Toward efficient carbon nanotube/P3HT solar cells: active layer morphology, electrical, and optical properties

We demonstrate single-walled carbon nanotube (SWCNT)/P3HT polymer bulk heterojunction solar cells with an AM1.5 efficiency of 0.72%, significantly higher than previously reported (0.05%). A key step in achieving high efficiency is the utilization of semiconducting SWCNTs coated with an ordered P3HT layer to enhance the charge separation and transport in the device active layer. Electrical characteristics of devices with SWCNT concentrations up to 40 wt % were measured and are shown to be strongly dependent on the SWCNT loading. A maximum open circuit voltage was measured for SWCNT concentration of 3 wt % with a value of 1.04 V, higher than expected based on the interface band alignment. Modeling of the open-circuit voltage suggests that despite the large carrier mobility in SWCNTs device power conversion efficiency is governed by carrier recombination. Optical characterization shows that only SWCNT with diameter of 1.3-1.4 nm can contribute to the photocurrent with internal quantum efficiency up to 26%. Our results advance the fundamental understanding and improve the design of efficient polymer/SWCNTs solar cells.     

Direct‐Patterning SWCNTs Using Dip Pen Nanolithography for SWCNT/Silicon Solar Cells

Dip pen nanolithography (DPN) is used to pattern single‐walled carbon nanotube (SWCNT) lines between the n‐type Si and SWCNT film in SWCNT/Si solar cells. The SWCNT ink composition, loading, and DPN pretreatment are optimized to improve patterning. This improved DPN technique is then used to successfully pattern >1 mm long SWCNT lines consistently. This is a 20‐fold increase in the previously reported direct‐patterning of SWCNT lines using the DPN technique, and demonstrates the scalability of the technique to pattern larger areas. The degree of the uniformity of SWCNTs in these lines is further characterized by Raman spectroscopy and scanning electron microscopy. The patterned SWCNT lines are used as thin conductive pathways in SWCNT/Si solar cells, similar to front contact electrodes. The critical parameters of these solar cells are measured and compared to control cells without SWCNT lines. The addition of SWCNT lines increases power conversion efficiency by 40% (relative). Importantly, the SWCNT lines reduce average series resistance by 44%, and consequently increase average fill factor by 24%.     

Preparation of properties of SWNT/graphene oxide type flexible transparent conductive films

Single walled carbon nanotube (SWNT)/graphene oxide (GO) hybrid films were prepared by a facile bar coating method on a polyethylene terephthalate substrate using a mixed solution of SWCNTs and GO. An acryl type polymer was employed as a dispersion agent to obtain SWCNT and GO suspension in ethyl alcohol. The SWCNT/GO hybrid films were highly transparent and electrically conductive, showing 80% transmittance and 1.8 x 10(3) ohm/sq surface resistance. The surface resistance of the SWCNT/GO film could be further improved to 750 ohm/sq by hydrazine vapor reduction.     

Molecular dynamics simulation of SWCNT–polymer nanocomposite and its constituents

Elastic and engineering properties of nanoparticle enhanced composites and their constituents (matrix, reinforcement and interface) are calculated. The nanocomposites considered in this study consist of a single-wall carbon nanotube (SWCNT) embedded in polyethylene matrix. Molecular dynamics simulations are used to estimate the elastic properties of SWCNT, interfacial bonding, polyethylene matrix and composites with aligned and randomly distributed SWCNTs. The elastic properties of bundles with 7, 9, and 19 SWCNTs are also compared using a similar approach. In all simulations, the average density of SWCNT–polymer nanocomposite was maintained in the vicinity of CNTs, to match the experimentally observed density of a similar nanocomposite. Results are found to be in good agreement with experimentally obtained values by other researchers. The interface is an important constituent of CNT–polymer composites, which has been modeled in the present research with reasonable success.     

