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ADVANCED LABORATORY FOR THE NANO-ANALYSIS OF NOVEL FUNCTIONAL MATERIALS

Final Report Summary - AL-NANOFUNC (ADVANCED LABORATORY FOR THE NANO-ANALYSIS OF NOVEL FUNCTIONAL MATERIALS)

Executive Summary:
The AL-NANOFUNC project has been designed to install and fully develop at the Materials Science Institute of Seville (ICMS, CSIC-Univ.Seville Spain) an advanced laboratory for the Nano-analysis of novel functional materials. The Advanced Nanoscopy facilities, based on latest generation electron microscopy equipment, are devoted to breakthrough research in specific topics of high interest: i) Nanomaterials for sustainable energy applications; ii) functional nanostructured materials and coatings.

To take the ICMS laboratories to a leading position, the AL-NANOFUNC project was executed to up-grade the actual research potential in several directions:
i) To improve equipment capabilities by acquisition and commissioning of an analytical high resolution transmission electron microscope (TEM: Tecnai-G2-F30) equipped with a set of advanced detectors. The equipment was fully operative by March 2013 and is open to internal and external users.
ii) To improve the impact and excellence of basic research through hiring of experienced researchers and transnational exchange with the reference centers in Europe. In total 8 individuals were hired by the project: 3 experienced researchers, 2 early-stage researchers, 1 experienced engineer, 1 technician and 1 administrative manager. Project scientists and technicians received advanced training and benefited from the transnational exchange of researchers within the Network of collaborative centers. More than 65 short visits and 25 stays were executed during the project.
iii) To improve the research outreach and impact. During the complete duration of the project more than 70 projects benefited from the general microscopy services at the ICMS and produced more than 100 articles using these facilities. A total number of 28 papers in SCI journals were published reporting the results of the common research program within the network of collaborative centers.
iv) To develop and improve the innovation potential of the ICMS’s research by opening the new facilities to companies and stakeholders. Technical services were given and specific training courses and brokerage events were organized. Five research contracts were concluded with companies.
v) To improve the research visibility by organizing workshops and conferences. Three Al NanoFunc Workshops were organized together with a Final Conference highlighting the topics: i) Nanofilms & nanoparticles for sustainable energy conversion and storage; and ii) Last trends in electron nanoscopies.
vi) Dissemination activities to the general public included presentations at open door events, the organization of two scientific Photo-contests, and two sections in the web site “Al-NanoNews” and “Tiny(µ)scope”.

Close collaborations with reference centers and companies in Liège (Belgium), Graz (Austria), Jülich (Germany), Oxford (England), Cambridge (England), Dübendorf (Switzerland), Namur (Belgium) and Rabat (Morocco), as well as with laboratories at Andalusian Universities, were carried out in this project. Seven companies in Andalusia also collaborated in close synergies to promote long-term strategic lines of interest for the region.

The project execution was completed with the managing and coordination activities and the evaluation facility program mainly devoted to the set-up of a long-term sustainability plan.
Project Context and Objectives:
Project background:
In recent years the Materials Science Institute of Seville (ICMS, CSIC-Univ. Seville, Spain) has carried out significant work in the field of advanced functional materials. In particular, significant developments have been made within the following topics:
--Nanomaterials and nanostructures for energy and environmental applications: solar cells, catalysts for removing pollutants and green chemistry, hydrogen storage and sensors among others.
--Protective coatings: low friction, wear and corrosion resistance, UV-protection, and decorative applications, among others.
The Electron Microscopy facilities played a key role in the progress achieved by the research Institute and were continuously playing a fundamental role for the development of novel functional nanomaterials and competitive research lines. However further developments were severely limited by obsolete instruments, both the transmission electron microscopes and the associated spectroscopic equipment. Therefore the AL-NANOFUNC project was designed to up-date our equipment by incorporating latest-generation facilities for High Resolution Analytical TEM (transmission electron microscopy) as an essential tool to achieve breakthrough progress in the strategic research lines. The continuous development of research projects in the Institute funded by different agencies in the context of Nanotechnology was also an important driving force for the REGPOT project due to the increasing need of the scientific community to study materials at the nanoscale.
In addition the need of a deeper integration of the Institute in the ERA and in the research strategic lines of the Andalusian region was also considered in the context of the project. Close collaboration with a network of collaborating centres of excellence as well as bridge-building actions with stakeholders and companies in the Andalusian region were considered of high strategic interest for the Institute. Because of the strategic situation of Seville in the southernmost region of Spain, collaborations with research centres in the Maghreb region were additionally considered.

Project objectives:
In this context the AL-NANOFUNC project was set up for the installation and comprehensive development at the ICMS of an advanced laboratory for the nano-analysis of novel functional materials. It was intended to devote advanced nanoscopy facilities, based on latest generation electron microscopy equipment and techniques, to achieve breakthroughs in research on specific topics of high interest: i) nanomaterials for sustainable energy applications; and ii) functional nanostructured materials and coatings. With the aim of placing the ICMS laboratories at the leading edge in a field that is highly competitive on the world scale, the general objectives set for the AL-NANOFUNC were to generate new knowledge, increase visibility, and drive excellence at ICMS by upgrading the research infrastructures and human resources, and collaborating with partner Institutions, both in Europe and in the Maghreb region. Success would make a significant contribution to improving the potential in Andalusia and Europe for research in the specific strategic lines defined by the regional government. The potential of the research carried out at ICMS for developing commercially-valuable innovations would also be pursued in collaboration with selected stakeholders. Specific objectives have been defined, and associated with the work packages, as follows:

i) To increase equipment capacities through the acquisition of new Analytical High Resolution Electron Microscopy facilities, and the updating of capabilities and ‘best practice’ in the microscopy laboratories (WP1).

