一种基于聚合物绝缘层的TIPS-pentacene晶体管性质研究

采用顶接触结构研究制备了以TIPS-pentacene为有源层、聚甲基丙烯酸甲酯(PMMA)为绝缘层的有机场效应晶体管(OFET),其中绝缘层采用溶液旋涂法制备,电极采用Au电极。通过原子力显微镜(AFM)和X射线衍射(XRD)技术对TIPS-pentacene在PMMA上的生长特性进行了详细分析,结果表明,器件获得了良好的电学特性,其场效应迁移率、阈值电压以及开关电流比分别为0.137 cm2/Vs、-19 V和9.74×104。对器件的稳定性也做了详细研究。     

Improved mobility and lifetime of carrier for highly efficient ternary polymer solar cells based on TIPS-pentacene in PTB7: PC71BM

Highly efficient ternary polymer solar cells (T-PSCs) realized by the improved mobility and lifetime of carrier in PTB7: PC₇₁BM: TIPS-pentacene blends were fabricated. By adjusting the weight ratios of third component TIPS-pentacene in the binary PTB7: PC₇₁BM blends, we found that the short circuit current and fill factor (FF) were simultaneously enhanced, resulting in a maximum power conversion efficiency (PCE) of 8.09% with 21.3% improvement. The improved photovoltaic performance of T-PSC was mainly due to the enhanced light absorption, energy level cascading, optimized blend morphology, and increased hole mobility. It was also found that the incorporation of TIPS-pentacene increased the average hole lifetime, ensuring efficient hole transport and collection with suppressed bimolecular recombination, contributing to the photocurrent. Additionally, the low thickness dependent row-off of FF indicates TIPS-pentacene is a promising third component for the realization of thick film T-PSC. The improved PCEs were obtained as well for other ternary donor: acceptor: TIPS-pentacene systems, demonstrating that the incorporation of TIPS-pentacene is a wide practicable methodology for the development of highly efficient T-PSCs.     

Time-dependent degradation of AlGaN/GaN heterostructures grown on silicon carbide

The AlGaN/GaN heterostructure field-effect transistors (HFETs) were grown on 4H-SiC substrates by metal-organic chemical-vapor deposition (MOCVD) with a range of Al compositions (30–35%) and AlGaN barrier thicknesses. Films with higher strains exhibited a time-dependent degradation of the two-dimensional electron gas (2DEG) that varied from days to weeks. Atomic force microscopy (AFM) measurements of the degraded films revealed a hexagonal cracking pattern with an increase in the medium-scale surface roughness. The localized strain relaxation of AlGaN barriers and increased roughness of the AlGaN/GaN interface and AlGaN surface result in a broad shoulder at the lower angle of the AlGaN peak and a loss of satellite fringes in the (0006) reflection x-ray diffraction (XRD) curve. This degradation raises serious questions with regard to reliability and survivability of AlGaN HFETs and may complicate device fabrication.     

Soluble pentacene thin-film transistor using a high solvent and heat resistive polymeric dielectric with low-temperature processability and its long-term stability

Solution processable organic thin-film transistors (OTFTs) were fabricated using 6,13-bis(triisopropyl-silylethynyl) pentacene (TIPS-pentacene) and low-temperature processable polyimide gate dielectric. The TIPS-pentacene OTFT with the dielectric was found to have a field-effect mobility of 0.15 cm²/Vs, which is comparable to that of OTFT with an inorganic dielectric. The OTFTs with the polyimide dielectric did not show any significant performance degradation as time passed. A field-effect mobility of the OTFTs in 60 days was found to be almost identical to that of pristine OTFT. The combination of TIPS-pentacene and our polyimide gate dielectric can be one of the potential candidates for the fabrication of stable OTFTs for large-area flexible electronics.     

