Development of emerging materials for non-conventional energy generation and storage devices

The main Research activity of CIEMAT in this project is the development of materials for innovation in (i) selective contacts, (ii) transparent electrodes free of crytical raw materials, and (iii) alternative active layers for applications in non-conventional energy generation and storage devices.

The Photovoltaic Solar Energy Group at the Centro de Investigaciones Energéticas Medioambientales y Tecnológicas (CIEMAT) is pioneering, together with the University of Barcelona, in the research of silicon-based solar cells in Spain. The group has a lot of experience in developing a complete silicon heterojunction solar cell technology. In this Project, CIEMAT investigates about non-conventional materials fabricated at low-temperature and by low-cost processes for silicon-based solar devices. Among them, it is worth mentioning transition-metal-oxides and organic compounds as novel selective contactsmetal nitrides as alternative light absorbers; and graphene to be implemented in the front electrode architecture. In addition, CIEMAT also takes part in the evaluation of the researched materials as possible solution for anodes of lithium batteries; and it is also involved in the creation of the environment needed for the exchange of information within the consortium and for the dissemination of results to the society.
Finally, CIEMAT coordinates the work package associated with the development of alternative absorbers and the improvement of the electrodes through the graphene incorporation.


Sputtered Non-Hydrogenated Amorphous Silicon as Alternative Absorber for Silicon Photovoltaic Technology

Susana Fernández, J. Javier Gandía, Elías Saugar, Mª Belén Gómez-Mancebo, David Canteli, Carlos Molpeceres

Non-hydrogenated amorphous-silicon films were deposited on glass substrates by Radio Frequency magnetron sputtering with the aim of being used as precursor of a low-cost absorber to replace the conventional silicon absorber in solar cells. Two Serie of samples were deposited varying the substrate temperature and the working gas pressure, ranged from 0.7 to 4.5 Pa. The first Serie was deposited at room temperature, and the second one, at 325 °C. Relatively high deposition rates above 10 Å/s were reached by varying both deposition temperature and working Argon gas pressure to ensure high manufacturing rates. After deposition, the precursor films were treated with a continuous-wave diode laser to achieve a crystallized material considered as the alternative light absorber. Firstly, the structural and optical properties of non-hydrogenated amorphous silicon precursor films were investigated by Raman spectroscopy, atomic force microscopy, X-ray diffraction, reflectance, and transmittance, respectively. Structural changes were observed in the as-deposited films at room temperature, suggesting an orderly structure within an amorphous silicon matrix; meanwhile, the films deposited at higher temperature pointed out an amorphous structure. Lastly, the effect of the precursor material’s deposition conditions, and the laser parameters used in the crystallization process on the quality and properties of the subsequent crystallized material was evaluated. The results showed a strong influence of deposition conditions used in the amorphous silicon precursor.

Optical Characterization of H-Free a-Si Layers Grown by rf-Magnetron Sputtering by Inverse Synthesis Using Matlab: Tauc–Lorentz–Urbach Parameterization

Emilio Márquez, Juan J. Ruiz Pérez, Manuel Ballester, Almudena P. Márquez, Eduardo Blanco, Dorian Minkov, Susana Fernández, Elías Saugar

Several, nearly-1-µm-thick, pure, unhydrogenated amorphous-silicon (a-Si) thin layers were grown at high rates by non-equilibrium rf-magnetron Ar-plasma sputtering (RFMS) onto room-temperature low-cost glass substrates. A new approach is employed for the optical characterization of the thin-layer samples, which is based on some new formulae for the normal-incidence transmission of such a samples and on the adoption of the inverse-synthesis method, by using a devised Matlab GUI environment. The so-far existing limiting value of the thickness-non-uniformity parameter, Δd, when optically characterizing wedge-shaped layers, has been suppressed with the introduction of the appropriate corrections in the expression of transmittance. The optical responses of the H-free RFMS-a-Si thin films investigated, were successfully parameterized using a single, Kramers–Krönig (KK)-consistent, Tauc–Lorentz oscillator model, with the inclusion in the model of the Urbach tail (TLUC), in the present case of non-hydrogenated a-Si films. We have also employed the Wemple–DiDomenico (WDD) single-oscillator model to calculate the two WDD dispersion parameters, dispersion energy, Ed, and oscillator energy, Eso. The amorphous-to-crystalline mass-density ratio in the expression for Ed suggested by Wemple and DiDomenico is the key factor in understanding the refractive index behavior of the a-Si layers under study. The value of the porosity for the specific rf-magnetron sputtering deposition conditions employed in this work, with an Ar-pressure of ~4.4 Pa, is found to be approximately 21%. Additionally, it must be concluded that the adopted TLUC parameterization is highly accurate for the evaluation of the UV/visible/NIR transmittance measurements, on the H-free a-Si investigated. Finally, the performed experiments are needed to have more confidence of quick and accurate optical-characterizations techniques, in order to find new applications of a-Si layers in optics and optoelectronics.

