Facile patterning of reduced graphene oxide film into microelectrode array for highly sensitive sensing

In this study, we develop a new technique to fabricate a reduced graphene oxide (rGO)-based microelectrode array (MEA) with low-cost soft lithography. To prepare patterned rGO, a polydimethylsiloxane (PDMS) mold with an array of microwells on its surface is fabricated using soft lithography, and GO is assembled on an indium tin oxide (ITO) electrode with a layer-by-layer method. The rGO pattern is formed by closely contacting the assembled GO film onto the ITO electrode with the PDMS mold filled with hydrazine solution in the microwells to selectively reduce the localized GO into the rGO. The MEA with patterned rGO as the microelectrode is characterized with Kelvin probe force microscopy (KFM), atomic force microscopy (AFM), and cyclic voltammetry (CV) with ferricyanide in aqueous solution as the redox probe. The KFM and AFM results demonstrate that each rGO pattern prepared under the present conditions is 3 μm in diameter, which is close to that of the PDMS mold we use. The CV results show that the rGO patterned onto the ITO exhibits a sigmoid-shaped voltammogram up to 200 mVs(-1) with a microampere level current response, suggesting that the rGO-based electrode fabricated with soft lithography behalves like a MEA. To demonstrate the potential electroanalytical application of the rGO-based MEA, prussian blue (PB) is electrodeposited onto the rGO-based MEA to form the PB/rGO-based MEA. Electrochemical studies on the formed PB/rGO-based MEA reveal that MEA shows a lower detection limit and a larger current density for the detection of H(2)O(2), as compared with the macroscopic rGO electrode. The method demonstrated here provides a simple and low-cost strategy for the fabrication of graphene-based MEA that are useful for electroanalytical applications.     

外电场下氧化石墨烯薄膜的微观摩擦行为

氧化石墨烯是一种准二维片层结构炭材料,具有独特的物理化学性能,其中摩擦性能的好坏对其构成的一些微／纳机电体系的稳定应用起着重要作用。为了研究外加电场作用对氧化石墨烯薄膜微观摩擦行为的影响,采用原子力显微镜,对针尖施加一定电压,测量其与氧化石墨烯薄膜表面的微观摩擦力大小,实验结果表明,针尖外加负电压时摩擦力不受影响,而正电压下摩擦力会明显上升,且随外加正电压值的增加而增大。同时结合针尖在外加电压时与氧化石墨烯薄膜表面的粘附力和静电力的测量,对外加电压的影响机制进行了探讨。     

Crystallization,mechanical performance and hydrolytic degradation of poly(butylene succinate)/graphene oxide nanocomposites obtained via in situ polymerization

Poly(butylene succinate) (PBS)/graphene oxide (GO) nanocomposites were fabricated via in situ polymerization with very low GO content (from 0.03 to 0.5 wt%). The microstructures of the nanocomposites were characterized with Raman spectroscopy, fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), sedimentation experiments and atomic force microscopy (AFM). The results showed that PBS chains have been successfully grafted onto GO sheets during in-situ polymerization, accompanied by the thermo-reduction from GO to graphene. The grafted GO displayed a great nucleating effect on PBS crystallization, resulting in largely improved crystallization temperature and decreased spherules size. A simultaneous enhancement in tensile strength and elongation was achieved for PBS/GO nanocomposites fiber. Meanwhile, increase in hydrolytic degradation rate was also observed for these nanohybrids. Our result indicates that using very low content GO is a simple way to achieve good dispersion yet with remarkable property enhancement for polymer/GO nanocomposites.     

Hybrids of carbon nanotubes and graphene/graphene oxide

This paper reviews recent progress in hybrids based on carbon nanotubes (CNTs) and graphene (G) or graphene oxide (GO). The combination of CNTs, including single-walled (SW), double-walled (DW) and multi-walled (MW), and G or GO resulted in various hybrids. CNTs–G/GO hybrid thin films are usually prepared by using solution/suspension casting and layer-by-layer (LbL) deposition, free-standing sheets are fabricated by using vacuum filtration and 3D hierarchical structures are produced by using chemical vapor deposition (CVD). CNTs–G/GO hybrids have also been used as fillers to fabricate polymer composites with synergistic effects. The composites have significantly improved electrical, mechanical and thermal properties, which make them very useful for various potential applications, such as transparent electrodes replacing ITO, electrodes for supercapacitors, lithium-ion batteries and dye-sensitized solar cells.     

