Toward clean and crackless polymer-assisted transfer of CVD-grown graphene and its recent advances in GFET-based biosensors

Ever since the more than decade-old discovery of the mechanical exfoliation method for graphene isolation, this miraculous 2-dimensional material is still widely used in various applications because of its exceptional electron mobility and thermal conductivity. Graphene, commonly grown on a metallic substrate using chemical vapor deposition (CVD), needs to be transferred onto dielectric substrates compatible with complementary metal oxide–semiconductor (CMOS) technology for various electronic and optical applications. However, the ultra-clean transfer of graphene with defect-free is still crucial for large-area graphene devices' efficiency. This review introduces a comprehensive and up-to-date account of the transfer of the most attention kinds of CVD-grown graphene on copper substrates. The advances and main challenges of both wet and dry transfer methods are also carefully described. Particular emphasis is also given on graphene-based BioFET devices, revising their sensing mechanism and the optimum operational conditions toward high specificity and sensitivity. The authors have been convinced that upgrading the transfer process to accomplish the cleanest graphene surface and exploiting the optimum operating conditions will undoubtedly be of considerable significance to fabricate graphene-based devices.     

Growth and characterization of ultrathin carbon films on electrodeposited Cu and Ni

Ultrathin carbon films were grown on different types of metallic substrates. Free‐standing foils of Cu and Ni were prepared by electroforming, and a pure Ni film was obtained by galvanic displacement on a Si wafer. Commercial foil of Ni 99.95% was used as a reference substrate. Carbon films were grown on these substrates by chemical vapour deposition in a CH₄‐H₂ atmosphere. Obtained films were characterized by Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy, and ultraviolet photoemission spectroscopy. The XPS at grazing collection angle was used to determine the thickness of carbon films. Depending on the deposition parameters, the films of graphene or graphite were obtained on the different substrates. The uniformity of graphene and its distribution over the sample area were investigated from Raman data, optical images, and XPS chemical maps. The presence of graphene or graphite in the films was determined from the Raman spectra and Auger peak of C KVV. For this purpose, the D parameter, which is a fingerprint of carbon allotropes, was determined from C KVV spectra acquired by using X‐rays and electron beam. A formation of an intermediate layer of metal hydroxide was revealed in the samples with graphene overlayer.     

Multilayer graphene/amorphous carbon hybrid films prepared by microwave surface‐wave plasma CVD: synthesis and characterization

Hybrid films of multilayer graphene (MG) containing amorphous carbon (a‐C) were synthesized on Al substrates by microwave surface‐wave plasma chemical vapor deposition. Raman scattering and surface transmission electron microscopy showed that the carbon films contained a large quantity of MG when a radio frequency (RF) substrate bias was not applied. Amorphization of graphene in the carbon film was promoted by applying an RF bias, which generated Ar⁺ in the plasma. The bandgaps of the films were found to increase as the Raman intensity ratios between the 2D‐band (at 2700 cm^?1) and D‐band (at 1350 cm^?1) decreased, indicating the formation of a‐C. The MG/a‐C all‐sp² phase of carbon hybrid films exhibited an increase in current density under 5 mW/cm² of AM1.5G solar simulated irradiation as the RF bias increased because of Ar⁺‐induced amorphization of the graphene. Copyright © 2016 John Wiley & Sons, Ltd.     

GaSb纳米线的CVD可控制备及其光学表征

采用CVD法合成GaSb纳米线,并分析生长时间对其长度的影响,随后对其进行光学表征.实验过程中,分别采用喷金法和滴金法对硅片进行预处理,再置于相同条件下制备GaSb纳米线;之后对其进行表征分析,根据扫描电子显微镜（SEM）表征结果证实,两种方法制备的纳米线都满足VLS生长机制.且发现GaSb纳米线的生长长度,可以通过改变其生长时间来进行控制.通过该纳米线的透射电子显微镜图（TEM）、X射线衍射图（XRD）等结构表征,表明该纳米线为结晶品质优良的立方闪锌矿结构;同时,从GaSb纳米线的拉曼光谱（Raman）及光致发光谱（PL）可以反映该纳米线具有优良的光学性质.由此证明,采用CVD法制得的纳米线光学性质优异,且可以实现可控制备.     