Indium tin oxide obtained by high pressure sputtering for emerging selective contacts in photovoltaic cells

D.Caudevilla, E.García-Hemme, E.San Andrés, F.Pérez-Zenteno, I.Torres, R.Barrio, R.García-Hernansanz, S.Algaidy, J.Olea, D.Pastor, A.del Prado.

This article studies the physical and electrical behavior of indium tin oxide layers (ITO) grown by an unconventional technique: High Pressure Sputtering (HPS), from a ceramic ITO target in a pure Ar atmosphere. This technique has the potential to reduce plasma induced damage to the samples. The aim is to obtain, at low temperature via HPS, good quality transparent conductive oxide layers for experimental photovoltaic cells with emerging selective contacts such as transition metal oxides, alkaline metal fluorides, etc. We found that the resistivity of the films was strongly dependent on Ar pressure. To obtain device-quality resistivity without intentional heating during deposition a pressure higher than 1.0 mbar was needed. These films deposited on glass were amorphous, presented a high electron mobility (up to 45 cm2V−1s−1) and a high carrier density (2.9 × 1020 cm−3 for the sample with the highest mobility). The optimum Ar pressure range was found at 1.5–2.3 mbar. However, the resistivity degraded with a moderate annealing temperature in air. Finally, the feasibility of the integration with photovoltaic cells was assessed by depositing on Si substrates passivated by a-Si:H. The film deposited at 1.5 mbar was uniform and amorphous, and the carrier lifetime obtained was 1.22 ms with an implied open circuit voltage of 719 mV after a 215 °C air anneal. The antireflective properties of HPS ITO were also demonstrated. These results show that ITO deposited by HPS is adequate for the research of solar cells with emerging selective contacts.

Roles of Low Temperature Sputtered Indium Tin Oxide for Solar Photovoltaic Technology

Susana Fernández, José Pablo González ,Javier Grandal, Alejandro F. Braña, María Belén Gómez-Mancebo, José Javier Gandía.

Different functionalities of materials based on indium tin oxide and fabricated at soft conditions were investigated with the goal of being used in a next generation of solar photovoltaic devices. These thin films were fabricated in a commercial UNIVEX 450B magnetron sputtering. The first studied functionality consisted of an effective n-type doped layer in an n-p heterojunction based on p-type crystalline silicon. At this point, the impact of the ITO film thickness (varied from 45 to 140 nm) and the substrate temperature (varied from room temperature to 250 °C) on the heterojunction parameters was evaluated separately. To avoid possible damages in the heterojunction interface, the applied ITO power was purposely set as low as 25 W; and to minimize the energy consumption, no heat treatment process was used. The second functionality consisted of indium-saving transparent conductive multicomponent materials for full spectrum applications. This was carried out by the doping of the ITO matrix with transition metals, as titanium and zinc. This action can reduce the production cost without sacrificing the optoelectronic film properties. The morphology, chemical, structural nature and optoelectronic properties were evaluated as function of the doping concentrations. The results revealed low manufactured and suitable films used successfully as conventional emitter, and near-infrared extended transparent conductive materials with superior performance that conventional ones, useful for full spectrum applications. Both can open interesting choices for cost-effective photovoltaic technologies.

High Pressure Sputtering of materials for selective contacts in emerging photovoltaic cells

Enrique San Andrés, Rodrigo García-Hernansanz, Gloria Patricia Moreno, Eric García Hemme, Rocío Barrio, Ignacio Torres, Daniel Caudevilla, David Pastor, Javier Olea, Álvaro Del Prado, Sari Algaidy, Francisco Zenteno.

In this work we have explored the growth by high pressure sputtering (HPS) of materials intended for novel selective contacts for photovoltaic cells. This technique shows promise for the low-damage low-temperature deposition of PV materials. We studied the deposition of ITO, MoO x and TiO x using pure Ar and mixed Ar/O 2 atmospheres as well as ceramic or metallic targets. We show that HPS deposition of these materials is feasible. The growth rate is greatly reduced when oxygen is added to the argon sputtering atmosphere. The best sputtering RF power was 20-45 W for the pressure range studied. Finally, as-deposited films present high surface recombination, but a mild hot plate anneal at 200°C recovers long effective lifetimes.

Sputtered Ultrathin TiO2 as Electron Transport Layer in Silicon Heterojunction Solar Cell Technology

Susana Fernández, Ignacio Torres, José Javier Gandía.

