Roadmap on thermoelectricity.

The increasing energy demand and the ever more pressing need for clean technologies of energy conversion pose one of the most urgent and complicated issues of our age. Thermoelectricity, namely the direct conversion of waste heat into electricity, is a promising technique based on a long-standing physical phenomenon, which still has not fully developed its potential, mainly due to the low efficiency of the process. In order to improve the thermoelectric performance, a huge effort is being made by physicists, materials scientists and engineers, with the primary aims of better understanding the fundamental issues ruling the improvement of the thermoelectric figure of merit, and finally building the most efficient thermoelectric devices. In this Roadmap an overview is given about the most recent experimental and computational results obtained within the Italian research community on the optimization of composition and morphology of some thermoelectric materials, as well as on the design of thermoelectric and hybrid thermoelectric/photovoltaic devices.

Interplay between transparency and efficiency in dye sensitized solar cells.

In this paper we analyze the interplay between transparency and efficiency in dye sensitized solar cells by varying fabrication parameters such as the thickness of the nano-crystalline TiO(2) layer, the dye loading and the dye type. Both transparency and efficiency show a saturation trend when plotted versus dye loading. By introducing the transparency-efficiency plot, we show that the relation between transparency and efficiency is linear and is almost independent on the TiO(2) thickness for a certain thickness range. On the contrary, the relation between transparency and efficiency depends strongly on the type of the dye. Moreover, we show that co-sensitization techniques can be effectively used to access regions of the transparency-efficiency space that are forbidden for single dye sensitization. The relation found between transparency and efficiency (T&E) can be the general guide for optimization of Dye Solar Cells in building integration applications.

Formulations and processing of nanocrystalline TiO2 films for the different requirements of plastic, metal and glass dye solar cell applications.

We carried out a systematic study on the effect of nanocrystalline TiO2 paste formulations and temperature treatment on the performance of dye solar cells (DSCs) over a large temperature range, to provide useful information for the fabrication of both plastic and metal flexible devices. We compared conventional screen-printable and binder-free TiO2 pastes with a new formulation which includes hydroxylethyl cellulose (HEC), enabling the study of the effect of organic materials in the TiO2 layer in the whole 25-600 °C temperature range. Differently from the binder-free formulations where the device efficiency rose monotonically with temperature, the use of cellulose binders led to remarkably different trends depending on their pyrolysis and decomposition thresholds and solubility, especially at those temperatures compatible with plastic foils. Above 325 °C, where metal foil can be used as substrates, the efficiencies become similar to those of the binder-free paste due to effective binder decomposition and inter-nanoparticle bonding. Finally, we demonstrated, for the first time, that the simultaneous application of both temperature (110-150 °C) and pressure (100 MPa) can lead to a large improvement (33%) compared to the same mechanical compression method carried out at room temperature only.

Technical-economic analysis to identify the acceptable maximum attenuation on PON FTTH lines for wholesale network operators.

Telecommunications companies are constantly chasing continuous technological advances with their management methods of Operations & Maintenance (O&M) that still struggle to turn their eye toward innovation and simplification of processes. In a future that aims at fully fiber-optic networks, the objective of the research is to propose guidelines and provide data to support the Wholesale Operator for the definition of the acceptable attenuation threshold on the Passive Optical Network Fiber-To-The-Home (PON FTTH) infrastructure to determine the Service Level Agreements (SLA) to be contracted with Retail Operators. Following exceeding the threshold, the Retail Operator has the right to open a Trouble Ticket to request the resolution of the anomaly. Consequently, the definition of the attenuation threshold strongly affects the number of Trouble Tickets to be managed and the related costs the Wholesale Operator bears. This paper analyzes a specific case of the PON FTTH network of the Italian wholesale operator Open Fiber. The studied infrastructure, with a length of 11 km, allows a maximum attenuation of 37 dB without degrading the service. An economic model has been proposed to assess the cost impact of moving the attenuation threshold in the SLA.

Physical and electrochemical analysis of an indoor-outdoor ageing test of large-area dye solar cell devices.