ii) To achieve scientific excellence in nano-analysis and advanced functional nanomaterials through the recruitment of experienced researchers, and the execution of transnational research programs supported by international exchanges of researchers with recognized reference centres: Namur (Belgium), Graz (Austria), Jülich (Germany), Oxford (UK), Cambridge (UK), Dübendorf (Switzerland) and Rabat/Fez (Morocco) (WP2, WP3, WP4).

iii) To become an Institute of prime interest for Andalusian and European stakeholders and fully integrated in the European Research Area. Publication of work; the organization of, and participation in, specialized conferences; dissemination of results; and take-up activities are important objectives for generating valuable synergies contributing to the long-term strategic lines of interest for the region of Andalusia (WP5, WP6).

iv) To promote excellence and sustainability through continuous evaluation, and to achieve the long-term sustainability of the Institute’s research potential and impact through preparation of a five years strategic plan after the AL-NANOFUNC project (WP8).
Project Results:
Specifically in WP 4 “Improving research outreach and impact through exchange of know-how” a common program for the execution of research has been included in AL-NANOFUNC, by definition of internal projects. The research plan is a rolling document that makes evidence of the common research strategy of the Institute, the network of collaborative centers, and the selected stakeholders. Researcher mobility and exchanges are linked to this research plan.

Three main strategic research lines have been identified as main topics to promote the ICMS research. These topics represent the ongoing research lines at the Institute and intend to improve the excellence and research potential in nanomaterials:
i) Nanomaterials for sustainable energy and protection of the environment.
ii) Thin films, coatings and multilayered structures.
iii) Fundamental studies of nanoparticles and nanostructures.
The knowledge of the microstructure of these new materials is crucial if we are to develop new products. Therefore nano-analysis is of noteworthy relevance in the development of the main scientific and technological results described below.

THIN FILMS, COATINGS AND MULTILAYERED STRUCTURES
Over the last decades the progress in thin films processing and surface treatment has enabled the development of tailored coatings and functionalization of surfaces, with enhanced performances and great potential for applications in microelectronics, nanotechnology, mechanics, optics, chemistry, and medicine, among others. Protective and multifunctional nanostructured coatings are examples of structures where the distribution of elements at the nanoscale is the key factor in determining their hardness and resistance to oxidation.
In particular main topics of interest in this project have been the fabrication, characterization, study of optical properties and applications of porous thin films.

In this project a new bottom-up methodology for producing porous silicon layers with closed porosity was deeply investigated.
The introduction of porosity in nanomaterials has been over the last decade a topic of increasing interest and research efforts have been focused on the synthesis and characterization of the newly designed porous materials. The fundamental understanding of the nanostructure allows to control and design materials with tailored functionalities.
Within many others, porous silicon is still nowadays one of the most actively researched materials for diverse applications such as sensors, photonic devices, microelectronics and solar energy conversion. Being fully compatible with the established microelectronics technology, the most attracting feature of porous silicon is the wide range of refractive indexes that can be achieved by varying the percentage of porosity.
As an alternative to the traditional electrochemical based processes of porous silicon production, we have demonstrated the possibility of producing porous silicon coatings with tailored refractive index (from 3.75 to 4.75 at 500 nm) by magnetron sputtering.
Our approach is a new bottom-up methodology where the deposition of amorphous layers with different porosity can be achieved by using He or Ar as deposition gas. The low refractive index coatings produced present a singular microstructure of closed pores that can be oriented on the coating’s growing direction. The influence of different deposition parameters (such as power supplied to the target, deposition geometry, gas composition and pressure, substrate bias and substrate temperature) in the pores nanostructure and its control was deeply investigated by electron microscopy. The main results of this research can be found in: “A new bottom-up methodology to produce silicon layers with a closed porosity nanostructure and reduced refractive index”. V.Godinho J. Caballero-Hernández, D. Jamon, T.C. Rojas, R. Schierholz, J. García López, F.J. Ferrer, A. Fernández, Nanotechnology, 24 (2013)275604. To emphasize here is the collaboration with the National Accelerator Center (CNA) from the University of Seville, CSIC and Junta de Andalucía in the evaluation of total He amount in the coatings not possible to perform by other characterization techniques.
Up to this point of the research it was needed to understand the mechanisms behind the formation of this porous structure. The low solubility of He in silicon, forming bubbles was previously reported for ion implantation, but was not explained the formation of closed porosity during thin film growth. To shed light on the microstructural evolution of magnetron sputtered a-Si coatings computer simulations were needed. Collaboration with the University of Namur and the SINCAF group at the ICMS was started to propose a model to understand the formation of the pores. As a first approximation a simple Monte Carlo model (NASCAM- developed at the University of Namur) was used to understand the influence of atomistic processes on the formation of the film nanostructure during growth when He and/ or Ar were employed. Selected deposition conditions were chosen and experimental results (by transmission electron microscopy (TEM)) were compared with simulations. The model fairly describes the main features of the coatings structure when using Ar as deposition gas. However in the case of He some pore dynamics would be expected, since it is known that He pores in metals grow through diffusion and coarsening of smaller pores. The main findings of this research up to now can be found in: “On the formation of the porous structure in nanostructured a-Si coatings deposited by dc magnetron sputtering at oblique angles”. V Godinho, P Moskovkin, R Álvarez, J Caballero-Hernández, R Schierholz, B Bera, J Demarche, A Palmero, A Fernández and S Lucas, Nanotechnology, Volume 25, 355705. The collaboration with the University of Namur is active beyond the project to further work on the simulation of porous coatings growth. It is important to mention that thanks to these first promising results the ICMS and the University of Namur have participated in a call for H2020 Research and Innovation Action(Call H2020-FoF-2015, Topic: ICT-enabled modelling, simulation, analytics and forecasting technologies) through the application of a project entitled “Infrastructure for modelling synthesis and intrinsic properties of advanced coatings - I2”

