Solution-processed silicon films and transistors

The use of solution processes-as opposed to conventional vacuum processes and vapour-phase deposition-for the fabrication of electronic devices has received considerable attention for a wide range of applications, with a view to reducing processing costs. In particular, the ability to print semiconductor devices using liquid-phase materials could prove essential for some envisaged applications, such as large-area flexible displays. Recent research in this area has largely been focused on organic semiconductors, some of which have mobilities comparable to that of amorphous silicon (a-Si); but issues of reliability remain. Solution processing of metal chalcogenide semiconductors to fabricate stable and high-performance transistors has also been reported. This class of materials is being explored as a possible substitute for silicon, given the complex and expensive manufacturing processes required to fabricate devices from the latter. However, if high-quality silicon films could be prepared by a solution process, this situation might change drastically. Here we demonstrate the solution processing of silicon thin-film transistors (TFTs) using a silane-based liquid precursor. Using this precursor, we have prepared polycrystalline silicon (poly-Si) films by both spin-coating and ink-jet printing, from which we fabricate TFTs with mobilities of 108 cm2 V(-1) s(-1) and 6.5 cm2 V(-1) s(-1), respectively. Although the processing conditions have yet to be optimized, these mobilities are already greater than those that have been achieved in solution-processed organic TFTs, and they exceed those of a-Si TFTs (< or = 1 cm2 V(-1) s(-1)).     

Patterning organic single-crystal transistor arrays

Field-effect transistors made of organic single crystals are ideal for studying the charge transport characteristics of organic semiconductor materials. Their outstanding device performance, relative to that of transistors made of organic thin films, makes them also attractive candidates for electronic applications such as active matrix displays and sensor arrays. These applications require minimal cross-talk between neighbouring devices. In the case of thin film systems, simple patterning of the active semiconductor layer minimizes cross-talk. But when using organic single crystals, the only approach currently available for creating arrays of separate devices is manual selection and placing of individual crystals-a process prohibitive for producing devices at high density and with reasonable throughput. In contrast, inorganic crystals have been grown in extended arrays, and efficient and large-area fabrication of silicon crystalline islands with high mobilities for electronic applications has been reported. Here we describe a method for effectively fabricating large arrays of single crystals of a wide range of organic semiconductor materials directly onto transistor source-drain electrodes. We find that film domains of octadecyltriethoxysilane microcontact-printed onto either clean Si/SiO(2) surfaces or flexible plastic provide control over the nucleation of vapour-grown organic single crystals. This allows us to fabricate large arrays of high-performance organic single-crystal field-effect transistors with mobilities as high as 2.4 cm(2) V(-1) s(-1) and on/off ratios greater than 10(7), and devices on flexible substrates that retain their performance after significant bending. These results suggest that our fabrication approach constitutes a promising step that might ultimately allow us to utilize high-performance organic single-crystal field-effect transistors for large-area electronics applications.     

High-mobility ultrathin semiconducting films prepared by spin coating

The ability to deposit and tailor reliable semiconducting films (with a particular recent emphasis on ultrathin systems) is indispensable for contemporary solid-state electronics. The search for thin-film semiconductors that provide simultaneously high carrier mobility and convenient solution-based deposition is also an important research direction, with the resulting expectations of new technologies (such as flexible or wearable computers, large-area high-resolution displays and electronic paper) and lower-cost device fabrication. Here we demonstrate a technique for spin coating ultrathin (approximately 50 A), crystalline and continuous metal chalcogenide films, based on the low-temperature decomposition of highly soluble hydrazinium precursors. We fabricate thin-film field-effect transistors (TFTs) based on semiconducting SnS(2-x)Se(x) films, which exhibit n-type transport, large current densities (>10(5) A cm(-2)) and mobilities greater than 10 cm2 V(-1) s(-1)--an order of magnitude higher than previously reported values for spin-coated semiconductors. The spin-coating technique is expected to be applicable to a range of metal chalcogenides, particularly those based on main group metals, as well as for the fabrication of a variety of thin-film-based devices (for example, solar cells, thermoelectrics and memory devices).     

