In recent years, photovoltaic cell technology has grown extraordinarily as a sustainable source of energy, as a consequence of the increasing concern over the impact of fossil fuel-based energy on global warming and climate change. The different photovoltaic cells developed up to date can be classified into four main categories called generations (GEN), and the current market is mainly covered by the first two GEN. The 1GEN (mono or polycrystalline silicon cells and gallium arsenide) comprises well-known medium/low cost technologies that lead to moderate yields. The 2GEN (thin-film technologies) includes devices that have lower efficiency albeit are cheaper to manufacture. The 3GEN presents the use of novel materials, as well as a great variability of designs, and comprises expensive but very efficient cells. The 4GEN, also known as “inorganics-in-organics”, combines the low cost/flexibility of polymer thin films with the stability of novel inorganic nanostructures (i.e., metal nanoparticles and metal oxides) with organic-based nanomaterials (i.e., carbon nanotubes, graphene and its derivatives), and are currently under investigation. The main goal of this review is to show the current state of art on photovoltaic cell technology in terms of the materials used for the manufacture, efficiency and production costs. A comprehensive comparative analysis of the four generations is performed, including the device architectures, their advantages and limitations. Special emphasis is placed on the 4GEN, where the diverse roles of the organic and nano-components are discussed. Finally, conclusions and future perspectives are summarized.

Graphene (G) and its derivatives, graphene oxide (GO) and reduced graphene oxide (rGO) have enormous potential for energy applications owing to their 2D structure, large specific surface area, high electrical and thermal conductivity, optical transparency, and huge mechanical strength combined with inherent flexibility. The combination of G-based materials with polymers leads to new nanocomposites with enhanced structural and functional properties due to synergistic effects. This review briefly summarizes recent progress in the development of G/polymer nanocomposites for use in polymer solar cells (PSCs). These nanocomposites have been explored as transparent conducting electrodes (TCEs), active layers (ALs) and interfacial layers (IFLs) of PSCs. Photovoltaic parameters, such as the open-circuit voltage (Voc), short-circuit current density (Jsc), fill factor (FF) and power-conversion efficiency (PCE) are compared for different device structures. Finally, future perspectives are discussed.

Graphene oxide (GO), the oxidized form of graphene, shows unique properties including high mechanical strength, optical transparency, amphiphilicity and surface functionalization capability that make it attractive in fields ranging from medicine to optoelectronic devices and solar cells. However, its insolubility in non-polar and polar aprotic solvents hinders some applications. To solve this issue, novel functionalization strategies are pursued. In this regard, this study deals with the preparation and characterization of hexamethylene diisocyanate (HDI)-functionalized GO. Different reaction conditions were tested to optimize the functionalization degree (FD), and detailed characterizations were conducted via elemental analysis, Fourier-transformed infrared (FT-IR) and Raman spectroscopies to confirm the success of the functionalization reaction. The morphology of HDI-GO was investigated by transmission electron microscopy (TEM), which revealed an increase in the flake thickness with increasing FD. The HDI-GO showed a more hydrophobic nature than pristine GO and could be suspended in polar aprotic solvents such as N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO) as well as in low polar/non-polar solvents like tetrahydrofuran (THF), chloroform and toluene; further, the dispersibility improved upon increasing FD. Thermogravimetric analysis (TGA) confirmed that the covalent attachment of HDI greatly improves the thermal stability of GO, ascribed to the crosslinking between adjacent sheets, which is interesting for long-term electronics and electrothermal device applications. The HDI-GO samples can further react with organic molecules or polymers via the remaining oxygen groups, hence are ideal candidates as nanofillers for high-performance GO-based polymer nanocomposites.

Graphene oxide (GO) has emerged as an ideal filler to reinforce polymeric matrices owing to its large specific surface area, transparency, flexibility, and very high mechanical strength. Nonetheless, functionalization is required to improve its solubility in common solvents and expand its practical uses. In this work, hexamethylene diisocyanate (HDI)-functionalized GO (HDI-GO) has been used as filler of a conductive polymer matrix, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The nanocomposites have been prepared via a simple solution casting method, and have been characterized by scanning electron microscopy (SEM), UV–Vis and Raman spectroscopies, X-ray diffraction (XRD), thermogravimetric analysis (TGA), tensile tests, and four-point probe measurements to get information about how the HDI-GO functionalization degree (FD) and the HDI-GO concentration in the nanocomposite influence the final properties. SEM analysis showed a very homogenous dispersion of the HDI-GO nanosheets with the highest FD within the matrix, and the Raman spectra revealed the existence of very strong HDI-GO-PEDOT:PSS interactions. A gradual improvement in thermal stability was found with increasing HDI-GO concentration, with only a small loss in transparency. A reduction in the sheet resistance of PEDOT:PSS was found at low HDI-GO contents, whilst increasing moderately at the highest loading tested. The nanocomposites showed a good combination of stiffness, strength, ductility, and toughness. The optimum balance of properties was attained for samples incorporating 2 and 5 wt % HDI-GO with the highest FD. These solution-processed nanocomposites show considerably improved performance compared to conventional PEDOT:PSS nanocomposites filled with raw GO, and are highly suitable for applications in various fields, including flexible electronics, thermoelectric devices, and solar energy applications.