ZnO thin films prepared on titanium substrate by PLD technique at different substrate temperatures

ZnO thin films were grown by pulsed laser deposition on titanium substrates at different substrate temperatures ranging from 300 to 700 °C. X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS),photoluminescence, and Raman spectroscopy are employed to investigate the change of properties. XRD, XPS, and Raman data showed that the films consisted of TiO₂ at high substrate temperature, which will deteriorate the crystallization quality of ZnO films. The optimum temperature for the growth of ZnO films on the Ti substrate is about 500 °C in this paper. The ZnO films grown on titanium substrate can be used in direct current, microwave, and medical applications. Copyright © 2014 John Wiley & Sons, Ltd.     

基片温度对LiCoO2薄膜结构与电化学性能的影响

采用射频(RF)磁控溅射技术制备了用于全固态薄膜锂电池的非晶态和多晶LiCoO2阴极薄膜,利用XRD和SEM研究了沉积温度对LiCoO2薄膜结构和形貌的影响,并研究了高温退火后薄膜的电化学性能.研究结果表明,随著基片温度的不同,薄膜成分、表面形貌以及电化学行为有明显差异.室温沉积的薄膜很难消除薄膜中Li2CO3的影响,经过高温退火处理后也无法形成有效的多晶LiCoO2薄膜,而150℃沉积的薄膜经过高温退火后形成了有利于锂离子嵌入的多晶LiCoO2结构,薄膜显示出了较好的电化学性能.     

Effects of hydroxyl group on H2 dissociation on graphene: A density functional theory study

Graphene-based materials are promising for hydrogen production and storage. In this work, using density functional theory calculations, we explored how a hydroxyl group influences H₂ dissociation on graphene. Presence of the hydroxyl group makes the binding of H atom with graphene stronger, as the binding energy of H atom with the hydroxyl-modified graphene is higher than that with the pristine graphene. The para-site is the most favorable site for H₂ dissociation on both the pristine and hydroxyl-modified graphene. The energy barrier of H₂ dissociation at para-site on the pristine graphene is 3.10 eV whereas that on the hydroxyl-modified graphene is 2.46 eV, indicating a more facile H₂ dissociation on the hydroxyl-modified graphene.     

Plasma enhanced synthesis of N doped vertically aligned carbon nanofibers on 3D graphene

Graphene and carbon nanotubes/fibers (CNT/CNF) hybrid structures are emerging as frontier materials for high-efficiency electronics, energy storage, thermoelectric, and sensing applications owing to the utilization of extraordinary electrical and physical properties of both nanocarbon materials. Recent advances show a successful improvement in the structure and surface area of layered graphene by incorporating another dimension and structural form—three-dimensional graphene (3DG). In this study, vertically aligned CNFs were grown using plasma enhanced chemical vapor deposition on a relatively new form of compressed 3DG. The latter was synthesized using a conventional thermal chemical vapor deposition. The resulting free-standing hybrid material is in-situ N doped during synthesis by ammonia plasma and is produced in the form of a hybrid paper. Characterization of this material was done using electrochemical and spectroscopic measurements. The N doped hybrid showed relatively higher surface area and improved areal current density in electrochemical measurements than compressed pristine 3DG, which makes it a potential candidate for use as an electrode material for supercapacitors, sensors, and electrochemical batteries.     

Electrochemistry of graphene: new horizons for sensing and energy storage

Graphene is a new 2D nanomaterial with outstanding material, physical, chemical, and electrochemical properties. In this review, we first discuss the methods of preparing graphene sheets and their chemistry. Following that, the fundamental reasons governing the electrochemistry of graphene are meaningfully described. Graphene is an excellent electrode material with the advantages of conductivity and electrochemistry of sp² carbon but without the disadvantages related to carbon nanotubes, such as residual metallic impurities. We highlight important applications of graphene and graphene nanoplatelets for sensing, biosensing, and energy storage. © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 211–223; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900008     

Selective Growth of GaN on Slope Cone-shaped Patterned Sapphire Substrate

Cone-shaped patterned sapphire substrate was prepared by inductively coupled plasma etching and GaN nucleation layer was grown on it by metal-organic chemical vapor deposition.A selective growth of GaN nucleation layer was found on the slope of the cone-shaped patterned sapphire substrat,and the distribution morphology of GaN had significantly changed after it was recrystallized.GaN selective growth and redistribution were analyzed by investigating the distribution of crystallographic planes on the cone surface and the atom array of specific planes at atom level.     