One‐Step Macroscopic Alignment of Conjugated Polymer Systems by Epitaxial Crystallization during Spin‐Coating

The one‐step preparation of highly anisotropic polymer semiconductor thin films directly from solution is demonstrated. The conjugated polymer poly(3‐hexylthiophene) (P3HT) as well as P3HT:fullerene bulk–heterojunction blends can be spin‐coated from a mixture of the crystallizable solvent 1,3,5‐trichlorobenzene (TCB) and a second carrier solvent such as chlorobenzene. Solidification is initiated by growth of macroscopic TCB spherulites followed by epitaxial crystallization of P3HT on TCB crystals. Subsequent sublimation of TCB leaves behind a replica of the original TCB spherulites. Thus, highly ordered thin films are obtained, which feature square‐centimeter‐sized domains that are composed of one spherulite‐like structure each. A combination of optical microscopy and polarized photoluminescence spectroscopy reveals radial alignment of the polymer backbone in case of P3HT, whereas P3HT:fullerene blends display a tangential orientation with respect to the center of spherulite‐like structures. Moreover, grazing‐incidence wide‐angle X‐ray scattering reveals an increased relative degree of crystallinity and predominantly flat‐on conformation of P3HT crystallites in the blend. The use of other processing methods such as dip‐coating is also feasible and offers uniaxial orientation of the macromolecule. Finally, the applicability of this method to a variety of other semi‐crystalline conjugated polymer systems is established. Those include other poly(3‐alkylthiophene)s, two polyfluorenes, the low band‐gap polymer PCPDTBT, a diketopyrrolopyrrole (DPP) small molecule as well as a number of polymer:fullerene and polymer:polymer blends.     

Solution-processed organic crystals for field-effect transistor arrays with smooth semiconductor/dielectric interface on paper substrates

Large surface roughness is a major obstacle for electronic systems fabricated on paper substrates. Here, a mixture solution of organic semiconductor and polymer dielectric was spin-coated on paper substrate with a patterned wettability. This spin-coating process produced organic crystals and a very smooth semiconductor/dielectric interface with a low trap density in well-confined patterns. Despite the large roughness of the paper substrate, the fabricated transistor arrays exhibited high performance with a field-effect mobility reaching 1.3 cm²/V s and an on/off ratio of 10⁸. The presented results offer a simple fabrication method for the current rapidly developing technology of paper electronics.     

Fabrication of organic semiconductor crystalline thin films and crystals from solution by confined crystallization

Highly crystalline thin films of organic semiconductors processed from solution for electronic devices are difficult to achieve due to a slow and preferential three-dimensional growth of the crystals. Here we describe the development of a processing technique to induce a preferential two-dimensional crystalline growth of organic semiconductors by means of minimizing one dimension and confining the solution in two dimensions into a thin layer. The versatility of the process is demonstrated by processing small molecules (TIPS-pentacene and C₆₀) and a polymer (P3HT), all from solvents with a relatively low boiling point, to obtain crystalline thin films. The thin films show an improved in-plane packing of the molecules compared to films processed under similar conditions by spin coating, which is beneficial for the use in organic field-effect transistors.     

1D versus 2D Growth of Soluble Acene Crystals from Soluble Acene/Polymer Blends Governed by a Residual Solvent Reservoir in a Phase‐Separated Polymer Matrix

The growth mechanism of soluble acene is highly dependent on the remaining residual solvent following solution processing. The relationship between the amount of residual solvent and the growth modes of a prototypical soluble acene, 6,13‐bis(triisopropylsilylethynyl)pentacene (TIPS‐pentacene) are examined under spin casting TIPS‐pentacene/insulating polymer blends. Changing spin time of the blend solution allows to control the amount of residual solvent, which significantly determines the growth modes of TIPS‐pentacene vertically segregated onto the insulating polymer. In situ observation of crystal growth reveals that excess residual solvent in short spin time induces a convective flow in a drying droplet, thereby resulting in 1D growth of TIPS‐pentacene crystals. On the other hand, optimal amount of residual solvent in a moderate spin time results in 2D growth of TIPS‐pentacene crystals. The well‐developed 2D spherulites allow for higher field‐effect mobility than that of the 1D crystals because of the higher perfectness and coverage of TIPS‐pentacene crystals. The use of other types of soluble acene and insulating polymer only changes the kinetics of crystallization, while the transition of growth mode from 1D to 2D is still observed. This general growth mechanism facilitates the understanding of crystallization behavior of soluble acene for the development of high‐performance organic transistors.     

