Simultaneous control of molecular orientation and patterning of small-molecule organic semiconductors for organic transistors

Triethylsilylethynyl anthradithiophene (TES-ADT) has been shown to be a promising soluble semiconductor for the active layer of organic field-effect transistors (OFETs) due to its solution processability, chemical stability and excellent electrical properties. However, there are still some problems that need to be resolved for the utilization of TES-ADT in OFETs. One of these problems is a patterning issue to minimize crosstalk between neighboring TES-ADT FETs. To this end, TES-ADT crystals of various shapes need to be patterned at the desired positions. Here, we demonstrated a simple method to fabricate patterned TES-ADT crystals by using a PDMS mold containing 1,2–dichloroethane (DCE) solvent. This method serves the dual purpose of preparing a variety of pattern shapes while simultaneously changing as-spun TES-ADT thin films into crystal patterns. The top-contact OFETs with the TES-ADT crystal patterns exhibited high performance, reaching a field-effect mobility of ∼0.3 cm² V⁻¹s⁻¹.     

Addressable growth of oriented organic semiconductor ultra-thin films on hydrophobic surface by direct dip-coating

Oriented organic field-effect transistor (OFET) stripe arrays on hydrophobic substrates were fabricated by fast dip-coating technique. The addressable growth was achieved by decreasing surface energy of the channel areas with respect to the electrodes via hydrophobic treatment. The higher surface energy of the electrodes allows solution to adhere and then organic semiconductors nucleate and bridge the channels after evaporation of the solvent. Area-selective behaviour can be controlled by adjusting surface property of transistor channel, geometry features of the gold electrodes, pulling speed and evaporation atmosphere. The mechanism behind is the competition between receding of the solution and evaporating of the solvent that generate the organic semiconductor films on the substrate. The patterned bottom-contact transistor arrays exhibit carrier mobility of 2.0 × 10⁻³ cm² V⁻¹ s⁻¹, while no field-effect characteristics can be detected for bottom-contact arrays without hydrophobic treatment. Such reliable, fast and solution-based patterned OFET arrays are highly desirable for large-scale and low-cost production.     

聚对二甲苯类薄膜用于有机电致发光器件的封装

采用热解化学气相沉积聚合(TCVDP)方法制备了聚对二甲苯(PPX)和聚一氯对二甲苯(PCPX)薄膜材料,利用其对有机电敛发光器件(OLED)进行了封装.利州紫外可见光谱、扫描电镜(SEM)对薄膜的相关性能进行了表征.比较了器件经过两种薄膜封装前后器件的工作寿命.实验结果表明:利用TCVDP方法,可以制备出透明的表面平整、结构致密的聚对二甲苯类薄膜材料;用于OLED)的封装能大幅度地提高器件的工作寿命,经过PPX封装后的寿命为1215 h,经过PCPX封装后的寿命为1 558 h,比未封装的器件寿命(197 h)提高了6～8倍.     

Relationship between microscopic and macroscopic structures of organic thin films for SHG

The experiments described in this paper were undertaken in order to obtain information about the relationship between the structure and non-linear optical properties (second-harmonic generation) of organic thin films. For this purpose, two closely related dyes, diones and tetrones, were compared, both of which are shown to have large hyperpolarisabilities. Their microscopic properties are investigated by conformational analysis and electron diffraction. It could be shown that detailed knowledge about the structure and the adjacent neighbour packing can be obtained from conformational analysis and electron diffraction in order to understand the non-linear optical properties of the two dyes.     

Characterization of organic thin films for OLEDs using spectroscopic ellipsometry

We report the optical characterization of thin, evaporated organic films used in fabrication of organic light emitting diodes (OLEDs): N,N'-diphenyl-N,N'-bis(3-methyl-phenyl)-l,l'biphenyl-4,4'diamine,or TPD,andtris(8-hydroxy)quinolato aluminum, or Alq3. In particular, we have obtained and analyzed spectroscopic eliipsometry (SE) data using a multi-sample approach, to determine the optical constants for Alq₃ and TPD films over the wavelength range 250-850 nm. We show that bi-layer Alq₃/TPD films on Si can be analyzed for individual layer thicknesses, even though the refractive index is nearly identical for these films in the visible region. Simulations of in situ monitoring are also presented, which show sub-nm thickness resolution for organic layer growth on a Si monitor wafer. SE has great utility for process control, either by ex situ or in situ thickness measurement.     

