WO2010100345A2

WO2010100345A2 - Smart system for the high-yield production of solar energy in multiple capture chambers provided with nanoparticle photovoltaic cells

Info

Publication number: WO2010100345A2
Application number: PCT/FR2010/000180
Authority: WO
Inventors: Alex Hr Roustaei; Abdelmadjid Djemai
Original assignee: Alex Hr Roustaei; Abdelmadjid Djemai
Priority date: 2009-03-02
Filing date: 2010-03-02
Publication date: 2010-09-10
Also published as: FR2956869A1; FR2956869B1; WO2010100345A3

Abstract

The invention relates to an innovative solution for producing solar energy based on nanoparticles. The invention has an efficient design and has a low cost per generated watt, and is based on the principle of multiple chambers for multispectral capture provided with optical concentrators and a novel antireflective coating capable of absorbing the light spectrum, from ultraviolet rays to infrared rays, independent of the angle of incidence of the ray. The photovoltaic cells can consist of organic and/or inorganic thin-films deposited by grafting particles using ion or plasma beams and/or printed on the cells by piezoelectric inkjet or laser printing. The invention covers methods for improving the deposition surface and relates to an efficient, high-yield direct logistics flow roll-to-roll system, as well as to real-time quality control during the production (figure 1). Using a nanometric preparation of CIGS/CIS in the form of an ink or a powder for visible rays, doped layers of TiO₂ are formed for trapping ultraviolet (UV) rays and/or infrared (IR) rays and are applied by inkjet, laser and/or continuous rotary printing on any rigid or flexible substrate. Other innovative aspects of the invention include an increase of the overall yield thanks to the flattening of the deposited or printed layers, either by laser or by a chemical processing of the surface receiving the solar rays for the CIGS/CIS layers. The device is capable of following the sun and thus generates electricity at a high yield. The device respects cleanliness and environmental restrictions and is designed for producing clean electricity without toxic elements. The device has a favourable energy ratio as it can compensate for the energy required for the production thereof in a few days (fig. 2 to 10). The invention can be used, inter alia, for the household and industrial fields. The product has a general form of rigid or flexible panels or discretely deployable films providing energy for generating electricity. Due to the flexible structure and lightweight properties of the invention, it can easily be integrated into buildings or into the bodywork of cars as well as into vehicles travelling outside Earth's atmosphere. Moreover, a variant of the invention can be used for converting calories into piezoelectric current and/or into WiFi, OE or OS wave current, thereby ensuring providing wireless energy transfer. The present application is an extension and a continuation of a subsequent patent application with internal priority claim of invention patent application N° 1000828 filed on 1 March 2010; which is in turn an extension and further patent application with internal priority claim of a first invention patent application N°0901503 filed on 27 March 2009; which is in turn an extension and further patent application with internal priority claim of a first invention patent application N°0900921 filed on 2 March 2009; which is in turn an extension and further patent application with internal priority claim of a first invention patent application N°0900267 filed on 22 January 2009; which is in turn an extension and further patent application with internal priority claim of a first invention patent application N°08 06821 filed on 5December 2008; which is in turn an extension and further patent application with internal priority claim of a first invention patent application N°0806820 filed on 5 December 2008; which is in turn an extension and further patent application with internal priority claim of a first invention patent application N°0804598 filed on 14August 2008; which is in turn an extension and further patent application with internal priority claim of a first invention patent application N°08 03019 filed on 2 June 2008; said applications being attached in the entirety thereof for reference.

Description

INTELLIGENT SYSTEM FOR PRODUCING HIGH PERFORMANCE SOLAR ENERGY IN MULTIPLE CAPTURE CHAMBERS WITH PHOTOVOLTAIC CELLS BASED ON NANO PARTICLES

FIELD OF THE INVENTION The present invention proposes an innovative solution for the production of solar energy based on nanoparticles. Efficient design with a very low cost per watt produced, it is based on the principle of multiple chambers, multispectral capture with optical concentrators and a new antireflection coating capable of absorbing the spectrum of light from ultraviolet rays to rays. infrared regardless of the angle of incidence of the beam. The photovoltaic cells may be of the organic and / or inorganic type in thin layers deposited by grafting the particles using ionic or plasma beams and / or printed on the latter by piezoelectric ink jet or by laser printing. The invention covers methods for improving the surface area of the repository and provides an efficient, high throughput and "roll-to-roll" system and real-time quality control during production (Figure 1). ). Using a nanometric preparation of CIGS / CIS as an ink or as a powder for visible light, TiO 2 layers doped to trap ultraviolet (UV) and / or red infra (IR) and deployed by printing ink jet, laser and / or continuous rotating on any rigid or flexible support. Other innovative aspects of the present invention include increasing the overall yield by surface planing the deposited or printed layers, either by laser, or by chemically treating the solar-receiving face for the diselenide layers and / or disulfide layer. copper and indium and / or gallium called CIGS / CIS. Able to follow the sun, (Patent Applications No. 0804598, 0900267 and 0900921), the device produces high efficiency electrical energy. Respecting the environment's cleanliness constraints by replacing Cadmium (Cds) with a non-toxic element of the Indium Sulfide (ln2S3) type, II is designed for clean electricity production without toxic elements. It has a very favorable energy balance, as it compensates in a few days the energy that has been used to produce it (Fig.2 to 10). Areas of use include habitat and industry. The product is generally in the form of rigid or flexible panels or in the form of a film that can be unfolded at will and provides energy for the production of electricity. Due to its flexible structure and lightness it fits easily into the building or the bodywork of cars as well as vehicles intended to travel outside the Earth's atmosphere. In addition, a variant of this invention makes it possible to transform the calories into piezoelectric currents and / or the current in WiFi waves, electromagnetic waves (EO) and scalar waves (OS) ensuring thermal regulation as well as energy transfer without queue. This application is an extension and a continuation of a subsequent patent application with claiming the internal priority of a patent application number 1000828 filed on March 01, 2010; itself an extension and a subsequent patent application with claiming the internal priority of a first patent application number 0901503 filed on, 27 March 2009; itself an extension and a subsequent patent application claiming the internal priority of a first patent application number 0900921 filed on, 02 March 2009; itself an extension and a subsequent patent application claiming the internal priority of a first patent application number 0900267 filed on, 22 January 2009; itself an extension and a subsequent patent application claiming the internal priority of a first patent application number 0806821 filed Dec. 5, 2008; Itself an extension and a subsequent patent application claiming the internal priority of a first patent application number 0806820 filed on, December 5, 2008; Which is an extension and a subsequent patent application with claiming the internal priority of a first patent application number 0804598, filed on, August 14, 2008; Itself an extension and a subsequent patent application with claiming the internal priority of a first patent application number 0803019, filed on, 2 June 2008, and are all fully integrated by referencing within the limit of their date validity.

INTRODUCTION Born in 1954, the first-generation photovoltaic (PV) technology is based on crystalline silicon and still dominates the solar panel market. It offers marketed equipment a 15% return between the electrical energy produced and the solar energy captured.

Silicon is a chemical element that does not fail because it constitutes 28% of the mass of the earth's crust. However, the purification and crystallization of which it must be subjected are complex and expensive processes. The second-generation photovoltaic cells, based on thin-film materials, are more concerned with reducing costs than increasing yields. The main materials used are amorphous silicon, cadmium telluride (CdTe) and selenium CulnSe2 and Cu6aSe2 (the various possible combinations are grouped under the name CIGS). Photovoltaic cells of the third generation must therefore be low cost and high efficiency. The phenomenon of photovoltaic conversion is based on the interaction between solar radiation and the materials it penetrates. In the second-generation device, the light energy is partly transferred to electrons of the CIGS layer (selenides) which becomes mobile. Thanks to an electric field present between the ZnO: Al layer (in zinc oxide "doped" with aluminum) and the CIGS layer, the electrons are attracted towards this first one. This results in a potential difference between ZnO: Al and the Mo layer (in molybdenum). In the external circuit, the electrons return to the Mo layer. The light energy acquired by the electrons is then electrically transferred in this circuit. Currently, during the production of electricity by photovoltaic cells, the manufacturers of these cells, in the form of films, are confronted with two types of problems:

Adhesion and bonding of the substrate to the film and energy efficiency of the cells for low cost production.

Photovoltaic cells are also often limited by physical equations (technology limitation and theoretical yield related to the type of materials used).

Deployment and implementation of nanoparticles are the answers to obtain the expected performances in energy efficient devices, as described in patent applications Nos. 0804598, 0900267 and 09 00921. The yield of almost 13% obtained industrially is currently the world record for flexible photovoltaic cells, and interesting prospects are opening up for these cells that could be mass-produced. Flexible solar panels should be used in space or mobile applications (for example, one kilogram of flexible cells in CIGS technology could provide 1500 watts of electrical power, almost six times more than the same mass of cells using crystalline silicon In addition, the CIGS layer is more resistant to radiation. Soft cells, moreover, are not necessarily linked to mechanical structures They can also be glued on uneven surfaces, walls or cars for example The flexible solar cells can be integrated with cards like credit card Other applications are still possible STATE PRIOR ART

The recent development and new methods for producing thin-film photovoltaic cells currently have a best-case performance of 199% (source NREL National Renewable Energy Labratory, 2008-2009 USA) [00001] At best, the current state of art 1 is based on the simultaneous use of silicon juxtaposed layers tandems monocπstallm coated by amorphous silicon layers developed by SANYO ^® known technology of the heterojunction with intrinsic thin layer called HIT (Heterojunction w / ith IntπnsicThm layer) delivering a yield not exceeding 22%. US Pat. Nos. 4,705,589, 4,878,357, 4,388,483, WO 2008/004791, WO 2008/026581, WO 2007/022221, WO 2007/065096 and WO 2007/106756 describe methods and Hybrid solar systems with photovoltaic cells in which large-scale manufacturing processes are based on tandems of crystalline and amorphous cells or CIGS layers, deposited by the method of Rapid Thermal Treatment called RTP (Rapid Thermal Processsmg) giving yields ranging from 14% to 21% Moreover, none of the techniques developed in the patents of inventions mentioned above makes it possible to envisage a production of electricity with a very high efficiency exceeding 60%, whether from hybrid components or solutions comprising methods of increasing the means of absorbing energy [00002] Among the processes used in the state In the prior art, we can mention the TιO2 deposition processes of hybrid solar cells, based on an inorganic material (silicon Si) and a polymer (P3HT). This structure has been chosen to improve the cells at low cost. base of organic materials The heterojunction between silicon and P3HT has been studied on planar bilayer devices It provides electrical energy and both materials can contribute to the production of the photocurrent The yields obtained require the use of the means of amplification and reliability of the manufacturing processes Two new types of nano-structured silicons called "nano-filε" and "nano sponges", whose typical size of the pores is 20 nm, were obtained using metal catalysts by plasma-assisted deposition at 175 ° C. Silicon nanowires were formed on transparent conducting oxide substrates, the catalysts are generated in situ and the growth temperature is below 300 ° C. The wurtzite phase has been demonstrated in certain wires, and various growth modes have been observed. These two new types of thin layers are also used in inorganic solar cells. WO / 2005/102953, WO 2000/75087 and WO / 2005/040056 process ceramic or fibrous materials, as well as the substrate used in glazing as well as the modifications of a photocatalytic, antifouling, titanium dioxide-based layer (TιO2) are not interested in the improvements of the TιO2 layer yields for all UV spectra (Ultra violet, λ <420 nm), Visible (420 nm <λ <750 nm) and IR (Infra red, λ> 750 nm) Other techniques developed by Y Kenjι et al, CR Chemistry 9 (2006) modifies the surface of solid materials by cold plasma This modification Plasma surface is used to prepare photoactive particles in the TiO ₂ visible whose surface is doped with nitrogen A layer consisting of particles was deposited by "spm coatmg" of a TiO ₂ sol, on a glass substrate, followed by annealing at 673 K The layer was treated in series with argon and nitrogen plasmas for the IR region (λ> 750 nm) The plasma-treated layer absorbs not only the ultraviolet but also the visible light The catalytic activity of The layer has been evaluated using methylene blue and visible light (wavelength> 420 nm). The increase in photocatalytic activity of the layer is due to the formation of Ti-N bonds, which are origin of the activity in the visible