Efficient bilayer heterojunction polymer solar cells with bumpy donor–acceptor interface formed by facile polymer blend

We demonstrated a facile method for the fabrication of bilayer polymer solar cells with a controlled heterojunction structure via simple polymer blends. The spontaneous phase separation of poly(3-hexylthiophene)/polyethylene glycol blends provides a bumpy electron-donor layer with characteristic circular depressions. The diameter and depth of the circular depressions can be controlled by varying the PEG content of the blend. The deposition of -phenyl-C61-butyric acid methyl ester as an electron-acceptor layer then creates an interpenetrating donor–acceptor interface for bilayer heterojunction polymer solar cells. The bumpy morphology of the interface results in a significant enhancement in the power conversion efficiency over that of the bilayer polymer solar cells with a typical planar interface, which is mainly due to an increase of photocurrent. An estimation of the field-dependent possibility of charge separation indicates that charge extraction is more efficient than charge recombination in the bilayer devices and the increase in the interfacial area of solar cells with a bumpy-interface leads to generate more electron-hole pairs at the interface.     

Comparative study of spectral and morphological properties of blends of P3HT with PCBM and ICBA

We report a comparative study on spectral and morphological properties of two blend systems for polymer solar cells: the donor material poly(3-hexylthiophene) (P3HT) in combination with the acceptor material of either [6,6]-phenyl-C₆₁ butyric acid methyl ester (PCBM) or indene-C₆₀ bisadduct (ICBA) that was reported to enhance efficiencies of polymer solar cells. Optical microscopy and grazing incidence X-ray scattering reveal the stronger tendency of PCBM to from larger and more ordered domains/grains than ICBA either in pure or blend films. Compared to PCBM, the presence of ICBA also substantially perturbs the organization and longer-range ordering of P3HT in increasing the ICBA ratio in blends. With larger and more ordered phase-separated domains, the P3HT/PCBM blend films exhibit significant optical scattering at higher PCBM ratios. Yet, such optical scattering is not significant for P3HT/ICBA blends (even with high ICBA ratios). Overall, results here suggest the reported higher efficiencies of P3HT/ICBA solar cells (vs. P3HT/PCBM cells) cannot be attributed to larger and/or more ordered phase-separated donor–acceptor domains and other characteristics play more important roles in this case.     

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.     

Study of rectifying property of ITO/PI/TIPS-pentacene/Au diodes by electric field induced optical second harmonic generation

By using time-resolved electric field induced optical second harmonic generation (TR-EFISHG) measurement, we studied the rectifying property of organic double-layer diodes with a structure of indium-tin-oxide/polyimide/6,13-Bis(triisopropylsilylethynyl)-pentacene/gold (ITO/PI/TIPS-pentacene/Au). Upon application of a step voltage to the diodes, the TR-EFISHG probed the electric field changes induced in the TIPS-pentacene layer by hole injection from the ITO electrode, followed by the hole accumulation at the PI/TIPS-pentacene interface. Consequently, the electric field distributions in the diodes before and after the carrier injection were traced with accumulated charges at the PI/TIPS-pentacene interface, depending on the DC biasing applied to the diodes. Analyzing the carrier behavior in ITO/PI/TIPS-pentacene/Au on the basis of a Maxwell–Wagner model, we discussed the rectifying property of the diodes in terms of DC biasing effect, i.e., threshold-voltage shift, and concluded that space charge limited current process that flows across the PI layer governs the rectification of the diodes. Using the TR-EFISHG measurement is an effective way to study the rectifying property of organic double-layer diodes.     

TIPS-pentacene crystalline thin film growth

The crystalline film growth of TIPS-pentacene thin films by confined solution deposition is investigated. The crystalline thin films grow dendritic in the initial stage and continue to grow to elongated plate-like crystals when the solution is deposited in a confined space in-plane. The majority of the thin film, containing smaller thin crystals, is formed within the first 10 s after depositing the solution and continues to grow in minutes to millimeter sized single crystals. By atomic force microscopy we show that impurities are expelled by the growing crystals and clusters accumulate at step edges on the surface of the larger crystals. The influence of crystal thickness and orientation on the electronic transport in field-effect transistors is studied, and shows an optimum performance for devices with thin elongated crystals that are aligned parallel to the electric field between the source–drain electrodes.     