Apart from the advantages in industrial scale up of magnetron sputtering process, the low temperatures achieved during deposition allow to deposit over a wide range of substrates, including sensible substrates like polymers. Another important advantage of this procedure is flexibility for the design and production of different devices. For example single material Bragg reflectors or Optical Microcavities can be produced alternating porous and dense silicon layers in a single batch changing the deposition gas with an adjusted control of multilayer thicknesses. Results on the feasibility of photonic devices to work on IR- range can be found in the work: “Fabrication of optical multilayer devices from porous silicon coatings with closed porosity by magnetron sputtering” J.Caballero-Hernández, V.Godinho B.Lacroix M.C. Jiménez de Haro, D. Jamon, A. Fernández, submitted.

---The relevance of the advanced TEM techniques---

New analytical high-resolution electron microscopy techniques being pioneered by the Al-Nanofunc consortium gave the opportunity to better visualize these microstructures, helping to the development of new and improved low reflectivity coatings for solar cells and photonic devices.
Some the most relevant results concerning the incorporation of He in the coatings were only possible thanks to the advanced nano-analytical tools available in the new laboratory. The incorporation of high He amount (around 30 at%) inside the coatings was detected by proton backscattered Spectroscopy; but only by means of spatially resolved electron microscopy was possible to localize and evaluate the density and pressure of the He inside the pores. To this matter adequate TEM cross-sectional sample preparation was crucial. Quantitative STEM/EELS analysis of individual pores requires the preparation of thin lamella of less than 100nm thickness, which should include closed filled individual pores (note that the overlap of pores hampers the analysis). On the other hand, the data were acquired in a spectrum image data cube that required a dedicated analysis. For this purpose a MATLAB program was developed that is able to process the complete data cube at the same time.
The analysis proved that He is located inside the pores. The high density values obtained (~0.30GPa) point out that He inside the pores must be in a condensed state. Details on this work and the MATLAB program can be found in: “STEM-EELS analysis reveals stable high-density He in nanopores of amorphous silicon coatings deposited by magnetron sputtering”. R. Schierholz, B. Lacroix, V. Godinho, J Caballero-Hernández, M. Duchamp, A. Fernández, Nanotechnology 26(2015)075703

Finally we may emphasize that these materials allow storing a high amount of Helium at room temperature, to store a similar amount in a macroscopic container at room temperature a pressure of about 1kbar would be needed.


NANOMATERIALS FOR SUSTAINABLE ENERGY AND PROTECTION OF THE ENVIRONMENT
The strategic research orientation of this topic was a multidisciplinary research in which materials science is explored down to the nano-scale to develop novel solutions for energy applications. Within the different orientation lines of this topic, materials for hydrogen production and storage, metal catalysts, solar cells, photonic devices are topics of great interest for the ICMS, for regional stakeholders and also for the network of collaborative centers.
The scarcity of fossil fuels together with the environmental issues derived from their extensive use makes necessary to move to a greener energetic paradigm. Hydrogen economy appears as a good alternative because hydrogen is really abundant on earth and the production of energy through its combustion produces water as only by-product. However, for the implementation of a “hydrogen economy” the development of hydrogen storage, release and further combustion methods is identified as a bottleneck. Regarding hydrogen production and storage, many efforts was done during this project to produce relevant scientific results. In particular, the study of catalytic sodium borohydride (SB) hydrolysis was a key topic based on the development and study of catalytic materials, catalytic reactions and reactor design. Sodium borohydride is a safe and high hydrogen content storage materials which produces hydrogen on demand through its catalytic hydrolysis reaction.
Among catalytic materials, cobalt based materials are the most used for SB hydrolysis because they are cost effective. Though less active, they are the best candidates to replace noble metals which are expensive and scarce. To really fulfil the requirement of high activity and durability (typical of noble metals), cobalt based materials must be improved. Nanostructuring, doping and alloying were the strategies employed in our work to enhance the activity of the prepared materials.

i) Fundamental studies--
In particular, we have studied cobalt boron (Co-B) and bimetallic-boron (Co-M´-B) nanoalloys in powdery form as catalysts for sodium borohydride hydrolysis. Materials were prepared by wet chemical methods to produce highly amorphous or nanocrystalline catalytic materials. A first study on a Co-B material was performed from a structural and chemical point of view. The results of this study permitted to explain its high activity and stability for sodium borohydride hydrolysis. The role of boron in structure and activity of this material was elucidated by using many characterization techniques, including advanced EM (Electron Microscopy). This work set the basis for the study of catalysts from a fundamental point of view and the correlation of nanostructure, chemistry and catalytic activity.

It is known that the addition of a second metal to a M-B material to produce bimetallic-boron (M-M´-B) nanoalloys produces a synergistic effect improving catalytic activity respect to the single-metal nanoalloys (M-B and M´-B). This effect was studied for the Co-Ru-B as a case study in the form of ultrafine nanopowders. The Ru content was varied from 0 to 100%. All materials shown similar nanostructure by EM except for the Ru-B material which shown bigger particles. It was found that for the 13% Ru atomic content the enhancement in activity was three fold respects to the Co-B material. Further increase in Ru content produced even higher increase in activity. The main result of this work was the correlation of catalytic activity, found to be linear with Ru surface composition as measured by XPS (X-Ray-Photoelectron Spectroscopy). Cobalt surface segregation was found for the series of catalysts. Surface studies also shown a high tendency of Co containing catalysts to adsorb borates. These findings permitted not only explain activity tendencies by also predict catalysts´ stability respect to one deactivation mechanism. (G.M. Arzac, T.C. Rojas, A. Fernández, New insights into the synergistic effect in bimetallic-boron catalysts for hydrogen generation: The Co–Ru–B system as a case study, Appl. Catal B. Environ, 2012, 128, 39-47)

