Spin coated graphene films as the transparent electrode in organic photovoltaic devices

Many research efforts have been devoted to the replacement of the traditional indium-tin-oxide (ITO) electrode in organic photovoltaics. Solution-based graphene has been identified as a potential replacement, since it has less than two percent absorption per layer, relative high carrier mobility, and it offers the possibility of deposition on large area and flexible substrates, compatible with roll to roll manufacturing methods. In this work, soluble reduced graphene films with high electrical conductivity and transparency were fabricated and incorporated in poly(3-hexylthiophene) [6,6]-phenyl-C₆₁-butyric acid methyl ester photovoltaic devices, as the transparent electrode. The graphene films were spin coated on glass from an aqueous dispersion of functionalized graphene, followed by a reduction process combining hydrazine vapor and annealing under argon, in order to reduce the sheet resistance. The photovoltaic devices obtained from the graphene films showed lower performance than the reference devices with ITO, due to the higher sheet resistance (2 kΩ/sq) and the poor hydrophilicity of the spin coated graphene films.     

Low temperature processing of hybrid nanoparticulate Indium Tin Oxide (ITO) polymer layers and application in large scale lighting devices

We report on transparent conductive indium tin oxide (In₂O₃:Sn; ITO) nanoparticle films processed at a low temperature of 130 °C for the application in lighting devices using spin coating and doctor blading techniques. Major emphasis is put on the beneficial application of the particular transparent electrode material for the fabrication of patterned large area electroluminescence lamps. In order to improve film properties like adhesion and conductivity, hybrid nanoparticle-polymer blends out of ITO particles and organic film-forming agent polyvinylpyrrolidone (PVP) and the organofunctional coupling agent 3-methacryloxypropyltrimethoxysilane (MPTS) have been developed. The layers were cured by UV-irradiation, which was also used for lateral structuring of the transparent, conductive electrode. Additional low-temperature heat treatment (T = 130 °C) in air and forming gas improved the electronic properties. While pure ITO nanoparticulate layers processed at 130 °C exhibited conductance of up to 3.1 Ω^− 1 cm^− 1, the nanocomposite coatings showed a conductance of up to 9.8 Ω^− 1 cm^− 1. Corresponding layers with a sheet resistance of 750 Ω/□ were applied in electroluminescent lamps.     

Femtosecond laser induced micropatterning of graphene film

Micropatterning of CVD synthesized large area graphene film is demonstrated with femtosecond laser cutting process. Homogenous microribbon or other patterned structure can be fabricated without using any resist or other material containing the graphene surface within a very short duration. Once the suitable laser beam doses are determined, sharp edge profile and clean etching are obtained. Scanning electron microscopic study shows that the patterned microribbon is having 5 μm width and mm in length. The width of the patterned microribbon can be controlled with control of laser energy and preprogramming of laser ablation process. Raman study at the edge of the microribbon shows increase in D peak and appearance of D + G mode, signifying edge defects. The defect can be explained from the breaking of sp² carbon hybridization with oxidation due to laser etching. The Raman study shows no amorphous carbon formation with laser cutting of the graphene film. The presented process shows a simple way to make patterned microribbon on large area graphene sheet which can be extremely necessary for microelectronics fabrication.     

Improving low pressure chemical vapor deposited zinc oxide contacts for thin film silicon solar cells by using rough glass substrates

Compared to zinc oxide grown (ZnO) on flat glass, rough etched glass substrates decrease the sheet resistance (R_sq) of zinc oxide layers grown on it. We explain this R_sq reduction from a higher thickness and an improved electron mobility for ZnO layers deposited on rough etched glass substrates. When using this etched glass substrate, we also obtain a large variety of surface texture by changing the thickness of the ZnO layer grown on it. This new combination of etched glass and ZnO layer shows improved light trapping potential compared to ZnO films grown on flat glass. With this new approach, Micromorph thin film silicon tandem solar cells with high total current densities (sum of the top and bottom cell current density) of up to 26.8 mA cm^− 2 were fabricated.     