Photolithographic patterning of organic photodetectors with a non-fluorinated photoresist system

We report on the fabrication of organic photodetectors (OPD) based on isolated islands of P3HT:PCBM. Pattern transfer to the active material was done with photolithography based on non-fluorinated solvents and the excessive organic semiconductor was removed with oxygen plasma reactive ion etching. The photoresist system used was found to be benign to the P3HT:PCBM layer as confirmed by absorption, thickness and roughness measurements. Current–voltage characteristics and external quantum efficiency (EQE) remained unchanged after the patterning process. It was demonstrated that it is possible to photolithographically pattern isolated islands with 200 μm edge length with the same dark current density (<10⁻⁵ A/cm² at −2 V bias voltage) and photocurrent density (>5 × 10⁻³ A/cm² at −2 V). Furthermore, concerning the solar cell performance, the patterned, small-area devices showed power conversion efficiency of 2.1% and fill-factor of 60%. Dark current was observed to depend on the size of the remaining semiconductor island, which was demonstrated on OPDs with diameter of 50 μm. The presented results show the feasibility of fabrication of isolated devices based on organic semiconductors patterned with non-fluorinated photolithography.     

Determination of crystal orientation in organic thin films using optical microscopy

The electrical behavior of devices based on highly crystalline thin films of organic semiconductors is inherently anisotropic. Thin film optimization requires simple and accessible means to characterize the orientation of the constituent crystals. The standard polarized light microscopy (PLM) provides a contrast between different crystallites but fails to distinguish crystals with relative orientation of 90°. In this paper, we discuss two methods that enable the unambiguous identification of crystal orientation in thin films of optically anisotropic materials: PLM with a full-wave retardation plate and differential interference contrast (DIC). The latter is standard on most microscopes and delivers images with high contrast and good color balance.As an illustration, we use DIC to extract the optical properties of highly crystalline thin films of three high-performance organic semiconductors: rubrene, 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C₈-BTBT). Building on the relation between optical properties and crystal orientation, we demonstrate how DIC characterizes the in-plane crystal orientation of these thin films. This leads to the identification of the fast growth direction of the crystal front.     

Parametric optimization of micro-contact printing based thermal transfer of electrospun nanofibers

We report on the results of a parametric optimization of micro-contact printing based thermal transfer of electrospun nanofibers. Fiber electrospinning was performed with a solution of thermoplastic polymer and a collector having a rectangular open area. After electrospinning, a piece of elastomer polydimethylsiloxane (PDMS) was used to scratch nanofibers from the open area and to thermally transfer them to the surface of a glass substrate by micro-contact printing at a temperature slightly higher than the glass transition temperature of the polymer. With the help of optical measurements, we optimized the printing conditions including the temperature and printing duration. Then, the stability of the transferred nanofibers was studied with sonication at different power rates. As expected, the printed nanofibers showed a much enhanced adhesion stability, comparing to the as-deposited nanofibers. Furthermore, the nanofibers after thermal transfer could be used for patterning by using conventional photolithography and reactive ion etch techniques.     

Printing-induced improvements of organic thin-film transistors

To understand the observation of improved pentacene (Pn) thin-film transistor mobility in flexible printed devices, a method for performing electrical measurements of organic thin-film transistors (OTFT) during the process of transfer printing has been developed. Different sample configurations were designed to test two aspects of the printing process: (1) the formation of the source/drain contacts a Pn thin-film, and (2) the formation of the transfer printed Pn/dielectric interface. In situ measurements show that pressure-induced contacts of gold (Au) electrodes result in a factor of seven mobility improvement compared with evaporation of top Au electrodes on an otherwise identical device configuration. Annealing the laminated device up to 90 °C caused no further improvement, and heating above 90 °C degraded performance. The mobility of a transfer printed device with the rough, as-grown top surface of the Pn in contact with the dielectric was found to increase dramatically with subsequent annealing for a sample temperature up to 120 °C. This is attributed to annealing-induced structural changes in the Pn film at elevated temperatures, consistent with X-ray bulk measurements showing enhanced crystal morphology in transfer printed Pn thin-films.     

