Innovative Switchable Shading Appliances based on Nanomaterials and Hybrid Electrochromic Device Configurations

Final Report Summary - INNOSHADE (Innovative Switchable Shading Appliances based on Nanomaterials and Hybrid Electrochromic Device Configurations)

Executive Summary:
The FP7 Large Collaborative Project INNOSHADE concerned an innovative flexible electrochromic (EC) device technology with enormous application potential. Core of the achievement is a novel conducting polymer-polysiloxane nanocomposite coating with outstanding electro-optical properties: In seconds, it changes its visible light transmittance with high optical contrast upon application of a small electric voltage. The technology is envisaged for use whereever the modulation of light transmittance is desired, either for reasons of safety, comfort or energy saving. The novel EC devices have been evaluated with respect to different fields of application: ophthalmic lenses, domestic appliances as well as aircraft cabin and automotive windows. The development is characterised by a unique property profile beyond the state-of-the-art:
Large-scale, cost- and resource-efficient, and plastic-based technology.
Fast response for large-area devices and low power consumption.
Electrically triggered colour change between a fully colorless and a blue-to-neutral tint state.
Modular device set-ups and hybrid configurations, implying high flexibility of application.
Novel transparent electrodes with decreased resistance and improved TCO compositions.

To achieve this property profile several core steps had to be accomplished successfully:
Up-scaling of chemical precursor and substrate production to the pilot-line level.
Determination of essential structure/property relationships in roll-to-roll production of EC polymers, ion storage layers and transparent electrodes.
Optimisation of energy consumption and environmental impact by taking into account findings from life cycle assessment.
Development of viable device assembly protocols.
High precision coating and lamination machinery adaptation and fabrication.
Comprehensive application testing and device evaluation.

Different manufacturing options have been explored. The high-throughput production of device components was found to be feasible employing customised roll-to-roll machinery and semi-automatic pilot scale electrophoretic deposition. After adapation of slot die and pump configurations and the implementation of suitable quality control systems, high coating homogeneity and consistent electro-optical response was achieved. Life Cycle Assessment studies confirmed the low environmental impact of the technology. To fullfill the harsh standards of application under real-life conditions, a number of crucial parameters have been determined such as current and power consumption, optical transparency, level of haze, response time, cycle-life, optical homogeneity, application-related ageing, thermal stability, and mechanical ruggedness. Corner points are:
120.000 cycles without appreciable performance degradation under lab conditions;
High-temperature stability: operation -25 to 80 °C, survival -50 to 120 °C;
Power consumption <160 mA/switch for A3 sized device.
Mechanically flexible film for retrofitting purposes.

In a nutshell the INNOSHADE technology offers a new concept for fast responding large, light-weight, and flexible light transmittance modulation devices compyling with basic requirements concering lifetime, response time, and cost-effectiveness due to the employment of high-throughput manufacturing processes. The industrial participation of 5 SMEs and 4 multinational global players reflects the attractive economic perspectives of the project. Particular attention is now supposed to be paid to identifying potential producers that could establish a full prototype production based on the pilot-line findings.
Project Context and Objectives:
The Large Collaborative Project INNOSHADE was concerned with an innovative switchable light transmittance technology developed previously for small-sized objects (eyewear) [FP6 STReP NANOEFFECTS, #505664]. The core of this previous achievement was a new electrochromic (EC) conducting polymer-polysiloxane nanocomposite coating with outstanding electro-optical properties that changes its optical absorption properties (i.e. its colour) within seconds with a high optical contrast upon the application of a small electric voltage. The main polymerogenic precursor for this coating is a novel side-chain modified derivative of 3,4-ethylene dioxythiophene (EDOT), which is referred to as Monomer of Choice (MoC). MoC-based polymers show a high colouration efficiency (eta), implying that, inter alia, a lower energy consumption can be achieved in EC devices compared to the use of low eta materials.

The principle device configuration comprises the main EC layer (the polythiophene-polysiloxane nanocomposite), a counter electrode (CE) layer made from a high charge capacity ion storage material (e.g. Prussian Blue or nickel oxide) and a ion conducting solid polymer electrolyte layer (SPE) inbetween. This functional layer stack is situated between two transparent electrodes. Electrochromic devices based on this technology can be mechanically flexible and are intended for use in a multitude of applications where the degree of visible or infrared light transmittance must be controlled for reasons of safety, comfort and energy saving. INNOSHADE was supposed to enable the low cost production of such electrochromic shading elements. The work was performed by a well-balanced consortium of 17 partners from 7 member states, an associated, a candidate, and a third country, representing the entire value chain.

The overall objective of the project has been to scale up and study the underlying nanotechnology-based processes from laboratory to pilot line production, and explore the application potential of the new technology by creating interest of potential user groups and industries across sectors.

Procedures were to be implemented in order to establish pilot production lines for the individual device components as well as for their assembly to run-capable devices. Appreciable cost reduction was anticipated to be accomplished via high-throughput manufacturing such as continuous R2R (R2R) processing. A number of special aspects was addressed, such as transparent electrode conductivity, operating voltage, power drain, colour, (optical) contrast, and thermal working range.

Plastic-based EC devices (i.e. laminated film stacks as described above) may be attached to any surface such as plastic sheets or lenses, windows, doors, and even reflective surfaces, hence, can be used in multiple ways and for retrofitting purposes. The work was performed in three inter-related sub-projects representing the different application fields envisaged, namely ophthalmic lenses, home appliances, and aircraft cabin and vehicle windows.

The work has been performed in three strongly inter-related sub-projects:

Sub project I: Ophthalmic lenses (sub-project leader ESSILOR)
Sub project II: Domestic appliances (sub-project leader ARCELIK)
Sub project III: Aircraft and vehicle windows (sub-project leader EADS)

The project had a duration of four years and brought about all-plastic EC devices with unique property profiles presenting significant progress beyond the state-of-the art, such as:
A large-scale, cost- and resource-effective EC device technology, compatible with plastics (desirable for reasons of formability, flexibility, weight, and impact resistance);
A faster response for large-area devices and lower power consumption (use of materials with high colouration efficiency);
An EC colour change between a fully colourless state and a blue-to-neutral tint state;
Modular device set-ups and hybrid configurations, enabling:
- High-throughput pilot line production;
- A high flexibility of application (film-to-film, film-to-glass, film stack-to-lens);
- Retrofitting and outdoor use (e.g. flexible device attached to carrier).
Extraordinary cycling stability (blue tint only) due to charge balancing and adaptation of materials;
Novel hybrid transparent electrodes with decreased resistance and improved TCO compositions.

The INNOSHADE work plan comprised twelve work packages (WPs) overarching the three Sub-projects. It covered the whole range from a specification and screening phase (WP 1) to pilot line production of demonstrators (WP 8) via up-scaling (WP 2) and modelling tasks (WP 3), materials development (WPs 4 and 5), application testing (WP 6), and the implementation of the developed processes (WP 7). The technical work is being accompanied by a variety of training and staff exchange activities (WP 9). Efficient and continuous reviewing of the project and an assessment of its progress towards the set objectives have been performed in WP 10, which also included the task Use and Dissemination Planning. WP 11 comprised the overall project coordination and the implementation of management procedures, while WP 12 was addressing environmental issues, life cycle assessment, and occupational safety.

The technical project objectives of INNOSHADE (type and duration of work packages in parentheses):

WP 1 - Customer requirement specifications & state-of-the-art reports (RTD; 9 months)
Generate a working basis for work plan implementation by comprehensively defining the status and the functional and aesthetic requirements for the respective application.
Benchmarking

WP 2 - Up-scaling (RTD; 24 months)
Scale up and study underlying nanotechnology-based processes from laboratory to a pilot line production scale.
Overcome time-consuming batch processes and instrumental limitations in laboratory coating machinery.
Achieve cost reduction via high-throughput manufacturing.

WP 3 - Simulation & Modelling (RTD; 27 months)
Simulate the effect of thermal and mechanical stress on the components of EC devices.
Use software tools a) for screening material compositions, b) to design and pre-estimate processes and production lines and establish quality control systems for pilot line production.
Establishment/development/adaptation of relevant metrology

WP 4 - Thermal Operation Range (RTD; 18 months)
Determine the thermal working range of the underlying technology, in particular of critical components such as the electrolytes.
Identify polymeric materials capable of expanding the thermal survival range of the EC devices with regard to applications in aircrafts.
Check applicability in hot (up to 85 °C) environments.

WP 5 - Colour Modification & Optical Characterisation (RTD; 36 months)
Establish and prove colour modification concepts to obtain neutral tints mandatory for ophthalmic applications.
Realise a technology based on conducting polymer nanocomposites presenting a colourless state and a darkened state of adaptable tint.
Optical characterisation and durability testing.

WP 6 - Application Testing & Cycling (RTD; 36 months)
Assess the performance of the EC devices by means of application testing, long-term cycling, and environmental testing.
Optimise materials and device configurations in a targeted manner taking into account experimental and theoretical findings.

WP 7 - Design of Coating Machinery & Implementation (RTD; 24 months)
Check existing machinery in terms of suitability for the coating materials used or developed in the project.
Take findings as a basis for the conception of pilot-line machinery and accomplish the transfer from laboratory coating to high-throughput in-line coating.
Controlling coating homogeneity and thickness.
Consideration on the employment of quality control systems for all manufacturing steps.
Implement the designed processes and perform production research to develop a manufacturing strategy.

WP 8 - Pilot Line Production & Demonstrator Evaluation (DEM; 18 months)
Produce innovative shading device demonstrators based on nanomaterials on a pilot line scale. Focus on cost- and resource-efficient environmentally friendly processes.
Technology validation.
Consider potential applications for the new technology, as the case may be, beyond those targeted in the project (possible side-applications and spin-offs).

WP 12 - Environmental Aspects & Occupational Safety (RTD; 48 months)
Define a clear concept for the evaluation of environmental acceptability for products and processes.
Life cycle assessment of the new technology
Address occupational safety matters and potential environmental issues.
Elaborate on a concept for disposal or recycling.
Determine energy saving potentials

Non-technical objectives related to project management and other activities:

WP 9 - Training Activities & staff exchange (OTH; 30 months)
Advance science and underpin innovation by highly trained researchers
Attract and sustain public and private investment in research.
Contribute to the development of an open European labour market (ERA) for researchers and the diversification of their skills (incl. gender aspects).
Increase transnational and intersectoral mobility of researchers.

