THIN-FILM HETROJUNCTION BY CARBON NANOTUBE DERIVATIVES WITH ENHANCED SOLUBILITY AND OPTICAL PROPERTIES

The combination of single-walled carbon nanotubes (SWNTs), characterized by high electron mobility, with p-type semiconducting polymers could lead to an overall improvement in the exciton dissociation and carrier extraction efficiencies in practical devices.1However, one of the main concern in the use of SWNTs, relates to the their scarce solubility. Chemical modification has been widely employed to increase the solubility of SWNTs, but usual reaction conditions limit such syntheses to a small scale with low productivity. Here, we employ SWNTs which have been functionalized with aromatic and heteroaromatic moieties via 1,3-dipolar cycloaddition and through diazotization reaction under batch…

Poly(naphthalenediimidequaterthiophene):Poly(hexyilthiophene) Heterojunctions. Efficient Polymer-to-Polymer Electron Transfer Interfaces

Organic thin films solar cells and plastic solar cells [1] have attracted the attention of the scientific community especially as regards the performance of new conjugated polymers including their interfaces [2-4]. In this work, poly(naphthalenediimidequaterthiophene) (PNDIT4) and poly(hexyilthiophene) (P3HT) have been employed, for the first time, for engineering planar and bulk heterojunctions by the synergetic use of two techniques: electropolymerization and layer by layer deposition. Electropolymerization has been used for obtaining PNDIT4 thin films on transparent ITO/PET electrodes, starting from the synthesized monomer. Inverse Langmuir-Schaefer technique has been employed for deposi…

Engeneering 3D Nanoscale Order in Molecular thin films for organic photovoltaics

ELECTRODEPOSITION OF NOVEL POLY(NAPHTHALENEDIIMIDE-QUATERTHIOPHENE) THIN FILMS AND APPLICATIONS IN PLASTIC OPTOELECTRONICS DEVICES

A novel symmetric naphthalenediimide-quaterthiophene derivative (NDIT4d) has been polymerized on different substrates including glassy carbon and ITO/PET electrodes by means of electrochemical methods. XPS and UV-VIS spectroscopy as well as cyclic voltammetry have been employed for characterizing the thin film chemical features, the band gap and the HOMO and LUMO levels. DFT computational studies were in close agreement with the experimental observables also showing intriguing geometrical effects on the band gap energy values. The comparison of the energy levels locations of the electrodeposited poly(naphthalenediimide-quaterthiophene) derivative (e-PNDIT4) and P3HT thin films transferred b…

INCORPORATION OF METAL-PORPHYRIN DERIVATIVES IN TITANIA NANOSTRUCTURED 3D NETWORKS: THIN FILM PROPERTIES AND APPLICATIONS

Self-organization and nanostructural control in thin film heterojunctions.

In spite of more than two-decades of studies of molecular self-assembly, the achievement of low cost, easy-to-implement and multi-parameter bottom-up approaches to address the supramolecular morphology in three-dimensional (3D) systems is still missing. In the particular case of molecular thin films, the 3D nanoscale morphology and function are crucial for both fundamental and applied research. Here we show how it is possible to tune the 3D film structure (domain size, branching, etc.) of thin film heterojunctions with nanoscale accuracy together with the modulation of their optoelectronic properties by employing an easy two-step approach. At first we prepared multi-planar heterojunctions w…

3D nanoscale ordered architectures in thin films for organic electronics

Order in molecular thin films is of fundamental importance to gain and exploit a series of properties in nanotechnology. In this contest, engineering 2D supramolecular and molecular superstructures is of particular interest. They offer great possibilities for several applications whose achievement also allows for new theoretical approaches and nanoscale laws [1]. A natural extension of 2D nanopatterning concerns the attainment of a 3D nanoscale control in molecular films [2]. This question is complex to challenge and it is of ultimate importance in emerging fields like organic and hybrid photovoltaics, organic thin film transistors and sensors as well as plastic electronics. For example, th…