Diketopyrrolopyrrole (DPP)‐Based Donor–Acceptor Polymers for Selective Dispersion of Large‐Diameter Semiconducting Carbon Nanotubes

Low‐bandgap diketopyrrolopyrrole (DPP)‐based polymers are used for the selective dispersion of semiconducting single‐walled carbon nanotubes (s‐SWCNTs). Through rational molecular design to tune the polymer–SWCNT interactions, highly selective dispersions of s‐SWCNTs with diameters mainly around 1.5 nm are achieved. The influences of the polymer alkyl side‐chain substitution (i.e., branched vs linear side chains) on the dispersing yield and selectivity of s‐SWCNTs are investigated. Introducing linear alkyl side chains allows increased polymer–SWCNT interactions through close π–π stacking and improved C–H–π interactions. This work demonstrates that polymer side‐chain engineering is an effective method to modulate the polymer–SWCNT interactions and thereby affecting both critical parameters in dispersing yield and selectivity. Using these sorted s‐SWCNTs, high‐performance SWCNT network thin‐film transistors are fabricated. The solution‐deposited s‐SWCNT transistors yield simultaneously high mobilities of 41.2 cm² V^?1 s^?1 and high on/off ratios of greater than 10⁴. In summary, low‐bandgap DPP donor–acceptor polymers are a promising class of polymers for selective dispersion of large‐diameter s‐SWCNTs.     

Polydiacetylene single-walled carbon nanotubes nano-hybrid for cellular imaging applications

The functionalization of single-walled carbon nanotubes (SWCNTs) by forming self-assembled supramolecular structure of 10,12-pentacosadiynoic acid (PCDA) on the carbon nanotube wall is reported. PCDA assemblies on SWCNTs (PCDA/SWCNTs) were polymerized by UV irradiation to extensively conjugated polydiacetylene (PDA). PDA/SWCNT was identified by absorption and emission spectroscopy, scanning and transmission electron microscopies (SEM and TEM) and atomic force microscopy (AFM). PDA/SCWNTs showed strong near-infrared (NIR) fluorescence caused by fluorescence resonance energy transfer (FRET) between PDA network and semiconducting SWCNT core. The micro-patterning of biotinylated PDA/SWCNT with FITC-avidin on biotinylated glass surface demonstrated the potential application for a bio-sensing device. Furthermore, the biocompatibility for mammalian cancer cells was tested by viability experiments, which revealed that the PDA/SWCNTs had very low toxicity below 31.3 mg/L in terms of pristine SWCNTs concentration. Also, PDA/SWCNTs inside the cells can be observed by NIR microscopy. This unique modular method of preparation can contribute to diverse functionalities for practical applications in various non-invasive cellular imaging.     

Unavoidable front contact model of Si solar cell through a generalized effective medium approximation approach

Fill factor of the solar cell mainly depends on series resistance and contact resistance, which are the most effective parameters to collect carriers (electrons and holes) from both electrodes of C-Si solar cells. We have used both mathematical and experimental approaches to reduce these resistances for enhancement of power conversion efficiency (PCE) by increasing fill factor. After processing by light-induced plating (LIP) for metal contact, the PCE of solar cell is obtained as 14.43%, which is 8.8% more than that before LIP processing.     

The manipulation of carbon nanotubes on a polymer surface using a laser beam

Controlled noninvasive manipulation of porphyrin-doped single-walled carbon nanotubes (SWCNT) by laser beam is described. SWCNT/porphyrin complexes have been deposited on a polymer surface and irradiated by a scanning beam of laser light with the wavelength of 405 nm. Laser energy was absorbed by the porphyrin and converted into heat through an energy transfer within the complexes. This led to periodical deformation of the initially flat polymer surface. As a result of the surface deformation the SWCNTs or SWCNT bundle move in the direction given by the laser scanning. It was proved that SWCNTs can be moved to a desired position using the focused laser beam.     