Flexible metal-oxide devices made by room-temperature photochemical activation of sol-gel films

Amorphous metal-oxide semiconductors have emerged as potential replacements for organic and silicon materials in thin-film electronics. The high carrier mobility in the amorphous state, and excellent large-area uniformity, have extended their applications to active-matrix electronics, including displays, sensor arrays and X-ray detectors. Moreover, their solution processability and optical transparency have opened new horizons for low-cost printable and transparent electronics on plastic substrates. But metal-oxide formation by the sol-gel route requires an annealing step at relatively high temperature, which has prevented the incorporation of these materials with the polymer substrates used in high-performance flexible electronics. Here we report a general method for forming high-performance and operationally stable metal-oxide semiconductors at room temperature, by deep-ultraviolet photochemical activation of sol-gel films. Deep-ultraviolet irradiation induces efficient condensation and densification of oxide semiconducting films by photochemical activation at low temperature. This photochemical activation is applicable to numerous metal-oxide semiconductors, and the performance (in terms of transistor mobility and operational stability) of thin-film transistors fabricated by this route compares favourably with that of thin-film transistors based on thermally annealed materials. The field-effect mobilities of the photo-activated metal-oxide semiconductors are as high as 14 and 7?cm(2)?V(-1)?s(-1) (with an Al(2)O(3) gate insulator) on glass and polymer substrates, respectively; and seven-stage ring oscillators fabricated on polymer substrates operate with an oscillation frequency of more than 340?kHz, corresponding to a propagation delay of less than 210?nanoseconds per stage.     

Tuning charge transport in solution-sheared organic semiconductors using lattice strain

Circuits based on organic semiconductors are being actively explored for flexible, transparent and low-cost electronic applications. But to realize such applications, the charge carrier mobilities of solution-processed organic semiconductors must be improved. For inorganic semiconductors, a general method of increasing charge carrier mobility is to introduce strain within the crystal lattice. Here we describe a solution-processing technique for organic semiconductors in which lattice strain is used to increase charge carrier mobilities by introducing greater electron orbital overlap between the component molecules. For organic semiconductors, the spacing between cofacially stacked, conjugated backbones (the π-π stacking distance) greatly influences electron orbital overlap and therefore mobility. Using our method to incrementally introduce lattice strain, we alter the π-π stacking distance of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) from 3.33?? to 3.08??. We believe that 3.08?? is the shortest π-π stacking distance that has been achieved in an organic semiconductor crystal lattice (although a π-π distance of 3.04?? has been achieved through intramolecular bonding). The positive charge carrier (hole) mobility in TIPS-pentacene transistors increased from 0.8?cm(2)?V(-1)?s(-1) for unstrained films to a high mobility of 4.6?cm(2)?V(-1)?s(-1) for a strained film. Using solution processing to modify molecular packing through lattice strain should aid the development of high-performance, low-cost organic semiconducting devices.     

有机场效应晶体管的研究与应用进展

有机场效应晶体管(Organic Field Effect Transistors,OFETs)是以有机半导体材料作为有源层的晶体管器件。和传统的无机半导体器件相比,由于其可应用于生产大面积柔性设备而被人们广泛的研究,在有机发光、有机光探测器、有机太阳能电池、压力传感器、有机存储设备、柔性平板显示、电子纸等众多领域具有潜在而广泛的应用前景。文中对OFET结构和工作原理做了简要介绍,之后重点讨论了最近几年来OFET中有机材料和绝缘体材料的发展状况,接着总结了OFET制备技术及其应用新领域,最后对OFET发展面临问题及应用前景做了归纳和展望。     

Inkjet printing of single-crystal films

The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science. Whether based on inorganic or organic materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. 'Printed electronics' is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials. However, because of the strong self-organizing tendency of the deposited materials, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid-air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C(8)-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4?cm(2)?V(-1)?s(-1). This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.     