[00003] Recall that CIGS is a technique for the deposition of thin layers of a compound of copper, indium, gallium and selenium (CIGS) that Zurich researchers have developed and managed to adhere to a plastic sheet The yield of almost 13% obtained is currently the world record for industrially produced flexible photovoltaic cells. [00004] The inventors have noted that the prior state of the art does not provide a solution. actually adapted to the roll-a-roll production process (RoII to RoII) allowing a low-cost production of flexible films In fact, photovoltaic solar cells are currently manufactured on the basis of silicon in large majority. Generally, thin-film cells ( thin film) are produced from amorphous silicon (A Si), cadmium telluride (CdTe) and copper diselenide (Cu) -ιrιdιum (ln) -gallιum (Ga) generally called CIGS CIGS cells are often produced by a technique of evaporation or sputtering (or Spulterπng) selenization or by electrochemical deposition under vacuum (usually with pure basic elements constituting the oxide) which is well defined by state of the art. previous to know

1- V K Kapur, B M Basol, A Halani, C R Leidholm and A Minnick, Technical and Business Factors Affecting commercialization of

Thin Film CIS Technology "12 ^th European Photovoltaic Solar Energy Conference Amsterdam, The IMetherlands 1994, p 1608 2 BuIent M Basol, Vijay K Kapur, Craig R Leidholm and Arvind Halani, 'Flexible and LightWeight Copper lndium Diselenide Solar CeIIs' 25th IEEE Photovoitaïc Specialist Conf, Washington, DC, 1996 IEEE New York 1996, p 157 3 Wl H Hannon, MW Dashiell, LC Dinetta, AM Barnelt, Proceedings of the 25th IEEE Photovoltaic Speαalists Conference

Washington DC, 1996, p 191

4 V K Kapur, B M Basol, C R Leidholm, R Roe, U S Patent No. 6127202, 3 October 2000

Nanosolar Patent No. WO 2004/042432 A2, WO 2005/044551 A1, WO 2007/106756 A2 (Ionization manufacturing and deposition technique) 5- A Boden D BraunigJ Klaer, FH Karg, B Hosselbarth, G La Roche, Proceedings of the 28th IEEE Photovoltaic Speαalists

Conference, Anchorage, Alaska, 2000, p 1038

[00006] The patent (WO / 2006/008410) deals with a technique for making such an assembly is the molecular adhesion which avoids the use of an adhesive substance. Moreover, the state of the art uses the deposit on film by cathodic sputtering technology (sputteπng) We know for example that to extract an atom from the target and give it a velocity, the argon ion must have an energy higher than the energy that binds this atom to the other atoms of the target The remaining energy will be used to communicate a speed to the atom extracted In the classical magnetron sputtering technology, an electric field is created between the target and the substrate. In Magnetron sputtering technology, a magnetic field is added

The combination of this (new) magnetic field and the (existing) electric field will communicate to the electrons a helicoidal trajectory, trapping the electrons in the vicinity of the target. Thus, the number of electrons per unit volume increases at this point, as well. the density of argon ions and hence the velocity of deposition If the target is circular, the region or rate of erosion is the highest, induced by local magnets, is called the "trace of stroke", also known as the "racetrack" If this technology can increase the deposition rate, it poses other problems in fact, the target is not consumed _é e evenly precisely because of the location of the plasma, resulting very limited use of the target (of the order of 30% to 35%) Consequently, the target must be changed before being completely consumed a disadvantage which necessarily has an impact on the cost of p roduction The profile of the erodee region of the target varies, over time The stronger the magnetic field (closer to the magnets) the narrower the profile This has the effect of modifying the characteristics of the process and making the process difficult to reproduce Indeed, in this technique the film deposited on the substrate is not only form of the atoms of the target II is the product of a chemical reaction between the atoms expelled from the target on the one hand and a reactive gas (02, N2) introduced into the chamber on the other hand Unfortunately, the regions remote from the "racetrack" can form an oxide or a nitride on the surface of the target resulting in contamination of the target This leads to instabilities in the plasma from which variations in the properties of the material deposit, which can be partially compensated by using pulsed DC power or plasma emission technologies Known anomalies of the sputtering technology by magnetrons, are Non-uniform consumption of the target

Low target utilization (increasing the cost of deposits) - Contamination of substrates

Difficulties in maintaining stoichiometry from multi-component targets (due to racetrack formation) Difficulty in controlling reagent spray processes due to poisoning of αbles, requiring retroactive controls or by DC pulsing (instability )

Difficulties in depositing magnetic materials due to the reduction of the magnetic field strength of the target side facing the plasma Normally this requires the use of thinner targets and stronger local magnets

Complex methodologies to control reactive deposition processes (process instability and reactions during deposition)

Difficulties of deposition on organic substrates sensitive to heat

Low deposition rate during reactive sputtering and when using ferromagnetic targets It should be noted that part of this application deals with the influence of post-implantation treatments on the size and shape of nanoparticles prepared by implantation. is devoted to classical heat treatments by studying the influence of annealing temperatures, times and atmospheres The second part highlights the effect of treatments involving energy beams (electron ions) We note that these treatments induce significant modifications particle size and shape Studies and publications "DJ Barber, IC Freestone, Archaeometry 32, 33, 1990", "FE Wagner, S Haslbeck, L Stievano, S Calogero, QA Pankhurst, KP Martinek, Nature Vol 4Q7, 2000 "," DN Lambeth, EMT

Hairy, GH Bellesis, LL Lee DE Caughin, J Appl Phys 79, 4496 1996, "H Otsuka, Y Nagasaki, Kataoka Advanced Drug Delivery Revuews 55 (3), 403, 2003" A Meldrum, RF HagluπdJr, LA Boatner, CW Whιte, Adv Mater 13 (19), 1431 2001 "," Qπtora-Gonzalez, Structure and Magnetic Properties of Transition Metal Nanoparticles Developed by Ion Implantation in Silica Glasses, Thesis, Louis Pasteur University, Strasbourg, 2000 " , "C of ORLEANS, Physics of condensed matter, July 11, 2003", do not allow to consider the grafts of the nanoparticles serving of receiver or absorber of a thin layer or a substrate

[00007] The technique of thin layers (1-3 microns) CIGS was known but it was hitherto used only on a support such as glass, rigid and relatively heavy It uses only very little material which reduces the manufacturing costs The benefits are multiplied if we can use a support that is also thin and flexible - and this is what Zurich researchers have managed to do

To obtain the required quality, the CIGS layer is produced under vacuum by vapor deposition at a temperature of about 500 degrees. At this temperature, the polymer sheets are mechanically unstable. The Zurich group bypasses the difficulty by depositing the layer in two stages According to Ayodhya Nath Tiwaπ, who developed the IQE process, the synthetic material is first spread on a glass plate to ensure its stability, then the thin layer is deposited there. Previously, the glass plate was covered with NaCl sodium, more commonly known as table salt or cooking salt At the end of the deposition process, the salt is dissolved in water. The cooled polymer sheet then detaches from its glass support. To date, the various deposition techniques used on the continuous lines "roll-to-roll" are

Rapid Thermal Treatment (RTP), which is a well-known technique as an efficient depositing method since the discovery of CMOS technology. This technique is very simple to implement because the heating can be controlled locally and This technique uses methods of heating and rapid heat transfer often based on fast radiation (such as tungsten halogen lamps). The Vacuum Multiple Source Deposition Technique (MSVD) (Wlulti Source Vacuum Deposition) is A technique, as described by Invention Patent No. WO 2003/093529, which allows large areas to be deposited under vacuum with accuracy in deposit thickness and uniformity. Optical Drying Furnace (OPF) By selecting a light having a particular melting spectrum illuminating a Semiconductor and Metal interface, creating a zo which generates a structure in the form of an alloy on the silicone surface with a very low ohmic resistance By selecting a light having a particular spectrum of fusion illuminating an epitaxial surface with a concentration on a specific area In this case the ink dries quickly without undergoing changes in its molecular structure Screenprinting (SPR), screen printing techniques offer the cumulative advantages of low equipment cost and 100% use of materials This technique consists of screen printing a CIGS paste on a glass covered with molybdenum, the selemsation of the layers in an oven at 500 ° C, the deposition of the CdS window layer by CBD and the deposition of the ZnO layer by "sputteπng" The screen printing process (SPR) is a simple procedure in principle, but it remains difficult to control in the case of deposition of thin layers, because of the problem of adhesion to the substrate. The various methods are representative of the prior state of the art as described in WO 2006/073437, WO 2005/033858 and other publications dealing with the subject.

[00008] Other printing methods are developed as variants for the production of CIGS cells Let us quote for reference the well-known publication by state of the art dealing with the thin-film aspects of CIGS, that is to say

1- V K Kapurand B M Basol, 'Status of Polycrystalline Solar CeII Technologies' (invited) Proc 22nd IEEE Photovσltaïc Speaahst Conf, Las Vegas Nevada, 1991, IEEE, New York, 1991, p 23, Washington DC, 1996, p 297

2 B M Basol, V K Kapur, C R Leidholm, A Halani, Proceedings of the 25th IEEE PhotovoltaicSpecialist Conference Washington DC, 1996, p 157

3 R Walters G Summers, T Morton, G La Roche, C Signoπni O Anzawa S Matsuda, Proceedings of the 16th European Photovoltaic Solar Energy Conference, Glasgow, UK, 2000 [00010] In the prior state of the art, the cells Cu (ln, Ga) Se2 (CIGS) polycomponents are currently the most efficient thin-film devices. However, the structure is complex with the presence of several ZnO / CdS / CIGS or ZnO / ln2S3 / CIGS interfaces. _evelopment of this industry requires a perfect mastery of these interfaces

Optimizing the performance of photovoltaic cells based on CIGS requires an understanding of the formation mechanisms of the CdS / CIGS junction However, a study of the different chemical treatments shows a different impact on the surface of the CIGS - HCl> elimination of oxides,

H2SO4 -> Se formation on the surface,

NH3 -> elimination of oxides and tightening of the surface composition Several series of different experiments have thus shown a notable improvement in the performance of the cells following the brominated treatment, in particular on the values Vco and FF of the open circuit voltage and the form factor which become very high. Other studies in this field produce performance improvements ranging from 75 to 90% a recent publication on the work conducted in Japan con _j ointement by the chemistry Department of materials Ryukoku University, the Matsushita Electric Ind Co Ltd research center and the Department of Electrical and Electronics Engineering of the University of Mie, titled "High Effiαency CIGS Solar CeIIs with Modifiεd CIGS Surface" treats the subject and proposes an effective solution with yields of up to 17.6% (VoC = O 649V, Jsc = 36 lmA / cm2 and FF = 75 1%), without antireflection treatment

Other publications on joint work by the Department of Electrical and Computer Engineering, the Department of Chemistry and the Department of Materials Science at the University of Florida USA, and the SOPRA Institution, France, appeared in at the conference "NCPV and Solar Program Review Meeting 2004" under the title "Investigation of Pulsed Laser Annealing (PLA) of CIGS Based Solar CeIIs" deals with alternative solutions by PLA [00011] Regarding the realization of the layer Cds on the layer CIGS by deposition, the state of the art is realized either

By the technique of vacuum thin layer deposition (relatively expensive technique, requiring stresses in vacuum chambers during the production of the film in tension) - By thin layer deposition techniques at pressure and ambient temperature by electrodeposition on a substrate CIGS, covered with molybdenum (Mo) beforehand In this case, the substrate is initially covered with an additional layer, conductive, electronic, for example metal or in the form of oxide This conductive layer may also be based on a or several sublayers for a specific application (mirror diffusion or other barrier) in the manufacture of photovoltaic cells The work and publications of VK Kapur, Fisher M, Roe Roe, McCoπnell RD, VK Kapur (eds), Proceedings on Photovoltaic'sforthe 21st Century, vol 2001-10, The Electrochemical Society Inc, New Jersey, 2001 p 309, and VK Kapur, A Bansal P The OI Asen sio, 29th IEEE Photovoltaic Speclahsts Conference, New Orleans, LA 2002, p 688 as well as C Eberspacher, C Fredπc, K Pauls, J Serra, Thin Solid Films 387 (2001) 18 explain the state of art on these processes D ' Other techniques of depositing this film consisting of printing by screen printing and offset recrstalling processes The publications VP Klad 'ko, Lytvyn OS, PM Lytvyn NM Osipenok, GS Pekar, IV Prokopenko, AF Siπgaevsky AA

Korchevoy, on the 'Recrystallization processes in screen-printed CdS films' of the Institute of Semiconductor Physics, NAS of Ukraine, 45 prospect Nauky, 03028 Kyiv, Ukraine (2002), does not deal with the just-in-time performance aspect of a Such proceeds [00012] Regarding the heat transfer in current. US Patent 4733121 only discusses the use of

I solar energy through solutions other than photovoltaic and does not bring innovation for a transformation of calories in current related to the technology of photovoltaic cells

Moreover. It is logical to consider that a solar cell captures the maximum of light energy when it is perpendicular to the rays of the sun, but the angle of incidence of these rays varies during the day and during the seasons The power heliostat Devices in the prior art are often based on mechanical systems to track the sun's course, so that the sun can be directed all day to a small fixed area. A conventional silicon photovoltaic cell can absorb 674% of the sun's light. This means that almost a third of this light is reflected and therefore irretrievable The publications of Lyot's work, B, "The polarizing monochromatic filter and its applications in solar physics", in the journal Annales d'Astrophysique Vol 7 , p 31, 1944, show simple means of polarization and crystals in visualization screens and momtorage On the other hand, the studies of Heinz-Siegfπed Kitzerow and Christian Bahr, from the Department of Chemistry, Paderborn University, Marburg, Germany, treat the concentration of solar lights by a magnifying glass effect WO 2009/008996 describes a procedure applicable to photovoltaic cells allowing sun tracking by using This invention fails to deal with the important subject of light reflection caused by the proposed optical arrangements. These existing techniques and publications do not describe a nanometric means realizing the two functions, namely quasi-total absorption and the tracking of sunlight. only one surface of light coming in optimally and in the X and Y directions [00015] The transfer of energy by current of the type "WIFI" or Wireless Fidelity ensuring a transfer of data without file existed for many years Indeed Recall that the technique is not new since it was invented by Nicolas Tesla in 1892 and is co Induced under the name of induction coupling The prior state of the art on the transport of electrical energy by partial influence through a dielectric medium has been discussed in Invention Patent No. WO 2007/107642

The novelty consists in carrying out a purely magnetic action (definition of a scalar magnetic potential) combined with a purely electrical action which corresponds to the repulsion / mechanical attraction of two distant charges, resulting in an electromagnetic wave propagation.