Inverted organic solar cells with ZnO nanowalls prepared using wet chemical etching in a KOH solution

We report on the photovoltaic (PV) performances of inverted organic solar cells (IOSCs) that were fabricated from PCBM:P3HT polymer with a ZnO thin film and ZnO nanowalls as electron transport and hole block layers. ZnO thin film on ITO/glass substrate was deposited using a simply aqueous solution route. ZnO nanowall structures were obtained via wet chemical etching of ZnO thin films in a KOH solution. The power conversion efficiency (PCE) of the IOSC with ZnO nanowalls was significantly improved by 44% from 1.254% to 1.811% compared to that of the IOSC with ZnO thin film. The short circuit current in IOSCs fabricated with the ZnO nanowalls was increased mainly due to the increase in the charge transport interface area, as a result of enhancement in the PCE. This work suggests a method for fabricating efficient PV devices with a larger charge transport area for future prospects.     

Synthesis and characterization of polyurethane-grafted single-walled carbon nanotubes via click chemistry

Polyurethane (PU)-grafted carbon nanotubes were synthesized by the coupling of alkyne moiety decorated single walled carbon nanotube (SWCNT) with azide moiety containing PU using Cu(I) catalyzed Huisgen [3 + 2] cycloaddition click chemistry. The azide moiety containing poly(s-caprolactone)diol was synthesized by ring-opening polymerization and further used for PU synthesis. Alkyne-functionalizion of SWCNT was completed by the reaction of p-aminophenyl propargyl ether with SWCNT using a solvent free diazotization procedure. Nuclear magnetic resonance, Fourier transform infrared, and Raman spectroscopic measurements confirmed the functionalization of SWCNT. Scanning electron microscopy and transmission electron microscopy images showed an excellent dispersion of SWCNTs, and specially debundling of SWCNTs could be observed due to polymer assisted dispersion. A quantitative grafting was successfully achieved even at high content of functional groups.     

A Benzo[1,2-b:4,5-c′]Dithiophene-4,8-Dione-Based Polymer Donor Achieving an Efficiency Over 16%

It is of great significance to develop efficient donor polymers during the rapid development of acceptor materials for nonfullerene bulk-heterojunction (BHJ) polymer solar cells. Herein, a new donor polymer, named PBTT-F, based on a strongly electron-deficient core (5,7-dibromo-2,3-bis(2-ethylhexyl)benzo[1,2-b:4,5-c′]dithiophene-4,8-dione, TTDO), is developed through the design of cyclohexane-1,4-dione embedded into a thieno[3,4-b]thiophene (TT) unit. When blended with the acceptor Y6, the PBTT-F-based photovoltaic device exhibits an outstanding power conversion efficiency (PCE) of 16.1% with a very high fill factor (FF) of 77.1%. This polymer also shows high efficiency for a thick-film device, with a PCE of ≈14.2% being realized for an active layer thickness of 190 nm. In addition, the PBTT-F-based polymer solar cells also show good stability after storage for ≈700 h in a glove box, with a high PCE of ≈14.8%, which obviously shows that this kind of polymer is very promising for future commercial applications. This work provides a unique strategy for the molecular synthesis of donor polymers, and these results demonstrate that PBTT-F is a very promising donor polymer for use in polymer solar cells, providing an alternative choice for a variety of fullerene-free acceptor materials for the research community.     

Conformational-induced doping effect of sodium dodecyl benzene sulfonate on single walled carbon nanotubes

The doping behavior of single-walled carbon nanotubes (SWCNTs) was investigated with an emphasis on the control of the conformation of sodium dodecylbenzene sulfonate (NaDDBS) with sulfonate groups acting as an electro-withdrawing group. The conformation of adsorbed NaDDBS on SWCNTs was controlled as a function of the amount of NaDDBS. The doping behavior of SWCNTs was significantly affected by the dosing amount of NaDDBS due to the conformational change of NaDDBS adsorbed on the SWCNT surface, which affected the spatial distance between the SWCNT surface and the sulfonate groups in NaDDBS. At a higher concentration, the spatial distance between the sulfonate group in NaDDBS and SWCNT was not sufficiently close enough to dope SWCNT due to the repulsive forces between the sulfonate groups in NaDDBS. Alternatively, at a lower concentration, NaDDBS acted as a p-type dopant for SWCNTs. To this end, this paper demonstrates a new tendency of doping that is related to the adsorbed behavior of a dispersant.     