WP 10 - Review & Assessment incl. Use & Dissemination Planning (MGT; 42 months)
Efficient and continuous review of the project and assessment of its progress towards the set objectives.
Continuous patent and literature search and watch.
Continuous assessment of the potential of competitive technologies.

Project Management & Co-ordination - WP 11 (MGT; 48 months)
Implementation of management procedures such as appointment of a Steering Group and the nomination of the Exploitation Managers.
Launch and maintenance of the INNOSHADE website and web-based tools for conferencing and safe data interchange.
Make available web-based tools for conferencing and safe data interchange.
Day-to-day and overall project coordination.
Progress reporting to the European Commission.
Strategies for communication and dissemination of knowledge.

Project Results:
CUSTOMER REQUIREMENT SPECIFICATIONS & STATE OF THE ART

In order to generate a basis for the implementation of the work plan, the status and requirements for the respective electrochromic (EC) application were evaluated in the initial stage of INNOSHADE. The industrial representatives precisely laid down functional and aesthetic customer requirement specifications and finalised strategies how to address the multiple requirements set for the end-user applications. In addition, energy saving and health aspects as well as cost issues have been ad-dressed.

Sub-Project I Ophthalmic lenses: Specifications (specs) have been designed based on the last gen-eration photochromic lenses. The most important requirements were the darkened state colour (neu-tral), the bleached state transmittance (colourless), and the response time (less than 5 s). A cycle life stability lower than 105 was considered acceptable for a first generation EC product. Full devices were supposed to be thermoformable onto curved lenses (1 to 3 % of strain in every direction). The final product must not affect optical correction and comply with CE, FDA and EN standards (EN 1836 for solar lenses).

Sub-Project II Domestic appliances: Specs have been developed from aesthetic and energy saving points of view, taking into account consumer habits. The darkened state in an oven appliance should be powerless, the heat loss should be reduced in either state of the EC device (the window is the weakest point in terms of heat isolation). The maximum working temperature depends on the posi-tioning of the film in the appliance window the outer door of a standard oven reaches 60 °C max. For refrigerators or wine coolers, saturated colours are preferable and the power consumption should be less or equal to 2 W (transparent) and 0.5 W (shaded) for the entire appliance door. Opacity for thermal radiation is desired in either case. RoHS compliance 2002/95/EC is compulsory for any application. The final device was expected to be an EC plastic film laminated between two glass panes or, alternatively, attached to one glass pane.

Sub-Project III Aircraft and vehicle windows: A main motivation for EC cabin windows is the possible replacement of mechanical shutters for available space reasons. The temperature of opera-tion depends on the location of application and is not as low as the ambient temperature in cruising altitude. For the darkened state, a very low visual transmittance was desired (block 150.000 down to 100 Lux) and the window was supposed to return to a transparent (see-through) state when cur-rent-less. Aircraft cabin windows have a two years maintenance cycle, which may be used to replace deteriorated parts. Plastic-based EC technology is mandatory (weight!). Further, good mechanical resistance against vibrations and very low power consumption are important. For automotive window retrofits, huge markets were identifiable. Two sets of specs (Tier 1 and 2) were developed here, representing two different levels of sophistication.

Due to the large device sizes required particularly in sub-projects II and III and the high cost pres-sure for the corresponding applications, continuous in-line processing was considered imperative. A more cost-effective solution than the state-of-the-art vacuum technology based devices is required to be in line with the evolution and needs of the markets. This particularly holds for the domestic appliance and white ware market where margins are comparatively small.

The majority of companies and research centres active in the field work on inorganic electrochromes using glass as conductive substrate. EC sunglasses from PPG (WO3-based) were very expensive, highly power consuming and had an inacceptable design, hence flopped. Chromogenics AB were trying to commercialise EC films for motorcycle helmets (TintOnDemand?), but recently focused on architectural applications. Other players solely work on EC architectural glazing (Sage, EControl-Glas). A new dimmable EC aircraft cabin window comprising a glass-based EC device currently introduced by Boeing is probably employing viologens (organic dyes) from Gentex, although the chemistry is not disclosed. Sekurit-SaintGobains Lightuning product for automotive sunroofs is based on all-solid state technology (sputtered inorganic film stack between glass panes) and suffers from limited transparency levels and high cost. A lost-cost lab-scale eyewear device based on conductive polymer was reported by University of Washington in US2008/0239452. It changes colour from light green to dark blue but employs liquid electrolytes. Eyeonics (now Baush & Lomb) describe how to manufacture EC ophthalmic devices in terms of electric path frame construction and other. Regarding domestic appliances with active or passive energy saving glazing, apparently only PDLC technologies are used. The EC technology proposed in INNOSHADE was thus entirely new in the home appliance market. For home cooker doors, the benchmark was multiple heat protection glass with IR reflecting transparent conducting oxide (TCO) coatings.

The targeted INNOSHADE device configuration was clearly confirmed to be addressing the technical requirements of the market (in terms of colour, efficiency, stability, cost-effective production). Bringing this technology to a pilot-line level is cutting-edge research. There is only one other company working on roll-to-roll (R2R) production of EC devices, in this case, however, sputter deposition of metal oxides, i.e. a completely different and more expensive technology, is used. The INNOSHADE approach is novel and ahead of research performed elsewhere. This particularly concerns the innovative monomer (MoC) and colour modifier (ISO-x) systems, the high-performance self-standing solid polymer electrolyte (SPE) membranes, and the new approaches for cost-effective TCO (e.g. doped zinc oxides) pursued in the project.

UP-SCALING

The principle device configuration comprises the main EC layer (a polythiophene-polysiloxane nanocomposite), a counter electrode (CE) nanolayer made from a complementary colouring high charge capacity ion storage material (such as nickel oxide or Prussian Blue) and an ion conducting solid polymer electrolyte layer (SPE) in between. This functional layer stack is situated between two transparent electrodes.

[Figure 1. Basic sandwich-type EC device configuration pursued in INNOSHADE.]

Extensive and wide-ranging up-scaling activities presented a core part of the project, the intention of which was to scale up and study the underlying nanotechnology-based processes from laboratory to pilot-line production scale. This concerned all materials/layers of the EC devices. Different manufacturing options have been explored that were expected to converge towards the end of the project. One important aspect was the quest for a plastic-compatible TCO, highly conductive and transparent at the same time, thus enabling fast response in large EC devices. A main bottleneck for a fast response in EC devices is the limited electrical conductivity of the transparent electrodes.

The seven-step synthesis and purification of a crucial intermediate for the Monomer of Choice (MoC), i.e. the 3,4-ethylene dioxythiophene (EDOT) derivative used for the preparation of the main EC layer, has been transferred to a glass pilot plant (100 litres reactor volume), including the necessary process adaptation and elimination of upscaling-related issues. The synthesis and purifi-cation of MoC was optimised and an analytical procedure for quality control developed. Multiple and joint efforts had to be spent to alleviate the problem of interfering impurities and find a viable procedure to obtain a product with an impurity level of <0.5 % and an overall yield of around 55 %. After that, the MoC compound was readily available on a kilogramme level with high and constant purity.

To prepare the EC nanocomposite films, an in-situ chemical oxidative polymerisation procedure has been employed comprising the mixing of a formulated oxidiser solution with MoC and additives such as silane coupling agents. Thereafter, the polymerisation starts and the sol is applied to the substrate to be coated. In a third step, the wet film is thermally treated to complete the polymerisation. Eventually, the oxidant must be rinsed off the film (Scheme 1).

[Scheme 1. In-situ chemical oxidative polymerisation of MoC to form polyMoC films.]

The transfer of the in-situ polymerisation technique from laboratory coating techniques to R2R coating was established successfully. Eventually, the size of the substrate was limited only by the machinery used (maximum working width 500 mm) and the length of the plastic film rolls. The up-scaling activities converged in the preparation of run-capable sample devices complying with aircraft cabin window requirements in terms of size, weight, and transparency. Due to the moisture-sensitive nature of the technology, the entire device assembly has been performed during joint research visits to special dry room facilities.

Starting from small 0th generation devices, the sample dimensions have subsequently been scaled up to A5/A4 = 15 x 20 cm2/20 x 30 cm2 (1st/2nd sample generation), A3 = 30 x 40 cm2 (3rd sample generation), and A3+ = 30 x 45 cm2 (4th sample generation). Beforehand, working and counter electrodes (the so-called half-cells) had to be produced, which was achieved by employing R2R and electroplating pilot line equipment. Moreover, special doctor blade equipment was designed for polymer electrolyte resin application and installed in a dry room. Scaling up from small laboratory samples to A4 was straightforward; the lamination process and attainable response times (usually in the range of tens of seconds) proved to be essentially unchanged, regardless of the size of devices. A3+ size samples have been created to fit home cooker and refrigerator prototypes as well as A380 aircraft cabin windows. Figure 2 shows an A4 sized EC film device in relation to a standard aircraft cabin window frame (Airbus 320). The absence of any residual colouration in the bleached state and the high optical contrast are evident.

[Figure 2. A4 sized EC film positioned behind a standard aircraft cabin window frame. Photo: K. Dobberke for Fraunhofer ISC.]

Electrodeposited Prussian Blue (PB) films a well-suitable counter electrode material for polyMoC films and others are usually prepared via a time consuming batch processes. Economically more viable is the deposition from stable PB nanosuspensions, which can be used as inks for R2R coating. Thus obtained nano-PB films showed a highly reversible EC response up to the charge density required for fully balancing the polyMoC films. Further interesting high charge capacity ion storage materials are vanadia and nickel oxides that can be processed at temperatures as low as 150 °C via the sol-gel technique. Nickel oxides, though toxicologically questionable, were employed as model compounds to study possibilities to adapt the reduced state colour of EDOT polymers (blue to blue-violet), hence creating a mixed, more neutral colour.

In order to identify a material that could outperform ITO on PET film as transparent conductor, a considerable amount of work was devoted to the optimisation of the deposition conditions of TCO thin films using Pulsed Laser Deposition and Magnetron sputtering. Zinc oxides were found particularly favourable in terms of conductivity, abundance, and price (Indium shortage!). Among the various dopants tested, tetravalent Si and trivalent Ga led to the best performance. A value of 10 Ohm/sq. was achieved with 200 nm thick films of ZnO:Ga (GZO) on PET. The preparation of this material (including sputter target production) was implemented in an industrial pilot line for magnetron sputter deposition.