Optimization of ZnO/Ag/ZnO multilayer electrodes obtained by Ion Beam Sputtering for optoelectronic devices

We investigated the electrical and optical properties of ZnO/Ag/ZnO multi-layer electrodes obtained by ion beam sputtering for flexible optoelectronic devices. This multi-layer structure has the advantage of adjusting the layer thickness to favor antireflection and the surface plasmon resonance of the metallic layer. Inserting a thin (Ag) metallic layer between two (ZnO) oxide layers decreases the sheet resistance while widening the optical transmittance window in the visible. We found that the optimal electrode is made up of a 10 nm thin Ag layer between two 35 nm and 20 nm thick ZnO layers, which resulted in a low sheet resistance (R_sq = 6 Ω/square), a high transmittance (T ≥ 80% in the visible) and the highest figure of merit of 1.65 × 10^-2 square/Ω.     

Electrostatic deposition of graphene

Loose graphene sheets, one to a few atomic layers thick, are often observed on freshly cleaved HOPG surfaces. A straightforward technique using electrostatic attraction is demonstrated to transfer these graphene sheets to a selected substrate. Sheets from one to 22?layers thick have been transferred by this method. One sheet after initial deposition is measured by atomic force microscopy to be only an atomic layer thick (～0.35?nm). A few weeks later, this height is seen to increase to ～0.8?nm. Raman spectroscopy of a single layer sheet shows the emergence of an intense D band which dramatically decreases as the number of layers in the sheet increase. The intense D band in monolayer graphene is attributed to the graphene conforming to the roughness of the substrate. The disruption of the C-C bonds within the single graphene layer could also contribute to this intense D band as evidenced by the emergence of a new band at 1620?cm(-1).     

The production of nitrogen-doped graphene from mixed amine plus ethanol flames

A simple process is described for directly synthesizing pure graphene and N-doped graphene sheets from ethanol flame and amine plus ethanol flames respectively. The microstructures and nitrogen contents of the graphenes were characterized using scanning and transmission electron spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. The results reveal that: (1) The graphene sheets from flame exhibit good transparency and a large size up to 400 μm² with few layers and folded edges; (2) The nitrogen-doped graphene sheets have a dominant ‘pyridine-type’ structure with CN bonds (one N atom bonded to two C atoms); (3) Compared with other methods, the graphene sheets from flame have more surface defects due to the environmental conditions and introduction of nitrogen atoms, which makes it a promising material for supercapacitors and catalyst supports.     

Highly Conductive and Transparent Large‐Area Bilayer Graphene Realized by MoCl5 Intercalation

Bilayer graphene (BLG) comprises a 2D nanospace sandwiched by two parallel graphene sheets that can be used to intercalate molecules or ions for attaining novel functionalities. However, intercalation is mostly demonstrated with small, exfoliated graphene flakes. This study demonstrates intercalation of molybdenum chloride (MoCl₅) into a large‐area, uniform BLG sheet, which is grown by chemical vapor deposition (CVD). This study reveals that the degree of MoCl₅ intercalation strongly depends on the stacking order of the graphene; twist‐stacked graphene shows a much higher degree of intercalation than AB‐stacked. Density functional theory calculations suggest that weak interlayer coupling in the twist‐stacked graphene contributes to the effective intercalation. By selectively synthesizing twist‐rich BLG films through control of the CVD conditions, low sheet resistance (83 Ω ?^?1) is realized after MoCl₅ intercalation, while maintaining high optical transmittance (≈95%). The low sheet resistance state is relatively stable in air for more than three months. Furthermore, the intercalated BLG film is applied to organic solar cells, realizing a high power conversion efficiency.     