Synthesis of mono layer graphene oxide from sonicated graphite flakes and their Hall effect measurements

Graphene, a single atom thick sheet is considered a key candidate for the future nanotechnology, due to its unique extraordinary properties. Researchers are trying to synthesize bulk graphene via chemical route from graphene oxide precursor. In the present work, we investigated a safe and efficient way of monolayer graphene oxide synthesis. To get a high degree of oxidation, we sonicated the graphite flakes before oxidation. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) results confirmed graphene oxide formation and high degree of oxidation. Raman spectroscopy and atomic force microscopy (AFM) results revealed a monolayer of graphene oxide (GO) flakes. The sheet like morphology of the GO flakes was further confirmed by scanning electron microscopy (SEM). The Hall effect measurements were performed on the GO film on a silica substrate to investigate its electrical properties. The results obtained, revealed that the GO film is perfectly insulating, having electrical resistivity up to 8.4 × 10⁸ (Ω·cm) at room temperature.     

Synthesis of graphene soluble in organic solvents by simultaneous ether-functionalization with octadecane groups and reduction

Octadecane-functionalized graphene (OD-G) soluble in organic solvents was produced by combining the Hummers process for graphite oxidation and a simultaneous ether-functionalization and reduction approach with 1-bromooctadecane in pyridine and dimethylformamide (DMF). The exfoliated OD-Gs were testified to be monolayer sheets by transmission electron microscope (TEM) and atomic force microscopy (AFM). The functionalization with octadecane (OD) groups and the effective deoxygenation of graphene oxide (GO) were confirmed by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). It is proved that the effective reduction and functionalization of GO could be simultaneously completed during the refluxing process. The functionalization with OD groups can effectively prevent the aggregation of GO during the reduction.     

10 micrometer-scale SPM local oxidation lithography

10 micrometer-scale scanning probe microscopy (SPM) local oxidation lithography was performed on Si. In order to realize large-scale oxidation, an SPM tip with a contact length of 15 microm was prepared by focused-ion-beam (FIB) etching. The oxidation was carried out in contact mode operation with the contact force ranging from 0.1 to 2.1 microN. The applied bias voltage was 50 V, and scanning speed was varied from 10 to 200 microm/s. The scan length was 15 microm for one cycle. The influence of contact force on the large-scale oxidation was investigated. At high contact force, the Si oxide with good size uniformity was obtained even with high scanning speed. The SPM tip with larger contact length may increase the spatial dimensions of the water meniscus between the SPM tip and sample surface, resulting in the larger dimensions of the fabricated oxide. Furthermore, the throughput of large-scale oxidation reached about 10(3) microm2/s by controlling the scanning speed and contact force of the SPM tip. It is suggested that SPM local oxidation can be upscaled by using a SPM tip with large contact length.     

One-step electrochemical synthesis of PtNi nanoparticle-graphene nanocomposites for nonenzymatic amperometric glucose detection

We report a facile one-step ultrasonication-assisted electrochemical method to synthesize nanocomposites of graphene and PtNi alloy nanoparticles (NPs) and their uses for highly selective nonenzymatic glucose detection. We have demonstrated that the obtained nanocomposites exhibit a collection of unique features including well-dispersed NPs with alloy features, high NP loading, and effective reduction of graphene oxide (GO). And the resulting nanoelectrocatalyst shows significantly improved electrochemical performance in nonenzymatic amperometric glucose detection, compared to a number of control electrode materials including the PtNi NP-chemically reduced GO nanocomposites fabricated in two steps (chemical reduction of GO followed by the electrodeposition of metal NPs). Under the physiological condition, the response current of the sensor is linear to glucose concentration up to 35 mM with a sensitivity of 20.42 μA cm(-2) mM(-1) at a substantially negative potential (i.e., -0.35 V). Operation under this potential eliminates the impact from the oxidation of common interfering species. This sensor with excellent sensitivity and selectivity also allows for reproducible detection of glucose in human urine samples.     

All graphene-based thin film transistors on flexible plastic substrates

High-performance, flexible all graphene-based thin film transistor (TFT) was fabricated on plastic substrates using a graphene active layer, graphene oxide (GO) dielectrics, and graphene electrodes. The GO dielectrics exhibit a dielectric constant (3.1 at 77 K), low leakage current (17 mA/cm(2)), breakdown bias (1.5 × 10(6) V/cm), and good mechanical flexibility. Graphene-based TFTs showed a hole and electron mobility of 300 and 250 cm(2)/(V·s), respectively, at a drain bias of -0.1 V. Moreover, graphene TFTs on the plastic substrates exhibited remarkably good mechanical flexibility and optical transmittance. This method explores a significant step for the application of graphene toward flexible and stretchable electronics.     