To get to even more flexible and conductive transparent electrodes, Cu grids have been employed. A grid of 1 micron thick Cu lines with only 5 % coverage of the surface provides an average sheet resistance lower than 1 Ohm/sq.. Although the mere Cu grids have been found to be unsuitable for use in EC devices, a combination with a thin layer of conductive coating was rewarding. Indeed, with a hybrid system GZO + Cu on PET, excellent 8 Ohm/sq. at 83 % transmittance could be achieved. The mechanical properties of such hybrid electrodes are better than the mere TCO (validated on randomly selected samples). The consortium have been working on a production process for Cu grids in combination with transparent coatings including vacuum thermal evaporation, mask printing, electroplating, chemical etching, and sputtering.

In order to overcome the necessity of sandwich lenses, the thermoforming (TF) capability of transparent electrodes and other EC device components have been evaluated. In this process, the films and devices must withstand a minimum of 1 to 3 % of relative elongation in every direction and retain the electro-optical performance after the operation. A number of TCO-plastic systems have been validated to fit the purpose. The brittleness of ITO layers was identified as the main limiting factor for the mechanical stability, the EC materials tolerated much stronger bending. The interfacial adhesion within the device turned out to be a second important parameter.

SIMULATION & MODELLING

Under one umbrella, diverse activities have been collected regarding the appliance- or software-based simulation and modelling of a variety of relevant effects, such as the environmental or application-related stress on plastic device components or the influence of TCO or EC material compositions on the electro-optical properties. In addition, special metrology useful for the characterisation and quality control of EC devices has been established.

For energy consumption modelling, unique prototypes have been designed by modifying domestic oven doorframes and the corresponding production machine in such a way that the frame could bear EC windows or films. The energy consumption tests were performed according to EN 50304:2001 at three different set temperatures.

In flexible organic electronic devices, the high brittleness and limited mechanical ruggedness of requisite inorganic thin films are a likely source of failure. It is, therefore, important to understand and improve the mechanical limits of these functional layers. Several PET/TCO films have been subjected to unidirectional tensile loading (fragmentation test) to record nominal stress-strain curves and to evaluate the maximum stress-strain within the linear elastic region. The fragmentation test enabled the accurate determination of failure mechanisms in the thin films, hence can be use as a benchmark for numerical simulations. It also provides quantitative values of the coating cohesion and adhesion to the substrate. A numerical computer simulation has been performed to simulate the number of cracks, the crack distribution, and the film fracture strength using a Weibull statistical analysis. The simulation successfully predicted the crack density and the distribution of fragment lengths during the progress of multiple cracking. The method has eventually been applied to full EC devices to identify the locations of mechanical failure and determine the elastic region. Two sample devices were then subjected to accelerated traction bending tests, each for 1000 cycles within the anticipated elastic limits of the samples. The sample devices survived both tests without any micro-scopically visible defects and still operating, which indicates excellent mechanical durability.

Essential for the targeted development of a fully balanced EC device is a reliable, time- and cost-effective technique to determine the thickness of nanoscale films. The method of Cross-Section Pol-ishing (CSP) has been employed to prepare well-defined cross-sections of very thin EC layers. From the respective high resolution scanning electron micrographs, the film thicknesses could be accurately determined without destroying the sensitive layers. The data were used to calibrate a white light interferometry set-up in order to establish a viable tool for reliable thickness measurements. To the same effect, ellipsometry has been used to determine important optical constants of the relevant layers.

A standard protocol for spectro-electrochemical device testing and cycling has been developed: a reference measurement for the transmittance (T%) of the bleached and coloured states, the response time, and the memory effect, followed by a cycling procedure to switch the devices between both states for a pre-selected number of cycles. The whole process was iterated until the desired cycle number was reached. A spectro-electrochemical procedure was established to monitor the presence and the cycling dynamics of short circuits in assembled devices. In order to determine colour coordinates and ascertain uniform hues of EC layers and devices, special algorithms to calculate from the optical spectra the colour coordinates have been made available. Further, a three-tool metrological system comprising electronic control units (ECU), dataloggers, and an automated optical inspection system with high optical resolution based on LED technology has been employed.

THERMAL OPERATION RANGE

The thermal working range of the underlying technology has been determined by means of climatic chambers and testing prototypes (ovens). The most critical component of an EC device (in terms of thermal working range) is the electrolyte layer, because the EC response is mainly controlled by the ion diffusion rate through this layer. A second important factor is a potential mismatch of the thermal expansion coefficients of the different layers and substrate films of an EC device. In a typical sandwich-type EC device five different interfaces exist, all of which can show delamination, when the mismatch is too strong to be borne by the compound.

A number of potentially suitable solid and gel polymer electrolyte systems have been evaluated:
Sol-gel processable ionic liquid-polysilsesquioxanes with low glass transition temperatures (typically below -57 °C), high transparency, and good gluing properties.
Very low Tg electrolyte (Tg = -87 °C) based hydrophobic non-inflammable ionic liquid-polyacrylate mixtures yielding homogeneous, sticky, and highly transparent polymer electrolyte membranes processable by R2R machinery. The material was useful for processing in ambient (i.e. moist) atmosphere.
UV-crosslinkable polyether acrylate resins forming leakage-free solid polymer electrolytes (SPE) with low Tg (< -62 °C). The materials have been processed on a Line Coater of working width 500 mm, which provided proof-of-concept for the pilot line production of SPE overcoatings on in-line fabricated EC layers.

A 1st generation EC film device employing SPE of the third type was tested in a tailor-made test cabinet allowing the simulation of all required environmental working conditions of a civil airplane. The latter consisted of a climate chamber with a programmable control of temperature from -55 to +85°C and humidity levels from 0 to 95% rel.H. Figure 3 shows an exemplary optical measurement at different temperatures between -50 and +50 °C. Although the EC response expectedly slows down going from high to low temperatures because of the slower ion diffusion rate, the dynamic range of the colour change remained unaffected, regardless of the temperature. Against the background of the decreased dynamic range of commercial smart glass windows at low temperatures, this behaviour goes well beyond the state-of-the-art. The film survived a temperature span of 100 °C and was operational at acceptable response times down to -25 °C. To prevent from bending due to thermal expansion mismatch, the films may be attached to thin Plexiglas sheets, which resembles the envisaged build-up of an airplane cabin window.

[Figure 3. Determination of the optical transmittance in clear and coloured state of an IN-NOSHADE EC film sample at temperatures from -50 to +50°C.]

1st and 2nd generation devices have been subjected to high temperature ageing tests employing special prototypes. Attached to the curved doors of air circular ovens, the EC films survived both short (60 °C for 360 h) and long term (80 °C for 720 h) ageing tests and worked well at testing temperatures up to 120 °C (the maximum thermal exposure at the outer pane of a standard home cooker is 60 °C). No remarkable changes were observed in terms of the switching function, transmittance, haze, and clarity.

All thermal testing results are consistent and indicate that INNOSHADE EC devices can survive in the temperature range of -50 to +120 °C and are operational in the range of -25 to +80 °C.

COLOUR MODIFICATION AND OPTICAL CHARACTERISATION

A special aspect of the project concerned the modification of the colours attainable with the polythiophene nanocomposite constituting the main EC layer. As required, this polymer is fully colourless in the oxidised state. The deep blue tint in the reduced state, however, is not suitable for a use in ophthalmic sunglasses due to colour distortion and marketability concerns. Among different strategies evaluated, the employment of EC redox dyes (co-polymerisation approach) and ion storage materials (counter electrode approach) capable to complement the colour of parent polymer and attain a neutral tint in the full EC device were most promising. One of the central challenges was to figure out dyes that would take on an orange-red or brown colour in the reduced form and show complete colourlessness in the oxidised state. The so-called ISO-x dyes, novel and unique azinium dyes with tailored pending side groups enabling homo- and co-polymerisation with EC host polymers, fitted the purpose (patent pending). Nickel oxides fulfil this criterion as well.

A large colour palette was achieved from reddish/violet via brown to grey hues with ISO-x polymers. The system of choice, polyISO-7 is a polymer (a material) far beyond the state of the art that can be reversibly switched between a fully colourless and a neutrally coloured state (Figure 4). There is no other material known that could outperform polyISO-7 in terms of transparency in the colourless state and colour neutrality in the reduced state (proven by comparative chromaticity analysis of and other neutral tint polymers from competitors).

A cycle-life exceeding 1000 cycles was demonstrated in a half-cell experiment with liquid electrolyte and the film deposited on a plastic substrate. The main limitation of the material seemed to be an incompatibility with lithium-based electrolytes, which turned out to be particularly relevant in the solid state, i.e. for full-cell performance. The limited solid-state performance has been attributed to charge trapping effects and the morphological evolution of the EC layer including its interfaces upon cycling. This conclusion was supported by Electrochemical Quartz Crystal Microbalance studies.

[Figure 4. Bleached (left) and coloured (right) states of a polyISO-7 colour modifier layer. Photos: R. Ruffo/UMIB.]

After technology transfer from laboratory synthesis, the synthetic route for the ISO-x dyes was adapted systematically to the framework conditions for industrial pilot-plant production (elimination or substitution of undesirable solvents, reduction of amounts of harmful compounds, improvement of yields, etc.). ISO-2 (six steps) was prepared on a 100 g scale in 90 % yield (calculated from final intermediate) as raw material. ISO-7 (10 steps, some of which identical with ISO-2 procedure) was prepared in 50-100 g batches in a glass autoclave, with a quality comparable to the reference material produced in the laboratory. The process of isolating and purifying the ISO-x dyes was demanding, but eventually a reliable procedure suitable for up-scaling could be proposed.