Surface-enhanced Raman scattering of single- and few-layer graphene by the deposition of gold nanoparticles

Surface-enhanced Raman scattering (SERS) of graphene on a SiO(2)(300 nm)/Si substrate was investigated by depositing Au nanoparticles using thermal evaporation. This provided a maximum enhancement of 120 times for single-layer graphene at 633 nm excitation. SERS spectra and scan images of single-layer and few-layer graphene were acquired. Single-layer graphene provides much larger SERS enhancement compared to few-layer graphene, while in single-layer graphene the enhancement of the G band was larger than that of the 2D band. Furthermore, the D bands were identified in the SERS spectra; these bands were not observed in a normal Raman spectrum without Au deposition. Appearance of the D band is ascribed to the considerable SERS enhancement and not to an Au deposition-induced defect. Lastly, SERS enhancement of graphene on a transparent glass substrate was compared with that on the SiO(2)(300 nm)/Si substrate to exclude enhancement by multiple reflections between the Si substrate and deposited Au nanoparticles. The contribution of multiple reflections to total enhancement on the SiO(2)(300 nm)/Si substrate was 1.6 times out of average SERS enhancement factor, 71 times.     

Reduced graphene oxide/iron oxide hybrid composite material as an efficient magnetically separable heterogeneous catalyst for transfer hydrogenation of ketones

Reduced graphene oxide was synthesized and functionalized with FeSO₄⋅7H₂O to form a reduced graphene oxide/iron oxide hybrid composite. The hybrid composite was extensively characterized using various techniques. Its application for transfer hydrogenation of various ketones was studied. The investigation showed that it serves as a good catalyst for transfer hydrogenation of aromatic and some aliphatic ketones resulting in excellent isolated yields (97–99%) of products. It is magnetically separable showing good reusability. The products were characterized and compared with authentic ones.     

Effect of the conditions of transfer on the structure and optical properties of Langmuir graphene oxide films during deposition on a substrate

The effect the solvent and transfer pressure of graphene oxide (SLGO) Langmuir–Blodgett films on the physicochemical properties of monolayers, and on their structural and optical properties, is studied. Examination of the physicochemical properties of SLGO monolayers on subphase surfaces that are formed from SLGO dispersions in different organic solvents reveals that monolayer behavior is virtually independent of the solvent. Electron microscope and optical studies show that the monolayers formed from SLGO dispersions in DMF and acetone have the highest transfer coefficients. It is concluded that the structural heterogeneity of the surfaces of graphene oxide films results from simultaneous effect of electrostatic interactions between graphene oxide particles and Van der Waals interactions with the solvation shell of the particles. Studies focusing on the effect the pressure of transferring a graphene oxide monolayer onto the surface of a solid substrate has on structural features of LB films show that films produced at low surface pressures have more homogeneous structures.     

Effect of different types of substrate surface treatments on the graphene device performance

Graphene–substrate interface is very crucial for analyzing graphene device performance. In this article, we have shown how the graphene device performance got affected because of different types of substrate surface treatment techniques used before graphene transfer. For fabrication of graphene devices, monolayer chemical vapor deposition (CVD) graphene was transferred onto SiO₂ grown thermally on Si substrate. Forming gas annealed SiO₂/Si shows better device performance as compared with as-grown SiO₂ on Si substrate. A further effect of oxygen plasma and argon plasma cleaning of SiO₂ surface before graphene transfer was investigated. Forming gas annealing improves the performance and plasma treatment degrade the graphene devices' performance.     

Visible‐light‐driven self‐cleaning SERS substrate of silver nanoparticles and graphene oxide decorated nitrogen‐doped titania nanotube array

Graphene oxide (GO) and silver nanoparticles (Ag NPs) sequentially decorated nitrogen‐doped titania nanotube array (N‐TiO₂ NTA) had been designed as visible‐light‐driven self‐cleaning surface‐enhanced Raman scattering (SERS) substrate for a recyclable SERS detection application. N‐TiO₂ NTA was fabricated by anodic oxidation and then doping nitrogen treatment in ammonia atmosphere, acting as a visible‐light‐driven photocatalyst and supporting substrate. Ag/GO/N‐TiO₂ NTA was prepared by decorating GO monolayer through an impregnation process and then depositing Ag NPs through a polyol process on the surface of N‐TiO₂ NTA, acting as the collection of organic molecule and Raman enhancement. The SERS activity of Ag/GO/N‐TiO₂ NTA was evaluated using methyl blue as an organic probe molecule, revealing the analytical enhancement factor of 4.54 × 10⁴. Ag/GO/N‐TiO₂ NTA was applied as active SERS substrate to determine a low‐affinity organic pollutant of bisphenol A, revealing the detection limit of as low as 5 × 10^?7 m . Ag/GO/N‐TiO₂ NTA could also achieve self‐cleaning function for a recycling utilization through visible‐light‐driven photocatalytic degradation of the adsorbed organic molecules. Ag/GO/N‐TiO₂ NTA has been successfully reused for five times without an obvious decay in accuracy and sensitivity for organic molecule detection. The unique properties of this SERS substrate enable it to have a promising application for the sensitive and recyclable SERS detection of low‐affinity organic molecules. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of the Reaction Alkaline Environment on the Morphology and Spectroscopic Characterizations of ZnO‐Graphene Composite