Controlled 3D Interfacing of Three Components Thin Films for Photovoltaics

One of the main problems related to the low performance of the organic photovoltaic (OPV) devices, concerns the low mobility of the materials forming the heterojunction. For this reason, there is competition between the sweep-out and recombination of the photogenerated carriers within the thin film bulk heterojunction (BHJ). To overcome this problem, it is usual to operate by reducing the thickness of the active layer, so that the recombination of charge carriers is inhibited. This choice, however, also translates into a lower absorption of light by the active film itself. Plasmonic structures allow to reduce the "physical" thickness of heterojunction, maintaining constant the "optical" thi…

CONTROLLED CHEMICAL FUNCTIONALIZATION OF CARBON NANOSTRUCTURES FOR ORGANIC PHOTOVOLTAICS AND FUNCTIONAL MATERIALS

Inkjet Printing Quasi-Miscible Droplets for Pseudo-Planar Organic Heterojunctions

Improved performance in flexible organic solar cells by using copolymeric phase-separation modulators

One of the main problems related to the low performance of the organic solar cells (OSCs), concerns the low mobility of the materials constituting the heterojunction. Indeed, the poor charge transport in the active layer is the principal cause of a competition between separation and recombination of the photogenerated carriers. In this regard, a major obstacle to enhance OSCs efficiency is developing strategies to optimize the exciton dissociation and, consequently, the charge collection at the electrodes. Donor and acceptor systems must be well mixed on the length scale of 5 – 20 nm (exciton diffusion length) to meet the criteria for efficient exciton dissociation. In addition, the network…

Eterogiunzioni bulk a base di polimeri di borani per celle fotovoltaiche flessibili

An insight into the functionalisation of carbon nanotubes by diazonium chemistry: Towards a controlled decoration

The derivatisation of materials including iron, gold, and carbon by addition of diazonium salts is a reliable process to tune their interfacial interaction with the surrounding media. In this regard, the functionalisation of carbon nanostructures by diazonium chemistry is a versatile strategy to obtain soluble nanomaterials with degrees of functionalisation among the highest ever reported. Starting from these premises we have studied the functionalisation of multi-walled carbon nanotubes by addition of the aryl diazonium salts generated in situ by treatment of 4-methoxyaniline with isopentylnitrite. Following a thorough purification and characterisation protocol (UV-vis, TGA, ATR-IR, cyclic…

Assembling 3D Ordered Architectures in Thin Films for Organic Solar Cells

Multifunctional hybrid Polyoxometalates for silicone gels with improved thermal and mechanical properties

3D-ORDERED NANOSCALE HETEROJUNCTIONS IN MOLECULAR THIN FILMS FOR ORGANIC PHOTOVOLTAICS

Donor–Acceptor Interfaces by Engineered Nanoparticles Assemblies for Enhanced Efficiency in Plastic Planar Heterojunction Solar Cells

Precisely positioning functionalized gold nanoparticles assemblies at planar donor-acceptor interfaces results in 14-fold enhancement of power conversion efficiency in P3HT/PCBM organic solar cells on plastic (ITO/PET) substrates. This result has been achieved by employing naphthalenethiol-capped gold nanoparticles (NT-Au-NPs) produced by laser ablation in liquid and size varied in the 10-30 nm range. Upon surface functionalization with the aromatic thiol, these particles self-assemble in submicrometer aggregates, which give increased light scattering. When these aggregates are deposited in the planar heterojunction between the donor and the acceptor systems, the localized scattering leads …

ORGANOTIN(IV)-PORPHINATE FOR PHOTOVOLTAIC BULK HETEROJUNCTIONS

Due to the versatility and variability of their molecular structures, optical spectra, electrical properties, and supramolecular organization potential, porphyrins related compounds have been widely studied in organic solar cells [1,2]. Indeed, these applications are a natural function for these compounds, and they have been extensively investigated in a variety of formats including single molecules, macromolecular and supramolecular structures. In this work, poly(hexylthiophene) (P3HT) and organotin(IV)-[meso-tetra(4-carboxyphenyl) porphinate] have been employed for engineering planar and bulk heterojunctions by layer by layer deposition. Improving the overall efficiencies of photovoltaic …

Thiophene pyrenyl derivatives for the supramolecular processability of single-walled carbon nanotubes in thin film heterojunction

