Publications

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2016
Grey, P., Pereira Pereira Barquinha Cunha Martins Fortunato L. S. P. "Transistors: Solid State Electrochemical WO3 Transistors with High Current Modulation (Adv. Electron. Mater. 9/2016)." Advanced Electronic Materials. 2 (2016). AbstractWebsite
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Besleaga, C.a, Stan Pintilie Barquinha Fortunato Martins G. E. a I. "Transparent field-effect transistors based on AlN-gate dielectric and IGZO-channel semiconductor." Applied Surface Science. 379 (2016): 270-276. AbstractWebsite

The degradation of thin-film transistors (TFTs) caused by the self-heating effect constitutes a problem to be solved for the next generation of displays. Aluminum nitride (AlN) is a viable alternative for gate dielectric of TFTs due to its good thermal conductivity, matching coefficient of thermal expansion to indium-gallium-zinc-oxide, and excellent stability at high temperatures. Here, AlN thin films of different thicknesses were fabricated by a low temperature reactive radio-frequency magnetron sputtering process, using a low cost, metallic Al target. Their electrical properties have been thoroughly assessed. Furthermore, the 200 nm and 500 nm thick AlN layers have been integrated as gate-dielectric in transparent TFTs with indium-gallium-zinc-oxide as channel semiconductor. Our study emphasizes the potential of AlN thin films for transparent electronics, whilst the functionality of the fabricated field-effect transistors is explored and discussed. © 2016 Elsevier B.V. All rights reserved.

2015
Wojcik, P.J., Santos Pereira Martins Fortunato L. L. R. "Tailoring nanoscale properties of tungsten oxide for inkjet printed electrochromic devices." Nanoscale. 7 (2015): 1696-1708. AbstractWebsite

This paper focuses on the engineering procedures governing the synthesis of tungsten oxide nanocrystals and the formulation of printable dispersions for electrochromic applications. By that means, we aim to stress the relevancy of a proper design strategy that results in improved physicochemical properties of nanoparticle loaded inks. In the present study inkjet printable nanostructured tungsten oxide particles were successfully synthesized via hydrothermal processes using pure or acidified aqueous sol-gel precursors. Based on the proposed scheme, the structure and morphology of the nanoparticles were tailored to ensure the desired printability and electrochromic performance. The developed nanomaterials with specified structures effectively improved the electrochemical response of printed films, resulting in 2.5 times higher optical modulation and 2 times faster coloration time when compared with pure amorphous films. © The Royal Society of Chemistry 2015.

Águas, H.a, Mateus Vicente Gaspar Mendes Schmidt Pereira Fortunato Martins T. a A. a. "Thin Film Silicon Photovoltaic Cells on Paper for Flexible Indoor Applications." Advanced Functional Materials. 25 (2015): 3592-3598. AbstractWebsite

The present development of non-wafer-based photovoltaics (PV) allows supporting thin film solar cells on a wide variety of low-cost recyclable and flexible substrates such as paper, thereby extending PV to a broad range of consumer-oriented disposable applications where autonomous energy harvesting is a bottleneck issue. However, their fibrous structure makes it challenging to fabricate good-performing inorganic PV devices on such substrates. The advances presented here demonstrate the viability of fabricating thin film silicon PV cells on paper coated with a hydrophilic mesoporous layer. Such layer can not only withstand the cells production temperature (150 C), but also provide adequate paper sealing and surface finishing for the cell's layers deposition. The substances released from the paper substrate are continuously monitored during the cell deposition by mass spectrometry, which allows adapting the procedures to mitigate any contamination from the substrate. In this way, a proof-of-concept solar cell with 3.4% cell efficiency (41% fill factor, 0.82 V open-circuit voltage and 10.2 mA cm-2 short-circuit current density) is attained, opening the door to the use of paper as a reliable substrate to fabricate inorganic PV cells for a plethora of indoor applications with tremendous impact in multi-sectorial fields such as food, pharmacy and security. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Águas, H.a, Mateus Vicente Gaspar Mendes Schmidt Pereira Fortunato Martins T. a A. a. "Thin Film Silicon Photovoltaic Cells on Paper for Flexible Indoor Applications." Advanced Functional Materials (2015). AbstractWebsite