Improved efficiency of organic/inorganic photovoltaic devices by electrospun ZnO nanofibers

The efficiency of the photovoltaic (PV) device based on P3HT and PCBM bulk heterojunction is improved by introducing small-diameter electrospun ZnO diffused nanofibers network. Diameter, diffusion and melting of nanofibers are controlled by calcination temperature. The thickness of the active layer is optimized for efficient PV devices by varying electrospinning (ES) time. Increased nanofiber's mat thickness by an increase in electrospinning time beyond a certain optimum value reduces the device performance due to increased series resistance, increased traps and reduced blend infiltration through the nanofiber pores. ES time suggests optimized active area for energy absorption and exciton dissociation. In this study, we report the improvement in power conversion efficiency (PCE) from 0.9% to 2.23%, for optimum ES time (∼300 s).     

Enhanced UV photoresponse of KrF-laser-synthesized single-wall carbon nanotubes/n-silicon hybrid photovoltaic devices

We report on the KrF-laser ablation synthesis, purification and photocurrent generation properties of single-wall carbon nanotubes (SWCNTs). The thermally purified SWCNTs are integrated into hybrid photovoltaic (PV) devices by spin-coating them onto n-Si substrates. These novel SWCNTs/n-Si hybrid devices are shown to generate significant photocurrent (PC) over the entire 250-1050 nm light spectrum with external quantum efficiencies (EQE) reaching up to ~23%. Our SWCNTs/n-Si hybrid devices are not only photoactive in the traditional spectral range of Si solar cells, but generate also significant PC in the UV domain (below 400 nm). This wider spectral response is believed to be the result of PC generation from both the SWCNTs themselves and the tremendous number of local p-n junctions created at the nanotubes/Si interface. To assess the prevalence of these two contributions, the EQE spectra and J-V characteristics of these hybrid devices were investigated in both planar and top-down configurations, as a function of SWCNTs' film thickness. A sizable increase in EQE in the near UV with respect to the silicon is observed in both configurations, with a more pronounced UV photoresponse in the planar mode, confirming thereby the role of SWCNTs in the photogeneration process. The PC generation is found to reach its maximum for an optimal the SWCNT film thickness, which is shown to correspond to the best trade-off between lowest electrical resistance and highest optical transparency. Finally, by analyzing the J-V characteristics of our SWCNTs/n-Si devices with an equivalent circuit model, we were able to point out the contribution of the various electrical components involved in the photogeneration process. The SWCNTs-based devices demonstrated here open up the prospect for their use in highly effective photovoltaics and/or UV-light sensors.     

High efficiency graphene solar cells by chemical doping

We demonstrate single layer graphene/n-Si Schottky junction solar cells that under AM1.5 illumination exhibit a power conversion efficiency (PCE) of 8.6%. This performance, achieved by doping the graphene with bis(trifluoromethanesulfonyl)amide, exceeds the native (undoped) device performance by a factor of 4.5 and is the highest PCE reported for graphene-based solar cells to date. Current-voltage, capacitance-voltage, and external quantum efficiency measurements show the enhancement to be due to the doping-induced shift in the graphene chemical potential that increases the graphene carrier density (decreasing the cell series resistance) and increases the cell's built-in potential (increasing the open circuit voltage) both of which improve the solar cell fill factor.     

Enhancement of the power conversion efficiency of polymer solar cells by functionalized single-walled carbon nanotubes decorated with CdSe/ZnS core–shell colloidal quantum dots

In this paper, we demonstrated an enhanced performance of polymer solar cells by incorporating functionalized single-walled carbon nanotubes (SWCNTs) decorated with CdSe/ZnS core–shell colloidal quantum dots (CQDs) into copolymers of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as active layer. Short-circuit current density and power conversion efficiency of the ITO/PEDOT:PSS/P3HT:PCBM:(CdSe/ZnS-SWCNTs)/Al solar cells can be enhanced by more than 31 and 23 %, respectively, as compared with the control device ITO/PEDOT:PSS/P3HT:PCBM/Al. This enhancement is due to the high electron-transporting ability of SWCNTs and the increased absorption of CdSe/ZnS CQD in visible region. It shows an applicable way to improve the efficiency of polymer solar cells by incorporating suitable quantity of CQDs-decorated SWCNTs with suitable kinds of CQDs and suitable acid treatment to the SWCNTs.     