A long-term life test (3200 h) on large-area dye-sensitized cells is performed both under outdoor conditions, in the sunny Mediterranean climate in Rome (Italy), and under continuous light soaking (1 Sun, 85 °C). Different degradation rates are investigated for the outdoor samples with horizontally and vertically oriented cells (azimuth South, tilt angle 25°). Thirty identical photocells (active area=3.6 cm(2), conversion efficiencies=(4.8±0.2)%) are aged using a robust master-plate configuration. After the first 1000 h of testing in open-circuit conditions, some of the test samples are set near the maximum power point (MPP) and the life test continued further until 3200 h. A detailed analysis of the physical parameters obtained by electrochemical impedance is given together with electrolyte transmittance variation with time as a function of the ageing conditions. Faster degradation in devices working at the MPP is observed, due mainly to a progressive decrease of the triiodide concentration in the electrolyte and a likely alteration at the titania/electrolyte interface. Outdoor devices working with vertically oriented cells show clearly that the orientation of long-striped cells can affect the lifetime. The aged cells suffer an increase of recombination rate, change in the chemical capacitance, and positive shift of the titania conduction band level. A strong correlation between the increase of the electrolyte diffusion resistance and degradation phenomena is found.

Electrochemistry in reverse biased dye solar cells and dye/electrolyte degradation mechanisms.

Mismatched or shadowed individual cells in a module can operate in the reverse bias (RB) regime. We investigate and identify key mechanisms for RB operation and degradation in dye solar cells (DSCs). Current-voltage characteristics in RB are sensitive to the type of dye utilised and to TiCl(4) substrate treatment. Subjecting the cell to a RB of 0.4 V over 740 h has little effect on conversion efficiency whereas a significant lowering is observed for the harsher stress tests at 0.6 V and by forcing a constant current equal to its I(SC). For more prolonged reverse biases at I(SC) (>740 h), we show that depletion of [I(3)(-)] inside the DSC can lead the reverse bias potentials across the cells to considerably increase in time. Electrochemical impedance measurements show that the overpotentials at the counter electrodes (CEs) can eventually reach values high enough to cause hydrogen evolution. Clear evidence of gas bubbles forming inside a complete dye solar cell under reverse bias stress, leading to severe device degradation, is presented. We also show that reactions of iodine with water present in the electrolyte can play an important role in [I(3)(-)] depletion and in the formation of hydrogen at the Pt CE.

Graphene with Ni-Grid as Semitransparent Electrode for Bulk Heterojunction Solar Cells (BHJ-SCs).

In this work, we present the fabrication and characterization of bulk-heterojunction solar cells on monolayer graphene (MLG) with nickel-grids (Ni-grid) as semitransparent conductive electrode. The electrodes showed a maximum transmittance of 90% (calculated in 300-800 nm range) and a sheet resistance down to 35 Ω/□. On these new anodes, we fabricated TCO free BHJ-SCs using PTB7 blended with PC70BM fullerene derivative as active layer. The best device exhibited a power conversion efficiency (PCE) of 4.2% in direct configuration and 3.6% in inverted configuration. The reference solar cell, realized on the ITO glass substrate, achieved a PCE of 6.1% and 6.7% in direct and inverted configuration respectively; for comparison we also tested OSCs only with simple Ni-grid as semitransparent and conductive electrode, obtaining a low PCE of 0.7%. The proposed approach to realize graphene-based electrodes could be a possible route to reduce the overall impact of the sheet resistance of this type of electrodes allowing their use in several optoelectronic devices.

The Golden Fig: A Plasmonic Effect Study of Organic-Based Solar Cells.

An optimization work on dye-sensitized solar cells (DSSCs) based on both artificial and natural dyes was carried out by a fine synthesis work embedding gold nanoparticles in a TiO2 semiconductor and perfecting the TiO2 particle sizes of the scattering layer. Noble metal nanostructures are known for the surface plasmon resonance peculiarity that reveals unique properties and has been implemented in several fields such as sensing, photocatalysis, optical antennas and PV devices. By embedding gold nanoparticles in the mesoporous TiO2 layer and adding a scattering layer, we were able to boost the power conversion efficiency (PCE) to 10.8%, using an organic ruthenium complex. The same implementation was carried out using a natural dye, betalains, extracted from Sicilian prickly pear. In this case, the conversion efficiency doubled from 1 to 2% (measured at 1 SUN illumination, 100 mW/cm2 under solar simulation irradiation). Moreover, we obtained (measured at 0.1 SUN, 10 mW/cm2 under blue light LED irradiation) a record efficiency of 15% with the betalain-based dye, paving the way for indoor applications in organic natural devices. Finally, an attempt to scale up the system is shown, and a betalain-based- dye-sensitized solar module (DSSM), with an active area of 43.2 cm2 and a PCE of 1.02%, was fabricated for the first time.