Radical polymers improve the metal-semiconductor interface in organic field-effect transistors

Modifying the organic-metal interface in organic field-effect transistors (OFETs) is a critical means by which to improve device performance; however, to date, all of the interfacial modifying layers utilized in these systems have been closed-shell in nature. Here, we introduce open-shell oxidation-reduction-active (redox-active) macromolecules, namely radical polymers, in order to serve as interfacial modifiers in pentacene-based OFETs. Through careful selection of the chemistry of the specific radical polymer, poly(2,2,6,6-tetramethylpiperidine-1-oxyl methacrylate) (PTMA), the charge transport energy level of the interfacial modifying layer was tuned to provide facile charge injection and extraction between the pentacene active layer and the gold source and drain electrodes of the OFET. The inclusion of this radical polymer interlayer, which was deposited in through straightforward inkjet printing, led to bottom-contact, bottom-gate OFETs with significantly increased mobility and ON/OFF current ratios relative to OFETs without the PTMA interlayer. The underlying mechanism for this improvement in device performance is explained in terms of the charge transport capability at the organic-metal interface and with respect to the pentacene grain growth on the radical polymer. Thus, this effort presents a new, open-shell-based class of materials for interfacial modifying materials, and describes the underlying physics behind the practical operation of these materials.     

Influence of Annealing and Interfacial Roughness on the Performance of Bilayer Donor/Acceptor Polymer Photovoltaic Devices

Through controlled annealing of planar heterojunction (bilayer) devices based on the polyfluorene copolymers poly(9,9‐dioctylfluorene‐co‐bis(N,N′‐(4,butylphenyl))bis(N,N′‐phenyl‐1,4‐phenylene)diamine) (PFB) and poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) we study the influence of interface roughness on the generation and separation of electron–hole pairs at the donor/acceptor interface. Interface structure is independently characterized by resonant soft X‐ray reflectivity with the interfacial width of the PFB/F8BT heterojunction observed to systematically increase with annealing temperature from 1.6 nm for unannealed films to 16 nm with annealing at 200 °C for ten minutes. Photoluminescence quenching measurements confirm the increase in interface area by the three‐fold increase in the number of excitons dissociated. Under short‐circuit conditions, however, unannealed devices with the sharpest interface are found to give the best device performance, despite the increase in interfacial area (and hence the number of excitons dissociated) in annealed devices. The decrease in device efficiency with annealing is attributed to decreased interfacial charge separation efficiency, partly due to a decrease in the bulk mobility of the constituent materials upon annealing but also (and significantly) due to the increased interface roughness. We present results of Monte Carlo simulations that demonstrate that increased interface roughness leads to lower charge separation efficiency, and are able to reproduce the experimental current‐voltage curves taking both increased interfacial roughness and decreased carrier mobility into account. Our results show that organic photovoltaic performance can be sensitive to interfacial order, and heterojunction sharpness should be considered a requirement for high performance devices.     

TIPS-triphenodioxazine versus TIPS-pentacene: Enhanced electron mobility for n-type organic field-effect transistors

A new soluble n-type material based on the 2,9-bis(triisopropylsilylethynyl)triphenodioxazine (TIPS-triphenodioxazine) has been designed as a quinonoid equivalent of TIPS-pentacene and synthesized using an innovative synthetic pathway. Both materials showed identical electronic affinities, intermolecular arrangements and thin film topographies. However, the TIPS-triphenodioxazine led to better performances than TIPS-pentacene in n-channel organic field-effect transistors (OFETs) evidencing the potentialities of this π-conjugated core in the field of organic electronics.     