The structure of the series of Co-Ru-B materials was further studied using advanced EM studies. This work was conducted in collaboration with the Ernst Ruska centre in Jülich (Germany) and the Univ. of Cádiz from the network of collaborative centres and permitted to deeply study the materials from a structural, chemical and magnetic point of view with high lateral resolution in the nanoscale. This work completed the study of the series of Co-Ru-B materials prepared by wet chemistry in powder form (G. M. Arzac, T. C. Rojas, L. C. Gontard, L. E. Chinchilla, E. Otal, P. Crespo and A. Fernández, Chemistry, Nanostructure and magnetic properties of Co-Ru-B nanoalloys, RSC Adv, 2014, 4, 46576).

Going a step beyond in the preparation and elucidation of structure-chemistry-activity relationships of catalytic materials we implemented the use of magnetron sputtering as a preparation technique. Basic knowledge developed in this project regarding the sputtering technique was employed to prepare cobalt based materials as catalysts for sodium borohydride hydrolysis and ammonia borane in the form of thin films. The methodology has an added value in permitting to use a wide range of supports from metallic foams (Ni) to polymeric membranes. A series of Co based materials was prepared on Ni foam and tested as catalysts. Conditions were varied and it was found a correlation between deposition pressure, nanostructure, amorphous degree, column width and catalytic activity. This work permitted to set the basis in the preparation of catalysts by magnetron sputtering and tailoring their nanostructure for enhanced activity. (M. Paladini, G.M. Arzac, V. Godinho, M.C. Jiménez De Haro, A. Fernández. Supported Co catalysts prepared as thin films by magnetron sputtering for sodium borohydride and ammonia borane hydrolysis. Applied Catalysis B Environmental, 2014, 158-159, 400-409).

A new research line was started during the project regarding the catalytic combustion of hydrogen. This research is also a key topic in the context of the “hydrogen economy” and the field of application ranges from heating to safety devices. This work was performed in collaboration with EMPA (the Swiss Federal Laboratories for Materials Science and Technology) from the network of collaborative centres. In this work a platinum based washcoat supported on silicon carbide previously employed by EMPA laboratory for the design of a cooker, was studied from a fundamental point of view as catalyst for hydrogen combustion. The use of silicon carbide as support is a novelty of the work. The kinetics of the reaction was followed by a new methodology and the characterization of the catalyst permitted to explain its high activity (A. Fernández, G.M. Arzac, U.F.Vogt F.Hosoglu A.Borgschulte M.C. Jimenez, O. Montes, A. Züttel, Investigation of a Pt containing washcoat on SiC foam for hydrogen combustion applications, Submitted to: Applied Catalysis B Environmental) .

--The relevance of the advanced TEM techniques--
In the above mentioned works, the relevance of TEM techniques is very high. EM was used as a tool to characterize the prepared materials. EM was employed not only for obtaining images (nanostructure) but also for spectroscopy through EELS (core loss) to obtain chemical information (oxidation states) in the nanoscale with high lateral resolution. The information obtained with EELS was for the Co-Ru-B series complementary to EXAFS measurements. EELS and EDX elemental maps were fundamental in the study of bimetallic nanoalloys and surface segregation. Electron tomography shows 3D structure and connectivity of pores, which is important to understand catalytic processes.

ii) Practical applications--
Another scientific field within the study of hydrogen storage and release is reactors design, construction and study for practical applications. In particular we have worked with Abengoa Hidrógeno (a company in the Al-NanoFunc network) in the development of systems and reactors based on sodium borohydride hydrolysis to produce hydrogen for portable applications. Requirements on-demand of one liter per minute H2 generation, high hydrogen storage capacity, safety and low reactor volume were fulfilled. One of the designed reactors was connected to a 60W fuel cell and control devices where developed by the company for an automatic operation of the whole system. The methodology for producing hydrogen was the addition of stabilized borohydride solutions to a supported catalyst on a specially designed reactor through a pump. The methodology and conditions can be found in (M.A. Jiménez, M.M. Jiménez, B. Sarmiento, A. Fernández, G. M. Arzac, E. Jiménez. Process for the production of hydrogen by catalysed hydrolysis of a complex hydride, and facility with semi continuous reactor for carrying out the method. Patent ES 2387171 B1, US 201201565576 A1, owned by Abengoa Hidrógeno). A special monolith was constructed to deposit a Co-B catalyst by wet chemical methods. Knowledge obtained from fundamental studies above mentioned was employed in reactor design, catalyst election and preparation methods. Catalyst durability studies were performed on the Co-B material operating in the reactor in real practical conditions. These studies have the added value of studying durability on exactly the same operation conditions of the required applications (G.M. Arzac, D. Hufschmidt, M.C. Jiménez de Haro, A. Fernández, B. Sarmiento, M.A. Jiménez, M.M. Jiménez, Deactivation, reactivation and memory effect on Co-B catalyst for sodium borohydride hydrolysis operating in high conversion conditions, Int. J. Hydrogen Energy, 37, 2012, 14373-14381). The scanning electron microscopy facilities were also fundamental tools to characterize monoliths and supported catalysts.