Nitrogen-doped carbon nanotube arrays grown on graphene substrate

Nitrogen-doped carbon nanotube (N-doped CNT) arrays have been synthesized on graphene substrate by chemical vapor deposition process, in which iron nanoparticles (NPs) assembled on the graphene sheet were generated in situ from the reduction of Fe₃O₄ NPs/reduced graphene oxide (RGO) and were used as catalyst. The morphology and structure of the N-doped CNT arrays were investigated by field emission scanning electron microscope and high-resolution transmission electron microscope. The N-doped CNTs were bamboo-shaped and the density can be controlled by modulating the density of catalyst NPs on RGO sheets. The concentration and incorporation of nitrogen were studied by elemental analysis, X-ray photoelectron spectroscope and Raman analysis, and the results showed that the nitrogen content was around 3 wt.%. Because of the good conductivity of graphene structure, N-doped CNT arrays grown on graphene substrate may be promising candidates as noble metal-free electrodes for oxygen reduction reaction in the future.     

The role of transparent conducting oxides in metal organic chemical vapour deposition of CdTe/CdS Photovoltaic solar cells

A systematic study is made between the relationship of Cd_0.9Zn_0.1S/CdTe photovoltaic (PV) device properties for three different commercial transparent conducting oxide (TCO) materials and some experimental CdO to determine the role of the TCO in device performance. The resistance contribution from the TCO was measured after depositing the gold contact architectures directly onto the TCOs. These were compared with the Cd_0.9Zn_0.1S/CdTe device properties using the same contact arrangements. Series resistance for the commercial TCOs correlated with their sheet resistance and gave good agreement with the PV device series resistance for the indium tin oxide (ITO) and fluorine doped tin oxide (FTO) 15 Ω/Sq. superstrates. The devices on the thicker FTO 7 Ω/sq superstrates were dominated by a low shunt resistance, which was attributed to the rough surface morphology causing micro-shorts. The device layers on the CdO substrate delaminated but devices were successfully made for ultra-thin CdTe (0.8 μm thick) and compared favourably with the comparable device on ITO. From the measurements on these TCOs it was possible to deduce the back contact resistance and gave an average value of 2 Ω.cm². The correlation of fill factor with series resistance has been compared with the predictions of a 1-D device model and shows excellent agreement. For high efficiency devices the combined series resistance from the TCO and back contact need to be less than 1 Ω.cm².     

Determining the number of layers in graphene films synthesized by filtered cathodic vacuum arc technique

We have synthesized graphene film by the filtered cathodic vacuum arc (FCVA) technique and determined the number of layers in graphene films by various techniques. Amorphous carbon (a-C) films of different thicknesses (1, 2, 3, 6, 10 and 18 nm) were synthesized by the FCVA technique on Si/SiO₂/Ni substrate and then annealed in vacuum at 800°C and cooled down to room temperature naturally to obtain graphene. Prepared graphene films were transferred on different substrates and characterized by the Raman spectroscopy, UV-VIS-NIR spectroscopy, high-resolution transmission electron microscopy (HRTEM), optical microscopy, atomic force microscopy (AFM) and sheet resistance to determine the number of layers present in the graphene films. Raman spectra of the prepared graphene films exhibit that there is red shift in the position of D, G and 2 D peak. The value of I_2D/I_G varied from 0.18 to 0.51, I_D/I_G varied from 0.82 to 1.02 and full width at half maximum of 2 D peak varied from 101.2 to 128.0 cm^?1, for different thicknesses of graphene films, respectively. The value of transmittance decreases from 97 to 63.7% and that of sheet resistance increases from 460 to 1400 Ω/square with the increase in the thickness of the prepared graphene film. The HRTEM and AFM study revealed that the graphene synthesis from 1 nm thick a-C film possesses a single layer structure.     

Enhanced efficiency of tri-layered dye solar cells with hydrothermally synthesized titania nanotubes as light scattering outer layer

In the present study dye sensitized solar cells (DSSCs) have been fabricated with a tri-layer photo anode consisting of hydrothermally prepared titania nano tubes (TNT) having a diameter of 9-10 nm and length of several micrometers as outer layer, P25 TiO₂ powder as transparent light absorbing middle layer and a compact TiO₂ inner layer to improve the adhesion of different layers on a transparent conducting oxide coated substrate. In comparison to cells fabricated using TNTs or P25 alone, the tri-layer DSSCs exhibit an enhanced efficiency of 7.15% with a current density of 17.12 mA cm^− 2 under AM 1.5 illumination. The enhancement is attributed to the light scattering generated by TNTs aggregates, reduction in electron transport resistance at the TiO₂/dye/electrolyte interface and an improvement in electron life-time.     