The evaluation of potential counter electrode materials with regard to their capability to adapt the colours of (blue) polythiophene or (brown) polyISO-x-based EC devices revealed nickel oxides and PB to be the most promising systems, respectively. Besides, WO3 and TiO2 have been evaluated as well-known reference materials. A large number of potentially suitable metal oxide thin films prepared via the sol-gel technique have been screened. Because of the low temperature stability of plastic substrates, however, the crystalline structures and the required intercalation properties of the majority of materials studied did not develop to full extent and the EC performance of the corre-sponding counter electrode films was below expectations. Because of these issues, the focus was laid on a nanodispersion approach, which allowed the preparation of NiOx and TiO2 films at low temperature with favourable properties. The main innovation was the use of nanoparticles with a NiOOH surface modification for dispersing pre-prepared NiOx particles in a suitable dispersant. Ni3+ containing NiOx films are necessary if lithium ion electrolytes are used. Deposition on PET-ITO film yielded coatings with a haze level of a few %, and, in combination with TiO2, neutral tints can be generated (Figure 5). Other device configurations reversibly switching from colourless to neutral tint states were [lithiated NiOx (prepared by Pulsed Laser Deposition) / ionic liquid / PEDOT] and [NiOx (sol-gel) / ionic liquid / WO3 (sputtered)]. The transmittance spectra of the latter are displayed in Figure 6. The absorption throughout the entire visible spectrum producing a neutral tint (black spectrum) is obvious. The comparison to a EC polymer-based reference device (i.e. the configuration preferred for the window applications) revealed a very slow (colouration) to slow (bleaching) response and a three times higher power consumption for the WO3/NiOx device. NiOx films have been produced by sputtering on an industrial pilot line.

[Figure 5. Application of a Ni1-xO pigment suspension on PET-ITO film on a COATEMA Smart-coater. Photo: M. Mohor/NIC.]

[Figure 6. Transmittance spectra of a neutral tint EC device with exceptional optical contrast.]

According to a market study of the domestic appliance sector, possibilities to achieve a change in haze (besides the EC effect) have been investigated. Coupled EC-PDLC (polymer-dispersed liquid crystal) tandem devices showing four instead of two states, i.e. a hazy blue, a clear blue, a hazy colourless, and a clear colourless have been proposed as a viable solution. Figure 7 illustrates the optical performance of such device assembled from a colourless PDLC film and a flexible EC device based on polyMoC and PB.

[Figure 7. Optical states of a PDLC-EC tandem device: hazy-colourless (PDLC off, EC 2.0 V / blue curve), clear-colourless (PDLC on, EC 2.0 V / green curve), clear-blue (PDLC on, EC -2.0 V / red curve), and hazy blue state (PDLC off, EC -2.0 V / black curve).]

A leak-proof solid polymer electrolyte has been employed to prepare larger PDLC-EC tandem device demonstrators approx. A5 in size. The demonstrator had high optical quality and showed impressive transmittance and transparency modulation.

In the course of the colour modification activities, index matching and optical characterisation of commercial and developed TCOs have been addressed and an electro-optical data base established.

APPLICATION & CYCLABILITY TESTING

Application testing and the determination of cycle-life have been performed on operational sample devices according to internal and customer requirement specifications imposed on by the end-user partners. To exclude moisture that could affect the performance, the device assembly has been performed under dry conditions (20 ppm H2O max.). Figure 8 depicts the first prototype EC film device made (size 10 x 10 cm2). The good optical contrast as well as the high transmittance (colourlessness) in the bleached state are obvious. This type of device has systematically been scaled up in terms of size and number of available samples in the course of the project. Based on the feedback from application testing, technical issues were systematically tackled and taken into account for the preparation of the subsequent generation of sample devices. For benchmarking purposes, commercially available EC prototypes from the market have been purchased from the market.

[Figure 8. Flexible plastic-based electrochromic device. Left: Bleached state, +1.5 V; Right: darkened state, -1.5 V.]

Ophthalmic Applications Subproject I

Against the background of achieving a neutral colour, all layers of a solid-state EC device are critical: the EC layer, the counter electrode (an EC material in itself) and the polymer electrolyte membrane. PolyISO-7 vs PB solid-state devices behaved differently from the polymer alone in solution. Upon cycling, the high energy band of the polyISO-7 absorption gets progressively bleached, whilst the device colour in the transparent state becomes more and more bluish. This unexpected behaviour was attributed to the partial incompatibility of the colour modifier polymer with the electrolyte employed. The quality (and durability) of the corresponding interface was found to be crucial. Model experiments with a liquid electrolyte cell clearly showed that a device having a polyISO-7 co-polymer as the working electrode and PB as the counter electrode is indeed characterised by a neutral tint dark state and can be cycled in ambient atmosphere hundreds of times without appreciable degradation. However, the transfer of all findings to stable solid-state devices was not crowned with full success, even though a large number of materials and device assembly protocols were ex-plored with reasonable diligence.

It was concluded that processing, standardisation, and automation highly matter. Due to the large number of different factors (salt and electrolyte chemistry, pre-treatments and processing methods, curing and/or pressing times, etc.) and materials incompatibilities, Design-of-Experiment methods are probably necessary to figure out the optimum configuration and remove the shortcomings. The neutral tint issue thus presents a classical OFAT problem it is too complex to be solved by varying one factor at a time.

In accelerated weathering/light exposure tests, reasonable light stability has been achieved for blue colouring polyMoC-based devices under open circuit conditions (passed 80 h in a QSun-Test using a UV filter). For non-coloured ophthalmic coatings, it is anticipated that 80 h in a QSun-Test with an irradiance of 0.67 W/m2 at 340 nm and at 50 °C roughly correspond to 2 years of wear in terms of defects appearance. Application testing was supplemented by electronic compatibility checks with lens frames and lens wearer perception testing. A portable device power supply and electro-optical testing equipment have been designed and manufactured for cycling tests under different bias conditions.

Application in home appliances Subproject II

In view of an application in refrigerator appliances, current and power consumption, optical transparency, and haze measurements have been performed. Some samples have been enclosed between glass panes and sealed hermetically to simulate the situation in an appliance door. In the course of the project the optical homogeneity and cycling stability have been successively improved (Figure 9); the haze level has been considered well suited for the application. The visually conceivable response of the shown demonstrator was 30 s and 20 s for colouring and bleaching, respectively. According to the current consumption (drop below 20 mA level), the switching processes were fully completed after 140 s and 90 s. The same sample was re-tested after storage at ambient conditions for 3 months, which revealed unchanged characteristics. It was concluded that all major technical requirements were met for use in appliances such as refrigerators or wine coolers, but the targeted final size could not be attained. Moreover, because of the fast responding PDLC benchmark a faster response down to 1-3 s would have been desirable. However, it was acknowledged that electrochromic devices, as they are diffusion-controlled systems, are intrinsically slower than LC systems (merely orienting in an electric field, without mass flux).

[Figure 9. Left: Coloured state, right: bleached state of an INNOSHADE appliance door demonstrator. Photos: B. Kralj/ GORENJE.]

Automotive and aircraft applications Subproject III

Two different options have been defined based on the applicability of the technology in the automotive sector for applications with medium and high technical requirements. The results were assessed against both tiers:
Option 1: Applications for medium technical requirements (Tier 2 Retrofit option)
Option 2: Applications for high technical requirements (Tier 1 Inclusion in glazing)

A3 sized EC film samples were used to match selected Tier 2 performance indicators with the actual achievements. The devices were complying with the requirements in terms of power consumption (<500 mA), response time (around 30 s from bleached to coloured), cycle-life (1200 cycles/wk; total 5.000 cycles without appreciable degradation), thermal operation range (-20ºC to +65 ºC), memory (4 % variation in 24 hours), and colour homogeneity (below visual perception level). With regard to the high-level Tier 1 requirements, there are still some shortcomings to be solved such as larger dimensions and a higher contrast.

INNOSHADE devices have also been evaluated with respect to civil aerospace requirements. The envisaged application was the replacement of the mechanical curtain of airplane cabin windows with an electrically dimmable system. To be assessed were the stability against humidity and thermal loads, the determination of driving parameters (power consumption, voltage and current) in the service conditions of a civil airplane, the measuring of light shading and switching behaviour, and the development of possible concepts for device integration in an airplane infrastructure. Cabin windows consist of an outer and an inner window pane with a distance in between, where the EC device may be placed on the inside face of the inner pane. The frame of the window offers enough space - not visible for the passengers - to hide a good sealing and electric connections.

To assess the light stability, a sample device was exposed to simulated solar radiation according to ASTM/ISO specification and repeatedly characterised after certain periods of exposure (cumulated total exposure 456 h). The sample was loosely covered by an acrylic glass validated for aviation purposes with a UV transmittance of fewer than 1 % to simulate the situation in an aircraft cabin window. Further encapsulation or protection from moisture was not accomplished. Even though no weathering standard exists for EC windows and laboratory accelerated testing is known to not correlate to real-life ageing, the results indicated that effective UV protection is probably indispensable to extend long-term cyclability and colour fastness in outdoor applications such as car sunroofs and aircraft cabin windows. Also, the impact of moisture on the degradation of the material and the effect of post-crosslinking processes needs to be examined and understood.

Under ambient conditions and with simple adhesive tape as edge sealing, permeation of oxygen and moisture through the seals along the edges was found to cause degradation of the electrolyte, while the inner part of the device was still perfectly working after 10.000 cycles and beyond. Areal permeation of oxygen and water vapour through the substrate seemed to be negligible.

For this reason, 4th generation prototypes have been cycled under inert conditions to simulate optimised sealing properties. Protecting the devices so revealed an extraordinary cycling stability for the R2R processed system polyMoC vs nano-PB, i.e. 120.000 cycles without appreciable degradation, showing constantly homogeneous colouration and high contrast (Figure 10). The comparison with a 4th generation device having an electrodeposited PB counter electrode yielded a very similar picture, indicating there is no pronounced difference in terms of cycle-life between devices based on electrodeposited (i.e. batch processed) and R2R coated (i.e. continuously processed) counter electrodes. This is considered a highly important result with respect to processing cost and reproducibility.

[Figure 10. Cycle stability of an A5 sized polyMoC vs nano-PB sample device under laboratory conditions. From left to right: bleached state at cycle 1, coloured state at cycle 1, bleached state at cycle 120.000 and coloured state at cycle 120.000. Photos: M. Salamone/INSTM-UMIB.]

DESIGN OF COATING MACHINERY & IMPLEMENTATION

Based on preliminary coating trials, provisions for the pilot line production of device components were made in the early stages of the project. The transfer from laboratory coating to high-throughput in-line coating was successful. It was shown that Click&Coat R2R machinery from COATEMA can be used for the production of EDOT-based EC polymer coatings on flexible conducting film (= production of working electrode). With respect to the production of suitable counter electrodes, two approaches were pursued, i.e. the application of PB nanoparticle suspensions and the electrodeposition of PB thin films on a semi-automatic pilot scale electrophoretic deposition machine. Moreover, other potential counter electrode materials were investigated, such as vanadia and nickel oxide.