Nanopattern fabrication by tip plowing technology on 55 nm grating with stitching image method

An appropriate calibration positioning method is imperative to examine localized tip on nanoscale patterns for scanning probe microscopy (SPM). This paper is to develop a new nanofabrication processes for AFM tip positioning with image stitching method in tip plowing technology. Moreover, this paper adjusts the set-point amplitude (A(sp)) to develop the tip plowing technology for fabricating nanopattern on 55 nm grating gage of a silicon substrate. The developed image stitching program is based on an iterative closet point (ICP) algorithm which has six degrees of freedom alignment. A closed-loop piezo motor is used to tip approach and plow in Z-axis. Experimental result of fabricating nanobagua on 55 nm grating of silicon substrate show that the developed positioning processes with image stitching method verify the feasibility of repeatability for the tip plowing technology successfully. This developed method can be further performed by a commercial atomic force microscope (AFM) with CAD/CAM. This technology can also be applied in dip pen nanolithography (DPN), SPM oxidation lithography and related fabrication technology with AFM tips.     

氧化石墨烯/聚氨酯杂化膜的原位聚合构建及气体渗透性

采用Hummers法制备了3种不同氧化程度的氧化石墨烯(GO),通过聚氨酯(PU)单体(4,4’-二异氰酸苯酯(MDI)和1,4-丁二醇(BDO))与GO的原位聚合构建了GO/PU杂化膜。利用XRD、Raman、FTIR和TEM等表征了GO的结构;探讨了GO填充量对GO/PU杂化膜的形貌和CO2、N2渗透性的影响。结果表明:3种不同氧化程度的GO均呈完全剥离状态,为半透明片状结构;随着氧化程度的增加,拉曼D峰与G峰的相对强度比分别为0.947、1.103和1.245;GO的氧化程度对GO在溶剂和杂化膜中的分散性有较大影响,氧化程度越高,分散性越好。GO/PU杂化膜的CO2、N2渗透系数及CO2/N2渗透选择因子均随GO填充量的增加先增大后减小;当中等氧化程度的GO(M-GO)与(MDI+BDO)的质量比为1.0%时,M-GO/PU杂化膜的CO2渗透系数为63.6×10-13 cm3(STP)/(cm·Pa·s),其中STP表示标准温度及压力,CO2/N2渗透选择因子可达48.5;填充适量的GO能显著提高GO/PU杂化膜的CO2渗透性及CO2/N2渗透选择性。     

Fabrication of Ni nanostructures on p-Si by scanning probe lithography on Si3N4 films and selective electrodeposition

Ni-Si nano Schottky junctions are fabricated by the combined process of scanning probe lithography and electrodeposition. The Si3N4 film was patterned by probe-induced oxidation and became a mask for selective electrodeposition of Ni on p-Si substrate. The Ni pattern consists of Ni nano dots, whose diameter is less then 60 nm. The composition and ferromagnetism of Ni dots are verified by energy dispersive spectrum and magnetic force microscopy. The schottky barrier of Ni-Si nano contact is 0.52 V determined by the I-V measurement of conducting atomic force microscopy (CAFM). From current mapping images, it shows that chemical impurity at the Ni-Si interfaces can result in the poor conductance of the junctions.     

用SPM纳米刻蚀方法在Ti表面制备纳米结构的研究

本文用导电原子力显微镜 (AFM)针尖诱导局域氧化反应的方法 ,在Ti膜表面制备了TiO2 纳米结构。实验结果表明 ,Ti膜的氧化阈值为 - 7伏 ,制备的TiO2 纳米线的最小线宽达到 10nm ,TiO2 纳米线的高度和宽度随针尖偏压的增大而增大。在优化的氧化刻蚀条件下 ,通过控制针尖偏压和扫描方式制备出了图形化的TiO2 结构 ,本研究表明基于导电AFM的纳米刻蚀技术将成为构筑纳米电子器件的重要工具     

Fabrication of uniform and high resolution copper nanowire using intermediate self-assembled monolayers through direct AFM lithography

Electrochemical AFM lithography was used to directly fabricate copper nanowires. The copper ions were strongly reduced by a negative sample bias at the point where the AFM tip was localized, and copper metal wires were successfully fabricated following the direction of the electrical field of the bias. A TDA?HCl self-assembled monolayer (SAM) was found to play an important role as an intermediate layer for enhancing the capability of high resolution and complete development after the AFM lithographic process. The physical and electrical properties of the wires were analyzed by AFM, EFM, SEM, TEM and I-V measurement. The fabricated copper has promising potential for applications such as masks and interconnectors for nanoelectronic devices.     

Layer-by-layer thinning of graphene by plasma irradiation and post-annealing

A simple and efficient method of thinning graphene with an accuracy of a single layer is proposed, which includes mild nitrogen plasma irradiation and annealing in Ar/O2. On the basis of our data, plasma irradiation induces damages in the top-layer graphene and the annealing removes the damaged layer by fast oxidation. The process was used to turn bilayer graphene into monolayer as well as thin multilayer graphene layer-by-layer via repeated utilization. Combined with electron beam lithography, patterns were fabricated by selectively removing graphene planes. The thinned graphene possesses good quality verified by atomic force microscopic investigation and Raman analysis. The process presented here offers a very useful post-synthesis manipulation of graphene thickness, which may find important applications for graphene-based device fabrication.     