Since the year 2007, the MIT (Massachussets Institute of Technology) work on wireless electncite transmission deals with the future of the world's energy supply The "Technology Review" of the same MIT has classified this technique in the technologies 2008 and the commercial launch of various WIFI electπcite devices for

2010 horizon However, there is still a need to propose a solution without cabling for the implementation of renewable energy sources in nomadic or stationary form

It should be noted that a New York firm, "Powermat", has developed flexible films with magnetic induction that could be placed anywhere in a room to provide a relay to primary electric currents (Publication Wall Street newspaper, Power Play, January 10, 2008)

Another Japanese company, "Denpecki", is studying induction plasterboard on the same principle The American "Fulton Innovation" is also working on this type of electricity distribution system that would ensure the omnipresence of the current cache in walls and ceilings The transfer of electncite would be done in the electrical device to supply if it has a secondary coil

On the other hand, the techniques patented in the inventions WO / 2002/073 085 WO / 2004/071 632, WO / 2007/059996, EP0576342, US 4

641922, WO2008 / 053 109, none of these patents makes it possible to envisage a SUIVI of the sun (or sunshine) by liquid crystals, either in the form of naπo cylindrical tubes or hexagonal nanocnstals Furthermore, the WO20O7 patents / 085 636 WO2007 / 089554, and WO2002 / 081341 which deal with thermochromatic techniques, none does not allow to consider an automated heat exchange and optimized for use in the production of hot or cold

Similarly, the piezoelectric zinc oxide patents WO1992 / 001 631, WO2008 / 004657, WO2008 / 018402 and WO2006 / 052033, do not allow to consider a recovery of the electric current with yields close to 30%

Knowing that above 25 ° C, the production of electricity by photovoltaic cells decreases from 24 to 5% each time the temperature of the cell increases by 10 ° C on the one hand

And that the yield of photovoltaic cells is often limited by physical equations of the materials used (for example for the case of silicon the technological limitation or the theoretical yield is 40%) on the other hand

We can easily understand the advantages of the present invention

Recall that the applications No. 0803019, No. 0804598, No. 0806821 and No. 0900257 and 09 00921, deposited respectively on June 2, August 14, December 5, 2008, January 22, 2009 and March 02, 2009 mention the following points In electricity generators based on photovoltaic technology, the performance of the device depends on the morphology of the thin film placed between the two electrodes. Photo-induced charge separation at the origin of the photo-current can only be done at the interface of the contact zone between the two constituents (in the case of C ₆ o).

To optimize the performance of the photovoltaic cells, it is necessary both to promote the formation of charges within the thin film of the photovoltaic device and to increase the amount of light absorbed. One of the great advantages of this new approach is the possibility of establishing a relationship between the structure of the hybrid compound and its activity. It will then be easy to vary the structure of the molecule to modulate its electronic properties to promote the production of photocurrent. We find that the use of nano-crystalline polymers considerably increases the efficiency of photovoltaic cells. Indeed ; An 11% yield can be obtained by stacking two Dye-Sensitized CeIIs (DSC) cells to form a DSC tandem cell, thereby increasing the rate of

10 conversion. The upper cell absorbs light in the visible, the lower cell in the near infrared and the infrared. The dyes used are red-dye (N719) which has an absorption peak at 540 nm (green) and black dye (N749) whose peak is at 600 nm (orange) but absorbs up to 800 nm (near infrared). The photoelectric conversion of the low wavelengths makes it possible to obtain a high electrical voltage, that of the long wavelengths providing a strong current, all explaining the high conversion rate obtained. Recently, French teams from INL (Institute of Nano Technologies Lyon) obtained conversion efficiency

Nearly 18% measured on a 2nd generation photovoltaic cell made of thinned crystalline silicon. At a time when 50% of the cost of a crystalline silicon photovoltaic cell is due to the substrate, a lot of research work is done on so-called 2nd generation cells, with a thinned substrate. Although this reduction in thickness degrades the efficiency of conventional cells, new architectures can retain significant efficiencies as demonstrated by Pierre Papet during his thesis entitled "New concepts for the realization of photovoltaic cells with rear contacts on substrates thin crystalline silicon ".

His work presents the main studies and improvements made to cells made on a p-type crystalline silicon substrate of about 150 μm in thickness. The passivation of the front face is provided by depositing a single layer of hydrogenated silicon nitride on the previously micro-structured surface. On the back side, a deep, heavily doped emitter is produced by phosphorus diffusion. A repellent field made on the rear face by boron doping makes it possible to limit the recombinations. Finally, the efficiency of the cells is optimized thanks to the geometry of the metal contacts Iπters digits reported back. All of these studies helped to achieve

High efficiency cells and one of them has an efficiency of 17.9% (measured in the laboratory). This result is currently one of the highest conversion efficiencies achieved on silicon in a French laboratory.

One of the innovative aspects of this application is its photovoltaic component. In fact, the production techniques to date have been either by the capture of the infrared or by the capture of the visible spectrum. Infrared Spectroscopy (IRA) is based on the absorption of infrared radiation by the material analyzed. It allows, via the detection of the characteristic vibrations of

30 chemical complexes, perform the chemical analysis of a material.

The principle of IR spectroscopy is as follows: when the energy of the light beam is close to the vibrational energy of a chemical bond, the latter absorbs the radiation and there is a decrease in the intensity reflected or transmitted to this beam. wave length. The spectral range between 4000 cm ^-1 and 400 cm ^-1 (2.5-25 μm) corresponds to the vibration energy domain of various molecules.

35 ... In the context of this invention we used two modes: i) Reflection and (ii) Total Reflection Attenuated.

The first mode makes it possible to determine the porosity of a layer. Constructive or negative interferences between the incident beam reflected at the porous air - / Si interface and the beam reflected at the porous Si / Si monocrystalline interface can be clearly observed on the layers whose thickness (d) is less than or equal to e λ reflected. The optical index of the layer (n) is determined from the reflectivity spectrum, considering the difference in optical path between the two reflected beams. Conditions

40 for the order interference maximums k and k + N can thus be written: 2dn = kλi <or

2dn = (k + N) λ _{k + N} where λ _x is the wavelength corresponding to the maximum of the order x; k and N are integers; IM - the number of interference maximums between λ ^ and λy _{+ ti}

Thus, we get: n = - ()

The average porosity can be estimated from these reflection index measurements using either the Brouggeman or Maxwell-Garnett effective medium models. According to Brouggeman's model of the medium, for example, the equation correlating the reflection index and the porosity of a layer is:

640 cm ^-1 ), measured experimentally. Our FTIR hydrogen concentration measurements in ATR mode are in excellent agreement with hydrogen quantity measurements made by thermal desorption spectroscopy (TPD MS), another technique for measuring the amount of atomic hydrogen. This method is based on the analysis of the gas desorbed from the sample during its sublimation. MS TPD coupled with the mass spectrometer is a quantitative but destructive analytical technique. It is relatively difficult to implement ....

... Photovoltaic cells are characterized by current-voltage curves in the dark and under illumination. In the dark, the cell does not produce current; the device is passive. Under illumination, the cell generates current and therefore power. This power corresponds to the area between the axes at J = 0 and V = 0 and the curve J-V. At the point of operation (Jmax, Vmax), one is at the maximum of the power of the device. The photovoltaic conversion efficiency is then obtained by the following formula:

^{FF x V} , c * Jsc P where the FF corresponds to the form factor the V _oc to the open circuit voltage J _sc to the short circuit current density P to the incident power.

The incident light is standardized at 100 mW.cm ^'2 under AM 1.5 which corresponds to the solar spectrum taking into account the Earth's atmosphere and an incidence angle of 48.2 ".

The open circuit voltage corresponds to the measured voltage when no current flows in the active layer. In metal-insulator-metal type devices, the V _oc is determined by the difference in output work of each of the metals. In the case of solar cells, the V _oc is linearly dependent on the HOMO level of the electron donor semiconductor material and the LUMO energy level of the electron acceptor semiconductor material (connected respectively to the potential of the electron source). oxidation and reduction of each of the materials). Studies by Brabec and Scharber have clearly shown this dependence on acceptor materials and donor materials.

Other factors also affect the value of the V _oc such as the electrode interfaces. Indeed, the pressure losses at the electrodes reduce the value of the V _oc . Surface treatments of the electrodes or the addition of intermediate layers are necessary to improve the match between the output work of the electrode and the HOMO or LL) MO of the donor or acceptor material. For this purpose, the ITO anode is treated by plasma or UV ozone techniques, or else covered with a layer that carries the holes with a higher output work. PEDOT: PSS (polyethylenedioxythiophene doped with polystyrene sulfonate) is then used for this purpose. This intermediate layer improves the quality of the interface with the active layer. The cathode is modified by the addition of a layer of LiF between the organic layer and the metal. This additional layer makes it possible to improve the V ₀₁ delivered by the cells. The value of the V _oc is therefore related to the energy levels of each of the materials and also to their interfaces. The Jsc is the current density provided by the cell under short circuit conditions (voltage across the cell equal to 0). The current density is determined by the product of the charge density photogenerated by the mobility of the material. So we have :

n is the density of charge carriers (positive and negative) e the elementary charge μ ambipolar mobility

E the internal electric field

S the surface of the cell

If one has 100% efficiency of conversion of photons into charges, n is the number of photons absorbed per unit of volume. However efficiency is not at its maximum. This efficiency can be measured by the IPCE measuring technique

(Incident Photon to Current Efficiency) which corresponds to the number of electrons collected under short circuit conditions on the number of incident photons. This value is calculated for each wavelength according to the formula:

IPCE -: J--. _x ≥ £ ₌ ^1240χ Isc lxλ e Ixλ where H is the length of the incident beam (in nm) J _{sc the} short circuit current density of the cell (mA.nï ² )

I the incident power (Wm ^"2 )

Today the best cells with P3HT: PCBM blends have a maximum external conversion efficiency (IPCE) of 70%.

Another limiting factor in the value of J _sc is the mobility of the free carriers in the active layer. It is not only related to the mobility of each of the materials taken separately but the mobility of the materials in mixture. That is to say, we must take into account their structure and the morphology of the mixture.

The form factor is defined by the following formula:

^" v _oc ^χ j _sc where P _ma χ is defined as the product of Jmax by Vmax the V _oc corresponds to the open circuit voltage J _sc to the short-circuit current density Jmax and Vmax correspond to the values of the operating point maximum of the cell.

The form factor is related to the number of charge carriers collected at the electrodes at different operating voltages. Indeed, in the active layer, there is competition between charge transport and charge recombination. This competition is equivalent to the competition between the transit time of the charges in the active layer 'ttf and their life time Y. The migration distance of the charges' d' is defined by the product of the mobility of the charges by their key time. transit through the internal field of the cell 'E' according to the following formula: d ≈ μ x ttr x E where ttr ≈ ^

In order to limit the recombinations in the active layer and extract the charges at the electrodes, it is important to have t τ thus to have maximum mobility of the charges.