FUNDAMENTALS STUDIES OF NANOPARTICLES AND NANOSTRUCTURES
Apart from more applied research as described above, fundamental studies on nanoparticles and different nanostructures are considered to be priority topics to deeply understand the microstructure and properties of nanomaterials, and to be able to predict their properties. The properties of nanostructured materials are not entirely understood due to the complexity of systems and the multi-scale nature of the phenomena involved. This explains the increasing interest towards the better understanding of structure formation, dynamics and growth of systems on the nanoscale. In our project we have been focusing on the study of novel nanoparticles (NPs). In particular core-shell and heterodimer structures are structures of great interest specially to control the dynamics and growth towards a tailored geometry. The application of advanced electron microscopy techniques to the specific characterization of NPs is a unique tool. Thanks to the Al-NanoFunc project we were in a very good position to do breakthrough research for the development of NPs of controlled nanostructure. Main results have been obtained in two systems:
i) Nanoparticles formed by a cobalt core and an iron oxide shell--
This work is a collaborative research from the Universities of Cambridge and Oxford (UK) and the ICMS in Sevilla (Spain), and it is a good example of the scientific advances achieved thanks to the advanced microscopy analysis. Core-shell nanoparticles were formed from the sequential decomposition of Co and Fe carbonyls, with organic capping agents present. Using statistically refined EFTEM and a calibrated EELS analysis, the phases of the core and shell of the nanoparticles were determined using the fine structure of the energy loss peaks of cobalt and iron. Additionally the presence of a carbonaceous layer of capping ligand residues separating the core and shell of the particles has been identified, shedding light on the possible mechanisms of particle formation and suggesting potential new routes to the synthesis of core-shell particles. “Characterisation of Co@Fe3O4 core@shell nanoparticles using advanced electron microscopy”. B. R. Knappett , P. Abdulkin , E. Ringe , D. A. Jefferson , S. Lozano-Perez, T. C. Rojas, A. Fernández and A. E. H. Wheatley. Nanoscale, 2013, 5, 5765.
ii) Heterodimers nanoparticles constituted by two separated domains of Pt and Au--
This study shows how to use polyhedral Pt nanocrystals (cubeoctahedra, octahedra and octapods) as building blocks for the rational construction of Au-Pt nanodimers that demonstrate epitaxial relationships to control the formation of heterodiemrs. The study enhances our understanding of heterometallic dimer formation and the well-defined nanostructures obtained promise to be of potential interest for the application of the Au-Pt heterodimers in catalysis and plasmonics. The work was done also in collaboration between the laboratories at the Univ. of Cambridge and the ICMS in Seville and makes use of the new TEM facilities installed within Al-NanoFunc. Details on this work can be found in: “Shape-defined nanodimers by tailored heterometallic epitaxy”. C. A. García-Negrete, T.C. Rojas, B.R. Knappett, D.A. Jefferson, A.E.H. Wheatley and A. Fernández. Nanoscale, 2014, 6, 11090–11097.

---The special case of studying Nanoparticles in biological environments---
The methodology termed scanning transmission electron microscopy in scanning electron microscopy (STEM-in-SEM) has been used at the ICMS to study the uptake of gold nanoparticles into tissue samples upon in vitro exposure of the dissected
gills of the Ruditapes philippinarum marine bivalve to the nanoparticle suspensions. The methodology has been optimized for achieving optimum resolution under SEM low voltage operating conditions what allowed to both localizing of the internalized nanoparticles and imaging of ultrastructural disturbances in gill tissues. Ultrastructural imaging of bio-nano features in bioaccumulation experiments have been demonstrated in this study. Details on this work can be found in: STEM-in-SEM high resolution imaging of gold nanoparticles and bivalve tissues in bioaccumulation experiments. C.A. García-Negrete, M.C. Jiménez de Haro, J. Blasco, M. Soto, A. Fernández. Analyst, 2015, 140, 3082–3089.

As a summary of dissemination activities in WP 5 we can emphasize that 28 articles in SCI journals were published (and 2 more are under review) reporting the results of the common research program defined in WP4. To improve the impact of the generated knowledge, open access publications have been provided as well as information in suitable repositories following the publisher’s licensing rules. A complete list of the 28 articles representing the core research carried out during the AL-NANOFUNC project can be found in the project web page at url ( http://www.al-nanofunc.eu/v-publications ) together with their links to the editorial version.
In addition, up to 100 articles were published using the SEM and TEM general facilities. Specific activities were undertaken with companies mainly in the Andalusian region: 5 research contracts were signed and more than 90 technical services provided.