For the application of the coating solution, a slot die system was used. Spray/jet and knife coating were not an option. High-throughput cleaning can be accomplished by Corona treatment. MoC may be applied by the in-line coating procedure as easily as the reference monomer EDOT. Certain differences must be taken into account, though, such as the different solids content, viscosity, and reactivity of the MoC coating mixture. When going to lower coating thicknesses, mechanical assembly parameters of the slot die are found to be of outmost importance for wet film quality.
A very important and unique feature of the coating line is a proprietary air-conditioned in-situ polymerisation (ISP) module for polyMoC processing. In this in-situ polymerisation zone, the polymerisation of the liquid monomeric coating material and the evaporation of the solvent can proceed under controlled conditions. The ISP zone was optimised in terms of length and air-conditioning parameters, which was crucial for achieving reproducible degrees of polymerisation and adhesion results.

The findings from a large number of coating trials (scaling up, optimisation of slot die geometry, special air condition provisions) were taken into account to built a 17 m long ex-proof pilot line for the production of half-cells and full devices (Figure 11). The line is equipped for:
functional nanocoating and polymer electrolyte application,
pre-polymerisation under controlled conditions (air-conditioned in-situ polymerisation module),
feeding protecting film,
inclusion of a rinsing module, and
half-cell lamination under protective atmosphere (dry N2),

The machinery layout is consisting of 12 individual and movable process modules allowing the flexible arrangement of process steps. Each module is equipped with its own switch cabinet and plug connection. The maximum web width is 580 mm, with a maximum working width of 500 mm.

[Figure 11. CC09 Pilot line after assembly. Photo: N.N. for COATEMA.]

Besides, it was aimed to prepare EC lenses by transferring blue colouring polyMoC vs PB devices onto curved lenses by thermoforming (TF). The proprietary TF method was specially developed for this purpose and anticipated to present a high-throughput solution more viable than, for instance, the preparation of sandwich lenses. It was found that the EC films could be cut to the desired size by laser cutting and withstood the mechanical (1 to 3 % of relative elongation) and thermal load occurring during the TF process. However, limited or degrading (with time) interfacial adhesion remained an issue; doubts about the viability of the technology could not be fully dissipated. The laser cutting process was implemented in the final process to prepare eyewear demonstrators.

All procedures developed were implemented to produce the individual device components (device half-cells) as well as to accomplish their assembly to run-capable devices (lamination). During extensive coating trials several aspects were addressed, such as, for instance, the correlation of dry film thickness and the charge capacity of the films, the improvement of reproducibility of working electrode deposition in terms of degree of polymerisation and film thickness, and the improvement of nano-PB deposition from aqueous suspensions (avoiding agglomeration and improving of smudge resistance) as a R2R alternative to batch electrodeposition. In total, some 130 trials have been performed with different objectives set.

The INNOSHADE process and equipment development has entirely been performed such that the corresponding products show better performance and/or better environmental profiles compared to the state-of-the-art in electrochromic windows. From the very beginning, the research focused one issues hampering (or factors compulsory for) a competitive production.

The following important aspects (with actual achievements given in brackets) have been identified and addressed:
Fast adaptability of the processes (modular multifunctional pilot-line);
Market orientation (market studies performed by end user and supplier partners, strong demand for flexible, light-weight and cost-effective EC device system confirmed);
Sustainable economy (wet-chemical low-temperature processes, recyclable solvent emissions, no heavy metals, no toxic compounds, WEEE compliant processes);
Technological leadership (no similar development world-wide, unique characteristics or selling points)
Adaptable organisational structures (targeted qualification of staff, staff exchange).

PILOT LINE PRODUCTION & DEMONSTRATOR EVALUATION

The major processing and production steps developed in INNOSHADE have been demonstrated on a pilot-line level, i.e. the production of MoC in a glass pilot plant including purification and quality control, the production and post-treatment of EC working and counter electrode films on a custom made air-conditioned R2R pilot line, the continuous deposition and curing of polymer electrolyte membranes, and the lamination of working and counter electrodes to an EC film laminate by continuous roll pressing.

Considerable amounts (several hundreds of metres) of half-cells have been produced (including the determination of process windows, production conditions, scaling up), clearly demonstrating the feasibility of continuous processing. The material has been cut to A4, A3, or A3+ sized sheets for the assembly of sample devices and demonstrators. Figure 12 shows an in-situ polymerised poly-MoC coating on PET/ITO after thermal treatment (left) and rinsing (right). The coating shows stable electrochromic response and excellent film thickness homogeneity, as revealed by charge capacity measurements.

[Figure 12. Left: High-throughput in-line processing of PolyMoC on PET-ITO film (application width 450 mm). Right: lamination-ready rinsed PolyMoC film. Photos: U. Posset/Fraunhofer ISC.]

In systematic reproducibility checks the initially high value scattering and limited correlation between coating conditions and charge capacities (i.e. coating thicknesses) has strongly been improved. Besides mechanical or machinery parameters, the establishment of controlled atmospheres in the application and in-situ polymerisation zones was found to be crucial.

Quality control tools have been sought to guarantee homogeneous film thicknesses (on a nanoscale) during pilot-line production. White Light Reflectometry (WLI) turned out to be a highly suitable, in-line capable technique to determine film thicknesses of both TCO and electrochromic layers on moving PET film, hence, is appropriate for designing a production quality control system. The values determined for the polyMoC layer shown in Figure 12 and the underlying ITO layer were in perfect accordance with the actual layer thicknesses determined by means of SEM cross-section analysis.

The seven-step synthesis of MoC was systematically improved and successfully transferred to the pilot plant level (100 litres reactor volume, Figure 13). After having optimised the single steps, the full synthesis was verified in a glass pilot-plant and finally in full plant production. Undesirable impurities occurring during the glass pilot-plant tests first affected the quality of final monomer, in particular the isomeric ratio. Production research efforts revealed the reason for that and the synthetic procedure was changed accordingly to yield the desired EDOT derivatives isomerically pure in higher yield. The procedure was verified in the glass pilot-plant in three independent batches. The synthetic procedure for the main intermediate has been prepared for full plant verification to yield 26 kg from one batch.

Purification was found to be the key part of procedure. Column chromatography (CC) used initially is usually effective in removing undesired impurities, such as starting compounds, oligomers, or carryovers. What was hampering this discovery was the fact that these impurities were impossible to observe by spectrophotometric methods. Furthermore, CC is not an industrially viable preparative method to enable a high material throughput. Therefore, vacuum fractional distillation (VFD) was successfully evaluated, a method found highly effective in removing all impurities having low boiling points. VFD may also serve to recover unreacted starting materials, which is beneficial in environmental and life cycle terms. The method can advantageously be used to synthesise MoC of sufficient purity for the preparation of electrochromic polyMoC layers with high colour contrast, a low haze level and a highly transparent bleached state (patent pending). The synthetic procedure has been adapted for glass pilot-plant verification to yield 4 kg MoC from one batch.

[Figure 13. INNOSHADE glass pilot-plant for intermediate and MoC synthesis. Photo: L. Kubac/COC Ltd.]

The production of electrochromic dye-type colour modifiers on a 50-100 g scale was accomplished, too. The implementation of the pilot-line production was hampered by the fact that the most promising material (ISO-7) had been identified not before the last year of the project. From the 10-step synthesis, however, almost all stages were optimised in terms of yield, purification, and VOC, which lays an excellent base to scale-up the procedure to the pilot-line level in follow-up activities.

Besides working on the EC layers and their precursors, considerable effort was put in the development, optimisation, and up-scaling of TCO deposition to create transparent electrodes that could outperform ITO on plastics. Tin-doped Indium oxide (ITO) has a very strong environmental impact because of Indium scarcity and refinement, and its high sheet resistance of 50 Ohm/sq. presents a major bottleneck in plastic EC technology. Three alternative compositions, i.e. ZnO:Si, ZnO:Ga (GZO), and ZnO:Al (AZO) have been short-listed, of which GZO and AZO have been focused on in the last period for costs and LCA reasons. The preparation of the most promising material (including sputter target production) was supposed to be implemented in an industrial pilot line.

The solution to reach the objectives (Rs < 10 Ohm/sq. and T > 85 %) emerged to be a hybrid electrode made of a Cu-grid covered by a TCO, rather than a mere TCO layer. It was found to be necessary to cover the grids by TCO in order to create an overall conductive surface and passivate the fairly reactive copper. The hybrid GZO-Cu system presented a very good Ohmic behaviour and favourable electro-optical properties (see Figure 14). The results have been validated at high and low temperatures (+80 °C, -30 ºC). The system presents an elastic region close to 1 % of strain and typical mechanical behaviour (initial elastic regime followed by a plastic regime) without any abrupt failure even at -30 ºC. However, though Cu grids on PET film showed very good average sheet resistance, only moderate results were obtained in terms of optical transmittance and aesthetics, acceptable or not depending of the type of appliance. In response to this situation, new technologies have been developed to make narrower and hence invisible lines. Latest samples with R2R deposited GZO on top had Rs values around 1 Ohm/sq. and did not show any changes in Rs during 1000 cc in traction and bending tests implying exceptional mechanical stability and flexibility of such electrodes.

[Figure 14. Transmittance spectra of hybrid transparent electrodes: Left: ITO/Cu grids/PET; right: R2R-GZO/Cu grids/PET.]

One of the key activities in the later stages of the project was to transfer the device assembly as far as possible to a continuous process. To demonstrate a fully continuous EC film device production on a lamination line, rolls at least 50-100 m in length were required, namely of the working electrodes (PolyMoC), the counter electrode (n-PB), and the electrolyte films (SPE), the latter being applied either as an UV-curable over-coating or as a fully cured free-standing film to be co-laminated with the half-cell electrodes. Proof-of-concept was provided on a BC40 lamination line (working width 250 mm) showing that working and counter electrode half-cells can indeed be laminated in-line employing an over-coating process. Figure 15 illustrates the lamination of the working and counter electrode films by means of a lamination roll.

[Figure 15. Lamination of working and counter electrode on a BC40 lamination line. The electrolyte resin has been applied on the working electrode by slot die coating beforehand. Photo: U. Posset/Fraunhofer ISC.]

The lamination parameters as well as the direction of the cured film are of utmost importance: low pressing force may result in incomplete joining or poor interfacial adhesion in the laminate; stronger pressing may result in short cuts or even crack formation in the TCO layers. Undue re-direction of the laminate may result in puckering and delamination due to compressive or tensile stress.