On the other hand, the series resistances (contact resistance, resistance of the active layer) of the cell influence the FF. The first uses of organic semiconductor materials were demonstrated in the 1960s with the development of AC-powered electroluminescent cells powered by an alternating current. The low electrical conductivity of these materials limited the amount of light emitted, until the appearance of new polymeric materials such as polyacetylene, polypyrrole and polyaniline in the 1970s Heeger, MacDiarmid and Shirakawa showed that the conductivity of polyacetylene, an insulating polymer, increased strongly (by a factor of 7) when it was exposed to halogenated vapors. This was related to polymer doping by oxidation and simultaneous insertion. The work has since been carried out, with major advances in the field of photovoltaics since the 1990s with the work of Sanciftα, and the development of semiconducting polymers such as poly (p-phenylenevinylene) or polythiophene. Today, there are several major classes of conjugated polymers

The conjugated polymers can be used in many electronic (transistors) or optoelectronic (light-emitting diodes, photovoltaic cells) applications. As part of this innovation, we will focus on polymers dedicated to organic photovoltaics Several properties of polymers, in addition to the fact that they are easily implemented, are essential for obtaining high performance low-gap solar cells high oxidation potential and good charge transport These parameters govern the values of Voc, Jsc and FF which determine the efficiency of a solar cell. crucial parameters is the increase in the absorption of photons to increase the photocurrent This can of course be obtained by increasing the thickness of the active layer (but this solution is limited by the reduced mobility of the charge carriers and their time of short life) by extending the spectral absorption range of x and therefore by decreasing the HOMO-LUMO gap of the polymers The absorption of an active layer of a photovoltaic cell, based on P3HT and PCBM, absorbs UV up to approximately 650 nm In this case only 22.4% photons can be absorbed and converted into electricity However the solar spectrum is maximum around 700 nm and extends to the near infrared Improved performance is achieved by the use of polymers that absorb up to 800-1000 nm Another This approach consists in the use of block copolymers. These compounds consist of two thermodynamically incompatible polymer blocks. These two covalently bonded blocks are therefore immiscible. The use of such materials leads to the solid state at the spontaneous formation of separation domains. of highly ordered phases on the submicron scale of the order of 10 50 nm These organizations can be very complex It is mainly the molar masses of each of blocks which direct the morphology of the film and then lead to spheres, cylinders or lamellae These phase separation dimensions correspond to the dimensions necessary to have high conversion efficiencies in the active layers of the photovoltaic cells By developing block copolymers comprising an electron donor block and an electron acceptor block, these materials could lead to thermodynamically stable morphologies adapted for photovoltaic cells. Indeed one of the morphologies called "gyroid morphology" corresponds to two interpenetrating bicontinuous networks, the so-called "cylindrical" morphology Is also close to the ideal morphology of an active layer of photovoltaic cells. The presence of a strongly rigid conjugate block classifies these polymers in the family of rod-coil copolymers. First polymers were synthesized with a block of poly (p phenylene vmyl ene) (PPV) and a block of polystyrene (PS) functionalized with C60 Depending on the deposition solvent used and after heat treatment the morphology of the film can lead to a honeycomb structure with the use of carbon disulfide or Organized extended domains (fibril type) with o-dichlorobenzene Tests in photovoltaic devices were carried out The performances remain modest (Jsc of 5.8 uA cm ² , Voc of 0.52 V, FF of 023, under one monochromatic illumination at 458 nm, 1 mW cm-2) but the use of block copolymers shows a photovoltaic effect and an improvement in performance in terms of current density compared to a conventional mixture of the two compounds (C60 and PPV copolymer). b P (S stat-CMS))

The principle of the translucent liquid crystal axis control and orientation mechanism which is the subject of the present application is based on the fact that the display technique used in liquid crystal or translucent crystal displays is well known in the art. these days and can easily be implemented with highly optimized costs on a large scale It relies on the change of their optical properties induced by an electric field The nematic liquid crystals are organic compounds whose molecule has the shape of a stick, Because of the strong inter-molecular interactions, these molecules are aligned with each other. A nematic thin film of nematic liquid crystal orients then behaves like a polanser towards the light by changing the direction of orientation of the molecules, thus changing the direction of polarization For the record, let us recall that the molecules composing the nematic have a shape cylindrical, most of the characteristic properties of nematics derive from it Thus, the nematic fluid differs from the isotropic liquid by the spontaneous alignment of the molecules The nematic phase is born from this order of orientation of the molecules at great distance, it is a collective behavior Loπentation If the viscosity of the nematic phase is of the same order of magnitude as that of the isotropic liquid phase, a strong anisotropy exists, the substance flows more easily when the flow is in the sense of the director that when in a plane perpendicular ² In the latter case, the flow may tend to change the orientation of the director The study of the flow of a nematic under stress is called nematodynamic The phase diagram The classical phase is modified, the nematic phase being inserted between the liquid phase and the solid phase (or / and a smectic phase). some substances possessing a liquid-nematic-solid triple point and others capable of accepting the nematic phase for zero pressure Distribution of the orientation of the molecules

The order of orientation is measured in terms of the order parameter ^Λ 1 '*'"~ DU φ is the angle of a molecule with the director and the setting between the hook indicates the calculation of the average value over a large number of molecules Λ Like the distribution function, this function has a cylindrical symmetry according to the director In an isotropic liquid, no direction is preferred, we obtain s = 0 In the case of a perfect parallelism of the molecules, would have s = l

The expression of Oseen-Frank makes it possible to translate the free energy according to the spatial distortions of the molecules in the nematic. The expression includes four terms which depend on the orientation of the director, however, the fourth term, called "surface", is neglected in the majority of cases The expression of the free energy per unit of volume is written The first term splay translates the deformations in fan of the director, the second term twist translates the deformations in torsion of the director, the third term bend, translates the bending deformities of the director

The yarns observed under the microscope in the nematics are dislocation lines in the fluid To understand the disbeliefs it is possible to use the isotropic elasticity approximation we then set Kn = K ₂₂ = K ₃₃ = KL expression of the free energy simplifies itself and becomes f - ^• DDiissppoossiosstioonn of mmoolléeccuulleess ddaannss llee ccaass mm == 11 // 22 ^ 2 ^A ^ ^V "^ ⁺ ^ ^VA " ^

We consider a line of dismlining along the axis z the director being constrained in the plane (x, y), it makes an angle θ (x, y) with the axis x In this reference, the director TIa for coordinates (cos (θ), sιn (θ), O)

The expression is then calculated as a function of θ - 'Ox d' Ox Λj _ ¹ W <> v - Arrangement of the molecules in the case m = 1/2 This free energy is minimal when Δθ = 0

The solutions θ≈ constant correspond to a uniform field The solutions are of the type θ≈ m φ + constant or tg (φ) = y / x with m integer or half integer (because the director is defined π near), the corresponding constant a rotation of the director This equation makes it possible to draw the configurations of the director corresponding to the different disinclinations observed, with a singularity in the center The energy per unit of length of the distortion is written finally = Knfπln (r / r _c ),

_it is the cutoff radius * ^s (of the order of the molecular dimension) that can be estimated by comparing the energy of the nematic with that of the isotropic phase. Moreover, since free energy depends on m ² , configurations with m smaller are more favorable. The dielectric anisotropy ⁴ in the nematic is at the origin of most electro-optical applications. The molecules composing the nematic are particularly sensitive to electromagnetic fields. They carry a dipole moment (induced by the field and / or permanent, coming from the difference of distribution of the positive and negative charges within the molecule). Depending on the value of the permittivity coefficients, the molecules tend to orient themselves parallel or perpendicular to the electric field Ë and create a polarization field. The polarization field - the aligned molecules - counterbalance, in part, the initial field β (as in a capacitor in the presence of a dielectric). If we identify the z axis with that of the director, the matrix of dielectric constants is written ⁵ : \ ^α ° ^e v Where ε ₂ is the dielectric constant in the axis of the molecule (axis id z or axis of the director ). The vector polarization is written (approximation of the first order): P = eE or (according to its components): Pi = Σ εjEj j where the field Ë has components Ex, Ey, Ez. Note that the field Ë is not necessarily aligned with the vector polarization (anisotropy: ε _t ≠ ε ₂ ), nor initially with the molecule. The torque exerted on the director by the field: £ is: Ij ~ V ^ ^.

The components of the pair are therefore: (F _x = (εi - 8 ₂ IEyE ₁ , l ^" _v = fe - εi) E _x E ₂ , r _z = 0) If the difference ε _z - ε_ is negative, the pair tends to align the director perpendicular to the field, if it is positive, the director tends to align with the field Several types of liquid crystal devices known as "NCAP" (Nematic Curviliπearly Aligned Phases), or "PDLC"

(Polymer Dispersed Liquid Crystal) or the cholesteric liquid crystal polymers may be envisaged. All these systems need to be equipped with current leads supplying electrodes generally in the form of two electroconductive layers on either side of the layer or the various active layers of the system. These electrocoπductive layers (which may in fact be a layer superposition) commonly comprise a layer based on indium oxide, generally indium oxide doped with tin better known under the abbreviation ITO. These layers can be easily deposited by magnetic field assisted sputtering, either from an oxide target (non-reactive sputtering), or from an indium-tin target (reactive sputtering). presence of an oxidizing agent of the oxygen type). One approach is to insert, in a stack of oxide layers, a metal layer to improve the surface resistance of the electroconductive layer. This metal layer is otherwise thin enough to maintain a good level of light transmission. This TCO type: English abbreviation for "Conductive Transparent Oxide" is intended to be integrated into an electrochemical device of the electrochromic type in which the metal blocking layer constitutes a barrier to the diffusion of Li + ions between one of the active layers. and the metal layer. The aforementioned assembly is generally completed by a layer based on transparent conductive oxide such as zinc oxide, or indium oxide doped with tin. Note that an energy control stack structure incorporating a layer of silver or copper advantageously alloyed with a noble metal, for which protection against corrosion is obtained by coating a bilayer based on oxide or a mixture of oxide, for example I ¹ In ₂ O ₃ and ITO or ZnO ₂ / In ₂ O ₃ and ITO. In the case of the use of ZnO ₂ , the application as an electrode is impossible because of the insulating nature of this oxide.

Moreover, the use of mesogenic tubes makes it possible to highlight certain aspects of this invention. Indeed ; Generally, the molecules that make up the fluid are so small and numerous that they can be considered as continuous media. Physicists from Rennes (IPR), Saarbrϋcken, Saclay (Iramis / LLB) and Grenoble (ILL) have demonstrated that certain fluids made up of elongated molecules, called mesogenes, no longer have the same physical properties if the diameter of the tube in which they are place is of the order of 10 nanometers, or thirty times the diameter of these molecules.

Experimentation used channels of several hundred micrometers long, but only 8 nm in diameter, obtained by electrochemical etching of silicon sheets. After oxidation of these materials, they obtained silica membranes, perfectly transparent and pierced with an assembly of nanochannels. By optical measurements, they followed the preferential orientations of mesogenic molecules, impregnated in the channels. These molecules, which are involved in most liquid crystal applications, spontaneously align with each other below a specific temperature, whereas their orientation is arbitrary above this temperature. In addition, neutron scattering measurements at LLB and ILL have shown that in a channel the rotational and translational motions of the molecules are altered and depend significantly on the precise location of the sample. where is the molecule. These changes should have a significant effect on the viscosity of the fluid and its transport properties. We also observe that this type of fluid helps orient and maintain the nanocrystals in the sun tracking function of the present application.

A reference voltage integrating IR and Light of the medium will control the polarization voltage of the liquid cylinders so as to ensure the angular optimization of the cylinders with the captive surface of the ray-receiving cell. "

DESCRIPTION OF THE INVENTION

10000] Preliminary remark: The understanding of this innovation is simplified by the description of the major steps necessary in the realization of the multi chamber cells intended to trap the greatest energy of the solar spectrum with a tracking of the sun during rotation of the earth during the day . Therefore, we must consider that the realization of low-cost photovoltaic films by CIGS cells with performances going from 15% to more than 60% passes even more by the consideration of the different technological leaps on the process, process, material aspects. and the steps. It can therefore include several inventions from a regulatory point of view of the National Institute of Industrial and Intellectual Property. However, this is only one invention leading to a powerful product thus avoiding multiple iterations in the manufacture of photovoltaic cells in a minimum time. An indexing [5 digits] allows a simple identification of the chapters treated in this application.