Deep reactive ion etching of thermally co-evaporated Te-Ge films for IR integrated optics components

Due to their remarkable transparency in the infrared region, telluride glasses are very promising materials for the realization of IR integrated optics components for specific applications, such as the detection of pollutant gases in the atmosphere or the detection of exoplanetary systems. In order to prove the feasibility of channel waveguiding structures based on this kind of materials, deep etching of thermally co-evaporated Te-Ge films, one of the most important and critical steps, was investigated. Reactive ion etching was carried out using different mixtures of three gases CHF₃, O₂ and Ar, and for different chamber pressures and RF powers. The influence of each parameter on the quality of etched Te-Ge films, in term of rib dimensions and surface roughness for example, was studied. Finally optimized parameters i.e. a CHF₃/O₂/Ar ratio of 59.5/10.5/30, a chamber pressure of 30 mTorr and a RF power of 50 W were used to fabricate a pattern showing the achievement in term of etching resolution.     

Microstructure transformations induced by modified-layers on pentacene polymorphic films and their effect on performance of organic thin-film transistor

Phenyltrimethoxysilane was used to modify SiO₂ insulator and significantly enhanced the pentacene based organic thin-film transistors (OTFTs). The crystal structure, surface morphology, molecular structure and microstructure of pentacene polymorphic films with and without the modifications were investigated using X-ray diffraction (XRD), atomic force microscopy (AFM) and contact angle meter. XRD studies reveal a decreased tilt angle (θ_T) of pentacene molecules from c-axis toward a-axis, indicating that polymorphs transformation from the “triclinic bulk” phase to the “thin film” phase and orthorhombic phase occurs. AFM images show that the surface roughness of gate insulators has no influence on performance of the pentacene based OTFT. These results provide strong evidence that the performance improvement of OTFT after PhTMS modification of SiO₂ insulator surface is related to the microstructure transformation of the semiconductor. It suggests that the modified-layer may alter the molecular geometry and further induce structural phase transitions in the pentacene films for the performance improvement.     

Transfer Printing Water‐Soluble Inorganic Salts

This paper reports the first example of the fabrication of KNO₃, K₂CO₃, CuSO₄, NaOH, and mixed‐inorganic‐salt (KNO₃ and KOH) patterns using a transfer‐printing (TP) technique. The transfer quality is found to be related to the concentration of the salt solutions. By varying the immersion time, it is possible to control the heights of the raised features of the transfer‐printed salts from the nanoscale to the submicrometer scale. Utilizing these inorganic salts as water‐soluble masks for microfabrication is demonstrated using patterned NaOH films. The use of water as a developer solvent demonstrates the potential utility of the patterning of inorganic salts as a low‐cost, simple, and, more importantly, environmentally friendly route towards accurate patterning of different materials.     

Electric potential mapping by thickness variation: A new method for model-free mobility determination in organic semiconductor thin films

Charge transport, with charge carrier mobility as main parameter, is one of the fundamental properties of semiconductors. In disordered systems like most organic semiconductors, the effective mobility is a function of the electric field, the charge carrier density, and temperature. Transport is often investigated in a space-charge limited current (SCLC) regime in thin film single carrier devices, where an electric current is driven in the direction perpendicular to the surface. Direct evaluation of the current–voltage characteristics, however, is problematic, because parasitic contributions from injection or extraction barriers can falsify results.     

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.     

Achieving good bias stress reliability in organic transistor with vertical channel

Unlike organic field-effect transistor with accumulated channel at dielectric/semiconductor interface, vertical organic transistor exhibits bulk channel current and hence performs good bias stress reliability. Adding self-assemble-monolayer to treat vertical channel can further modulate the charge-trapping surrounding the base electrode and hence influence the bias stress reliability. During 4300-s positive/negative bias stresses, stable output current and on/off ratio are demonstrated by using octadecyltrichlorosilane (OTS)-passivated vertical channel. The good reliability together with the low operation voltage and the high output current make vertical organic transistors capable of driving organic light emitting diode.     