A single electron transistor on an atomic force microscope probe

We report fabrication as well as proof-of-concept experiments of a noninvasive sensor of weak nanoscale electric fields. The sensor is a single electron transistor (SET) placed at the tip of a noncontact atomic force microscope (AFM). This is a general technology to make any nanometer-sized lithography pattern at edges or tips of a cantilever. The height control of the AFM allows the SET to hover a few nanometers above the substrate, improving both the electric field sensitivity and lateral resolution of the electrometer. Our AFM-SET sensor is prepared by a scalable technology. It means that the probe can be routinely fabricated and replaced, if broken.     

Combined AFM nano-machining and reactive ion etching to fabricate high aspect ratio structures

In this paper, a new combined method of sub-micron high aspect ratio structure fabrication is developed which can be used for production of nano imprint template. The process includes atomic force microscope (AFM) scratch nano-machining and reactive ion etching (RIE) fabrication. First, 40 nm aluminum film was deposited on the silicon substrate by magnetron sputtering, and then sub-micron grooves were fabricated on the aluminum film by nano scratch using AFM diamond tip. As aluminum film is a good mask for etching silicon, high aspect ratio structures were finally fabricated by RIE process. The fabricated structures were studied by SEM, which shows that the grooves are about 400 nm in width and 5 microm in depth. To obtain sub-micron scale groove structures on the aluminum film, experiments of nanomachining on aluminum films under various machining conditions were conducted. The depths of the grooves fabricated using different scratch loads were also studied by the AFM. The result shows that the material properties of the film/substrate are elastic-plastic following nearly a bilinear law with isotropic strain hardening. Combined AFM nanomachining and RIE process provides a relative lower cost nano fabrication technique than traditional e-beam lithography, and it has a good prospect in nano imprint template fabrication.     

Formation of Air Stable Graphene p–n–p Junctions Using an Amine‐Containing Polymer Coating

An ultrathin layer of a polymer containing simple aliphatic amine groups, polyethylenimine ethoxylated (PEIE), is deposited on a back‐gated field effect graphene device to form graphene p–n–p junctions. Characteristic I–V curves indicate the superposition of two separate Dirac points, which confirms an energy separation of neutrality points within the complementary regions. This is a simple approach for making graphene p–n–p junctions without a need for multiple lithography steps or electrostatic gates and, unlike, the destructive techniques such as substitutional doping or covalent functionalization, it induces a minor defect, if any, as there is no discernible D peak in the Raman spectra of the graphene films after creating junctions and degradation in the charge carrier mobilities of the graphene devices. This method can be easily processed from dilute solutions in environmentally‐friendly solvents such as water or methoxyethanol and does not suffer any change upon exposure to air or heating at temperatures below 100 °C.     

磺化石墨烯及其导电炭薄膜的制备与性能

以石墨为原料, 采用Hummers法液相氧化合成了氧化石墨(GO), 通过低温真空剥离预还原、磺化反应、葡萄糖二次还原, 合成了高质量的磺化石墨烯(S-GNS), 有效避免了在此过程中石墨烯大量团聚的现象. 采用傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)、热重分析仪(TG)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和原子力显微镜(AFM)等分析手段对磺化石墨烯样品进行了表征. 实验结果表明: 对氨基苯磺酸成功地接枝到了石墨烯上, 磺化石墨烯还原彻底, 热稳定性能高; 石墨烯表面平整, 缺陷少; 单层磺化石墨烯厚度约为1.2 nm. 水溶性、分散性实验结果表明: 磺化石墨烯拥有高水溶性和高分散性. BET比表面积及电性能测试表明: 磺化石墨烯的比表面积高达806.4 m²/g, 薄膜材料的导电率为1150 S/m.     

Charge storage in mesoscopic graphitic islands fabricated using AFM bias lithography

Electrochemical oxidation and etching of highly oriented pyrolytic graphite (HOPG) has been achieved using biased atomic force microscopy (AFM) lithography, allowing patterns of varying complexity to be written into the top layers of HOPG. The graphitic oxidation process and the trench geometry after writing were monitored using intermittent contact mode AFM. Electrostatic force microscopy reveals that the isolated mesoscopic islands formed during the AFM lithography process become positively charged, suggesting that they are laterally isolated from the surrounding HOPG substrate. The electrical transport studies of these laterally isolated finite-layer graphitic islands enable detailed characterization of electrical conduction along the c-direction and reveal an unexpected stability of the charged state. Utilizing conducting-atomic force microscopy, the measured I(V) characteristics revealed significant non-linearities. Micro-Raman studies confirm the presence of oxy functional groups formed during the lithography process.