The present development of non-wafer-based photovoltaics (PV) allows supporting thin film solar cells on a wide variety of low-cost recyclable and flexible substrates such as paper, thereby extending PV to a broad range of consumer-oriented disposable applications where autonomous energy harvesting is a bottleneck issue. However, their fibrous structure makes it challenging to fabricate good-performing inorganic PV devices on such substrates. The advances presented here demonstrate the viability of fabricating thin film silicon PV cells on paper coated with a hydrophilic mesoporous layer. Such layer can not only withstand the cells production temperature (150 °C), but also provide adequate paper sealing and surface finishing for the cell's layers deposition. The substances released from the paper substrate are continuously monitored during the cell deposition by mass spectrometry, which allows adapting the procedures to mitigate any contamination from the substrate. In this way, a proof-of-concept solar cell with 3.4% cell efficiency (41% fill factor, 0.82 V open-circuit voltage and 10.2 mA cm-2 short-circuit current density) is attained, opening the door to the use of paper as a reliable substrate to fabricate inorganic PV cells for a plethora of indoor applications with tremendous impact in multi-sectorial fields such as food, pharmacy and security. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pavan, M.a, Rühle Ginsburg Keller Barad Sberna Nunes Martins Anderson Zaban Fortunato S. b A. b. "TiO2/Cu2O all-oxide heterojunction solar cells produced by spray pyrolysis." Solar Energy Materials and Solar Cells. 132 (2015): 549-556. AbstractWebsite

Here we present for the first time a TiO2/Cu2O all-oxide heterojunction solar cell entirely produced by spray pyrolysis onto fluorine doped tin oxide (FTO) covered glass substrates, using silver as a back contact. A combinatorial approach was chosen to investigate the impact of the TiO2 window layer and the Cu2O light absorber thicknesses. We observe an open circuit voltage up to 350 mV and a short circuit current density which is strongly dependent of the Cu2O thickness, reaching a maximum of  0.4 mA/cm2. Optical investigation reveals that a thickness of 300 nm spray pyrolysis deposited Cu2O is sufficient to absorb most photons with an energy above the symmetry allowed optical transition of 2.5 eV, indicating that the low current densities are caused by strong recombination in the absorber that consists of small Cu2O grains. © 2014 Elsevier Ltd. All rights reserved.

Branquinho, R., Salgueiro Santa Kiazadeh Barquinha Pereira Martins Fortunato D. A. A. "Towards environmental friendly solution-based ZTO/AlOx TFTs." Semiconductor Science and Technology. 30 (2015). AbstractWebsite

Solution based deposition has been recently considered as a viable option for low-cost flexible electronics. In this context research efforts have been increasingly centred on the development of suitable solution-processed materials for oxide based transistors. Nevertheless, the majority of synthetic routes reported require the use of toxic organic solvents. In this work we report on a new environmental friendly solution combustion synthesis route, using ethanol as solvent, for the preparation of indium/gallium free amorphous zinc-tin oxide (ZTO) thin film transistors (TFTs) including AlOx gate dielectric. The decomposition of ZTO and AlOx precursor solutions, electrical characterization and stability of solution processed ZTO/AlOx TFTs under gate-bias stress, in both air and vacuum atmosphere, were investigated. The devices demonstrated low hysteresis (ΔV=0.23 V), close to zero turn on voltage, low threshold voltage (VT=0.36 V) and a saturation mobility of 0.8 cm2 V-1 s-1 at low operation voltages. Ethanol based ZTO/AlOx TFTs are a promising alternative for applications in disposable, low cost and environmental friendly electronics. © 2015 IOP Publishing Ltd.

2014
Bahubalindruni, P.a, Tavares Duarte Cardoso Oliveira Barquinha Martins Fortunato V. a C. a. "Transparent current mirrors using A-GIZO TFTs: Simulation with RBF models and fabrication." Proceedings - UKSim-AMSS 16th International Conference on Computer Modelling and Simulation, UKSim 2014. 2014. 582-586. Abstract

This paper analyzes transparent two-TFT current mirrors using a-GIZO TFTs with different mirroring ratios. In order to achieve a high mirroring ratio, the output TFT in the circuit employed a fingered structure layout to minimize area and overlap capacitance. The analysis of the current mirrors is performed in three phases. In the first, a radial basis function based (RBF) model is developed using measured data from fabricated TFTs on the same chip. Then, in the second phase, the RBF model is implemented in Verilog-A that is used to simulate two-TFT current mirrors with different mirroring ratios. The simulations are carried out using Cadence spectre simulator. In the third phase, simulation results are validated with the measured response from the fabricated circuits. © 2014 IEEE.