COMPLETE LIST OF PUBLICATIONS REPRESENTING THE CORE S&T RESULS IN THE AL-NANOFUNC PROJECT
-- “Removing the effects of the “dark matter” in tomography”. Lionel C. Gontard. Ultramicroscopy, Volume 154, July 2015, Pages 64–72
-- “Hydrogen production through sodium borohydride ethanolysis”. G.M. Arzac, A. Fernández. International Journal of Hydrogen Energy, Volume 40, Issue 15, 27 April 2015, Pages 5326–5332
-- “STEM-in-SEM high resolution imaging of gold nanoparticles and bivalve tissues in bioaccumulation experiments”. Carlos Andrés García-Negrete, Maria Carmen Jimenez de Haro, Julian Blasco, Manu Soto and Asunción Fernández. Analyst, 2015, 140, 3082-3089, February 2015 - OPEN ACCESS
-- “Transmission electron microscopy of thiol-capped Au clusters on C: Structure and electron irradiation effects”. Lionel C. Gontard, Rafal E. Dunin-Borkowski. Micron, Volume 70, March 2015, Pages 41–49
-- “STEM–EELS analysis reveals stable high-density He in nanopores of amorphous silicon coatings deposited by magnetron sputtering”. Roland Schierholz, Bertrand Lacroix, Vanda Godinho, Jaime Caballero-Hernández, Martial Duchamp and Asunción Fernández. Nanotechnology, 26, 075703, January 2015
-- “Transmission electron microscopy of unstained hybrid Au nanoparticles capped with PPAA (plasma-poly-allylamine): Structure and electron irradiation effects”. Lionel C. Gontard, Asunción Fernández, Rafal E. Dunin-Borkowski, Takeshi Kasama, Sergio Lozano-Pérez, Stéphane Lucas. Micron, Volume 67, Pages 1–9, December 2014
-- “SUPPORTED Co CATALYSTS PREPARED AS THIN FILMS BY MAGNETRON SPUTTERING FOR SODIUM BOROHYDRIDE AND AMMONIA BORANE HYDROLYSIS”. M. Paladini, G.M. Arzac, V. Godinho, M.C. Jimenez de Haro, A. Fernández. Applied Catalysis B: Environmental, Volumes 158–159 Pages 400–409, October 2014
-- “Chemistry, nanostructure and magnetic properties of Co–Ru–B–O nanoalloys”. G. M. Arzac, T. C. Rojas, L. C. Gontard, L. E. Chinchilla, E. Otal, P. Crespo and A. Fernández. RSC Advances, Issue 87, 2014, 4, 46576-46586, September 2014
-- “Impregnation of carbon black for the examination of colloids using TEM”. Lionel C. Gontard, Benjamin R. Knappett, Andrew E.H. Wheatley, Shery L.-Y Chang, Asunción Fernández. Carbon, Volume 76 Pages 464–468, September 2014 - OPEN ACCESS
-- “On the formation of the porous structure in nanostructured a-Si coatings deposited by dc magnetron sputtering at oblique angles”. V Godinho, P Moskovkin, R Álvarez, J Caballero-Hernández, R Schierholz, B Bera, J Demarche, A Palmero, A Fernández and S Lucas. Nanotechnology, Volume 25 355705, August 2014 - OPEN ACCESS
-- “Tomographic Heating Holder for In Situ TEM: Study of Pt/C and PtPd/Al2O3 Catalysts as a Function of Temperature”. Lionel C. Gontard, Rafal E. Dunin-Borkowski, Asunción Fernández, Dogan Ozkaya and Takeshi Kasama. Microscopy and Microanalysis, Volume 20, Issue 03, June 2014, pp 982-990
-- “Shape-Defined Nanodimers by Tailored Heterometallic Epitaxy”. Carlos Andrés García, Cristina Rojas-Ruiz, Benjamin Knappett, D A Jefferson, Andrew Wheatley and Asunción Fernández. Nanoscale, June 2014, 6, 11090-11097 - OPEN ACCESS
-- “Bifunctional, Monodisperse BiPO4-Based Nanostars: Photocatalytic Activity and Luminescent Applications”. Ana Isabel Becerro, Joaquín Criado , Lionel C. Gontard , Sergio Obregón , Asunción Fernández , Gerardo Colón , and Manuel Ocaña. Crystal Growth & Design, 14 (7), pp 3319–3326, May 2014
-- “A Nanoscale Characterization with Electron Microscopy of Multilayered CrAlYN Coatings: A Singular Functional Nanostructure”. Teresa C. Rojas, Santiago Domínguez-Meister, Marta Brizuela, Alberto García-Luis, Asunción Fernández, Juan Carlos Sánchez-López. Microscopy and Microanalysis, Volume 20, Issue 01, Pages 14-24 , February 2014
-- “Plasma Deposition of Superhydrophobic Ag@TiO2 Core@shell Nanorods on Processable Substrates”. Manuel Macias-Montero, Ana Borras, Pablo Romero-Gomez, Jose Cotrino, Fabian Frutos, Agustin R. Gonzalez-Elipe. Plasma Processes and Polymers, Volume 11, Issue 2, Pages 164-174, February 2014
-- “Detecting single-electron events in TEM using low-cost electronics and a silicon strip sensor”. Lionel C. Gontard, Grigore Moldovan, Ricardo Carmona-Galán, Chao Lin and Angus I. Kirkland. Microscopy, Volume 63, Issue 2 pp 119–130, January 2014
-- “A new bottom-up methodology to produce silicon layers with a closed porosity nanostructure and reduced refractive index”. V. Godinho, J. Caballero-Hernández, D. Jamon, T.C. Rojas, R. Schierholz, J. García-López, F. J. Ferrer and A. Fernández. Nanotechnology, Volume 24, Number 27, June 2013 - OPEN ACCESS
-- “Characterisation of Co@Fe3O4 core@shell nanoparticles using advanced electron microscopy”. Benjamin R. Knappett, Pavel Abdulkin, Emilie Ringe, David A. Jefferson, Sergio Lozano-Perez, T. Cristina Rojas, Asunción Fernández, Andrew E. H. Wheatley. Nanoscale, Volume 5, Pages 5765-5772, June 2013 - OPEN ACCESS
-- “Structure and tribological properties of MoCN-Ag coatings in the temperature range of 25-700 °C”. D.V. Shtansky, A.V. Bondarev, Ph.V. Kiryukhantsev-Korneev, T.C. Rojas, V. Godinho, A. Fernández. Applied Surface Science, Volume 273, 15 May 2013, Pages 408–414
-- “Behaviour of Au-citrate nanoparticles in seawater and accumulation in bivalves at environmentally relevant concentrations”. C.A. García-Negrete, J. Blasco, M. Volland, T.C. Rojas, M. Hampel, A. Lapresta-Fernández, M.C. Jiménez De Haro, M. Soto, A. Fernández. Environmental Pollution, Volume 174, March 2013, Pages 134–141
-- “Strong quantum confinement effects in SnS nanocrystals produced by ultrasound-assisted method”. Yashar Azizian-Kalandaragh, Ali Khodayari, Zaiping Zeng, Christos S. Garoufalis, Sotirios Baskoutas, Lionel Cervera Gontard. Journal of Nanoparticle Research, January 2013, 15:1388
-- “New insights into the synergistic effect in bimetallic-boron catalysts for hydrogen generation: The Co–Ru–B system as a case study”. G.M. Arzac, T.C. Rojas, A. Fernández. Applied Catalysis B: Environmental, Volume 128, 30 November 2012, Pages 39–47
-- “Deactivation, reactivation and memory effect on Co-B catalyst for sodium borohydride hydrolysis operating in high conversion conditions”. G. M. Arzac, D. Hufschmidt, M. C. Jiménez De Haro, A. Fernández, B. Sarmiento, M. A. Jiménez, M.M. Jiménez. International Journal of Hydrogen Energy, Volume 37, Issue 19, October 2012, Pages 14373 - 14381
-- “Microstructural characterization of hydrophobic Ti1−xAlxN coatings with moth-eye-like surface morphology”. V. Godinho, C. Lopez-Santos, T.C. Rojas, D. Philippon, M.C. Jimenez de Haro, S. Lucas, A. Fernandez. Journal of Alloys and Compounds, Volume 536, Supplement 1, 25 September 2012, Pages S398–S406
-- “Microstructural and Chemical Characterization of Nanostructured TiAlSiN Coatings with Nanoscale Resolution”. Vanda Godinho, Teresa C. Rojas, Susana Trasobares, Francisco J. Ferrer, Marie-Paule Delplancke-Ogletree, Asunción Fernández. Microscopy and Microanalysis, Volume 18, Issue 03, June 2012, Pages 568 - 581
-- “Three-dimensional fabrication and characterisation of core-shell nano-columns using electron beam patterning of Ge-doped SiO2”. Lionel C. Gontard, Joerg R. Jinschek, Haiyan Ou, Jo Verbeeck and Rafal E. Dunin-Borkowski. Applied Physics Letters, Volume 100, Issue 26, June 2012
-- “Investigation of the Growth Mechanisms of a-CHx Coatings Deposited by Pulsed Reactive Magnetron Sputtering”. C. Lopez-Santos, J. L. Colaux, J. C. Gonzalez, and S. Lucas. The Journal of Physical ChemistryC, 116 (22), pp 12017 - 12026, May 2012
-- “Magnetron sputtered a-SiOxNy thin films: A closed porous nanostructure with controlled optical and mechanical properties”. V. Godinho, T.C. Rojas, A. Fernández. Microporous and Mesoporous Materials, Volume 149, Issue 1, 1 February 2012, Pages 142–146