SYSTEM INTEGRATION & ELECTRICAL CONTROL

Special electronic control units (ECU) have been designed and fabricated, able to supply voltage and current profiles tailored for INNOSHADE devices (Figure 16). In addition, a local ECU and RF ECU pair for the local and remote control of EC devices was proposed. The controls allow the EC devices to be used stand-alone as well as integrating them in the ECU of an automobile. The algorithms developed can be applied in many other applications.

[Figure 16. Electronic control unit for EC device testing. Left: Power source, upper right ECU, lower right: EC device. Photos: S. Lopez/MASER Microelectronica]

It has been demonstrated that INNOSHADE devices along with the corresponding ECUs can be integrated in the existing construction of a commercial airplane cabin window. The main outcome was a part of the cabin of an Airbus A320 aircraft endowed with two windows, both being equipped with the conventional mechanical shutter (curtain), but one having the additional option of electrical shading with the INNOSHADE device (Figure 17). The shading grade of the EC device can be controlled by means of a switch below the window. Inside a real airplane fuselage, the device would be placed in the space between the second inner window pane, which is part of the cabin wall nearest to the passenger, and the first window pane of the airplane fuselage. This position offers protection of the shading device, e.g. against extreme temperature changes or harsh UV exposure from the outside as well as damaging by the passenger. The INNOSHADE device clearly complied with Airbus' electrical requirements of a maximum power consumption of 350 mA at max. 12 V per window.

[Figure 17. Demonstrator of an Airbus A320 cabin wall equipped with an INNOSHADE EC device. Photo: H. Fietzek/EADS.]

In order to prepare an ophthalmic lens demonstrator, a specially designed frame was selected, endowed with dedicated voids to integrate electrical wires for connecting the lenses to the electrical supply. The sidepiece has been adapted to host the batteries and the switches. A flat-design blue-tint device has been used to prepare an operational, flat thick-rimmed spectacles demonstrator. The contacting and optical contrast of the lenses is demonstrated in Figure 18.

[Figure 18. Demonstrator lens in its bleached and darkened state. Photos: C. Biver/ESSILOR.]

INNOSHADE devices can also be integrated in home appliance glass doors. Two primary goals were the development of ECUs to trigger the EC device and the integration of the entire system into a refrigerator door assembly. As a PDLC-based shading technology was defined as the benchmark, it was aimed at integrating the EC device into existing appliances with little or no changes to other components. Two different drivers have been employed: the ECU described earlier and a custom-made test controller without current limiter intended to be integrated in the main board of the appliance after exhaustive testing. It was found that both controller units are suitable options, but the response times differed slightly. Eventually, real-life appliance demonstrators have been assembled according to the same process that would be used in regular production. Though the EC devices survived the assembling process very well, in some cases, failure was observed due to gradual development of short circuits between the electrodes during cycling.

Power consumption tests, response times, light transmittance measurements, reliability cyclic tests and tests of ambient temperature impact have been carried out. The results revealed that the EC device performance complied with or even exceeded most of the set requirement specifications. Power consumption was as low as 0.13 W for an A3 sized device, meaning that a full sized device for the target application would have around 0.3 W of power consumption. It was stated that the INNOSHADE technology also meets the requirements regarding colour, viewing angle, haze and temperature conditions, but not yet in terms of transition speed.

For energy consumption modelling in home cookers according to EN 50304:2001, unique prototypes have been constructed by modifying turbo oven doorframes and the corresponding production machine in such a way that the frame could bear EC windows or films (Figure 19). It was found that the energy consumption of the prototype (turbo mode) equipped with an INNOSHADE device is reduced by up to 1.5 and 2 % in the dark and clear states, respectively. This encouraging result has been fed into the life cycle assessment performed.

[Figure 19. Household oven prototype with included INNOSHADE EC film for energy consumption modelling. Left: dark state internal light off, middle: clear state internal light on, right: dark state internal light on. Photos: O. Ersoy/ARCELIK.]

The energy consumption tests were supplemented by a special cooking performance test ('real-life test') based on the Average Colour Index (Browning) according to EN 60350. The results correlated well with the energy consumption test findings. It was stated, from an aesthetic point of view, the devices were working properly in clear and dark condition and fulfilled the requirements in terms of switching time, while room for improvement was still seen concerning the optical homogeneity (unlike the observations made in other application tests). No failure was observed during the tests, even at high oven temperatures (temperature proof up to 80 °C).

ENVIRONMENTAL ASSESSMENT & OCCUPATIONAL SAFETY

All materials and processes were systematically called into question with regard to their potential effect on health and environment. This concerned both the industrial synthesis of coating materials as well as the use of processing aids and solvents during the production of the EC device components. Where possible, green solvents were employed. Processes requiring toxic solvents so far have been adapted accordingly. Substances with carcinogenic or mutagenic potential as well as compounds with high global warming potential or ozone-depleting substances have been completely excluded except for small-scale model studies to achieve a colour adaptation by colourless-to-brown switching nickel oxide.

A complete Life Cycle Assessment (LCA) has been performed regarding all product life-cycle stages from cradle to grave (according to ISO 14040 ff.), focusing on the environmental impacts of the design, manufacturing, and end-of-life stages. In a first step, an LCA of benchmark EC devices and their production routes was done in order to create a foundation for future work (benchmark study). Conventional electrically dimmable devices served as benchmarks. The main functional unit was defined to be one unit of shading device (one piece of product, size 20 x 30 cm2). Five benchmark systems have been identified (Figure 20) and modelled by means of the GaBi 4.3 LCA software, corresponding to products commercially available in the EU today. A Benchmark Toolbox was obtained, open for variation of important parameters such as the materials of substrates and functional layers, the thickness of layers, and the type of material deposition and lamination processes.

[Figure 20. LCA Benchmark Overview.]

For life cycle impact assessment, the following categories were chosen within the frame of INNOSHADE:
Global Warming Potential in [kg CO2 (carbon dioxide) equivalents];
Acidification Potential in [kg SO2 (sulphur dioxide) equivalents];
Eutrophication Potential in [kg PO43-(phosphate) equivalents];
Photochemical Ozone Creation Potential in [kg C2H4 (ethylene) equivalents];
Resource depletion, measured as depletion of non-renewable energetic resources (primary energy).

Since the layers of EC device may involve critical metals, as a second category for resource depletion, the Abiotic Resource Depletion Potential was taken into account, where the non-energetic resources are included. The energetic resource depletion results are detailed in Figure 21.

[Figure 21. Primary energy demand per functional unit]

The most important environmental problem fields were identified to be Resource Depletion, Greenhouse warming potential, and Acidification. The process of manufacturing the EC systems from the raw materials is of high environmental importance, hence the choice of appropriate manufacturing technology is crucial (INNOSHADE -> R2R!). The process of electrodeposition in Benchmark 1b is more environmentally friendly than the PVD sputtering process in Benchmark 1a. This is, however, overcompensated by the higher layer thickness of the working and counter electrodes. The all-solid-state Benchmark 2 has high energy requirements for the sputtering processes. The layers of conductors and electrodes have a high specific environmental impact. Consequently, they should be kept as thin as possible or replaced by less critical TCO or alternative materials (Cu grids). Benchmark 4 is different from the other benchmarks, since it does not comprise a glass substrate but a thin PET film. The substrate is a factor of strong environmental impact.

It is apparent that the manufacturing processes from the raw materials are of certain importance for primary energy, however, the materials used (including the substrates) can play a superior role. The benchmarking results clearly verified the objectives of the INNOSHADE project. They also provided sound justification for the necessity to put strong efforts in the development of new transparent electrodes. The full benchmark analysis was published in RSC Advances in 2012.

For the INNOSHADE system, a viable production process has been designed. Process steps and parameters have been fixed to fulfil a state-of-the-art process concerning legal requirements, e.g. VOC incineration of used solvents. Due to the process design status, not all parameters could be fixed for the time being, so best- and worst-case assumptions have been made for energy consumption factors of aggregates (ventilators, pumps) and the scrap factor. This provides the basis for energy and material flow simulations of the process steps, including air conditioning for production hall and clean room, VOC treatment and assembly processes.

[Figure 22. Comparison of devices, system boundaries: cradle to gate; bc: best case, wc: worst case scenario.]

Results of the environmental comparison are shown in Figure 22 by means of the primary energy parameter, which is comparable to the impact category Fossil Resource Depletion. The following statements can be derived:
Benchmark 4 (=ITO-coated polymer substrate, polymer electrolyte, EC films prepared via PVD) and the INNOSHADE device have a similar environmental performance.
The best and worst case scenario analysis for the INNOSHADE production process has a minor effect to the overall results.
Benchmarks 1 to 3 have a significantly worse environmental performance than the INNOSHADE system.

LCA methodology has been applied during the complete development activities in the project to provide feedback about optimisation potentials from a life cycle perspective, i.e. support sustainable development. Important examples and aspects are:
The LCA revealed a tremendous environmental impact of the initial monomer production process that had a relatively low yield alongside a high material demand for solvents. The LCA feedback helped to optimise the process; the new eco-profile of the working electrode material is about 30 % better.
ITO layers can have extraordinarily high environmental impact, i.e. 30 % of primary energy of the INNOSHADE system in Figure 22. A LCA performed on alternative TCOs, like AZO and GZO shows significant environmental advantages for these materials.
During the INNOSHADE project, many surface coating technologies or treatments have been analysed. Referring to energy efficiency, electricity needed for wet-chemical coating is less than for electrodeposition and a lot less than for sputtering.

Besides these aspects from the production point of view, the evaluation of the whole life cycle was of most interest. It was analysed for three selected target applications (basic use phase assumptions given in parentheses):
Home cooker window (energy consumption reduced by 2 %, lifetime 3 times usage per week, 5 switches per cooking and 20 years lifetime; approximately 20.000 cycles).
Car sunroof (anticipated energy savings approx. 15 %, life-time: 5 years, 20.000 cycles)
Aircraft cabin window (EADS data for fuel savings due to weight differences, life time of aircraft = 25 years and 55.000.000 km)

The main outcome of the whole life cycle analysis is summarised in the following:
For all applications, the entirety of production processes and the End-of-Life of the INNOSHADE device are negligible in reference to the energy savings that can be accomplished. The energy needed for switching the EC device is irrelevant compared to energy and fuel savings.
In cooker windows and automotive sunroofs, the additional thermal insulation effect of the EC device has the dominating environmental impact of the system's life cycle.
Integrated in oven doors and car sunroofs the INNOSHADE device generates a win-win situation: a new technical (and marketable) feature and the reduction of environmental impact. For aircraft cabin windows this only applies when no mechanical shutter is employed.
The INNOSHADE device has environmental advantages in the production in comparison to the Benchmark 2 device (= commercially available EC car sunroof).
The higher weight of glass vs. Plexiglas has a significant impact on the Use Phase, which is relevant for aircraft cabin windows. The INNOSHADE device is the lightest alternative and leads to least kerosene consumption.
All statements are only valid for use phase assumptions made above. Figure 23 exemplifies the effect of the INNOSHADE and one benchmark device on the primary energy demand (cradle-to-grave) for the automotive sunroof application.