[0001] One of the important advantages of the present invention is the capture of the multi spectral energy of the sun's radiation. This principle results in the design of a cell with three compartments capable of absorbing the energy of each spectrum during the passage of light rays. The first compartment crossed by the light rays retrieves the ultraviolet rays (UV) and lets the rest of the spectrum to the second compartment that traps the spectrum of visible rays and lets the remaining infrared spectrum (IR) to the third compartment. The chamber thus constitutes a basic cell (Multi Spectral Basic CeII or MSBC).

In another arrangement, a compartment for a range of the light spectrum may itself be composed of several other trapping compartments, a specific spectrum or the same spectral band. In order to recover all the photons of the solar spectrum, the chamber is surmounted by an antireflection layer capable of absorbing 96% of the light energy which reaches the exposed surface of the chamber and this under an angular range of 0 to 60 ^* relative to to normal, a cone of 120 °

The set is surmounted by an optical concentration device which, as its name indicates, concentrates at one point, 300 to 1500 times the radius received on its surface. The values indicated are given by way of example and are not limiting.

[10002] To describe the realization of a basic multi-spectral cell of the present application, we must consider that the spectral fraction actually used by standard Si cells is relatively small compared to solar radiation, the modification-based approach The incident spectrum by energy conversion of photons appears relevant The principle of double or multiple capture chamber has been developed in patent application 080 ₄ 598 The inventors have been interested in the work on oxides films suitably doped for applications such as conductive transparent electrode or as conversion layers of the solar spectrum in the field of photovoltaics The material mainly envisaged is titanium oxide, however, as mentioned in § [00002], other oxides may also be considered spectral multl cells that open the way to high yields with mechanical stacking or monolith of cells "EgI>Eg2>Eg3" Each cell converts a spectral band and transmits the rest The understanding of the invention goes first of all by the detailed description of each element constituting a compartment gives to know

1 The ultraviolet spectrum capture chamber by TιO2 doping consists of converting an incident photon in the UV-blue into a photon in the red ("down-shifting" phenomenon) or a photon in the UV-blue in two photons in the red (phenomenon of "down conversion") This same principle is applied to convert two photons in the infrared into a photon in the red (phenomenon of "Up conversion") To achieve such an objective the use of ions rare earths in a large gap matrix

For this application, TiO2 is a material of choice because of its high refractive index its excellent transparency in the visible its low phonon energy and its high chemical stability The doping of TιO2 by rare earth ions does not lead to segregation even for high doping levels (a few%) In addition, excitation of the rare earth ions via photons absorbed directly by TιO2 (gap 3 2 eV), followed by the transfer of energy towards certain levels of the rare earth ions ( Nd or Yb) is particularly effective Thus the doping of TιO2 by Nd or Yb ions makes it possible to envisage the "down shifting", the co-doping by Tm and Yb is envisaged for the "down conversion", while I " Up conversion is possible by the co doping Er and Yb The growth of the oxide films is carried out by laser ablation, a growth method particularly well suited to the formation of oxide films of complex composition. s, the growth of these films in a wide pressure range (1 - 10 mbar) of oxygen will make it possible to control the stoichiometry of the oxide films, and consequently the concentration of carriers and their conductivity. (elastic retrodiffusion of ions, determination by nuclear reactions) carried out with the accelerator Van de Graaff, give the exact composition of the films Recently, a publication of the University of Franca of Brazil proposes dopings based on natural pigment of the "Mulberry" type Cyanidine "with transmittance exceeding 98% for IR or UV (Publication Material Research vol 10, N4, 413-417,207 under the title" SoI-GeI TιO2 Thin Films Sensitized with the Mulberry Pigment Cyamdin ") [10003] The description of the capture layer of visible rays leads us naturally to describe the layer of CIGS / CIS Recall that the most important elements in the realization of this compartment in thin layer are the prepara CIGS / CIS in the form of ink or powder

The technique of deposition and adhesion on large surfaces while maintaining the performances performed on small samples in the laboratory The stoichiometry of the deposited solution Reproducibility of the processes

[10004] The ink printing process seems to be the most frequently used This procedure is briefly illustrated in the diagram (Figure 10b) The nanoparticles of the mixed oxides of Cu, In and Ga with a predefined mixing ratio of Cu / (ln + Ga) are synthesized using the appropriate chemical means (described in patent application No. 0806820). The oxide powder thus obtained (FIG. 10c) is then mixed with an alkaline solution (FIG. 10 a). to obtain the ink determining the parameters of the charge of the particles (size, sector and surface) using the standard techniques (ie, precipitation) The rheology of the ink can be adjusted by the choice of the solvent, dispersant and particle characteristics of the oxide powder, loading solids, ink pH and other suspension variables Moreover, the singular properties of the nanomaterials are influenced by two parameters volume reduction, and the increase of the surface / volume ratio These modifications confer optical properties specific to the nanoparticles, and also modify their magnetic properties by making the energy of amosotropy magnetocπstalline (proportional to the volume of the particle) preponderant before the thermal energy These particular properties will be thus controllable by adapting the size of the particles Therefore, it is necessary to use development procedures for adjusting the size of the nanoparticles as described in patent application No. 0806820 Knowing that most of the steps listed on the diagram (Figure 10b) are "non-vacuum" processes and require only standard equipment for implementation Molybdenum (Mo) sputtering of substrates is the only vacuum process used after deposition of a layer of Mo (from about 0 2 to 0 5 μm) This process can be carried out step by step separated and is usually sequenced independently of production procedures For our intermediate layers other types of translational metalllsations of the kind "ZnO ZnSe" are used (ref NANOSTRUCTURES BASED ON TWO BINARY H-VI SEMINCONDUCTORS WCH Choy, CF Guo, KH Pang, YP Leung, Department of Electπcal and Electronic Engineering, University of Hong Kong Hong Kong Pokfulam Road, China) There is also a new construction principle to reduce costs So far, the electrode of the photovoltaic cell was made of indium oxide etam (Indium Tm Oxyd or ITO), because this material is transparent but remains relatively expensive The alternative lies in a polymer electrode which is not very conductive transparent to a layer of highly conductive metal located on the affixed part of the solar cell, thanks to many small holes in the cell This new construction principle allows the use of trans polymer electrodes It should be noted that to date, the materials most frequently used in the field of TCOs (Transparent Conductiπg Oxide) are based on indium oxide (ITO). New TCO materials are therefore to be considered, because of the cost higher and higher indium transparent In this context titanium oxide is a good candidate to allow consumer applications of electronics, thanks to its high gap (3 2 eV), its very high chemical stability and its doping by various elements, which can give it new functional properties In particular certain dopants (Nb, Ta) induce a strong conductivity in this material [10005] At present, there exist BTU ⁸ machines (Massachüsette-USA) intended for Continuous production sites for thin films of photovoltaic cells as well as FujiFilm ^® USA DIMATIX ^® piezoelectric inkjet printing devices The ink-based manufacturing process by i CIGS / CIS cell expression has the following advantages

1- The control of the Cu, In, So2 stoichiometry (25%, 25%, 50%) of the absorbent layer resulting in a high process yield because the stoichiometry exhibits a strong absorption in the visible and a neighboring gap from 1 eV 2- A lower consumption of the raw material related to the fact that during deposition, all of the material is deposited on the substrate unlike other co-evaporation type techniques where the deposition of the material is a low percentage.

3- Lower cost of installation and manufacturing equipment. 4- Control of the deposit thickness.

5- Control of distribution in tense and continuous flow with servo and control system. The combined effect of the attributes of this process provides inexpensive CIGS / CIS cells in the form of flexible, lightweight and very thin modules. The important point in the realization of such an assembly is the molecular adhesion by graft or particle implantation which avoids the use of an adhesive substance. The invention provides a method of assembling two substrates by grafting or implanting particles into one or more conductive alloy films.

[10006] In this invention, we have implemented an ion implantation technique for depositing CIGS / CIS particle ink onto a thin layer. This technique involves bombarding a material with ions accelerated to a certain energy, until the desired level is obtained on the matrix of deposited atoms, while implanting some molecules buried in the substrate thus creating the point of attachment of the desired layer on the substrate (graft particles). The surplus can then cause the formation of particles in a region of the target surface by making a thin layer of the desired cell. This method has the enormous advantage of being very flexible compared to other methods and provides access to an almost unlimited number of particle / matrix combinations. Thanks to this method, it is to a certain extent possible to control the concentration and the size of the precipitates and physical properties can thus be optimized with a view to the particular application of deposition of the CIGS and TiO2 layers as well as their respective junctions and indispensable. The system proposed by the inventors improves the quality of deposition by eliminating the anomalies of a magnetron system (ref .: as described in Patents L) S 4 198 283, WO 2007/106732 or WO 2005/090632). Indeed ; if the plasma is generated outside the main chamber, in an adjoining room. It is possible to generate a stable plasma with a density of 5.1013 ions / cm3. Argon ions, generated in the arm (annex chamber), are extracted by the combination of electron density scattering and ambipolar diffusion, and introduced into the main chamber.The electric field present in the main chamber allows to control rigorously the velocity, thus the kinetic energy of the argon ions.The magnetic field (created, in the main chamber, by two electromagnets placed between the exit of the annexed room and the target) makes it possible to orient the ions let's argue on the target to control their trajectory.

The decoupling of the actuators (electric field for the speed, magnetic field for the trajectory) offers a great flexibility of use and degrees of freedom of the process. A high density plasma is generated in the launcher barrel due to the forces exerted on the thermionic electrons, due to the interaction of the 13.56MHz RF electric field and the static magnetic field from the electromagnet placed at the launcher exit.

Activation of the electromagnet placed behind the target and having the function of deflecting the ions towards the target causes a high density of argon ions, located directly on the surface of the target. This is due to a combination of electron scattering (due to scattering of electron density) and ambipolar scattering. Argon ion energy is low (30eV at 50eV) and is not sufficient to spray from the target directly. Applying a DC bias to the target accelerates the argon ions along the beam where they collide with the target, releasing atoms / ions / clusters and secondary electrons. This makes it possible to graft the molecule into the target substrate. With remotely generated plasma, not on the target as in the magnetron sputtering, this does not require local magnets behind the target and thus avoids the development of "racetrack" more commonly known as "racetrack" on the surface of the target. The result is: The high use of the target, due to the uniform erosion of the surface. - Reduction of target poisoning: no need for DC pulsed or retroactive process, and much higher deposition rates of reactive sputtering of dielectric materials, especially compared to the Magnetron process. Better reproducibility of spraying from multiple targets.

In addition, since the generation of the plasma is independent of the local magnets placed behind the targets, the deposition rate is not affected by the ferromagnetic nature of certain targets. Therefore, high deposition rates from ferromagnetic targets are possible. In this method, at the inverse of the magnetron method, the substrate is placed at the top of the vacuum chamber. Thus, only the atoms of the target, which have sufficient energy to overcome gravity, are absorbed on the substrate, thus ensuring the quality of the implant and / or deposited film. Indeed, another advantage of this method is that the pollutants of the chamber do not have sufficient kinetic energy to reach the substrate and absorb it. The preferred geometry for the plasma launcher tube is of the type perpendicular to the substrate surface. This system allows a deposit on moving film. In this geometry, the same plasma launch tube of the traditional system is used, but a cylindrical target is placed in the "beam" of the plasma. This geometry offers several advantages: more efficient use of the plasma, no requirement to scale the source relative to the target, a larger deposition area and implant speeds or higher deposits. The generated plasma beam consists of a tubular generation region where the electrons are magnetically confined (and responsible for the light discharge). This generation region can not be interrupted, but placing the target in this critical region has no effect on plasma propagation. This region has a high density of argon ions and provides a very efficient spraying process.

This chamber offers graft or deposition speeds even greater than the conventional chamber, up to 120 Cm / min for many tested materials. It also facilitates the manipulation of substrates of larger dimensions. For a target length of 60/60 cm, the system allows layers to be formed at the optimum 40/40 cm uniformity on substrates. In the linear system, several plasma generators can also be arranged next to each other in independent chambers, allowing the deposition of multilayer materials. To increase just-in-time speed, we align multiple graft heads. The effects observed during the experiments correspond to the results obtained by a simulation program based on a Kinetic Monte Carlo method.