Potential Impact:
An overview of obtained results and the impacts achieved, including socio-economic and societal implications, is presented here. A description of the main dissemination activities and the protection of IPR is also included.

1.- IMPACT FOR UNLOCKING AND IMPROVING THE RESEARCH CAPACITIES.

--In WP 1 “Upgrading of equipment and setting up of an up-date laboratory”: After the Al-NanoFunc project the ICMS has state-of-the-art facilities for the nano-analysis of novel functional nanomaterials properly installed and fully operative. This has broadened the range of new capabilities, multiplying our impact capacity significantly and increasing the attractiveness of the ICMS for other research and technological agents not only in Andalusia and the rest of Spain but also in Europe. The introduction of high standard quality control procedures and good practice has also been promoted.

--In WP 2 “Recruitment of research and other personnel”: The incorporation of experienced researchers in modern transmission electron microscopy methods had a significant impact on the quality and scope of our capacities in nano-analysis. The improvements achieved by working in close collaboration with the research groups developing new materials, has contributed significantly to improve the impact of our research in advanced functional materials. The hiring of a research manager with valuable scientific background in nanomaterials is having an evident beneficial impact on the efficiency of the organization, and is significantly improving take-up activities and relations with companies. Additional recruited personnel within the project included an early-stage researcher specialized in catalysis, a specialized engineer in electron microscopy equipment, an IT technician, and an administrative manager. The project had a positive impact on the recruited personnel which also played a critical role on the success of the project.
In total 8 individuals benefited from the project: 2 positions maintaining employment and 6 newly recruited. Among these 8 individuals, 4 have been retained after the project: 2 from the newly incorporated and 2 maintaining positions previous to Al-NanoFunc. These retained personnel represent important knowledge and expertise on advanced electron microscopy characterization coupled to the development of novel functional nanomaterials of high impact for the Institute research potential.

--In WP 3 “Transnational exchange of research personnel. Mobility plan”: Internationalisation and networking with the reference Centres of Excellence and stakeholders has increased strongly the visibility and exchange of know-how and knowledge in the specific topics of this project. Both young and experienced researchers have developed additional skills in new methods for nano-analysis through the mobility plan, thus improving research capacities at the ICMS in the field of functional nanomaterials.
In this work package our scientific impact was a continuously improved parameter during the life of the project, as our collaborations at both National and European levels improved strongly. The achievement of a substantial and good impact for the long term sustainability of the laboratory is foreseen. Incorporation in European programs like COST Action and applications to new European projects within H2020 are in progress.

It is important to mention here that the Institute and the new facilities especially after the REGPOT program fit very well the Research and Innovation Strategy for Smart Specialization (RIS3) of the Andalusian region. In addition actions were taken within the project to set up a collaborative network with other academic stakeholders in Andalucía. This network supported the acquisition and installation of complementary equipment in the available electron microscopy facilities at other Universities in Andalusia and organized a first workshop on “Electron Microscopy in Andalusia”. This orientation is also of high impact to unlock the research potential in the region.


2.- SOCIO-ECONOMIC IMPACT RELATED TO GENERATED FOREGROUND

--The project has an interdisciplinary character involving scientist from the main disciplines of Physics, Chemistry and Materials Engineering. These synergies are generating additional capacities to breakthrough research and to undertake more ambitious projects thanks to the REGPOT project.