Enhanced Thermoelectric Properties of Poly(3-hexylthiophene) through the Incorporation of Aligned Carbon Nanotube Forest and Chemical Treatments.

Carbon nanotube/polymer composites have recently received considerable attention for thermoelectric (TE) applications. The TE power factor can be significantly improved by forming composites with carbon nanotubes. However, the formation of a uniform and well-ordered nanocomposite film is still challenging because of the creation of agglomerates and the uneven distribution of nanotubes. Here, we developed a facile, efficient, and easy-processable route to produce uniform and aligned nanocomposite films of P3HT and carbon nanotube forest (CNTF). The electrical conductivity of a pristine P3HT film was improved from ∼10-7 to 160 S/cm thanks to the presence of CNTF. Also, a further boost in TE performance was achieved using two additives, lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) and tert-butylpyridine. By adding the additives to P3HT, the degree of interchain order increased, which facilitated the charge transport through the composite. Under the optimal conditions, the incorporation of CNTF and additives led to values of the Seebeck coefficient, electrical conductivity, and power factor up to rising 92 µV/K, 130 S/cm, and 110 µW/m K2, respectively, at a temperature of 344.15 K. The excellent TE performance of the hybrid films originates from the dramatically increased electrical conductivity and the improved Seebeck coefficient by CNTF and additives, respectively.

Carbon nanotubes/polydimethylsiloxanes systems for thermal management of miniaturized electronic components.

The thermal performances of nanocomposite layers formed by Single-walled Carbon Nanotubes (SWCNT) dispersed in 2 different kind of polydimethyl-siloxane (PDMSO) matrices has been investigated by measuring the thermal resistance under conditions similar to the ones used for thermal management in microelectronics. A series of nanocomposite samples with thickness in the range 25 microm(-1) cm have been tested. The nanocomposites were prepared varying the amounts of nanotubes embedded in the matrix (from 0.1 to 5%w). In some cases also microsized graphites were mixed to the nanotube's fillers. For 25 micron thick layers, the thermal resistance of the neat silicone specimen can be reduced of 54% with the addition of 2%w carbon nanotubes. The variation of thermal conductivity as a function of the SWCNT's loading is reported and discussed. Furthermore the dispersion's effects of the nanotubes in the layers and the effects on the realization of a net-like system have been investigated.

The Molecular Weight Dependence of Thermoelectric Properties of Poly (3-Hexylthiophene).

Organic materials have been found to be promising candidates for low-temperature thermoelectric applications. In particular, poly (3-hexylthiophene) (P3HT) has been attracting great interest due to its desirable intrinsic properties, such as excellent solution processability, chemical and thermal stability, and high field-effect mobility. However, its poor electrical conductivity has limited its application as a thermoelectric material. It is therefore important to improve the electrical conductivity of P3HT layers. In this work, we studied how molecular weight (MW) influences the thermoelectric properties of P3HT films. The films were doped with lithium bis(trifluoromethane sulfonyl) imide salt (LiTFSI) and 4-tert butylpyridine (TBP). Various P3HT layers with different MWs ranging from 21 to 94 kDa were investigated. UV-Vis spectroscopy and atomic force microscopy (AFM) analysis were performed to investigate the morphology and structure features of thin films with different MWs. The electrical conductivity initially increased when the MW increased and then decreased at the highest MW, whereas the Seebeck coefficient had a trend of reducing as the MW grew. The maximum thermoelectric power factor (1.87 µW/mK2) was obtained for MW of 77 kDa at 333 K. At this temperature, the electrical conductivity and Seebeck coefficient of this MW were 65.5 S/m and 169 µV/K, respectively.

Easy Strategy to Enhance Thermal Stability of Planar PSCs by Perovskite Defect Passivation and Low-Temperature Carbon-Based Electrode.