2013
Santos, R., Loureiro Nogueira Elangovan Pinto Veiga Busani Fortunato Martins Ferreira J. A. E. "Thermoelectric properties of V2O5 thin films deposited by thermal evaporation." Applied Surface Science. 282 (2013): 590-594. AbstractWebsite

This work reports the structural, optical, electrical and thermoelectric properties of vanadium pentoxide (V2O5) thin films deposited at room temperature by thermal evaporation on Corning glass substrates. A post-deposition thermal treatment up to 973 K under atmospheric conditions induces the crystallization of the as-deposited amorphous films with an orthorhombic V2O5 phase with grain sizes around 26 nm. As the annealing temperature rises up to 773 K the electrical conductivity increases. The films exhibit thermoelectric properties with a maximum Seebeck coefficient of -218 μV/K and electrical conductivity of 5.5 (Ω m) -1. All the films show NIR-Vis optical transmittance above 60% and optical band gap of 2.8 eV. © 2013 Elsevier B.V. All rights reserved.

Bahubalindruni, P.G.a, Tavares Barquinha Duarte De Oliveira Martins Fortunato V. G. a P. "Transparent current mirrors with a-GIZO TFTs: Neural modeling, simulation and fabrication." IEEE/OSA Journal of Display Technology. 9 (2013): 1001-1006. AbstractWebsite

This paper characterizes transparent current mirrors with n-type amorphous gallium-indium-zinc-oxide (a-GIZO) thin-film transistors (TFTs). Two-TFT current mirrors with different mirroring ratios and a cascode topology are considered. A neural model is developed based on the measured data of the TFTs and is implemented in Verilog-A; then it is used to simulate the circuits with Cadence Virtuoso Spectre simulator. The simulation outcomes are validated with the fabricated circuit response. These results show that the neural network can model TFT accurately, as well as the current mirroring ability of the TFTs. © 2005-2012 IEEE.

2012
Barquinha, P., Martins Pereira Fortunato R. L. E. Transparent Oxide Electronics: From Materials to Devices. Transparent Oxide Electronics: From Materials to Devices., 2012. AbstractWebsite

Transparent electronics is emerging as one of the most promising technologies for the next generation of electronic products, away from the traditional silicon technology. It is essential for touch display panels, solar cells, LEDs and antistatic coatings. The book describes the concept of transparent electronics, passive and active oxide semiconductors, multicomponent dielectrics and their importance for a new era of novel electronic materials and products. This is followed by a short history of transistors, and how oxides have revolutionized this field. It concludes with a glance at low-cost, disposable and lightweight devices for the next generation of ergonomic and functional discrete devices. Chapters cover: Properties and applications of n-type oxide semiconductors P-type conductors and semiconductors, including copper oxide and tin monoxide Low-temperature processed dielectrics n and p-type thin film transistors (TFTs) - structure, physics and brief history Paper electronics - Paper transistors, paper memories and paper batteries Applications of oxide TFTs - transparent circuits, active matrices for displays and biosensors Written by a team of renowned world experts, Transparent Oxide Electronics: From Materials to Devices gives an overview of the world of transparent electronics, and showcases groundbreaking work on paper transistors. © 2012 John Wiley & Sons, Ltd.

2011
Baptista, A.C.a, Martins Fortunato Martins Borges Ferreira J. I. b E. "Thin and flexible bio-batteries made of electrospun cellulose-based membranes." Biosensors and Bioelectronics. 26 (2011): 2742-2745. AbstractWebsite

The present work proposes the development of a bio-battery composed by an ultrathin monolithic structure of an electrospun cellulose acetate membrane, over which was deposited metallic thin film electrodes by thermal evaporation on both surfaces. The electrochemical characterization of the bio-batteries was performed under simulated body fluids like sweat and blood plasma [salt solution - 0.9% (w/w) NaCl]. Reversible electrochemical reactions were detected through the cellulose acetate structure. Thus, a stable electrochemical behavior was achieved for a bio-battery with silver and aluminum thin films as electrodes. This device exhibits the ability to supply a power density higher than 3μWcm-2.Finally, a bio-battery prototype was tested on a sweated skin, demonstrating the potential of applicability of this bio-device as a micropower source. © 2010 Elsevier B.V.