--In WP4 “Improving research outreach and impact”: The research program executed in this project has been designed to improve the quality and impact of our research in functional nanomaterials as a consequence of more profound micro-structural knowledge at the nanoscale. As described previously in this summary numerous publications reporting the work done at Al-NanoFunc have achieved high impact factors. The Institute has increased its visibility represented by an increase of the average impact factor of the publications starting from 3.11 in 2010 to an average value of 3.65 in the period 2011-2013. All the new knowledge generated within the project has a potential socio-economic impact into different directions:
i) Nanotechnology is a key driven force for future technological advances. As a general topic the fundamental research on functional nanomaterials is nowadays of great interest and impact both at the scientific community and also for the general public. In particular fundamental new knowledge has been developed within the project in highlighted publications: Characterization by using advanced TEM techniques of bimetallic nanoparticles and development of analytical tools at the scanning electron microscope for the characterization of nanoparticles in eco-toxicity experiments.
ii) An important expertise and knowledge was also generated related to the microstructural and chemical characterization of nanostructured materials. Especially the experience working with thin films and coatings and their sample preparation for electron microscopy studies constitutes an important contribution to the ICMS portfolio of technological offers. The number of technical services to companies has increased during the REGPOT project.
iii) The research results on the hydrogen production through the hydrolytic dehydrogenation of light-weight hydrides have a strong relevance in the context of the use of hydrogen as energy carrier. These investigations on hydrogen technologies are fundamental to our society when considering the use of renewable energies to eliminate our dependence on fossil fuels.
iv) A new bottom-up methodology for the production of porous materials based on the use of He plasmas have been developed. A strong part of the know-how of the core team in Al-NanoFunc is related to the efficient control of composition, nanostructure and porosity of coatings by plasma-based synthesis, in particular by magnetron sputtering. This fundamental knowledge has been applied within the project to the development of optical and catalytic coatings

--In WP 5 “Dissemination activities”: In order to improve the impact of the generated knowledge, open access publications have been provided as well as information in suitable repositories following the publisher’s licensing rules.


3.- SOCIO-ECONOMIC IMPACT RELATED TO TAKE-UP ACTIVITIES AND WORK WITH COMPANIES.

--In WP 5 “Dissemination activities”: A network of collaborative companies in Andalusia was created including a program of take-up activities and specific dissemination activities.
i) On one side the number of technical services and collaborations with these companies has increased, mostly related to the microstructural analysis of materials by electron microscopy and related techniques. More than 90 technical services provided and 5 research contracts signed represent a strong improvement in the innovation potential of the ICMS’s research. ii) On the other side specific training courses and brokerage events were organized: Two courses on protection of IP/IPR, a brokerage day to present the new advanced laboratory, and a specific training on “Vacuum Deposition Technologies”.
--Specific activities for companies are also knowledge generating activities particularly the work under research contracts. In this sense it is worth to mention the generation of a patent, owned by the company financing the research, which has been granted in USA in 2013.

The orientation towards stakeholders was therefore quite effective with a high socio-economic impact in the region and also opening new possibilities to undertake join initiatives for the application to new European projects.


4.- OTHER SOCIETAL IMPLICATIONS

--In WP 6, “Additional activities to improve socio-economic impacts”, several activities not covered in WP5 have been undertaken for an active dissemination and to improve societal implications of the project.
i) The project makes special attention to safety procedures when working with nanomaterials. A section called “Nanosafety” can be found in the project web page with wide information on safety protocols. Other ethical concerns are not applicable in the present project.
ii) The Al-NanoFunc project is a good example of strong participation / promotion of Women in Science. In fact the project coordinator and the research manager are both women. For the recruited personnel using the project’s budget 50% were women. Also for the staff researchers & technicians participating in the core team of the project 66.66% were women. Specific gender equality actions were undertaken to improve the work-life balance by using flexible schedules for all personnel involved in the project.
The role of “Women in Science” has been also promoted for scholars.
iii) Awareness of the project results towards the general public and the synergies with the science education community was also achieved by participation of the Al-NanoFunc in open door events like the “Science & Technology week”, “Science café” and the “Science Fair”. Two scientific photo-contests were organized and various press releases, coverages in general (non-specialist) press and brochures were issued targeting the general public.
iv) Science education material can be also found in the project webpage at the section “Tiny(µ)scope”

--The impact of the project on employment at the ICMS in comparison to the situation before the REGPOT project represent an increase in employment in 2 persons and safeguard employment on another 2 persons. Also jobs publicity is available through our web page in section “Jobs”.

As a summary, the project is achieving its objectives and is strongly promoting the application of exciting new developments in Nanotechnology. The “hot” topics of “materials for energy” and “functional nanostructured materials and coatings” generate widespread interest in society among the general public, not only experts. The availability of new posts in this modern laboratory have also produced a strong impact by attracting more competitive scientists and encouraging “leading edge” lines of research and collaborations.
It is worth to mention the WP8 “Evaluation Facility”: The activities in this work package had their main impacts to identify the key issues and recommendations to set-up a long-term sustainability plan. This strategic plan will be fundamental to continuously improving the research potential of the ICMS for the next five years.
List of Websites:
Public website: http://www.al-nanofunc.eu/
Project coordinator : Asunción Fernández, asuncion @icmse.csic.es
Research manager : Vanda Godinho, research.manager@al-nanofunc.eu
Address: Instituto de Ciencia de Materiales de Sevilla, Av. Américo Vespúcio 49, 41092 Sevilla, Spain
Phone: +34-954489531 / 9527
Fax: +34-954460165