Low-temperature synthesis of thin graphite sheets using plasma-assisted thermal chemical vapor deposition system

We report the low-temperature synthesis of thin graphite sheets using a hybrid chemical vapor deposition (HCVD) system that combines plasma and thermal CVD (TCVD). Electron beam deposited Ni films were used as catalytic substrates, and methane was used as a carbon feedstock. The quartz tube was into two regions: core plasma region for efficient dissociation of methane and a TCVD region for thermal synthesis, respectively. After the syntheses at different TCVD temperatures from 550 °C to 900 °C, as-grown films were transferred to transparent polymeric substrates to apply as flexible conductive electrodes. Finally, it was found that thin graphite sheets consisting of ~ 15 graphene layers were synthesized at 600 °C using the HCVD system and could be applicable as transparent conductive films.     

Synthesis and characterization of electrochemically-reduced graphene

Graphene has superior electrical conductivity than graphite and other allotropes of carbon because of its high surface area and chemical tolerance. Electrochemically processed graphene sheets were obtained through the reduction of graphene oxide from hydrazine hydrate. The prepared samples were heated to different temperatures such as 673 and 873 K. X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), transmission electron microscopy (TEM), Raman spectra and conductivity measurements were made for as-prepared and heat-treated graphene samples. XRD pattern of graphene shows a sharp and intensive peak centred at a diffraction angle (2θ) of 26·350. FTIR spectra of as-prepared and heated graphene were used to confirm the oxidation of graphite. TEM results indicated that the defect density and number of layers of graphene sheets were varied with heating temperature. The hexagonal sheet morphology and purity of as-prepared and heat treated samples were confirmed by SEM–EDX and Raman spectroscopy. The conductivity measurements revealed that the conductivity of graphene was decreased with an increase in heating temperature. The present study explains that graphene with enhanced functional properties can be achieved from the as-prepared sample.     

Microstructural and electrochemical properties of vertically aligned few layered graphene (FLG) nanoflakes and their application in methanol oxidation

Vertically aligned few layered graphene (FLG) nanoflakes were synthesised on silicon substrates by microwave plasma enhanced chemical vapour deposition (MPECVD) method. Transmission electron microscopy (TEM) shows that the structures have highly graphitized terminal planes of 1–3 layers of graphene. Raman spectroscopy revealed a narrow G band with a FWHM of ∼23 cm⁻¹ accompanied by a strong G′ (2D) band, with a FWHM of ∼43 cm⁻¹ and an I_G/I_G′ ratio of 1, which are all the characteristics of highly crystallized few layered graphene. The FLG electrodes demonstrate fast electron transfer (ET) kinetics for Fe(CN)₆^3−/4− redox system with an electron transfer rate, ΔE_p, of 60 mV. Platinum (Pt) nanoparticles of ∼6 nm diameter were deposited on as grown FLGs using magnetron DC sputtering for methanol oxidation studies. When used as electrodes for methanol oxidation, a mass specific peak current density of ∼62 mA mg⁻¹ cm⁻² of Pt is obtained with a high resistance to carbon monoxide (CO) poisoning as evident by a high value of 2.2 for the ratio of forward to backward anodic peak currents (I_f/I_b).     

Silicon metal-semiconductor-metal photodetector with zinc oxide transparent conducting electrodes