Organic-inorganic lead halide perovskite has recently emerged as an efficient absorber material for solution process photovoltaic (PV) technology, with certified efficiency exceeding 25%. The development of low-temperature (LT) processing is a challenging topic for decreasing the energy payback time of perovskite solar cell (PSC) technology. In this context, the LT planar n-i-p architecture meets all the requirements in terms of efficiency, scalability, and processability. However, the long-term stability of the LT planar PSC under heat and moisture stress conditions has not been carefully assessed. Here, a detailed study on thermal and moisture stability of large-area (1 cm2) LT planar PSCs is presented. In particular, the key role in thermal stability of potassium iodide (KI) insertion in the perovskite composition is demonstrated. It is found that defect passivation of triple-cation perovskite by KI doping inhibits the halide migration induced by thermal stress at 85 °C and delays the formation of degradation subproducts. T80, defined as the time when the cell retains 80% of initial efficiency, is evaluated both for reference undoped devices and KI-doped ones. The results show that T80 increases 3 times when KI doping is used. Moreover, an HTL-free architecture where the Au top electrode is replaced with low-T screen-printable carbon paste is proposed. The combination of the carbon-based HTL-free architecture and KI-doped perovskite permits T80 to increase from 40 to 414 h in unsealed devices.

Plasmon polaritons in the near infrared on fluorine doped tin oxide films.

Here we investigate plasmon polaritons in fluorine doped tin oxide (FTO) films. By fitting reflectance and transmittance measurements as a function of wavelength lambda epsilon [1.0microm, 2.5microm] we derive a Drude dispersion relation of the free electrons in the transparent conducting oxide films. Then we compute the dispersion curves for the bulk and surface modes together with a reflectance map over an extended wavelength region (lambda==>10microm). Although the surface polariton dispersion for a single FTO/air interface when neglecting damping should appear clearly in the plots in the considered region (since it is supposedly far and isolated from other resonances), a complex behaviour can arise. This is due to different characteristic parameters, such as the presence of a finite extinction coefficient, causing an enlargement and backbending of the feature, and the low film thickness, via coupling between the modes from both the glass/FTO and FTO/air interfaces. Taking into account these effects, computations reveal a general behaviour for thin and absorbing conducting films. They predict a thickness dependent transition region between the bulk polariton and the surface plasmon branches as previously reported for indium tin oxide. Finally, attenuated total reflection measurements vs the incidence angle are performed over single wavelengths lines R(theta) (lambda= 0.633,0.830,1.300,1.550microm) and over a two dimensional domain R(theta,lambda) in the near infrared region lambda epsilon [1.45microm, 1.59microm]. Both of these functions exhibit a feature which is attributed to a bulk polariton and not to a surface plasmon polariton on the basis of comparison with spectrophotometer measurements and modeling. The predicted range for the emergence of a surface plasmon polariton is found to be above lambda >or= 2.1microm, while the optimal film thickness for its observation is estimated to be around 200nm.

Laser-patterned functionalized CVD-graphene as highly transparent conductive electrodes for polymer solar cells.

A five-layer (5L) graphene on a glass substrate has been demonstrated as a transparent conductive electrode to replace indium tin oxide (ITO) in organic photovoltaic devices. The required low sheet resistance, while maintaining high transparency, and the need of a wettable surface are the main issues. To overcome these, two strategies have been applied: (i) the p-doping of the multilayer graphene, thus reaching 25 Ω□-1 or (ii) the O2-plasma oxidation of the last layer of the 5L graphene that results in a contact angle of 58° and a sheet resistance of 134 Ω□-1. A Nd:YVO4 laser patterning has been implemented to realize the desired layout of graphene through an easy and scalable way. Inverted Polymer Solar Cells (PSCs) have been fabricated onto the patterned and modified graphene. The use of PEDOT:PSS has facilitated the deposition of the electron transport layer and a non-chlorinated solvent (ortho-xylene) has been used in the processing of the active layer. It has been found that the two distinct functionalization strategies of graphene have beneficial effects on the overall performance of the devices, leading to an efficiency of 4.2%. Notably, this performance has been achieved with an active area of 10 mm2, the largest area reported in the literature for graphene-based inverted PSCs.

Synthesis of a novel unsymmetrical Zn(II) phthalocyanine bearing a phenyl ethynyl moiety as sensitizer for dye-sensitized solar cells.

A new unsymmetrical zinc phthalocyanine sensitizer has been synthesised. The anchoring of the molecule to nanocrystalline TiO(2) films is realised by a carboxylic group connected to a phenyl ethynyl moiety. Density Functional Theory (DFT) calculations show significant and positive effects of such a functionalization. Electron injection into the semiconductor and photocurrent generation in DSSC are also presented.