The incorporation of carbon-based nanostructures into polymer matrices is a relevant strategy for producing novel antimicrobial materials. By using nanofillers of different shapes and sizes, and polymers with different characteristics, novel antimicrobial nanocomposites with synergistic properties can be obtained. This article describes the state of art in the field of antimicrobial polymeric nanocomposites reinforced with graphene and its derivatives such as graphene oxide and reduced graphene oxide. Taking into account the vast number of articles published, only some representative examples are provided. A classification of the different nanocomposites is carried out, dividing them into acrylic and methacrylic matrices, biodegradable synthetic polymers and natural polymers. The mechanisms of antimicrobial activity of graphene and its derivatives are also reviewed. Finally, some applications of these antimicrobial nanocomposites are discussed. We aim to enhance understanding in the field and promote further work on the development of polymer-based antimicrobial nanocomposites incorporating graphene-based nanomaterials.

Graphene oxide (GO), the oxidized form of graphene, shows unique properties, such as strong mechanical strength, high thermal conductivity, amphiphilicity, and surface functionalization capability that make it very attractive in various fields, ranging from medicine to optoelectronic devices and solar cells. However, its insolubility in non-polar and polar aprotic solvents hinders some applications. To solve this issue, novel functionalization strategies are pursued. In this regard, the current study deals with the preparation and characterization of hexamethylene diisocyanate (HDI)-functionalized GO. Different reaction conditions were tested to optimize the functionalization degree (FD), and detailed characterization was conducted via Fourier-transformed infrared (FT-IR) spectroscopy to confirm the success of the functionalization reaction. The HDI-GO could further react with other organic molecules or polymers via the remaining oxygen groups, which makes them ideal candidates as nanofillers for high-performance GO-based polymer nanocomposites.

A polypyrrole-carboxylic acid derivative (PPy-COOH) was covalently anchored on the surface of hexamethylene diisocyanate (HDI)-modified graphene oxide (GO) following two different esterification approaches: activation of the carboxylic acids of the polymer by carbodiimide, and conversion of the carboxylic groups to acyl chloride. Microscopic observations revealed a decrease in HDI-GO layer thickness for the sample prepared via the first strategy, and the heterogeneous nature of the grafted samples. Infrared and Raman spectroscopies corroborated the grafting success, demonstrating the emergence of a peak associated with the ester group. The yield of the grafting reactions (31% and 42%) was roughly calculated from thermogravimetric analysis, and it was higher for the sample synthesized via formation of the acyl chloride-functionalized PPy. The grafted samples showed higher thermal stability (~30 and 40 °C in the second decomposition stage) and sheet resistance than PPy-COOH. They also exhibited superior stiffness and strength both at 25 and 100 °C, and the reinforcing efficiency was approximately maintained at high temperatures. Improved mechanical performance was attained for the sample with higher grafting yield. The developed method is a valuable approach to covalently attach conductive polymers onto graphenic nanomaterials for application in flexible electronics, fuel cells, solar cells, and supercapacitors.

Conducting polymers like polyaniline (PANI) have gained a lot of interest due to their outstanding electrical and optoelectronic properties combined with their low cost and easy synthesis. To further exploit the performance of PANI, carbon-based nanomaterials like graphene, graphene oxide (GO) and their derivatives can be incorporated in a PANI matrix. In this study, hexamethylene diisocyanate-modified GO (HDI-GO) nanosheets with two different functionalization degrees have been used as nanofillers to develop high-performance PANI/HDI-GO nanocomposites via in situ polymerization of aniline in the presence of HDI-GO followed by ultrasonication and solution casting. The influence of the HDI-GO concentration and functionalization degree on the nanocomposite properties has been examined by scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), tensile tests, zeta potential and four-point probe measurements. SEM analysis demonstrated a homogenous dispersion of the HDI-GO nanosheets that were coated by the matrix particles during the in situ polymerization. Raman spectra revealed the existence of very strong PANI-HDI-GO interactions via π-π stacking, H-bonding, and hydrophobic and electrostatic charge-transfer complexes. A steady enhancement in thermal stability and electrical conductivity was found with increasing nanofiller concentration, the improvements being higher with increasing HDI-GO functionalization level. The nanocomposites showed a very good combination of rigidity, strength, ductility and toughness, and the best equilibrium of properties was attained at 5 wt % HDI-GO. The method developed herein opens up a versatile route to prepare multifunctional graphene-based nanocomposites with conductive polymers for a broad range of applications including flexible electronics and organic solar cells.