Abstract A major problem for the use of single-wall carbon nanotubes (SWCNTs) in electronic devices relates to their poor processability. Chemical modification inevitably introduces defects in the nanotube lattice, resulting in a loss of electronic properties. In this contest, we report on a supramolecular approach with the aim of increasing the dispersion of SWCNTs in solution and in organic semiconductor matrices by ensuring the optoelectronic properties. In particular, new pyrenyl derivatives of thiophene have been synthesized and used to improve the solubility of SWCNTs for electron transfer in thin film heterojunction with poly(3-hexylthiophene) (P3HT) as donor system. Photoinduced ele…

3D ORGANIZATION OF THIN FILMS FOR THREE COMPONENTS ACTIVE LAYER IN PHOTOVOLTAIC DEVICES

Polymer-fullerene or polymer-polymer based bulk heterojunction (BHJ) solar cells can be fabricated by using low-cost manufacturing methods. However, because of the low mobility of organic materials, there is a competition between separation and recombination of the photogenerated carriers within the thin BHJ film. Thus, there is a need to develop strategies to increase light harvesting in the films without increasing the film thickness. Nanoparticles (NPs) have been receiving a lot of interest for exhibiting interesting optical, electrical, and magnetic properties. These novel properties can be exploited in nanotechnology by forming compact and ordered architectures of nanoparticles within …

CONTROLLING THE FUNCTIONALIZATION OF CARBON NANOTUBES AND GRAPHENE NANOPLATELETS

The functionalization of carbon nanostructures by diazonium chemistry is a versatile strategy to obtain soluble nanomaterials with degrees of functionalization among the highest ever reported.[1,2] Starting from these premises we have studied the functionalization of single, double and multi-walled carbon nanotubes and graphene nanoplatelets by addition of aryl diazonium salts generated in situ by treatment of 4-substituted anilines with isopentylnitrite. Taking advantage of highly controlled flow synthesis [3-5] and following a thorough purification and characterization protocol (UV-vis, TGA, ATR-IR, AFM and other surface tools), we have investigated the key parameters to obtain both funct…

Carbon nanotube derivatives for electro-optical active bulk heterojunctions

Exploring the Interplay Between Ligand Derivatisation and Cation Type in the Assembly of Hybrid Polyoxometalate Mn-Andersons

Herein a library of hybrid Mn-Anderson polyoxometalates anions are presented: 1, [(MnMo6 O18 )((OCH2 )3 -C-(CH2 )7 CHCH2 )2 ](3-) ; compound 2, [(MnMo6 O18 )((OCH2 )3 C-NHCH2 C16 H9 )2 ](3-) ; compound 3, [(MnMo6 O18 )((OCH2 )3 C-(CH2 )7 CHCH2 )1 ((OCH2 )3 C-NHCH2 C16 H9 )1 ](3-) ; compound 4, [(MnMo6 O18 )((OCH2 )3 C-NHC(O)CH2 CHCH2 )2 ](3-) and compounds 5-9, [(MnMo6 O18 )((OCH2 )3 C-NHC(O)(CH2 )x CH3 )2 ]), where x = 4, 10, 12, 14, and 18 respectively. The compounds resulting from the cation exchange of the anions 1-9 to give TBA (a) and DMDOA (b) salts, and additionally for compounds 1, 2 and 3, tetraphenylphosphonium (PPh4 ) (c) salts, are explored at the air/water interface using scan…

Enhanced power-conversion efficiency in organic solar cells incorporating copolymeric phase-separation modulators

A new class of copolymers containing oligothiophene moieties with different lengths and fullerene units have been designed and prepared by an easy and inexpensive one-step synthetic approach. The incorporation of small quantities of these copolymers into bulk heterojunction (BHJ) solar cells with donor regioregular polythiophene (P3HT) and an acceptor fullerene derivate (PCBM) results in good control of the phase separation process without further affecting the BHJ optoelectronic properties. Indeed, under thermal annealing these copolymers allow the modulation of the growth of domains whose size depends on the length of the copolymer repetitive units. Domain size on the same length scale as…

Pseudo-Planar Organic Heterojunctions by Sequential Printing of Quasi-Miscible Inks

This work deals with the interfacial mixing mechanism of picoliter (pL)-scale droplets produced by sequential inkjet printing of organic-based inks onto ITO/PET surfaces at a moderately high Weber number (~101). Differently from solution dispensing processes at a high Bond number such as spin coating, the deposition by inkjet printing is strictly controlled by droplet velocity, ink viscosity, and surface tension. In particular, this study considers the interfacial mixing of droplets containing the most investigated donor/acceptor couple for organic solar cells, i.e., poly(3-hexylthiophene) (P3HT) and (6,6)-phenyl-C61-butyric acid methyl ester (PCBM), showing how low-viscosity and low-surfac…