Elangovan, E., Saji Parthiban Goncalves Barquinha Martins Fortunato K. J. S. "Thin-film transistors based on indium molybdenum oxide semiconductor layers sputtered at room temperature." IEEE Electron Device Letters. 32 (2011): 1391-1393. AbstractWebsite

Thin-film transistors (TFTs) were fabricated using a 20-nm-thick indium molybdenum oxide (IMO) semiconductor layer at room temperature. The grazing incidence X-ray diffraction patterns confirmed that the deposited films are amorphous. The average transmittance (400-2500 nm) and the optical band gap are ∼88% and 3.95 eV, respectively. The TFTs fabricated on glass substrates showed a saturation mobility of 4.0 cm2/Vċ s with an I ON/IOFF ratio of 2 × 103 and a threshold voltage of-1.1 V, which are encouraging preliminary results in order to develop IMO as high-performance semiconductor layer. © 2011 IEEE.

2010
b Fortunato, E.a, Figueiredo Barquinha Elamurugu Barros Goņalves Park Hwang Martins V. a P. a. "Thin-film transistors based on p-type Cu2 O thin films produced at room temperature." Applied Physics Letters. 96 (2010). AbstractWebsite

Copper oxide (Cu2 O) thin films were used to produce bottom gate p-type transparent thin-film transistors (TFTs). Cu2 O was deposited by reactive rf magnetron sputtering at room temperature and the films exhibit a polycrystalline structure with a strongest orientation along (111) plane. The TFTs exhibit improved electrical performance such as a field-effect mobility of 3.9 cm2 /V s and an on/off ratio of 2× 102. © 2010 American Institute of Physics.

b Fortunato, E.a, Barros Barquinha Figueiredo Park Hwang Martins R. a P. a. "Transparent p-type SnOx thin film transistors produced by reactive rf magnetron sputtering followed by low temperature annealing." Applied Physics Letters. 97 (2010). AbstractWebsite

P-type thin-film transistors (TFTs) using room temperature sputtered SnOx (x<2) as a transparent oxide semiconductor have been produced. The SnOx films show p-type conduction presenting a polycrystalline structure composed with a mixture of tetragonal Β-Sn and α -SnOx phases, after annealing at 200 °C. These films exhibit a hole carrier concentration in the range of ≈ 1016 - 1018 cm-3; electrical resistivity between 101 - 102 cm; Hall mobility around 4.8 cm2 /V s; optical band gap of 2.8 eV; and average transmittance ≈85% (400 to 2000 nm). The bottom gate p-type SnOx TFTs present a field-effect mobility above 1 cm2 /V s and an ON/OFF modulation ratio of 103. © 2010 American Institute of Physics.

2009
Barquinha, P., Pereira Goņalves Martins Fortunato L. G. R. "Toward high-performance amorphous GIZO TFTs." Journal of the Electrochemical Society. 156 (2009): H161-H168. AbstractWebsite

This work analyzes the role of processing parameters on the electrical performance of GIZO (Ga2 O3: In2 O3:ZnO) films and thin-film transistors (TFTs). Parameters such as oxygen partial pressure, deposition pressure, target composition, thickness, and annealing temperature are studied. Generally, better devices are obtained when low oxygen partial pressure is used. This is related to the damage induced by oxygen ion bombardment and very high film's resistivity when higher oxygen partial pressures are used. Low deposition pressures and targets with richer indium compositions led to films with high carrier concentration, resulting in transistors with field-effect mobility as high as ∼80 cm2 Vs but poor channel conductivity modulation, becoming ineffective as switching devices. Nevertheless, it is demonstrated that reducing the GIZO thickness from 40 to 10 nm greatly enhances the switching behavior of those devices, due to the lower absolute number of free carriers and hence to their easier depletion. Annealing also proves to be crucial to control device performance, significantly modifying GIZO electrical resistivity and promoting local atomic rearrangement, being the optimal temperature determined by the as-produced films' properties. For the best-performing transistors, even with a low annealing temperature (150°C), remarkable properties such as μFE =73.9 cm2 Vs, onoff ratio≈7× 107, VT ≈0.2 V, and S=0.29 Vdec are achieved. © 2008 The Electrochemical Society.