场离子显微镜观测单壁碳纳米管

场离子显微镜是具有原子级分辨能力的尖端表面分析工具.它适用于纳米尺度的单壁碳纳米管(SWCNTs)末端表面原子排列的观测.利用范氏力将SWCNTs组装到钨针尖上,用场离子显微镜观察了这种针尖样品.在观察过程中对针尖样品进行了加热处理,既除掉非晶的C原子,也破坏了由于碳纳米管切割制造过程使用表面活化剂引起的高电阻层,得到了开口SWCNTs的场离子显微镜像,由此推断出SWCNTs束的顶端原子结构,估算出观察到的SWCNTs的直径,并且模拟了其中一个图像所代表的SWCNTs顶端开口的原子排列,推断出产生这个图像的SWCNTs是(7,7)型结构.     

Highly conductive interwoven carbon nanotube and silver nanowire transparent electrodes

Abstract

Electrodes fabricated using commercially available silver nanowires (AgNWs) and single walled carbon nanotubes (SWCNTs) produced sheet resistances in the range 4–24 Ω □^?1 with specular transparencies up to 82 %. Increasing the aqueous dispersibility of SWCNTs decreased the bundle size present in the film resulting in improved SWCNT surface dispersion in the films without compromising transparency or sheet resistance. In addition to providing conduction pathways between the AgNW network, the SWCNTs also provide structural support, creating stable self-supporting films. Entanglement of the AgNWs and SWCNTs was demonstrated to occur in solution prior to deposition by monitoring the transverse plasmon resonance mode of the AgNWs during processing. The interwoven AgNW/SWCNT structures show potential for use in optoelectronic applications as transparent electrodes and as an ITO replacement.     

Comparative analysis of electronic properties of tin,gallium, and bismuth chalcogenide-filled single-walled carbon nanotubes

In the present work, the channels of single-walled carbon nanotubes (SWCNTs) were filled with tin sulfide (SnS), gallium telluride (GaTe), and bismuth selenide (Bi₂Se₃). The successful encapsulation of the compounds was proven by high-resolution transmission electron microscopy. The electronic properties of the filled SWCNTs were studied by optical absorption spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was found that the embedded metal chalcogenides have different influence on the electronic properties of the nanotubes. The incorporation of tin sulfide into the SWCNTs does not result in sufficient changes in the electronic structure of SWCNTs, except for a minor influence on metallic nanotubes. The filling of SWCNTs with gallium telluride causes the charge transfer from the SWCNT walls to the encapsulated compound due to acceptor doping of the nanotubes. The insertion of bismuth selenide inside the SWCNT channels does not lead to the modification of the electronic properties of nanotubes.     

Preparation of single-walled carbon nanotube/silicon composites and their lithium storage properties

Single-walled carbon nanotube (SWCNT)/silicon composites were produced from the purified SWCNTs and Si powder by high-energy ball-milling and then electrochemically inserted with Li using Li/(SWCNT/Si) cells. The highest reversible capacity and lowest irreversible capacity of the SWCNT/Si composites were measured to be 1845 and 474 mAh g(-1) after ball-milling for 60 min, respectively. During the charge/discharge process, most of the Li ions were inserted into the SWCNT/Si composites by alloying with Si particles below 0.2 V and extracted from the SWCNT/Si composites by dealloying with Si particles around 0.5 V. The enhanced capacity and cycle performance of the SWCNT/Si composites produced by high-energy ball-milling were due primarily to the fact that SWCNTs provided a flexible conductive matrix, which compensated for the dimensional changes of Si particles during Li insertion and avoided loosening of the interparticle contacts during the crumbling of Si particles. The ball-milling contributed to a decrease in the particle size of SWCNTs and Si particles and to an increase in the electrical contact between SWCNTs and Si particles in the SWCNT/Si composites.