退火温度对ZnO薄膜晶体管电特性的影响

针对非晶硅和有机薄膜晶体管的低迁移率问题,以高纯Zn为靶材,反应磁控溅射沉积、且在不同温度下退火的ZnO薄膜作为半导体活性层,成功地制备出基于ZnO材料的薄膜晶体管(ZnO-TFT),研究了退火温度对ZnO -TFT电特性的影响.结果表明:ZnO- TFT的载流子迁移率随退火温度的升高而明显增大,700℃退火的样品迁移...     

Medium-scale carbon nanotube thin-film integrated circuits on flexible plastic substrates

The ability to form integrated circuits on flexible sheets of plastic enables attributes (for example conformal and flexible formats and lightweight and shock resistant construction) in electronic devices that are difficult or impossible to achieve with technologies that use semiconductor wafers or glass plates as substrates. Organic small-molecule and polymer-based materials represent the most widely explored types of semiconductors for such flexible circuitry. Although these materials and those that use films or nanostructures of inorganics have promise for certain applications, existing demonstrations of them in circuits on plastic indicate modest performance characteristics that might restrict the application possibilities. Here we report implementations of a comparatively high-performance carbon-based semiconductor consisting of sub-monolayer, random networks of single-walled carbon nanotubes to yield small- to medium-scale integrated digital circuits, composed of up to nearly 100 transistors on plastic substrates. Transistors in these integrated circuits have excellent properties: mobilities as high as 80 cm(2) V(-1) s(-1), subthreshold slopes as low as 140 m V dec(-1), operating voltages less than 5 V together with deterministic control over the threshold voltages, on/off ratios as high as 10(5), switching speeds in the kilohertz range even for coarse (approximately 100-microm) device geometries, and good mechanical flexibility-all with levels of uniformity and reproducibility that enable high-yield fabrication of integrated circuits. Theoretical calculations, in contexts ranging from heterogeneous percolative transport through the networks to compact models for the transistors to circuit level simulations, provide quantitative and predictive understanding of these systems. Taken together, these results suggest that sub-monolayer films of single-walled carbon nanotubes are attractive materials for flexible integrated circuits, with many potential areas of application in consumer and other areas of electronics.     

General observation of n-type field-effect behaviour in organic semiconductors

Organic semiconductors have been the subject of active research for over a decade now, with applications emerging in light-emitting displays and printable electronic circuits. One characteristic feature of these materials is the strong trapping of electrons but not holes: organic field-effect transistors (FETs) typically show p-type, but not n-type, conduction even with the appropriate low-work-function electrodes, except for a few special high-electron-affinity or low-bandgap organic semiconductors. Here we demonstrate that the use of an appropriate hydroxyl-free gate dielectric--such as a divinyltetramethylsiloxane-bis(benzocyclobutene) derivative (BCB; ref. 6)--can yield n-channel FET conduction in most conjugated polymers. The FET electron mobilities thus obtained reveal that electrons are considerably more mobile in these materials than previously thought. Electron mobilities of the order of 10(-3) to 10(-2) cm(2) V(-1) s(-1) have been measured in a number of polyfluorene copolymers and in a dialkyl-substituted poly(p-phenylenevinylene), all in the unaligned state. We further show that the reason why n-type behaviour has previously been so elusive is the trapping of electrons at the semiconductor-dielectric interface by hydroxyl groups, present in the form of silanols in the case of the commonly used SiO2 dielectric. These findings should therefore open up new opportunities for organic complementary metal-oxide semiconductor (CMOS) circuits, in which both p-type and n-type behaviours are harnessed.     

Low-voltage organic transistors with an amorphous molecular gate dielectric

Organic thin film transistors (TFTs) are of interest for a variety of large-area electronic applications, such as displays, sensors and electronic barcodes. One of the key problems with existing organic TFTs is their large operating voltage, which often exceeds 20 V. This is due to poor capacitive coupling through relatively thick gate dielectric layers: these dielectrics are usually either inorganic oxides or nitrides, or insulating polymers, and are often thicker than 100 nm to minimize gate leakage currents. Here we demonstrate a manufacturing process for TFTs with a 2.5-nm-thick molecular self-assembled monolayer (SAM) gate dielectric and a high-mobility organic semiconductor (pentacene). These TFTs operate with supply voltages of less than 2 V, yet have gate currents that are lower than those of advanced silicon field-effect transistors with SiO2 dielectrics. These results should therefore increase the prospects of using organic TFTs in low-power applications (such as portable devices). Moreover, molecular SAMs may even be of interest for advanced silicon transistors where the continued reduction in dielectric thickness leads to ever greater gate leakage and power dissipation.     