2005
Martins, R., Barquinha Pimentel Pereira Fortunato P. A. L. "Transport in high mobility amorphous wide band gap indium zinc oxide films." Physica Status Solidi (A) Applications and Materials Science. 202 (2005): R95-R97. AbstractWebsite

This paper discusses the electron transport in the n-type amorphous indium-zinc-oxygen system produced at room temperature by rf magnetron sputtering, under different oxygen partial pressures. The data show that the transport is not band tail limited, as it happens in conventional disordered semiconductors, but highly dependent on its ionicity, which explains the very high mobilities (≥ 60 cm 2 V -1 s -1) achieved. The room temperature dependence of the Hall mobility on the carrier concentration presents a reverse behaviour than the one observed in conventional crystalline/polycrystalline semiconductors, explained mainly by the presence of charged structural defects in excess of 4 × 10 10 cm -2 that scatter the electrons that pass through them. © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

2002
Fortunato, E.a, Nunes Marques Costa Águas Ferreira Costa Godinho Almeida Borges Martins P. a A. a. "Transparent, conductive ZnO:Al thin film deposited on polymer substrates by RF magnetron sputtering." Surface and Coatings Technology. 151-152 (2002): 247-251. AbstractWebsite

In this paper, we present the optical, electrical, structural and mechanical properties exhibited by aluminum-doped zinc oxide (ZnO:Al) thin films produced by RF magnetron sputtering on polymeric substrates (polyethylene terephthalate, PET; Mylar type D from Dupont®) with a standard thickness of 100 μm. The influence of the uniaxial tensile strain on the electrical resistance of these films was evaluated in situ for the first time during tensile elongation. In addition, the role of the thickness on the mechanical behavior of the films was also evaluated. The preliminary results reveal that the increase in electrical resistance is related to the number of cracks, as well as the crack width, which also depends on the film thickness. © 2002 Elsevier Science B.V. All rights reserved.

2001
Nunes, P., Fortunato Martins E. R. "Thin film combustible gas sensors based on zinc oxide." Materials Research Society Symposium - Proceedings. Vol. 666. 2001. F521-F526. Abstract

Sensitivity tests to reductive gases such as methane, hydrogen and ethane were performed on zinc oxide (ZnO) thin films. The highest value of sensitivity was obtained for the film with a high electrical resistivity and a low thickness. The variation of the operating temperature of the film leads to a significant change in the sensitivity of the sensor with an ideal operating temperature dependence of the gas used. The sensitivity of the ZnO thin films changes linear with the increase of the gas concentration. However these films seem to be more appropriated for the detection of hydrogen following by methane and than for ethane since the value of sensitivity obtained are higher and its variation with the gas concentration more pronounced.

Fortunato, E.a, Nunes Marques Costa Águas Ferreira Costa Martins P. a A. a. "Thin film metal oxide semiconductors deposited on polymeric substrates." Materials Research Society Symposium Proceedings. Vol. 685. 2001. 146-151. Abstract

Highly textured transparent conducting ZnO:Al thin films have been prepared by r.f. magnetron sputtering. The films were deposited on polyester (Mylar type D, 100 μm thickness) and glass substrates at room temperature. Surface stylus profiling, X-ray diffraction, scanning electron microscopy, transmission electron microscope and Hall effect measurements as a function of temperature, using the van der Pauw technique have characterized the films. The samples are polycrystalline with a hexagonal wurtzite structure and a strong crystallographic c-axis orientation (002) perpendicular to the substrate surface (columnar structure). The ZnO:Al thin films with a resistivity as low as 3.6×10-2 Ωcm have been obtained, as deposited. © 2001 Materials Research Society.

Fortunato, E., Nunes Marques Costa Águas Ferreira Costa Martins P. A. D. "Thin film metal oxide semiconductors deposited on polymeric substrates." Materials Research Society Symposium - Proceedings. Vol. 666. 2001. F1131-F1136. Abstract

Highly textured transparent conducting ZnO:Al thin films have been prepared by r.f. magnetron sputtering. The films were deposited on polyester (Mylar type D, 100 μm thickness) and glass substrates at room temperature. Surface stylus profiling, X-ray diffraction, scanning electron microscopy, transmission electron microscope and Hall effect measurements as a function of temperature have been used to characterize the produced films. The samples are polycrystalline with a hexagonal wurtzke structure and a strong crystallographic c-axis orientation (002) perpendicular to the substrate surface (columnar structure). The ZnO:Al thin films with a resistivity as low 3.6×10-2 Ωcm have been obtained, as deposited.