[Figure 23. Primary energy demand for the automotive sunroof EC application (cradle-to-grave).]

Experts of the participating companies, as proxies of other potential end users, have been analysing occupational safety, consumer protection, disposal and recycling requirements for appliances. Also, the hazard potential of the INNOSHADE production processes has been determined.

During the formation or processing of the nanomaterials employed in the INNOSHADE technology, no powders or fine dusts are liberated (under proper use). After coating, the nanocomposite films are densified thermally to solid films trapping any nanoparticulate components. However, subjecting the films to abrasive material may liberate abrasion debris or dust that may contain nanosized components. However, this scenario is considered unlikely. The substrate film, polymer electrolyte, protective liners, sealings, and contacts employed do not contain any nanoparticulate components. The full EC devices will be completely sealed or encapsulated so that any mechanical release of nanoparticles is prevented under normal operation.

To the best of the knowledge generated in the project, the INNOSHADE devices, once properly sealed, do not emit any substances in the normal thermal and electrical operation range. In case of breakage, the innerlying active films will be exposed, but will most likely not release any nanoparticles due to what has been outlined above. In case of incineration, however, the release of harmful or toxic gases and nanoparticulate material cannot be excluded. A thermal runaway as known from lithium ion batteries cannot occur.

All synthetic procedures were comprehensively optimised in terms of yields and solvent consumption, VOC contents, toxicity, and environmental friendliness. This has been accomplished by taking into account as far as any possible the results from the life cycle assessment performed. The technology does not employ any Substances of Very High Concern (SVHC).

Assessment against EC Regulation 1935(2004) (Food contact materials) and FDA material toxicity standards: In INNOSHADE, the term 'nanomaterial' besides the mere films' thickness typically ranging between 100-200 nm refers to the employment of suspensions of metal compounds or conducting polymers for the preparation of EC films. The latter are implemented and encapsulated in the full device (full-cell) such that a contact with food is ruled out (see above).

Assessment against WEEE Directive (Directive 2002/96/EC): The INNOSHADE system does not contain any lead, mercury, cadmium, hexavalent chromium compounds or polybrominated flame-retardants. Appliances equipped with the EC devices can be treated as normal WEEE waste. Because of the retrofit character of the INNOSHADE technology, communicating special recycling requirements, i.e. required removal of EC device from the appliance before recycling, is considered to be accomplished easily.

Assessment against the RoHS Directive (Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment, Directive 2002/95/EC): There is full compliance of the INNOSHADE technology with the 2002/95/EC RoHS directive as none of the substances restricted is used in the technology under concern.
Potential Impact:
POTENTIAL IMPACT

The overall objective of the project has been to scale up and study the underlying nanotechnology-based processes from laboratory to pilot line production, and explore the application potential of the new technology by creating interest in potential user groups and industries across sectors. Procedures were supposed to be implemented to establish pilot lines for the production of individual device components as well as for their assembly to run-capable devices.

This overall objective has clearly been accomplished. The four-year project yielded a novel and viable electrochromic (EC) device technology with a unique property profile representing significant progress beyond the state-of-the art, such as:
a large-scale, cost- and resource-effective plastic-compatible technology,
processable by high-throughput manufacturing (roll-to-roll processing).
showing fast response for large-areas and low power consumption,
showing a colour change between a fully colourless state and a blue-to-neutral tint state,
optionally comprising novel hybrid transparent electrodes with very low resistance,
providing high flexibility of application.

The INNOSHADE technology complies with major requirements set for an application in home appliances, aircraft and vehicles (power consumption, cycle-life, tint, contrast, thermal operation range, among others). Thus, a new cost- and resource-efficient EC device concept is available for exploration in response to market and customer demands. Particular attention is now supposed to be paid to identifying potential producers that could establish a full prototype production based on the pilot-line findings. First contacts and follow-up activities towards this goal have been established.

The development in INNOSHADE has been driven to the pilot-line production stage, the underlying nanotechnology-based processes have largely been understood, and the corresponding intellectual property (IP) has been protected in European patents and patent applications. However, the decisive step from research to innovation, i.e. the use of the newly developed materials and materials technologies by the industry could not yet be accomplished. The development has arrived at the so-called valley-of-death presumably for the following reasons:

The final processing steps (cutting, contacting, assembling, sealing) up to now have to be performed manually, which results in a large percentage of defective devices and high scrap rates. Process automation is strongly required.
Processing steps had to be performed in scattered laboratory sites, which hampered the progress.
No suitable producer could be identified though the necessary machinery exists to a large part and can be exploited for use.
Larger investments are probably necessary to bridge the gap in the innovation chain, which faces high technical risk associated with the multi-nanolayer technology pursued.
Small sale numbers are anticipated for the initial market introduction period (known from currently available 1st generation smart windows).
Other more speculative reasons (undercapitalisation, lack of suitable human resources, etc.).

These drawbacks are supposed to be tackled in follow-up projects by overcoming equipment limitations, using process automation, and establishing a high-throughput prototype production for flexible EC film devices in Europe. This ambitious task will be approached by joining efforts of European and overseas players to integrate nanotechnology, materials, and production knowledge.

With respect to eyewear applications, further basic research work and the employment of statistical methods such as Design-of-Experiments appears to be necessary to solve the remaining issues.

If the innovation process in the aftermath of INNOSHADE (including its potential successors) is successful the project is expected to have the following socio-economic impact:

The project would realise a case where previously obtained research results and European intellectual assets will be used by new or existing industries, presumably small or medium enterprises.

The project would contribute to relieve the European paradox. By establishing a highly innovative prototype production for smart electrochromic devices (cost-effective, mechanically flexible, light-weight, low embodied energy) in Europe, the discrepancy between the scientific and the commercial performance in high-technology sectors is anticipated to be reduced.

The valley of death would be overcome. The INNOSHADE development has come to a point where technical and economic difficulties are believed to hamper translating the ideas into marketable products. To bridge this gap, a well-established three-pillar strategy is supposed to be followed:
- Technological research on prototyping flexible EC device components including system integration and electronic control;
- Product demonstration and close-to-market dissemination activities (sampling, Memoranda-of-Understanding, participation to fairs etc.);
- Prototype production focused on world-class advanced manufacturing in Europe.

By focusing on these key stages of the innovation chain, a virtuous cycle will be triggered, from knowledge generation to market flow with feedback from the market.

Creation of new businesses in Europe: The innovation would create a new business on flexible EC devices in Europe. The new production is meant to generally increase the level of employment in EC technology business and complement the existing portfolio by a low-cost flexible product. On the long term, business agreements to join forces against US or Asian competitors are conceivable to strengthen the economic development in Europe.

Economic growth and creation of new jobs: Provided a prototype production can be established, new jobs would be created in the companies involved on the mid-term an increase by a factor of 1.5-2 on the long term by a factor of 4 is expected. The economic growth will depend on the achievable increase in demand and the level of subsequent market penetration.

From the successful transfer of project results to prototype production high societal impact would arise in terms of enhanced energy efficiency (reduction of air-conditioning needs cars and buildings, thermal insulation effects in home appliances), consumer protection (UV protection, impact resistance), and comfort (individual control of incident light intensity in eyewear, vehicles, aircraft, and appliances).

In general INNOSHADE addressed main scientific/technological, socio-economic, and policy objectives of the NMP work programme, enables environmental benefits, and contributes to Sustainable Development (reduction of mounting space/weight, heat loss reduction in appliances, retrofitting, energy savings). Nanotechnology research results are being transformed into a real competitive advantage for European industry against players from Asia and the US. The strong industrial participation (5 SMEs and 4 multinational global players) reflects the good economic development perspectives of the project.

TRAINING ACTIVITIES & EDUCATION

By a variety of training activities an effective information and technology transfer was established and, thereby, the transnational and intersectoral mobility of young researchers was increased. The activities also included workshops and other educational events in order to contribute to the development of an open European research area and labour market and the diversification of skills or career paths (incl. gender aspects). Some selected activities were:

training young technical staff for their future job as laboratory engineers in the develop-ment/laboratory laboratories of refrigerating and freezing appliance manufacturers.
sharing information about process standardization and how to work in controlled atmosphere laboratory (dry room) to assemble EC devices.
training staff in standards for automotive industry.
establishing periods of close cooperation (mutual staff exchange) permitting to join efforts and expertise to work effectively in solving different issues revealed during the project
training staff in in-situ polymerisation, a promising method for the high-throughput production of electrochromic and electrically conducting polymers.
enhancing knowledge in organic materials in the field of electronics by visiting relevant conferences and workshops.

All staff having been trained also helped with measurements on INNOSHADE samples and learned about handling technical instruments and writing engineering reports. They also learned about the particularities of implementing EU projects.

Besides, students were educated in the field of plastic electronic devices, inorganic and organic electrochromic materials, and nanotechnology in general. In total, five theses (one undergraduate, two master, two PhD) with topics related to INNOSHADE have been completed in the course of the project.

Specific SME training was not considered necessary in most cases. The SMEs involved were skilled in participating to European research projects. This held for both the implementation of the scientific approach and the financial reporting. Not any obstacles could be identified that could hinder the involvement of these SMEs in future European projects. The company COATEMA participated in a large European collaborative project for the first time. In two bilateral workshops, COATEMA staff was trained in issues such as cost categories, eligibility of costs, and financial reporting regulations.

WOMEN IN SCIENTIFIC RESEARCH & GENDER MAINSTREAMING

The INNOSHADE consortium was fully committed to the FP7 gender mainstreaming process, i.e raising the number of female researchers and achieving an equal gender mix in scientific research. Many female researchers have been integrated in responsible positions.