This work presents the implementation of ultrathin TiO2 films, deposited at room temperature by radio-frequency magnetron sputtering, as electron-selective contacts in silicon heterojunction solar cells. The effect of the working pressure on the properties of the TiO2 layers and its subsequent impact on the main parameters of the device are studied. The material characterization revealed an amorphous structure regardless of the working pressure; a rougher surface; and a blue shift in
bandgap in the TiO2 layer deposited at the highest-pressure value of 0.89 Pa. When incorporated as part of the passivated full-area electron contact in silicon heterojunction solar cell, the chemical passivation provided by the intrinsic a-Si:H rapidly deteriorates upon the sputtering of the ultra-thin TiO2 films, although a short anneal is shown to restore much of the passivation lost. The deposition
pressure and film thicknesses proved to be critical for the efficiency of the devices. The film thicknesses below 2 nm are necessary to reach open-circuit values above 660 mV, regardless of the deposition pressure. More so, the fill-factor showed a strong dependence on deposition pressure, with the best values obtained for the highest deposition pressure, which we correlated to the porosity of the films. Overall, these results show the potential to fabricate silicon solar cells with a simple
implementation of electron-selective TiO2 contact deposited by magnetron sputtering. These results show the potential to fabricate silicon solar cells with a simple implementation of electron-selective TiO2 contact.

Energy-band-structure calculation by below-band-gap spectrophotometry in thin layers of non-crystalline semiconductors: A case study of unhydrogenated 𝑎-Si

M. Ballester, A.P. Márquez, C. García-Vázquez, J.M. Díaz, E. Blanco, D. Minkov,
S.M. Fernández-Ruano, F. Willomitzer, O. Cossairt, E. Márquez.

We have in depth analyzed the refractive-index behavior and optical absorption of below-band-gap light, in order to calculate the basic parameters of the energy-band structure of thin layers of non-crystalline semiconductors. By carrying out a semi-empirical determination of the influence of the finite (non-zero) width of the valence and conduction electronic bands, we find the dependence of the index of refraction upon the photon energy, 𝑛(𝐸), which goes just one order beyond the Wemple–DiDomenico two-level single-oscillator expression, and we simultaneously obtain the spectral dependence of the absorption coefficient, 𝛼(𝐸). By model fitting the measured normal-incidence transmittance spectrum, we demonstrate that with a highlysensitive double-beam spectrophotometer, it can be accurately determined the energy distance, 𝐸M,Sol, between the corresponding ‘centers of mass’ of the bonding and anti-bonding electronic bands, and also a reasonable  estimate of the so-called effective width, 𝛥eff , of both valence and conduction bands. We have used this devised optical approach with a series of uniform and non-uniform thin layers of unhydrogenated fully 𝑎-Si, grown by RF-magnetron-sputtering deposition, onto room-temperature transparent glass substrates. The advantages of our novel approach are mainly due to the additional attention paid to the roles of the weak-absorption Urbach tail and the thickness non-uniformity of the studied 𝑎-Si films. We have also used a universal normalincidence transmission expression reported by the authors in an earlier paper, which can be applied even to strongly-wedge-shaped semiconductor layers. Together with the use of the improved Solomon formula for the normal optical dispersion of the refractive index, the complete approach with all its elements constitutes the main novelty of the present paper, in comparison with other existing works.

Hydrogenated Amorphous Silicon-Based Nanomaterials as Alternative Electrodes to Graphite for Lithium-Ion Batteries

Rocío Barrio, Nieves González, Álvaro Portugal, Carmen Morant, José Javier Gandía

Graphite is the material most used as an electrode in commercial lithium-ion batteries. On the other hand, it is a material with low energy capacity, and it is considered a raw critical material given its large volume of use. In the current energy context, we must promote the search for alternative materials based on elements that are abundant, sustainable and that have better performance for energy storage. We propose thin materials based on silicon, which has a storage capacity eleven
times higher than graphite. Nevertheless, due to the high-volume expansion during lithiation, it tends to crack, limiting the life of the batteries. To solve this problem, hydrogenated amorphous silicon has been researched, in the form of thin film and nanostructures, since, due to its amorphous structure, porosity and high specific surface, it could better absorb changes in volume. These thin films were grown by plasma-enhanced chemical vapor deposition, and then the nanowires were
obtained by chemical etching. The compositional variations of films deposited at different temperatures and the incorporation of dopants markedly influence the stability and longevity of batteries. With these optimized electrodes, we achieved batteries with an initial capacity of 3800 mAhg−1 and 82% capacity retention after 50 cycles

Effect of Argon on the Properties of Copper Nitride Fabricated by Magnetron Sputtering for the Next Generation of Solar Absorbers