一种优越的钝化膜(a-Si:O:H)

本文报道了用等离子放电SiH_4+H_2+H_2O混合气体淀积氢化非晶硅氧合金膜,均匀、致密、耐腐蚀、半绝缘、电中性、富含氢,是较理想的半导体器件钝化膜。兼有SiO_2和a-Si:H的优点,而又克服了它们各自的缺点。用它钝化的平面晶体管放在盐水里几小时后,特性不变。     

The path to ubiquitous and low-cost organic electronic appliances on plastic

Organic electronics are beginning to make significant inroads into the commercial world, and if the field continues to progress at its current, rapid pace, electronics based on organic thin-film materials will soon become a mainstay of our technological existence. Already products based on active thin-film organic devices are in the market place, most notably the displays of several mobile electronic appliances. Yet the future holds even greater promise for this technology, with an entirely new generation of ultralow-cost, lightweight and even flexible electronic devices in the offing, which will perform functions traditionally accomplished using much more expensive components based on conventional semiconductor materials such as silicon.     

Nanotechnology: high-speed integrated nanowire circuits

Macroelectronic circuits made on substrates of glass or plastic could one day make computing devices ubiquitous owing to their light weight, flexibility and low cost. But these substrates deform at high temperatures so, until now, only semiconductors such as organics and amorphous silicon could be used, leading to poor performance. Here we present the use of low-temperature processes to integrate high-performance multi-nanowire transistors into logical inverters and fast ring oscillators on glass substrates. As well as potentially enabling powerful electronics to permeate all aspects of modern life, this advance could find application in devices such as low-cost radio-frequency tags and fully integrated high-refresh-rate displays.     

Enhancing semiconductor device performance using ordered dopant arrays

As the size of semiconductor devices continues to shrink, the normally random distribution of the individual dopant atoms within the semiconductor becomes a critical factor in determining device performance--homogeneity can no longer be assumed. Here we report the fabrication of semiconductor devices in which both the number and position of the dopant atoms are precisely controlled. To achieve this, we make use of a recently developed single-ion implantation technique, which enables us to implant dopant ions one-by-one into a fine semiconductor region until the desired number is reached. Electrical measurements of the resulting transistors reveal that device-to-device fluctuations in the threshold voltage (Vth; the turn-on voltage of the device) are less for those structures with ordered dopant arrays than for those with conventional random doping. We also find that the devices with ordered dopant arrays exhibit a shift in Vth, relative to the undoped semiconductor, that is twice that for a random dopant distribution (- 0.4 V versus -0.2 V); we attribute this to the uniformity of electrostatic potential in the conducting channel region due to the ordered distribution of dopant atoms. Our results therefore serve to highlight the improvements in device performance that can be achieved through atomic-scale control of the doping process. Furthermore, ordered dopant arrays of this type may enhance the prospects for realizing silicon-based solid-state quantum computers.     

低电压并五苯薄膜场效应晶体管

利用全蒸镀法, 以并五苯作为有源层, 聚甲基丙烯酸甲 酯（PMMA）作为绝缘层, 制备了全有机薄膜场效应晶体管（TFT）. 测试结果表明, 器件具有较低的工作电压和较高的场效应迁移率. 对工作机理进行了探讨.     

