCBM) mixture as AL, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as hole extraction layer, and branched polyethyleneimine (BPEI) as electron extraction layer to prepare OSCs with different device structures, that is, normal type (PEDOT:PSS/P3HT:PCBM/BPEI) and inverted type (BPEI/P3HT:PCBM/PEDOT:PSS) structures. We discovered that although devices have similar layer components, they have different photovoltaic characteristics. Inverted devices demonstrated higher power conversion efficiency than normal devices. Various methods, including absorption spectroscopy and microscopy, were used to study AL microstructures of different devices. We observed that P3HT crystallites grown on BPEI had longer vertical size and shorter horizontal size compared with those grown on PEDOT:PSS; these properties could result from larger interfacial tension of P3HT with BPEI than with PEDOT:PSS. Observed shape of P3HT crystallites in inverted devices facilitated efficient charge transport to electrodes and suppressed current leakage. As a result, inverted devices generated improved photovoltaic performance.

Microstructural-dependent photovoltaic properties of polymer solar cells based on different fullerene derivatives

Chlorobenzene, o-dichlorobenzene, and 1,2,4-trichlorobenzene were used as solvents to fabricate active layers of poly(3-hexylthiophene) (P3HT) and fullerene derivatives for polymer solar cells. The fullerene derivatives employed in this study include indene-C60 bisadduct (ICBA) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The microstructural features of P3HT:ICBA and P3HT:PCBM thin films were studied using spectroscopy methods. Results show that an overgrowth of P3HT crystallites and the longer effective conjugation length of P3HT chains in thin films can reduce the power conversion efficiency of devices. The presence of ICBA in thin films can limit the growth of P3HT crystallites, which results in a higher fill factor of the ICBA-based devices compared with PCBM-based devices.