C. A. Figueira, G. Del Rosario, D. Pugliese, M. I. Rodríguez-Tapiador  and S. Fernández

Copper nitride, a metastable semiconductor material with high stability at room
temperature, is attracting considerable attention as a potential next-generation earth-abundant thinfilm solar absorber. Moreover, its non-toxicity makes it an interesting eco-friendly material. In this work, copper nitride films were fabricated using reactive radio frequency (RF) magnetron sputtering at room temperature, 50 W of RF power, and partial nitrogen pressures of 0.8 and 1.0 on glass and silicon substrates. The role of argon in both the microstructure and the optoelectronic
properties of the films was investigated with the aim of achieving a low-cost absorber material with suitable properties to replace the conventional silicon in solar cells. The results showed a change in the preferential orientation from (100) to (111) planes when argon was introduced in the sputtering process. Additionally, no structural changes were observed in the films deposited in a pure nitrogen environment. Fourier transform infrared (FTIR) spectroscopy measurements confirmed the presence of Cu–N bonds, regardless of the gas environment used, and XPS indicated that the
material was mainly N-rich. Finally, optical properties such as band gap energy and refractive index were assessed to establish the capability of this material as a solar absorber. The direct and indirect band gap energies were evaluated and found to be in the range of 1.70–1.90 eV and 1.05−1.65 eV, respectively, highlighting a slight blue shift wh

Impact of Graphene Monolayer on the Performance of Non-Conventional Silicon Heterojunction Solar Cells with MoOx Hole-Selective Contact

Eloi Ros, Susana Fernández, Pablo Ortega, Elena Taboada, Israel Arnedo, José Javier Gandía and Cristóbal Voz

In this work, a new design of transparent conductive electrode based on a graphene
monolayer is evaluated. This hybrid electrode is incorporated into non-standard, high-efficiency crystalline silicon solar cells, where the conventional emitter is replaced by a MoOx selective contact. The device characterization reveals a clear electrical improvement when the graphene monolayer is placed as part of the electrode. The current–voltage characteristic of the solar cell with graphene shows an improved FF and Voc provided by the front electrode modification. Improved conductance values up to 5.5 mS are achieved for the graphene-based electrode, in comparison with 3 mS for bare ITO. In addition, the device efficiency improves by around 1.6% when graphene is incorporated on top. These results so far open the possibility of noticeably improving the contact technology of non-conventional photovoltaic technologies and further enhancing their performance.

Impact of the RF Power on the Copper Nitride Films Deposited in a Pure Nitrogen Environment for Applications as Eco-Friendly Solar Absorber

Rodríguez-Tapiador M.I.,Merino, J., Jawhari, T.,Muñoz-Rosas, A.L.,  Bertomeu, J., Fernández, S.

This material can be considered to be an interesting eco-friendly choice to be used in the photovoltaic field. In this work, we present the fabrication of Cu3N thin films by reactive radio-frequency (RF) magnetron sputtering at room temperature, using nitrogen as the process gas. Different RF power values ranged from 25 to 200 W and gas pressures of 3.5 and 5 Pa were tested to determine their impact on the film properties. The morphology and structure were exhaustively examined by Atomic Force Microscopy (AFM), Fourier Transform Infrared (FTIR) and Raman Spectroscopies and X-ray Diffraction (XRD), respectively. The AFM micrographs revealed different morphologies depending on the total pressure used, and rougher surfaces when the films were deposited at the lowest pressure; whereas FTIR and Raman spectra exhibited the characteristics bands related to the Cu-N bonds of Cu3N. Such bands became narrower as the RF power increased. XRD patterns showed the (100) plane as the preferred orientation, that changed to (111) with the RF power, revealing a worsening in structural quality. Finally, the band gap energy was estimated from transmission spectra carried out with a Perkin Elmer 1050 spectrophotometer to evaluate the suitability of Cu3N as a light absorber. The values obtained demonstrated the capability of Cu3N for solar energy conversion applications, indicating a better film performance under the sputtering conditions 5.0 Pa and RF power values ranged from 50 to 100 W.


Influencia de la incorporación del Zn en absorbentes de células solares de lámina delgada

B. Asenjo, A.M. Chaparro, J.J. Gandía

Laminas delgadas semiconductoras de ZnO depositadas químicamente para aplicaciones fotovoltaicas

B. Asenjo, J.J. Gandía

Graphene‐based electrodes for non‐conventional crystalline silicon solar cells

E. Ros Costals, S. Fernández, P. Ortega, E. Taboada, I. Arnedo, J.J. Gandía, C. Voz

Pressure effect on the properties of sputtered copper nitride films as solar absorbers

M.I. Rodríguez-Tapiador, A.L Muñoz-Rosas, J. López-Vidrier, J.M. Asensi, J. Bertomeu, S.M. Fernandez Ruano


Barrio R., González N., Portugal A., Pinilla S., Morant C.