Transparent conducting oxides thin layers, due to their optical and electrical properties, can be used as transparent electrodes in various optoelectronic devices. We present a metal-semiconductor-metal photodiode (MSM-PD) on silicon as optically active layer with zinc oxide (ZnO) thin layer as interdigitated Schottky transparent electrodes. The advantage of using a ZnO thin layer as Schottky electrodes consists in the improvement of the photoresponse by eliminating the shadowing of the active area by opaque metallic electrodes. ZnO thin layers were deposited on 10 Ω cm resistivity silicon epitaxial wafers by the vacuum thermal evaporation method. High purity metallic powders were mixed with an (Al + Sn)/Zn ratio of 0.03. In order to obtain transparent layers the metallic depositions were thermally treated at 450 °C for 2 h. The Al, Sn co-doped ZnO layers of 0.5-0.8 μm were investigated regarding structural, optical and electrical properties and surface morphology. The obtained thin layers have a high transparency (T > 85%) over a large spectral range and the resistivity is quite low, ρ ~ 10^− 4 Ω cm. The interdigitated Schottky contacts of ZnO were configurated onto the optically active Si layer providing an MSM-PD structure of 0.143 mm² active area and finger spacing and finger width of 6 μm. The optoelectronic characteristics were measured and the Schottky barrier height of 0.62 eV was determined from the current-voltage characteristic. A responsivity of 0.2 A/W at 475 nm and a capacitance of 1.4 pF at 10 V bias were obtained for the MSM-PD structure with transparent conducting ZnO Schottky electrodes.     

Synthesis of graphene on SiC substrate via Ni-silicidation reactions

In this work, the features of graphene layers are studied with the aim of preparing the thinnest layers possible. The graphene layers were prepared by the annealing of Ni/SiC structures. The main advantage of this process is a relatively low temperature compared with the method of graphene epitaxial growth on SiC and short annealing times compared with the chemical vapor deposition method. We prepared graphene layers from several Ni/SiC structures in which the Ni layer thickness ranged from 1 to 200 nm. The parameters of the annealing process (temperature, rate of temperature increase, annealing time) were modified during the experiments. The formed graphene layers were analyzed by means of Raman spectroscopy. From the spectra, the basic parameters of graphene, such as the number of carbon layers and crystallinity, were determined. The annealing of the Ni(200 nm)/SiC structure at 1080 °C for 10 s, produced graphene in the form of 3-4 carbon monolayers. The value was verified by X-ray Photoelectron Spectroscopy (XPS). Good agreement was achieved in the results obtained using Raman spectroscopy and XPS.     

ZnO/Cu/ZnO multilayer films: Structure optimization and investigation on photoelectric properties

A series of ZnO/Cu/ZnO multilayer films has been fabricated from zinc and copper metallic targets by simultaneous RF and DC magnetron sputtering. Numerical simulation of the optical properties of the multilayer films has been carried out in order to guide the experimental work. The influences of the ZnO and Cu layer thicknesses, and of O₂/Ar ratio on the photoelectric and structural properties of the films were investigated. The optical and electrical properties of the multilayers were studied by optical spectrometry and four point probe measurements, respectively. The structural properties were investigated using X-ray diffraction. The performance of the multilayers as transparent conducting coatings was compared using a figure of merit. In experiments, the thickness of the ZnO layers was varied between 4 and 70 nm and those of Cu were between 8 and 37 nm. The O₂/Ar ratios range from 1:5 to 2:1. Low sheet resistance and high transmittance were obtained when the film was prepared using an O₂/Ar ratio of 1:4 and a thickness of ZnO (60 nm)/Cu (15 nm)/ZnO (60 nm).     

In situ synthesis of graphene/cobalt nanocomposites and their magnetic properties

Graphene, which possesses unique nanostructure and excellent properties, is considered as a low cost alternative to carbon nanotubes in nanocomposites. In this study, we present a simple in situ approach for the deposition of cobalt (Co) nanoparticles onto surfaces of graphene sheets by hydrazine hydrate reduction. The as-synthesized composites were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, transmission electron microscopy (TEM) and thermogravimetry and differential scanning calorimetry. It was shown that the as-formed Co nanoparticles were densely and homogeneously deposited on the surfaces of the graphene sheets and as a result, the restacking of the as-reduced graphene sheets was effectively inhibited. Magnetic studies reveal that the graphene/Co nanocomposite displays ferromagnetic behavior with saturation magnetizations of 53.4 emu g⁻¹, remanent magnetization of 6.0 emu g⁻¹ and coercivity of 226 Oe at room temperature, which make it promising for practical applications in future nanotechnology.