Cabrita, A., Figueiredo Pereira Águas Silva Brida Ferreira Fortunato Martins J. L. H. "Thin film position sensitive detectors based on pin amorphous silicon carbide structures." Applied Surface Science. 184 (2001): 443-447. AbstractWebsite

The performances of silicon carbide position sensitive detectors in relation to position color selection applications were presented. The devices were deposited on glass substrates coated with a transparent conductive oxide layer based on indium tin oxide film (ITO). On top of the ITP layer a pin structure produced by plasma enhanced chemical vapor deposition technique was deposited. The set of data achieved indicated that the undoped silicon carbide layers presented a low density of states, which explained high dark conductivity values obtained and the type of performances recorded on the PSD devices produced.

2000
Martins, R., A̧guas Ferreira Fortunato Guimares H. I. E. "Towards the improvement of the stability of a-Si:H pin devices." Solar Energy. 69 (2000): 257-262. AbstractWebsite

This paper deals with a new process to improve the stability of a-Si:H pin solar cells deposited in a single batch process by proper passivation of the interfaces. The process consists in removing partially a deposited sacrificial oxide layer grown between the p/i or i/n interfaces by SF6 etching. This layer is an absorber of defects and impurities that are introduced in the interfaces, mainly from the chamber walls and the substrate surface. The results achieved in laboratory samples lead to devices in which the fill factor and short circuit current density were improved respectively towards 75% and 16.5 mA cm-2, with a final working efficiency of about 9.5%. © 2001 Elsevier Science Ltd. All rights reserved.

Águas, H., Cabrita Tonello Nunes Fortunato Martins A. P. P. "Two step process for the growth of a thin layer of silicon dioxide for tunnelling effect applications." Materials Research Society Symposium - Proceedings. Vol. 619. 2000. 179-184. Abstract

In today's main crystalline silicon (c-Si) applications in MOS (metal-oxide-silicon), MIS (metal-insulator-semiconductor) or SIS (Semiconductor-Insulator-Semiconductor), the growing of the oxide layer plays the main role, dictating the device performances, in particular if it has to be grown by a low temperature process. Of fundamental importance is the SiO2 interface with the c-Si. A very low defect density interface is desirable so that the number of trapping states can be reduced and the devices performance optimised. A two step low temperature oxidation process is proposed. The process consists of growing first a layer of oxide by a wet process and then treating the grown oxide with an oxygen plasma. The oxygen ions from the plasma bombard the oxide causing compaction of the oxide and a decrease in the interface roughness and defect density. Infrared spectroscopy and spectroscopic ellipsometry measurements were performed on the samples to determine the oxide thickness, optical and structural properties. SIS structures were built and capacitance measurements were performed under dark and illuminated conditions from which were inferred the interface defect density and correlated with the oxide growth process.

1999
Grigore, L.a, Meghea Grigore Martins A. b O. c. "Thermodynamic properties of ternary aqueous electrolyte solutions." Physics and Chemistry of Liquids. 37 (1999): 409-428. AbstractWebsite

In previous papers the mean excess chemical potential, μ1(E), in ternary systems of the type I sulphate + II sulphate + H2O, at 25°C was determined. Results obtained for systems with CuSO4(I), and ZnSO4(I) respectively, pointed out an obvious disparity between their behaviours. They show the existence of some important association phenomena partially accounting for the substantial deviations from ideal behaviour. The ternary sulphate systems (CuSO4 + Me(I,II)SO4 + H2O; ZnSO4 + Me(I,II)SO4 + H2O) studied were characterized against the binaries of the same ionic strength, experimental data being obtained using both e.m.f. and spectrophotometric methods. Deviations from the ideal behaviour were discussed in terms of thermodynamic excess functions and association constants. A comparative study between the results obtained with the two above mentioned methods is presented. In previous papers the mean excess chemical potential, μ1 E, in ternary systems of the type I sulphate+II sulphate+H2O, at 25 °C was determined. Results obtained for systems with CuSO4(I), and ZnSO4(I) respectively, pointed out an obvious disparity between their behaviours. They show the existence of some important association phenomena partially accounting for the substantial deviations from ideal behaviour. The ternary sulphate systems (CuSO4+MeI, IISO4+H2O; ZnSO4+MeI, IISO4+H2O) studied were characterized against the binaries of the same ionic strength, experimental data being obtained using both e.m.f. and spectrophotometric methods. Deviations from the ideal behaviour were discussed in terms of thermodynamic excess functions and association constants. A comparative study between the results obtained with the two above mentioned methods is presented.