Ultrathin compound semiconductor on insulator layers for high-performance nanoscale transistors

Over the past several years, the inherent scaling limitations of silicon (Si) electron devices have fuelled the exploration of alternative semiconductors, with high carrier mobility, to further enhance device performance. In particular, compound semiconductors heterogeneously integrated on Si substrates have been actively studied: such devices combine the high mobility of III-V semiconductors and the well established, low-cost processing of Si technology. This integration, however, presents significant challenges. Conventionally, heteroepitaxial growth of complex multilayers on Si has been explored-but besides complexity, high defect densities and junction leakage currents present limitations in this approach. Motivated by this challenge, here we use an epitaxial transfer method for the integration of ultrathin layers of single-crystal InAs on Si/SiO(2) substrates. As a parallel with silicon-on-insulator (SOI) technology, we use 'XOI' to represent our compound semiconductor-on-insulator platform. Through experiments and simulation, the electrical properties of InAs XOI transistors are explored, elucidating the critical role of quantum confinement in the transport properties of ultrathin XOI layers. Importantly, a high-quality InAs/dielectric interface is obtained by the use of a novel thermally grown interfacial InAsO(x) layer (~1?nm thick). The fabricated field-effect transistors exhibit a peak transconductance of ~1.6?mS?μm(-1) at a drain-source voltage of 0.5?V, with an on/off current ratio of greater than 10,000.     

Ultralow-power organic complementary circuits

The prospect of using low-temperature processable organic semiconductors to implement transistors, circuits, displays and sensors on arbitrary substrates, such as glass or plastics, offers enormous potential for a wide range of electronic products. Of particular interest are portable devices that can be powered by small batteries or by near-field radio-frequency coupling. The main problem with existing approaches is the large power consumption of conventional organic circuits, which makes battery-powered applications problematic, if not impossible. Here we demonstrate an organic circuit with very low power consumption that uses a self-assembled monolayer gate dielectric and two different air-stable molecular semiconductors (pentacene and hexadecafluorocopperphthalocyanine, F16CuPc). The monolayer dielectric is grown on patterned metal gates at room temperature and is optimized to provide a large gate capacitance and low gate leakage currents. By combining low-voltage p-channel and n-channel organic thin-film transistors in a complementary circuit design, the static currents are reduced to below 100 pA per logic gate. We have fabricated complementary inverters, NAND gates, and ring oscillators that operate with supply voltages between 1.5 and 3 V and have a static power consumption of less than 1 nW per logic gate. These organic circuits are thus well suited for battery-powered systems such as portable display devices and large-surface sensor networks as well as for radio-frequency identification tags with extended operating range.     

Single-crystal metallic nanowires and metal/semiconductor nanowire heterostructures

Substantial effort has been placed on developing semiconducting carbon nanotubes and nanowires as building blocks for electronic devices--such as field-effect transistors--that could replace conventional silicon transistors in hybrid electronics or lead to stand-alone nanosystems. Attaching electric contacts to individual devices is a first step towards integration, and this step has been addressed using lithographically defined metal electrodes. Yet, these metal contacts define a size scale that is much larger than the nanometre-scale building blocks, thus limiting many potential advantages. Here we report an integrated contact and interconnection solution that overcomes this size constraint through selective transformation of silicon nanowires into metallic nickel silicide (NiSi) nanowires. Electrical measurements show that the single crystal nickel silicide nanowires have ideal resistivities of about 10 microOmega cm and remarkably high failure-current densities, >10(8) A cm(-2). In addition, we demonstrate the fabrication of nickel silicide/silicon (NiSi/Si) nanowire heterostructures with atomically sharp metal-semiconductor interfaces. We produce field-effect transistors based on those heterostructures in which the source-drain contacts are defined by the metallic NiSi nanowire regions. Our approach is fully compatible with conventional planar silicon electronics and extendable to the 10-nm scale using a crossed-nanowire architecture.     

Self-interstitials generated on silicon bulk surface

Pentacene for p-channel organic field effect transistors(OTFTs) and perfluoropentacene for n-channel OTFTs have attracted strong attentions to be used as CMOS type organic semiconductor materials for flexible organic displays.n-channel OTFTs with different gate insulators of polyimide(PI) and SiO_2 and perfluoropentacene as a semiconductor layer were fabricated,and their instability of the transistor characteristics measured in air,vacuum and oxygen was investigated.The results show that both of the tran...