[10007] The inventors have designed a production line based on the trio "Greffe, Impression, OPF". This choice allows for a high throughput and flow-through solution called a roller-roll that will enable future thin-film cells to be manufactured. To date, to enable just-in-time production, various depositing techniques

"Continue" are implemented. These methods have the advantage of being controlled at low speed but their output rate is poor and unprofitable. Hence our interest in high throughput continuous methods. Indeed ; In order to increase the output speed and the quality of the layers produced, the inventors have selected the drying method by optical drying oven (OPF). The advantage of this technique is that the selection of a light having a particular melting spectrum illuminating the epitaxial surface does not thermally affect the near areas (in our case the thin film), in this case the ink dries quickly without undergo changes in its molecular structure. This is a major advantage of this innovation compared to the prior art as described in WO 2006/073437; WO 2006/033858. To date, no industrial process for producing thin-film photovoltaic cells uses piezoelectric inkjet printing with OPF-based optical drying method. Another variant of this layer of CIGS can be achieved by a judicious choice of TiO2 instead of CIGS for future generations of photovoltaic cells this layer. We can also note that other nano-thin-film silicon-based processes offering hybrid solutions heterojunction (gravitation) are possible. [10008] The printing technique presented in this application aims to deposit on a substrate, a film with controlled characteristics: thickness, uniformity, morphology. Other variants of this technique are printing with toner ink (or drum) and / or laser printing. The inventors have decided to limit the explanations on these variant techniques for obvious reasons of the existence of numerous publications on the state of the art of these variants. Note that the printing technique described in the present invention can achieve speeds ranging from 30 to 45 m / minute in just-in-time and on a roll-to-roll chain. This speed is dependent on certain configurations during deposition and assembly of the layers and the constituent options of the device.

[10009] The understanding of the formation mechanisms of the CdS / CIGS junction can be broken down into two successive critical stages:

The first lies in the ultimate preparation of the CIGS surface which can lead to various surface compositions.

The second relates to the establishment of the CdS junction involving chemical interaction phenomena that depend on the initial conditions on the CIGS layer.

These two steps condition the electronic properties of the interface and therefore the performance of this type of solar cells. However ; Another aspect of the present invention is the use of non-toxic solutions to replace the Cds junction with Indium Sulfide Hydroxide (In2S3) deposited by the spray method, for example. The benefits of this equivalence are extensively described in the document "Lioudmila Larina, Ki Hwan Kim, Kyung Hoon Yoon, Byung Tae Ahn, Proceeding on Solar Cells Based on Indium CIGS absorb. Advanced Institute of Science and Technology, Department of Material Science and Engineering, Taejon, Korea, 305-701, 11-02-2003 "

Another aspect of the present invention is high power, low weight manufacturing for use both in space and on the ground of photovoltaic cells. For this purpose, the inventors have used the method of manufacturing thin film CIGS cells (ThinFilm) of the 'Kapton' or 'Upilex' type.

The performance of the photovoltaic cells thus constituted by the CIGS and Cds or ln2S3 layer (overall CIGS layer) are conditioned by the quality of the surface of this layer thus produced. In order to improve the efficiency of our CIGS layer, we considered treating the surface of the crystallized conglomerate with the following methods: - Chemical treatment without environmental impact; This treatment is based on the use of a chemical pickling of the surface of the CIGS by a solution containing bromine, known to allow to obtain a specular surface. The surface was analyzed by profilometry, SEM and XPS, allowing the determination of the surface roughness (up to 20 Å instead of 750 Å initially), the etching rate (from 0.5 to 9 μm / min) and the chemical nature of the surface species. This reduction of the surface roughness by the Bromine treatment is significant, passing it from a submicron scale to a nanometer scale in a few seconds (from 75 nm to only 2 nm). The pickling treatment is otherwise perfectly isotropic and independent of the crystalline orientation. Note that the pickling speed is strongly dependent on the Bromine concentration, and does not seem to be quite constant over time. A detailed study has been devoted to the influence of the CdS deposition bath on the surface of the CIGS. For this, a surface of CIGS was immersed in a solution containing only Cd2 + ions in an ammonia medium, which is equivalent to the first stage of deposition, that is to say before the hydrolysis step of thiourea and hence the formation of the CdS compound. The variations presented above are obviously related to those of the photovoltaic performances. Optimized conditions of surface treatment and CdS deposition thus lead to characteristic quantities comparable to the best published values: FF form factor and Voc open circuit voltage up to 81% and 690 mV respectively.

Laser treatment; The surface treatment on CIGS cells using a pulsed laser also called PLA (Pulsed Laser Annealing, on films and substrates provided with CIGS layer with a laser beam having a duration of 250ns and 308 nanometers in length. waves with a laser beam power chosen between 30 and 110 mJ / cm2 show (by reading the XRD, GIXD and SEM results) the external changes close to the structure Deep-Level Transient spectroscopy (Deep-Level Transient) Spectroscopy or DLTS) and CV results show that the defect density has reduced by half after PLA treatments.The reading of the XRD and GIXD curves also shows a greater efficiency of the treatment effect by decreasing the incident angle The results of CIGS cell-based film PLA processing and DLTS measurement are an effective alternative for increasing the efficiency of photovoltaic systems. Electrical tees of ClGS films from two (2) different sources clearly show that the treatment has altered the near outer region. Homogenization of the outer surface as shown in Fig. 5c, and uniformly changing CIGS / CdS diffraction peaks, shows that the energy density of 70 mJ / cm 2 could be a critical value of PLA.

An innovative aspect of the present invention for the deposition of the Cds layer on CIGS layer lies in the deposition of the layer Cds (or ln2S3) on the CIGS layer by electroplating. Indeed ; in this application we use a technique of electrolysis by adding temporary electrodes on or under the CIGS layer during the passage of the layer in an electrolysis bath (as described in patent application 0803019) by FBD and FBR (Fluidized Bed Design and Fluidized Bed Reactor). The electrodes can be mounted on a drum and positioned in the field at the boundary of the zone separators during electrolysis. The alkaline solution thus contains a mixture of Cd particles and / or positively charged Cd ² + ions which will deposit on CIGS during activation of the electrodes. The pH of the alkaline solution is modified to increase the reaction of the electrolysis during deposition of Cd particles and / or Cd ² + ions. This modification also makes it possible to control the stoichiometry and the morphology of the film thus deposited. The resulting reaction is substantially similar to the results obtained in the publication below where the electrolysis deposition appears uniform and smooth and represents a very good film quality. Indeed, these publications are from Mr Figen KADIRGAN on "P ro p erties o f Po rted S ectio n Ca dmium Su lfo fo r Fo il P fo otovo lta ic D ev ic es w ith Co mpa ry to Cd SF ilms P re pa re d by Ot her M and hods, "Department of Chemistry, Istanbul Technica l University, 80626, Maslak, Istanbul-TU RKEY; Duii WlAO, Wenjie SONG, Tim OHNO, Department of Physics, Colorado School of Mining, Golden, 80401, Colorado-USA; and Brian McCANDLESS, Institute of Energy Conversion, Delaware University, Newark, DE 19716-USA (1998).

A variation of this method is the use of the multi-head and inkjet piezoelectric printing technique mounted on a ramp. The width of the print head on the production line is often the same as the width of the deposited film as developed and described in the present invention. This variant has the advantage of printing the Cds layer (or ln2S3) in a context of tight flow and roller - to - roll, while preserving the control over the

10 quality and the thickness of the film thus deposited.

One of the innovative aspects of the present invention is the heat transfer into a current. It is important to note that the recovery of the calories and their transformation into electric piezoelectric currents were treated in the patent application No. 09 00921 filed March 2, 2009 and is incorporated by reference in this application. These currents thus collected add to the photocurrents by a simple summation circuit known by the state of

15 art (confirmed by the work of Adrien BADEL, energy recovery and vibration control by piezoelectric elements following a nonlinear approach, doctoral thesis in Mechanics and Materials, Graduate School of the University of Savoy, 2008). According to the CNRS studies (document entitled "Micro-energy sources - Microsystems of energy management, author Carole Rossi, LAAS-CNRS -Microsystem, page 14," the power density of a light photovoltaic cell in μW / cm3 is substantially identical to the power density of an equivalent surface cell equipped with a generator

Piezoelectric It is reasonable to consider that the energy thus converted remains modulatable and a function of the thickness of the piezoelectric layer. Thus, this efficiency is at least equivalent to the energy of the sun received at the exposed surface of the photovoltaic cells (a few microns for the photovoltaic cells compared to a variable value in micron for piezo). This current figure obtained has just been added to the bottom of the overall energy balance (overall yield) of the present invention. We can therefore consider that the solution proposed by the inventors, double, at least, the

The overall efficiency of the photovoltaic devices provided with the current thermal converter generator layer while producing a thermal evacuation of the cells avoiding a degradation of performance often caused by the increase of the temperature on the photovoltaic cells. Note that a variant of current caloric / thermal converters may be "thermocouples" that can replace piezoelectric generators. [0013] Another innovative aspect of this application is its ability to follow the sun in the daytime

30 (described in the patent application 09 00921) while absorbing almost all of the visible and invisible lights, by an "antireflection" phenomenon, comprising UV and IR, and this regardless of the angle of incidence.

Remember that most conventional photovoltaic silicon cells absorb about 67% of the sunlight that reaches it. Potential light thus lost represents a barrier to increasing the efficiency of photovoltaic devices. To recover all the photons of the solar spectrum, we have to make sure that the reflection of the

35 incident rays on the surface of a solar cell are eliminated. i Note that for an oblique incidence the simplified Fresnel reflection coefficients are defined by:

The nano structured multilayer film used by the inventors allows almost total absorption (97%) of the light energy that reaches its surface, and this for all the wavelengths of the spectrum. We measured a Fresnel reflection ranging from

40 only 1% at around 6.5%, on the 320nm (UV) spectrum at 1600nm (IR). The layer absorbs, on average, more than 96.5% of the light under an angular range (relative to the normal of the layer) of 0 to 58 °, a cone of 116 °. A variant of the antireflection film is composed of seven nano-structured layers to approach a continuous refractive index profile: The precise control of the porosity of these different layers makes it possible to reach refractive indices ranging from n = 1.09 at n = 2.6. Each layer has a particular thickness, the lower layers being the finest and

45 having the highest refractive index, respectively between 69 nm and 156 nm thick and between n = 2.6 and n = 1.09 index. The two lower layers are titanium dioxide (TiO 2). The three core layers are a combination of silicon dioxide (SiO2) and TiO2 to adjust the refractive index. The two upper layers are made of oblique nano sticks of SiO2, hooked to the substrate by chemical vapor deposition. Each layer transmits the light while helping to capture the light that would have been reflected by the lower layers. The principle of this phenomenon is described in

50 patent application No. 0804598. Indeed; The index gradient and the oblique sticks of the last layer make it possible to drastically minimize the Fresnel reflection for all wavelengths and angles of incidence, which is totally different from traditional quarter-wave antireflection coatings (each layer absorbs and reflects the captured light between the rods by directing them towards the surface of the photovoltaic cell). This new film can be applied to virtually any photovoltaic material, including multi-junctions Ml-V and Cadmium Telluride. The

The results obtained are a 25% improvement in the conversion efficiency between a conventional "quarter wave" coating and the index gradient multi-layer film. This characteristic allows heliostat tracking in the two X and Y axes. It should be recalled that the tracking method based on the liquid crystal cross-linked nematic technique described in patent application No. 0900921 may include polarization, which is a characterization of the waves. describing the orientation of their oscillations. Once polarized, the circular polarized waves can turn to the right or left in a defined direction

60 (as the direction of movement of the sun). These movements can also be conjugated with chiral properties of crystalline polymers globally presented and defined by waves called "chirality".

It should be noted that another aspect of the present invention is the use of crystal rods (or nanocrystals) or other polymers having Chiral characteristics to become an element of increase in efficiency and effectiveness by tracking the sun in both. X and Y axes. The combination of tracking techniques with the anti-reflective film produces an improvement of

65 35% the efficiency of photovoltaic cells.

The description of FIG. 7 provides a better understanding of the present invention:

1. Antireflection film (ZnO type: AI for example), allowing the almost total passage of incoming light. 2. Horizontal Filter Film, allowing almost total passage of incoming light.

3. Substrate comprising the common electrode film (ITO) with the horizontal tops aligned along the horizontal filter.

4. Twisted nematic liquid crystals. 5. Substrate of JTO electrodes. The position of the liquid crystal is determined when the system is turned on.

This voltage makes it possible to vary the position of the liquid crystals as a function of the position of the sun. It is generated by a simple light-current transforming device well known in the state of the art. The vertical light exit points (tips) are deep in the surface for aligning the liquid crystal with the polarizing light on the sensitive point of the absorbent layer. 6. Outgoing Light Polarization Vertical Filter Film.