ON THE 3D CONTROL OF THE FUNCTIONAL STRUCTURE OF MOLECULAR THIN FILMS

Apart from being a very challenging issue, three-dimensional order in molecular thin films is of critical importance to gain and exploit a series of key properties in emerging fields like organic/hybrid photovoltaics, organic thin film transistors, sensors and plastic electronics in general. For example, the development of nanostructured bi-continuous bulk heterojunctions (BHJs) is an important advancement leading to improved photovoltaic power conversion efficiency with respect to planar heterojunctions. Here we show an original low cost, easy-to-implement and multi-tasking bottom-up approaches to modulate the supramolecular morphology in three-dimensional (3D) systems together with their …

Synergies and compromises between charge and energy transfers in three-component organic solar cells

In this paper, we developed different three-component organic heterojunction structures supported by PET/ITO substrates with the aim to study the possible synergies and/or compromises between charge transfer (CT) and energy transfer (ET) processes in organic solar cells (OSCs). As components, we employed poly(3-hexylthiophene-2,5-diyl) (P3HT; donor), [6,6]-phenyl-C61-butyric acid methyl ester (PCBM; acceptor) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) that is known to give good ET to P3HT. At first, we observed that in a planar heterojunction (PHJ) solar cell, F8BT has to be properly located in between P3HT and PCBM to get a cascade energy level configuration allowing for a b…

On the trade-off between processability and opto-electronic properties of single wall carbon nanotube derivatives in thin film heterojunctions

A flow functionalization route has been employed to derivatize single wall carbon nanotubes (SWCNTs) by thienylphenyl groups. The SWCNT derivatives in the most soluble fraction have been characterized by thermogravimetric analysis, DLS analysis, DFT calculations, and UV-vis-NIR, microRaman and IR spectroscopies to study the degree of functionalization, the concentration of SWCNTs in solution, the dimension of the aggregates in solutions, the density of defects, and the presence of the thienylphenyl groups. Thin-film heterojunctions made of SWCNT derivatives and poly(3-hexylthiophene) (P3HT) have been prepared by various methods employing the Langmuir–Schaefer technique, spin-coating and the…

CCDC 903781: Experimental Crystal Structure Determination

Related Article: Mali H. Rosnes, Chiara Musumeci, Carine Yvon, Andrew Macdonell,Chullikkattil P. Pradeep, Camillo Sartorio, De-Liang Long,Bruno Pignataro, Leroy Cronin|2013|Small|9|2316|doi:10.1002/smll.201202510

CCDC 903785: Experimental Crystal Structure Determination

Related Article: Mali H. Rosnes, Chiara Musumeci, Carine Yvon, Andrew Macdonell,Chullikkattil P. Pradeep, Camillo Sartorio, De-Liang Long,Bruno Pignataro, Leroy Cronin|2013|Small|9|2316|doi:10.1002/smll.201202510

CCDC 903783: Experimental Crystal Structure Determination

Related Article: Mali H. Rosnes, Chiara Musumeci, Carine Yvon, Andrew Macdonell,Chullikkattil P. Pradeep, Camillo Sartorio, De-Liang Long,Bruno Pignataro, Leroy Cronin|2013|Small|9|2316|doi:10.1002/smll.201202510

CCDC 903782: Experimental Crystal Structure Determination

Related Article: Mali H. Rosnes, Chiara Musumeci, Carine Yvon, Andrew Macdonell,Chullikkattil P. Pradeep, Camillo Sartorio, De-Liang Long,Bruno Pignataro, Leroy Cronin|2013|Small|9|2316|doi:10.1002/smll.201202510

CCDC 903784: Experimental Crystal Structure Determination

Related Article: Mali H. Rosnes, Chiara Musumeci, Carine Yvon, Andrew Macdonell,Chullikkattil P. Pradeep, Camillo Sartorio, De-Liang Long,Bruno Pignataro, Leroy Cronin|2013|Small|9|2316|doi:10.1002/smll.201202510