A high ratio of women involved in large European collaborative projects dealing with top-notch research is anticipated to have indirect but significant impact on the number of female students in technical studies (role model function). Spain and France are known to be well advanced in gender issues while other countries (German, Austria, Italy) are usually behind. This was more or less reflected in INNOSHADE, where the one Czech, the two Spanish, and the three French partners all had appointed female researchers responsible persons for scientific affairs, while partners from Italy, Germany, Slovenia, Portugal, Turkey, Israel, and Canada appointed male researchers. One partner (from Slovenia) and the coordinator had established gender-neutral dual leaderships.

INNOSHADE had 19 female participants out of a total of 43 persons that have been integrated in responsible positions and/or involved in scientific activities, which corresponds to 44 %. 7 out of the 12 work packages were led or co-led by female scientists.

The basic principle of Equal Pay For Equal Work has been observed strictly by the Fraunhofer Gesellschaft (coordinator), the National Institute of Chemistry (NIC), and the large company ESSILOR. Non-exhaustive list; no mention here does not necessarily mean that the Equal Pay For Equal Work principle is not followed in the corresponding organisation or company. For the partners men-tioned, however, female researchers in responsible positions confirmed their organisations/companies pursue the principle. NIC has the certificate »Family friendly enterprise«. The overall work of CIDETEC has been carried out mostly by female researchers and technicians at all competence levels.

USE OF FOREGROUND & MAIN DISSEMINATION ACTIVITIES

The dissemination of foreground knowledge has been considered an important topic consequently addressed on each of the Consortium meetings. Key knowledge and important intellectual property such as the nature of the Monomer of Choice, the nature of the self-standing polymer electrolyte (SPE) and some technical processing aspects have been treated confidentially and protected by European patent applications. Apart from that, publications have been prepared dealing with basic research results and side aspects of the project that might be of interest to the scientific community (under special consideration of IPR protection and the industrial/end user partners commercial interests). This included:
writing peer-reviewed publications,
giving (invited) conference talks to introduce the project, and
presenting the project to other non-scientific audiences (the public, industrials, politicians, stakeholders)
making provision for follow-up projects dealing with system integration and industrialisation of the INNOSHADE technology (includes talks to potential manufacturers and end users).

Conferences

On the occasion of internationally well-known international conferences on electrochromism and materials science (partly hosted or co-chaired by project partners) the project was comprehensively presented to a wider scientific audience:
216th Electrochemical Society Meeting, Vienna/Austria, 2009.
European Materials Research Society Spring Meeting, Strasbourg/France, 2009.
9th International Meeting on Electrochromism, Bordeaux/France, 2010.
4th International Meeting on Developments in Materials, Processes and Applications of Emerging Technologies, Braga, Portugal, 2010.,
European Materials Research Society Fall Meeting, Warsaw/Poland, 2011.
5th International Meeting on Developments in Materials, Processes and Applications of Emerging Technologies, Algarve, Portugal, 2012.
10th International Meeting on Electrochromism, Holland/USA, 2012.
International Conference on Synthetic Metals, Atlanta/USA, 2012.
International Conference on Nanostructured Polymers and Nanocomposites, Prague/Czech Republic, 2012.
EU Commission Industrial Technologies Exhibition, Aarhus/Denmark, 2012

Selected peer-reviewed publications

Gray to colorless switching, crosslinked electrochromic polymers with outstanding stability and transmissivity from naphthalenediimmide-functionalized EDOT, M. Sassi, M.M. Salamone, R. Ruffo, C.-M. Mari, G.A. Pagani, L. Beverina, Advanced Materials 24 (2012) 2004-8.

Environmental Assessment of Electrically Controlled Variable Light Transmittance Devices, U. Posset , M. Harsch, A. Rougier, B. Herbig, G. Schottner, G. Sextl, RSC Advances 2 (2012) 5990.

Electrochromic properties of Ni(1-x) and composite Ni(1-x)O-polyaniline thin films prepared by the peroxo soft chemistry route, F. Svegl, A. Surca Vuk, M. Hajzeri, L. Slemenik Perse, B. Orel, Solar Energy Materials & Solar Cells 99 (2012) 1425.

Role played by chain length and polarity of n-substitutents in electrochromic polymers from the tri-heterocyclic monomer pyrrole-thiophene-pyrrole, M. M. Salamone, F. Silvestri, M. Sassi, C. M. Mari, R. Ruffo, L. Beverina, and G. A. Pagani. Solar Energy Materials and Solar Cells 99 (2012) 101-108.

Semi-Solid Gel Electrolytes For Electrochromic Devices (Semi-Trdni Gelski Elektroliti Za Elektrokromne Sklope), M. Hajzeri, M. Colovic, A. urca Vuk, U. Posset, and B. Orel, Materiali in Tehnologije (Materials and Technology) 45 (2011) 433-438.

Influence of dopant nature on the TCO properties of ZnO:M (M=Al, Ga, Sn, Si, Ge) thin films, J. Clatot, G. Campet M. Jean, M. Nistor and A. Rougier, Mat. Res. Soc. Sympos. Proc. (Electrochromic Materials and Devices) 1328 (2011) 1-10.

POSS based ionic liquid as an electrolyte for hybrid electrochromic devices, M. Colovic, I. Jerman, M. Gaberscek, B. Orel, Solar Energy Materials & Solar Cells (2011) 34723481.

Sol-gel vanadium oxide films for a flexible electronically conductive polymeric substrate, M. Hajzeri, A. urca Vuk, L. Slemenik Pere, M. ?olovi?, B. Herbig, U. Posset, M. Krmanc, B. Orel, Solar Energy Materials & Solar Cells 99 (2012) 6272.

Electrochromic devices based on in-situ polymerised EDOT and PB: Influence of transparent conducting oxide and electrolyte composition - Towards up-scaling, S. Duluard, A. Celik-Cochet, I. Saadeddin, A. Labouret, G. Cam-pet, G. Schottner, U. Posset, and M.-H. Delville, New Journal of Chemistry 35 (2011) 2314-2321.

Room Temperature Transparent Conducting Oxides based on Zinc Oxide thin films, J. Clatot, G. Campet, A. Zeinert, C. Labrugère, and A. Rougier, Applied Surface Science 257 (2011) 5181-5184.

Comparison of PEDOT Films Obtained via three Different Routes through Spectroelectrochemistry and the Dif-ferential Cyclic Voltabsorptometry Method (DCVA), M.-H. Delville, S. Duluard, B. Ouvrard, A. Celik-Cochet, G. Campet, U. Posset, G. Schottner, Journal of Physical Chemistry B 114 (2010) 74457451.

Use of Foreground - Exploitation strategy

A Exploitation Strategy Seminar (ESS) was held to facilitate the process of identifying the exploit-able results. This process was quite elaborate because of the variety of technical processes, technology, and materials considered by the project. After reading the project documents, the ESS Animator autonomously identified 16 exploitable results reported in the pertinent section of the ESS report (available upon request). The partners were successively requested to review the proposed list of exploitable results with the aim of evaluating the opportunity to merge or split some of them and, possibly, of proposing new ones. After group discussion at the seminar, the list of exploitable results was reduced to the following 13 ones. A matrix of interdependencies of the proposed exploitable results (IPR and exploitation claims) was produced (reported in the pertinent section of the ESS report).

N° Title
1 Electrochromic nanocomposite coating with outstanding electro-optical properties (Fraunhofer ISC)
2 Coating machinery (COATEMA)
4 Patent on Scaled up monomer and coating sol production (COC)
6 Process for transparent plastic electrodes with low resistance (SOLEMS, HANITA, CNRS, UMINHO)
7 Process for EC material with neutral tint (red) and 90 % VIS transmittance (ox) (INSTM-UMIB)
9 Process for EC film devices manufactured in continuous processes (IREQ, Fraunhofer ISC, INSTM-UMIB)
17 Plastic film + electronic control for automotive smart window applications (MASER)
20 LCA services for future customers using INNOSHADE processes (LCS)
22 EC ophthalmic lenses via thermoforming (ESSILOR)
24 Appliance window with adaptable tint (ARCELIK)
26/27 Shading of aircraft/helicopter interior/canopy windows by plastic film with electrical switchable transparency (EADS)
28/29 New adjustable colour device for home appliances (GORENJE)

As far as the external IPR situation is concerned, the characterisation sheets (for the exploitable results), the Doc search, the number of filed patents, and the number of ongoing projects indicate a worldwide intense activity on the technologies of interest of INNOSHADE. The attendees carried out a risk analysis exercise on two results, namely no. 7 and 9. Possible action plans for these risks have been indicated in the pertinent section of the ESS report.

PROJECT WEBSITE

A project website was launched in 2008 and streamlined in 2011. The content has continuously been updated throughout the project. The site comprises the following sections:
Home
Introduction
Partners
Objectives
Principle of Electrochromism
Events
Publications
EU Links
Members area

According to the access statistics, the number of page views from countries and companies not represented in the consortium has been risen, which points to continuously increasing public awareness. In order to differentiate between the provenances of the relevant web community players calling up the INNOSHADE website, countries with frequent access activities have been analysed. Apart from the mid-European EU countries with a highly developed research infrastructure, a remarkable number of enquiries has been monitored from eastern countries like Poland and Russia. Download of data volume has been initiated by e.g. commercial clients, (research) networks, non-profit organisations, and furthermore parties from all over the world including China, Japan etc., reflecting the international relevance of the project. In particular, a certain interest has been noticed from countries known for their strong electrochromism activities (e.g. Sweden, Belgium, and UK). The domain names filed since the launch of the website represent the whole variety of the related international research and business community.

To raise public awareness of the project website, all partners were encouraged to place web links on their company and institutional websites and forums. Many complied with this request. The INNOSHADE sites visibility was rated very well. A Google search for INNOSHADE performed on 30 August 2012 yielded 2000 entries and counting (13 September 2011: 855). The majority of entries are directly or indirectly related to the project. The first entry of the Google search results listed provides direct links to the Home page as well as to the pages Introduction, Objectives, Partners, Events, Publications, and EU Links.

Contact details:
Dr. Uwe Posset, FRAUNHOFER Gesellschaft für Angewandte Forschung e. V.
c/o Fraunhofer Institut Silicatforschung (ISC), Würzburg, Germany
Tel: +49-(0)931-4100-638
Fax: +49-(0)931-4100-698
E-mail: uwe.posset@isc.fraunhofer.de

Final Report Summary - INNOSHADE (Innovative Switchable Shading Appliances based on Nanomaterials and Hybrid Electrochromic Device Configurations)

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