ZnO‐graphene composite was synthesized by using graphene oxide (GO), zinc acetate (Zn(CH₃COO)₂⋅2H₂O), sodium hydroxide (NaOH) and ethylene glycol as precursors through a one‐pot hydrothermal process. The concentration of NaOH solution had an important effect on the morphology, defects and spectroscopic characterizations of the ZnO‐graphene composite. With the increase of concentration of NaOH solution, the morphology of the composite changed significantly. The morphological evolution was analyzed through SEM and TEM observations, and the Raman and PL spectral variations were discussed.     

Patterned growth of oriented 2D covalent organic framework thin films on single-layer graphene

Two-dimensional covalent organic frameworks (COFs) are polymer networks that organize molecular building blocks into porous, layered structures of interest for organic optoelectronic and energy storage devices. Current synthetic methods produce these materials as either insoluble, microcrystalline powders or as oriented thin films on various substrates, including single-layer graphene (SLG). Under these conditions, COF thin films form on both the graphene-coated and bare regions of the substrate, suggesting uncontrolled nucleation processes that occur either in solution or nonselectively on different surfaces. Here, we describe modified polymerization conditions that provide COF films selectively on SLG. This finding enables COF films to be grown on lithographically patterned SLG substrates, which provide insight into the uniformity of film growth across the substrate and factors relevant to their nucleation and growth. The ability to grow COF films selectively on lithographically patterned SLG will facilitate their integration into devices. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 378–384     

Solvent‐induced surface instability of thin metal films on a polymer substrate

The solvent‐provoked formation and evolution of thin film buckling‐delamination on a compliant substrate have been studied. The film surface is observed by an optical microscope showing a remarkable dynamic buckling‐delamination development and a subsequent stable branched‐straight state. It is revealed that the initiation, propagation, and the resulting patterns of film buckles are strongly dependent on the solvent type, film stress, interfacial adhesion, and film thickness. The buckling could be controlled further by a reasonable chemical solvent configuration and used to provide useful information for the pattern creation on polymer systems in diverse fields, such as micro/nanofabrication and optics.     

Non-functionalized oil palm waste-derived reduced graphene oxide for methylene blue removal: Isotherm,kinetics, thermodynamics,and mass transfer mechanism

The discharge of colored effluents from industries is one of the significant sources of water pollution. Therefore, there is a growing demand for efficient and low-cost treatment methods. An adsorption process with reduced graphene oxide (rGO) synthesized using a novel double carbonization and oxidation method from the natural precursor of oil palm empty fruit bunch (OPEFB) as adsorbent is a promising approach for addressing the problem. In this study, OPEFB biochar was mixed with ferrocene with a ratio of 5:1 (m/m) and oxidized under nitrogen flow at a temperature of 300 °C for 20 min, which resulted in 75.8 wt% of yield. The potential of the synthesized rGO as an effective adsorbent for dye removal from water and wastewater was explored using methylene blue (MB) as a model. Several factors were investigated, including adsorbent dosage, initial concentration, contact time, and pH, to obtain the optimum adsorption condition through batch studies. The physical and chemical characteristics of the rGO in terms of functional groups, surface morphology, elemental composition, and crystallinity phase were determined through characterization. The nonlinear isotherms were appropriated using several error functions to describe the adsorption isotherm with a maximum adsorption capacity of 50.07 mg/g. The kinetic study demonstrates that MB’s adsorption fits the PFO kinetic model and agrees with Bangham’s interpretation of pore diffusion. The adsorption mechanism was found to be physisorption on the multilayer heterogeneous surface of the rGO involving π-π interaction, hydrophobic association, and electrostatic interaction. The thermodynamics study showed that the process was spontaneous and exothermic. The mass transfer mechanism study shows that the adsorption is controlled by intraparticle diffusion and involves complex pathways. The study found that the novel non- functionalized rGO could remove cationic dyes from water and wastewater.