7. Absorbent layer (particles).

8. Photovoltaic or solar layer for receiving concentrated concentrated light.

9. Reflective layer in optional crystalline nano prisms

X-rays provide effective means of controlling homogeneities of CIGS cells by controlling the fluorescent dispersion of the materials by means of the "EDXRF" (Energy Dispersive X-ray Fluorescence) type equipment on a production line. Indeed, during the production of CIGS cells, the manufacturing process must respect a very acute tolerance on the thickness and the atomic concentration of Cu, In, Ga, Se mixtures defining the efficiency and the efficiency of the photovoltaic cells. The system is often mounted at the end of an online production line. It seems obvious that the same EDXRF control system is applicable on T1O2 film production lines. For the characterization of photovoltaic cells based on CuInGa (S, Se) 2 chalcogenide compounds (CIGS), we correlated more particularly the results of three techniques: Admittance spectroscopy

Current-voltage measurements over a wide temperature range and Spectral photoreponse. We can mention here two striking results:

A type of shallow energy defects probed by admittance spectroscopy has been located in the CIGS and not in the CdS buffer layer, and

The demonstration of a gradual gap at the CdS / CIS interface when the CIS absorber is obtained by electrodeposition. An advantage of the present invention consists in transforming the current resulting from the photovoltaic device into WiFi type current, electromagnetic or scalar waves, ensuring a transfer of energy without a line. FIG. 10 shows the operating principle of a photovoltaic device equipped with a scalar wave transformation and transmission system. Thus the current recovered in the photovoltaic module is converted into electromagnetic waves and then this wave is transmitted by a thin emitting layer to another receiving thin layer before its transformation into current. A copper coil connected to traditional electric currents via a socket creates a magnetic field. This magnetic field unintentionally influences another similar copper coil and creates an electric current that can ignite a light bulb. This is exactly what happens incidentally in a transformer between the primary circuit in which the current flows from the network and the secondary into which is induced a second current, all without wire contact between the two circuits. Thus, the inventors have considered the integration of this technology into the substrate or the support of photovoltaic solar cells (underlayer Mo metallization for example) and this in a production in tension roll-to-roll. A variant of this innovation consists in using one of the conductive layers (Mo for example) with a spiral pattern or else a generating pattern of the electromagnetic, WiFi or Scalar waves (these waves do not interfere with the expected photovoltaic performances of the present invention) . This allows in the short term to recover the energy without electrical wiring between the panels, to recharge the storage devices or to feed the networks. It goes without saying that the system can also charge any portable device (mobile phone for example) without having to connect it, or in a habitat without the connection of appliances or electrical outlet but only walls and ceilings inductors .

ADVANTAGES OF THE INVENTION The main outstanding advantages of the present invention are:

I- Improved efficiency of absorbed rays by adding anti-reflective layer and reflected light control. 2- Sun tracking system or heliostat in both X and Y axes, integrated into the device.

3- Increasing the energy efficiency of multi spectral photovoltaic cells by multiple capture chamber and the heat capture compartment and / or piezoelectric layer,

4- Preparation and / or pretreatment of the support or substrate by grafting (implants) of the particles before application of the thin layer intended to form a compartment, which is essential for creating the point of attachment (or hooking) of the layer to deploy,

5- Creation of the particulate layers on the already grafted substrate having a precise thickness.

6- Optimization of existing deposit and control processes for CIGS / CIS ink

7- Increased yield of CIGS cells by surface treatment and crystalline layers.

8- Printing on substrate previously grafted. 9- Use of piezoelectric inkjet printing devices.

10- Photovoltaic devices on thin film, for extreme environments.

II- Major economic advantages related to the use of materials of high availability and inexpensive (example Titanium Oxide TiO 2).

12- Greater environmental acceptability of the photovoltaic device by the use of non-toxic element of the Indium Sulfide type.

13- Reduced energy costs during production.

14- Real-time control of the dispersion of the materials of the cells produced.

15- Cost savings by a decrease in the quantity of materials (use of nano particles resulting in a reduction of layers) and deposition techniques (almost all deposited materials). 16- A continuous flow production system in the form of "roller rollers" at high speed.

17- Performance of the industrialized product equaling the results obtained in the laboratory. 18- Ability to transform calories into current through a piezoelectric layer and / or regulate the temperature of the photovoltaic cell

19- Capacity of transformation and optimization of energy transmission processes without files by WiFi, EM (electromagnetic) or OS {Scalar waves) integrated in the device. 20- Modularity of the composition of the capture chambers, hence the adaptability of the device to the materials most abundantly available.

21- Performance capacity in a continuous flow and continuous capture compartment by spectral band. BRIEF DESCRIPTION OF THE FIGURES

The set of figures describing the different points of the system through FIGS. 1 to 8, and which are the schematic representation and details of a system comprising a series of photovoltaic cells intended for the production of electricity being the object of the present invention.

Figure 1 shows a roller-to-roll production line subject of the present invention. Figure 2 shows a method of manufacturing CIGS ink subject of the present invention.

Figure 3 shows the plasma bombardment implant (or graft) steps as described in the present invention. Figure 4 represents the multi spectral compartments Ultraviolet, Visible and Infrared photovoltaic intended for capturing visible and invisible rays.

Figures 5a-5d show the different surface treatments and the deposition of the Cds bonding layer.

Figure S represents a snapshot X-ray image of the typical spectrum of CIGS cell composites on a film (depending on their stichometric value). The material concentration corresponds to a CIGS layer thickness of 2.7 μm and a Mo contact of 0.7 μm. Figure 7 shows the sun tracking system as described in the present invention.

Figure 8 shows the principle of piezoelectric inkjet printing of the present invention. FIG. 9 represents the spectral response of the transmittance of the doped TiO 2 layers for UV and IR

Figure 10 shows the principle of transforming the currents from the solar device into electromagnetic waves without a line. It should be noted that an absorbent layer as described in [00100] to [10006], generally consists of either: - An inorganic material of the group (TiO ₂ ) or TiO ₂ nanocrystalline, (ZnO), (CuO or Cu ₂ O or Cu _x Oy), (ITO), (CdSe), (CdS), (Cu ₂ S),

(CdTe), (CdTeSe), (CuInSe ₂ ), [CdO _x ), CuI, CuSCN, or any semiconductor material or combination above and / or,

Of an organic material of the group: Conjugated polymers, poly (phenylene) and its derivatives, ρoly (phenylene vinylene) and its derivatives (eg, poly (2-methoxy-5- (2-ethylhexyloxy) -1,4 phenylene vinylene (MEH-PPV), polyfpara-phenylene vinylene), (PPV)), PPV copolymers, poly (thiophene) and and its derivatives (eg, poly (3-octylthiophene-2,5-diyl), regioregular, poly (3-octylthiophene-

2.5, -dlyl) reglorandom, Poly (3-hexylthiophene- 2,5-diyl), regioregular, poly (3-hexylthiophene-2 ₅ 5-diyl), regiorandom), poly (thienylenevinylene) and its derivatives, and poly (isothianaphthene) and its derivatives, 2,27,7'tetrakls (N, N-di-p-methoxyphenylamine) -9,9'-spirobifluorene (spiro-Me OTAD), organometallic polymers, polymers containing perylene, poly (squaraines) and its derivatives, and discotic liquid crystals, organic or dyes pigments, dye based on Ruthenium, iodide / triiodide liquid electrolyte, azo-dyes with azo chromophores (-N = N-) connecting the aromatic group, phthalocyanines comprising metal phthalocyanine; (HPC), perylenes, derivatives of perylene, pthalocyanines of copper (CuPc), Zinc Pthalocyanines (ZnPc), naphthalocyanines, squaraines, merocyanines and their respective derivatives, poly (silanes), poly (germinates), 2 ₅ 9-Di ( pent-3-yl) anthra [2,1,9-def: 6,5,10-dif] diisoquinoline-1,3,8,10-tetrone and 2,9-bis-1 1H-hexyl-hept-1-yl) -anthra [2,1,9-def: 6,5,10-eTdi diisoquinoline-1,3,8,10-tetrone and pentacene, the pentacene derivatives and / or its precursors, a type-N polymer scale, poly (benzimidazobenzophenanthroline scale) (BBL), or,

Of a non-silicon layer and / or amorphous silicon and / or inorganic material and / or organic material and / or oligomeric group, micro-crystalline silicon, inorganic nanorods dispersed in an organic matrix, inorganic tetrapods dispersed in an organic matrix, nanomaterials quantum dots, nano-conductive ionic polymer gels composed of sol-gel comprising ionic liquid, ionic conductors, low molecular weight organic conductive Holes, C ₆ o and / or other minute molecules or any combination hereinbefore, and / or one of the following: A nano-structured layer having a porous inorganic tamplate filled with organic materials (doped or undoped), a polymer / blend cellular architecture, a microcrystalline silicon cell architecture. Or a combination of the above.

Work and studies on certain aspects of nanocrystals of interest to us in this application are described in the following publications: Investigation of Nanostructure-Polymer Blend Solar CeIIs, Susan Huang, Harry Efstathiadis, Pradeep Haldar, College of Nanoscale Science & Engineering, Albany, NY , 12203, Hee-Gyun Lee, Korean Polytechnic University, Siheung, Korea, and Brian Landi§ and Ryne P. Raffaelle, Rochester Institute of Technology, Rochester, NY, 14 (2004) "and" Awos Al Salman, Spectroscopy and Kinetic Studies of Electron- HoIe Recombiπation in CdSe Nanoparticles: Effect of Size, Shape, and Lattice Structure, UUSANNE'S FEDERAL POLYTECHNICAL SCHOOL (2007) ", and" Semiconductor Nanorod Liquid Crystals Liang-shi Li, Joost Walda, Liberato Manna and A. Paul Alivisatos, Department of Chemistry University of California, Berkeley Berkeley, CA 94720 USA, Materials Science Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720 (2001) »

Note also that the realization of the OS, EM or WiFi wave generating layer, as described in [00015] and [10015], is easily achievable using micro grooves (in spiral form for example) in a thin layer forming an integral part (or added by additional layer) of the photovoltaic device. DETAILED DESCRIPTION OF THE INVENTION WITH FIGURES

For a complete understanding of the present invention, we will detail all the figures describing the different points of the system.

According to the invention, and as indicated through FIG. 1, the assembly consists of a roll-to-roll production line (RoII to RoII) of multilayer photovoltaic cells. The figure describes the main production stations; in the central production line, the visible spectrum capture chamber is realized.

A translucent film is put on a unwinder 1-1 (Fig.l), the first phase is the deposition of the metallization layer in the block 1-2 (Fig.l), the film will then pass through the deposition phase. CIGS / CIS ink. This phase includes 3 steps

The step of the graft 1-3 (FIG. 1) wherein the substrate 3-2 (FIG. 3) is bombarded with ions 3-1 (FIG. 3) before grafting the particles 3-5 (FIG. which constitute the absorbent layer. The ion ion grafting process can realize the layer to be deposited 3-6 (Fig.3) with a homogeneous distribution.

Print step 1-4 (Fig. 1), where the CIGS ink is deposited by piezoelectric inkjet printing.

Preparation of the ink: The ink is produced according to the alkaline solution precipitation method on a mixture of nano powder Cu, In, Ga, Se and this by dissolving CIGS 2-1 nanoparticles (FIG. 2) in a solution alkaline 2-3 (Fig.2). The mixture of nano powder Cu, In, Ga, Se was sent by a fixed flow diaphragm pump 2-2 (Fig.2) to the mixing chamber 2-9 (Fig.2). The alkaline solution is precipitated by a diaphragm pump to the mixing chamber 2-9 (Fig.2). In the latter temperature probes 2-8 (Fig.2) and concentration PH 2-6 (Fig.2) are immersed in the preparation stirred by the mixer. The information on the temperature and the ionic concentration recovered by the probes are respectively processed by the temperature regulator 2-7 (FIG. 2) and the ionic dose controller 2-5 (FIG. When the mixture of CIGS nanoparticles 2-1 (Fig.2) and the alkaline solution 2-3 (Fig.2) is in accordance with the pre-established formula, it is poured into the ink tank 2-10 (Fig.2). ).

Piezoelectric inkjet printing: has a major advantage compared to other printing techniques in that the injection nozzle can deposit drops of a few nanometers which is unachievable by other printing techniques. As described in FIG. 8, the ink 8a-1 (FIG. 8a) arrives in a channel 8a-5 (FIG. 8a) surmounted by a membrane 8a-9 (FIG. 8a) which is under the constraint of a piezoelectric material 8a-8 (Fig.8a) and when the latter is subjected to an electric field, it reacts by causing a low acoustic vibration 8a-7 (Fig.8a) which echoes inside the pushing ink channel and a drop of ink 8a-4 (Fig.8a) through the nozzle 8a-3 (Fig.8a). The control of the size of the ink drops is in function of the electric field. Figures 8b to 8d illustrate the different movements of the membrane. The drying step 1-5 (Fig.l), the film passes through an Optical Processing Furnace (OPF) to dry the ink without altering the low layers and the molecular properties of the ink. The latter will form a CIGS / CIS crystalline conglomerate. The next phase is the surface treatment phase.