Doping of TIPS-pentacene via Focused Ion Beam (FIB) exposure

We report on the influence of Focused Ion Beam (FIB) exposure on TIPS-pentacene layers which are often used in solution-processable organic field-effect transistors (OFETs) and in many cases yield a field-effect mobility in the order of 1 cm²/V s. We exposed TIPS-pentacene layers to a Ga⁺ ion beam and measured the device characteristics of OFETs. We observed a strong influence of the FIB on J–V characteristics of TIPS-pentacene-based devices and determined an increase in the OFET mobility and on–off ratio and a decrease of the threshold voltage. To further investigate the underlying process we analyzed FIB-exposed and unexposed TIPS-pentacene samples via X-ray Photoelectron Spectroscopy (XPS). Exposed samples show a clear Ga XPS signature and the C1s peak shifts about 400 meV towards smaller binding energies which is an indicator for a Fermi energy shift closer to the valence states and hence p-doping of TIPS-pentacene. With Scanning Kelvin Probe Microscopy (SKPM) we could clearly distinguish FIB exposed areas from the unexposed areas. For exposed areas the work function increases about 200 meV which is consistent with XPS measurements and again displays that the implanted Ga⁺ ions serve as p-dopants. Furthermore we took SKPM measurements on operating OFETs and could investigate a dramatic change in local conductance on FIB exposed areas. This demonstrates a novel way of nanopatterning conductive paths in organic semiconductors.     

Controlling the crystal formation in solution-process for organic field-effect transistors with high-performance

We control the growth of high-quality organic semiconducting crystals in the aim of transistor application. By finely tuning the processing parameters, both isolated crystals showing characteristic facet angles and irregular-shaped, thin crystalline domains are obtained in large sizes (>400 μm). Structural investigations indicate that the various shapes of crystals are in the same crystal structure, and reveal that the irregular-shaped crystalline domains are composed by terrace of molecularly flat regions, which can be up to hundreds of microns in size. When applied in field-effect transistors, the thin crystalline domains exhibit the best performance showing μ_FET up to 4.4 cm²/V s. This is an order of magnitude higher than that of the transistors made from as-spun films and thick crystals. The approach well demonstrates the importance of fine control of crystal formation and can be generally used for getting organic crystal transistors.     

Using pyridal[2,1,3]thiadiazole as an acceptor unit in a low band-gap copolymer for photovoltaic applications

In this report, we explore the optoelectronic properties of a low band-gap copolymer based on the alternation of electron rich (thiophene and thienothiophene units) and electron deficient units (pyridal[2,1,3]thiadiazole (Py)). Initial density functional theory calculations point out the interest of using the Py unit to optimize the polymer frontier orbital energy levels. A high molecular weight (M_n = 49 kg/mol) solution-processable copolymer, based on Py, thiophene and thienothiophene units, has been synthesized successfully. From cyclic-voltammetry and UV–visible absorption measurements a relatively deep HOMO level (−5.1 eV) and an optical band-gap (1.48 eV) have been estimated. Charge transport both in horizontal and vertical directions were extracted from field-effect transistors and space charge limited current diodes, respectively, and led to a relatively high in-plane hole mobility in pure polymer films (0.7 × 10⁻² cm² V⁻¹ s⁻¹). GIWAXS results showed almost identical in-plane lamellar morphologies, with similar average size and orientation of the polymer crystalline domains in both, pure polymer films and polymer:fullerene blends. Also, the gate-voltage dependence of the field-effect mobility revealed that the energy disorder in the polymer domains was not altered by the introduction of fullerenes. The nevertheless significantly higher out-of-plane hole mobility in blends, in comparison to pure polymer films, was attributed to the minor amorphous polymer phase, presumably localized close to the donor/acceptor interface, whose signature was observed by UV–vis absorption. Promising photovoltaic performances could be achieved in a standard device configuration. The corresponding power conversion efficiency of 4.5% is above the value achieved previously with a comparable polymer using benzo [2,1,3]thiadiazole instead of Py as acceptor unit.     

Nitrogen Plasma Processing of SiO2/4H-SiC Interfaces

A nitrogen plasma annealing process for gate dielectric applications in 4H-SiC metal oxide semiconductor (MOS) technology has been investigated. This process results in substantially greater interfacial N coverage at the SiO₂/4H-SiC interface and lower interface trap densities than the state-of-the-art nitric oxide (NO) annealing process. Despite these exciting results, the field-effect mobility of MOS field-effect transistors (MOSFETs) fabricated by use of this process is very similar to that of NO-annealed MOSFETs. These results emphasize the importance of understanding mobility-limiting mechanisms in addition to charge trapping in next-generation 4H-SiC MOSFETs.