Analysis of electron traps formed in organic films with a sputtered cathode

To understand why performance degradation is reduced for sputtered cathodes on organic devices when the electron transport layer (ETL) is doped with Li, we analyze electron-only devices using the thermally stimulated current (TSC) technique and modeling of temperature-dependent current–voltage characteristics with a trapped-charge-limited current (TCLC) model. The combined results suggest that the trap density measured by TSC might also include a portion of the density of the hopping sites in the lowest unoccupied molecular orbital levels, which contributes to charge transport. Compared to undoped devices, doped devices maintain a high density of hopping sites even when the Al is sputtered. We propose that the reduced effect of sputtering on electron injection and transport properties is because radical anions of Alq₃ might still be formed by the strong reducer Li even if the organic material is partially damaged. An additional TSC peak and increased driving voltage for doped tris(8-hydroxyquinoline)aluminum (Alq₃) as an ETL with a sputtered cathode suggests the formation of new traps possibly because of damage even though the transport is better compared to the undoped device. Such traps are not found in doped bathophenanthroline (Bphen) as an ETL, which shows no change in driving voltage.     

Implication of molecular orientation on charge transport and gas sensing characteristics of cobalt–phthalocyanine thin films

Charge transport and gas sensing characteristics of cobalt phthalocyanine films deposited along (ATB) and perpendicular (PTB) to the natural twin boundaries of (0 0 1) LaAlO₃ substrate have been investigated. The charge carrier mobility of ATB films (∼5 cm² V⁻¹ s⁻¹) is five orders of magnitude higher compared to that of PTB films (∼7 × 10⁻⁵ cm² V⁻¹ s⁻¹), suggesting that twin boundaries acts like a template for ordering of molecules. The ATB films on exposure to ammonia showed a reversible increase of resistance, with fast response and recovery. In contrast PTB films showed same sensitivity, but exhibits base resistance drift along with sluggish response.     

Enhancement of organic solar cell efficiency by patterning the PEDOT:PSS hole transport layer using nanoimprint lithography

In order to improve the conversion efficiency of organic photovoltaic (OPV) cells, nano-patterned poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) (PEDOT:PSS) was used as a hole transfer layer (HTL). Using nanoimprint lithography, a process that is easily applied to large-area substrates, a spherical array of PEDOT:PSS droplets was formed. The effect of the PEDOT:PSS nanostructure was characterized by optical and electrical measurements. Because the hemispherical array of PEDOT:PSS scatters light efficiently, absorption of the incident light increases when the nanostructured layer is employed. The conversion efficiency of the nano-patterned OPV cells is 25% larger than that of non-patterned OPV cells, due to the increase in short-circuit current (J_sc).     

面向彩色有机微显示的有机白光顶发射器件

以比铝、银等金属材料透光性更好的铜作为白光有机顶发射器件的顶电极,将其应用到基于Al底电极的蓝、黄互补色顶发射白光有机电致发光器件(TEWOLED),通过合理设计器件结构,制备出的器件具有较低的驱动电压和较高的效率,4V下亮度超过1 000cd/m2、功率效率达到28.5lm/W,效率滚降较小。我们利用p型电学掺杂结构和电子注入缓冲层结构分别解决了铝和铜电极功函数同空穴传输层的HOMO能级和电子传输层的LUMO能级不匹配问题,并通过TcTa光学覆盖层的调节作用使器件具有较好的光谱稳定性。基于Cu顶电极的TEWOLED与采用Al作为互连金属的CMOS工艺兼容,我们将该器件与硅基CMOS驱动电路结合,获得了SVGA白光有机微显示器件,为彩色有机发光微显示的实现奠定了基础。     

Flexible organic phototransistors based on a combination of printing methods

Highly photosensitive organic phototransistors (OPTs) are successfully demonstrated on a flexible substrate using all-solution process as well as a combination of printing methods which consist of roll-to-plate reverse offset printing (ROP), inkjet printing and bar coating. Excellent electrical switching characteristics are obtained from heterogeneous interfacial properties of the reverse-offset-printed silver nanoparticle electrode and the inkjet-printed p-channel polymeric semiconductor. In particular, the OPTs exhibit remarkably photosensitivity with a photo-to-dark current ratio exceeding 5 orders. This optoelectronic properties of the combinational printed OPTs are theoretically and experimentally studied, and found the comparable tendency. In addition, excellent mechanical stability is observed with up to 0.5% of strain applied to the OPTs. Hence, by manufactured with a combination of various graphic art printing methods such as roll-to-plate ROP, inkjet printing, and bar coating, these devices are very promising candidates for large-area and low-cost printed and flexible optoelectronics applications.