The first treatment is a chemical treatment 1-6 (FIG. 1) which etches the large irregularities 5a-2 (FIG. 5a) of the crystalline blocks CIGS / CIS 5a-1 (FIG. 5a).

The second treatment is a laser treatment 1-7 (Fig.l) better known by (Pulsed Laser Annealing -PLA) which provides the finishing in the planarization of the surface 5c-1 (Fig.5c) of the crystalline blocks CIGS / CIS Following the surface treatment phase, the phase of deposition of the junction layer Cds as illustrated in FIG. 5d, the block 1-8 (FIG. 1) represents the apparatus which ensures the deposition of this material by electrodeposition. . Block 1-9 (FIG. 1) represents the deposition phase of the ZnO: Al layer. After these different phases, the CIGS / CIS photovoltaic cell constituted will pass into a block 1-10 (FIG. 1) of control of the quality of deposition and the stoichiometric distribution of materials by X-rays. X-rays provide efficient means of control of cell homogeneities (CIGS for example) by the control of fluorescent dispersion of the materials (Figure 6) by means of equipment of the "EDXRF" type on a production line. Indeed, during the production of the CIGS cells, the manufacturing process must respect a very acute tolerance on the thickness and the atomic concentration of the Cu, In, Ga, Se mixtures (depending on their stichometry value) defining the efficiency and the photovoltaic cell efficiency. The system is often mounted at the end of an online production line. It seems obvious that the same EDXRF control system is applicable on T02 production lines. The doping of TiO 2 films is customized to have the maximum spectral response of the layered transmittance for Ultraviolet and Infrared whose response curve is given by way of example in Figure 9. The module 1-11 (Fig.l ) represents the realization of the upper chamber which captures the UV, the module 1-12 (Fig.l) represents the realization of the lower chamber which captures the IR. The three modules thus produced pass into block 1-14 (FIG. 1) for an assembly that is either mechanical (by pressure) or other. Block 1-13 (FIG. 1) represents the phase of production of the antireflection and concentrator film with tracking of the sun. Indeed, the antireflection film 7-1 (FIG 7) (a combination of silicon dioxide (SiO 2) and TiO 2 for example) allows the total passage of the incoming light on the Horizontal Filter Film 7-2 (FIG. Fig. 7), the ruler on the substrate 7-3 (Fig. 7), comprising the common electrode film (ITO). The liquid crystals 7-4 (Fig. 7) are then positioned for a given voltage. The electrode substrate (ITO) 7-5 (Fig. 7) covers the base of the crystals. The position of the liquid crystal is determined when the system is turned on. This voltage makes it possible to vary the position of the liquid crystals as a function of the position of the sun. It is generated by a simple light-current transforming device well known in the state of the art. The vertical light exit points (tips) are etched into the surface 7-5 (Fig. 7) allowing the alignment of the liquid crystal with the polarizing light on the sensitive point of the absorbent layer. The Vertical Polarization Filter Film 7-6 (Fig. 7) then directs the outgoing light onto the absorbent layer 7-7 (Fig. 7). Part 7-8 (Fig. 7) is the outgoing concentrated solar light receiving photovoltaic or solar cell. An optional layer 7-9 (Fig. 7), reflecting in crystalline nano prisms allows to transfer the light to other compartments if necessary. Block 1-15 (FIG. 1) ensures the adhesion of the antireflection film to the multilayer photovoltaic cells and their encapsulation in a protective film (not shown). At the output of the production line, the film 1-16 (Fig.l) is wound on a cylinder. In order to better understand the routing of the multi spectral light rays through the different capture chambers, we will describe this routing represented by FIG. 4. Indeed, the light rays 4-1 (FIG. 4) pass through the first anti-reflection layer 4-2 (Fig.4) before passing through the liquid crystal layer 4-3 (Fig.4). After that, the rays pass through the first chamber 4-9 (FIG. 4) which traps the UV, then the light rays pass through the second chamber 4-11 (FIG. 4) where the visible rays are trapped before pass in the last room 4-5 (Fig.4) which in turn traps the IR. Figures 4-8 (Fig.4), 4-10 (Fig.4), 4-12 (Fig.4), 4-6 (Fig.4) show the different junction layers. The piezoelectric module 4-7 (Fig.4) transforms the calories into current as it has been described in the body of this application.

It is important to note that the present invention is more clearly evidenced by the description of the particular methods and embodiments as described. Nevertheless, the object of the invention is not limited to these methods or to these embodiments described because other methods or other embodiments of the invention are possible and can easily be performed by extrapolation. In particular by the manufacturers who manufacture layers of silicas and / or micro components with or without optical parts.

Claims

A method comprising: hooking a layer and / or substrate on other layers and / or substrate by grafting particles forming hook points for the layer or substrate to be deposited or printed. 2- A method comprising: forming a layer and / or substrate on other layers and / or substrate by grafting particles forming hook points and its continuation on the grafted points.

The method as described in claim 1 or 2 where the graft-receiving layer is an absorbent layer (on the substrate).

The method as described in claim 1 or 3 where the layer and / or the substrate is printed by a piezoelectric ink jet technique.

5. A method described in at least one of claims 1 to 4 wherein the absorbent layer comprises a non-silicon layer and / or amorphous silicon and / or inorganic material and / or organic material and / or oligomeric group, microcrystalline silicon. , inorganic nanorods dispersed in an organic matrix, inorganic tetrapods dispersed in an organic matrix, nanomaterials quantum dots, conductive ionic polymer gels, nano compounds composed of sol-gel comprising an ionic liquid, ionic conductors, low molecular weight organic conductive holes, C ₆₀ and / or other tiny molecules or any combination or above, and / or one of the following: a nanostructured layer having a

Inorganic porous template fills with organic materials (doped or undoped), a cellular polymer / blend architecture, microcπstalline silicon cell architecture or any combination above. 6- A method described in at least one of claims 1 to 5 or the device comprises at least one multi spectral absorption element.

7- A device resulting from the methods described in at least one of claims 1 to 5, wherein the layer has piezoelectric characteristics capable of generating current by absorption of calories

8- A device resulting from the methods described in at least one of claims 1 to 5 wherein the layer has at least one characteristic of converting solar energy into current.

9- A device resulting from the methods described in at least one of claims 1 to 5 where the latter is provided with a layer and / or an optical amplifier film and / or anti-reflection treatment

10- A device resulting from the methods described in at least one of claims No. 1 to 5 wherein the latter is provided with a layer and / or a film of concentration of sunlight with or without anti-reflection element . 11- A device comprising a plurality of photovoltaic cells provided with a system based on liquid crystals and / or thin film and / or prism rods serving as optical amplifier or concentrator, with or without anti-reflection elements. reflection, tracking the sun by directing and / or concentrating most of the sunlight on the cell at any time of the day. 12- A device comprising a plurality of photovoltaic cells with at least one system for transporting electrical energy remotely through the vacuum or insulating dielectric materials characterized by the absence of the use of any solid connecting conductor.

13- An effective power generation device consisting of at least two chambers / structured compartments, provided with at least one means for converting the outgoing energies, with at least one nano-scale element based on the materials or nanocπstallm polymers, or nano-scale tubes, said materials comprising nano particles from 1 to 50 nm, generally called nano elements.

14- An effective device for generating electricity, and provided with at least two chambers / structured compartments, provided with at least one means of converting the outgoing energies where the energy from a chamber is under form of calories.

15- A device according to at least one of claims 1 to 14 provided with a simplified intelligence system or complex control and control compartments and / or thermochromatic layers and where at least one current is obtained at using a nanoparticle-based system with piezoelectric characteristics.

16- A device according to at least one of claims 1 to 15, wherein the outgoing energy is in the form of current or voltage and / or provided with DC / DC or DC / AC converter, and / or a battery and / or a chemical solution for storing off-grid productions.

17- A device according to at least one of claims No. 1 to 16 stacked structure with reduced bulk and / or having a means for loading and / or circulation of the liquid or gaseous solution to facilitate the exchange of calories. An effective device for generating energy comprising nanometeπques materials or nanoparticle compounds, provided with at least one means for converting outgoing solar energies and possessing characteristics that can be deenergized by deenergizing the current. . 19- A device according to at least one of claims No. 1 to 18 and / or provided with a system for producing cold and / or hot.

20- A device according to at least one of claims 1 to 19 and provided with at least one solar energy conversion means, where the tracking of the sun is controlled and / or provided by a device consisting of a rigid wall and membrane pair and / or a system comprising liquid cylindrical or hexagonal tubes and / or nano tubes, which device is in the form of an independent element or integrated in the system and / or provided with a device for increase the efficiency of the rays, whether in the form of micro magnifiers or translucent liquid crystal with an enlargement effect at their ends.

21- A device according to at least one of claims 1 to 20, provided with a control intelligence and integrated control and / or radio frequency.

22- A device according to at least one of claims 1 to 21, characterized in that it comprises a plurality of heat exchanger solution, metallic particle shapes or not and similar or not geometries and distributed over a liquid or gaseous and / or any shape and / or appearance in the form of slab, panel, film and / or any shape.

23- A system for producing layers on a substrate comprising: a process chamber cyclically depositing the layers with at least one loading point, a means for selecting the surface face to be treated by plating and / or isolating the other surface, a plurality of inlet nozzles disposed along the surface to be treated so that the outputs of the nozzles are capable of transmitting one or more gases on the surface to be treated, provided with a determined inlet manifold per segment, a plurality of outlet nozzles disposed between each gas extraction nozzle, provided with an outlet manifold per segment than gas.

24- A system for producing layers on a substrate comprising: a cyclic deposition process chamber of the layers, a substrate swallowing system at the inlet and the interior of the process chamber, which system has an even distribution method for selecting the surface face to be treated, a plurality of inlet nozzles disposed along the surface to be treated so that the nozzle outlets are capable of transmitting one or more gases. on the surface to be treated, provided with a determined segment inlet manifold, a plurality of outlet nozzles disposed between each gas extraction nozzle, provided with an outlet manifold by segment than gas,

A system for producing layers on a substrate comprising: a process chamber with cyclic deposition of the layers in geometrically circumferential distributed shape decreasing or increasing, a system for swallowing at least two substrates simultaneously at the entrance and the long interior of the process chamber, which system has a uniform substrate transport and guide distribution, a non-processable surface isolation means, a module comprising a plurality of input nozzles disposed along the surface to be treated of so that the outputs of the nozzles are capable of transmitting a plurality of gases on the surface to be treated, provided with a determined inlet manifold per segment, a plurality of outlet nozzles arranged between each nozzle for extracting gas from the chamber .

A system for producing layers on a substrate comprising: a process chamber with cyclic deposition of the layers in geometrically circumferential distributed shape decreasing or increasing, a system for swallowing at least two substrates simultaneously at the entrance and the long interior of the process chamber, which system has a uniform substrate transport and guide distribution, a non-processable surface isolation means, a module comprising a plurality of gas inlet or outlet nozzles disposed along the the surface to be treated provided with an inlet or outlet manifold per segment, operating during transfer or stopping of the substrate in the process chamber and a substrate ejection system at the chamber outlet.

27- A system according to one of claims 23 to 26, provided with a heating device by segment significantly reducing the heating time and temperature stabilization. 28- A system according to one of claims 23 to 27, wherein process chamber consists of a succession of shape in a straight line and / or segmented.

29- A system according to one of claims 1 to 28, provided with a device having all or part of a variety of solution deposit methods or coatings including but not limited to printing, engraving or microgravure, inverted or direct, coated with rollers, capillary, inkjet, jet or piezo, integrated and / or separated.

30- A system according to one of claims 1 to 29, provided with a device for coating a solid layer of titanium dioxide followed by a deposit SoI-GeI or aerosol of TiO ₂ meso-porous Sol-Gel deposit or aerosol for flexible films. 31. A system according to one of claims 1 to 30, allowing a complex molecular construction of quaternary compounds.

32- A system according to one of claims 23 to 31 having at least one absorbent layer consisting of cells

CIQS and / or CZTSfit / or TiO2- ^Q S and / or, in general, of a tetraped and / or tetrahydric and / or tetrahedron and / or crystalline structure.