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    • 专利摘要:
    Organic-inorganic hybrid material and method for silicon surface passivation. An important technological challenge is the passivation of the surface of silicon in optoelectronic devices, such as solar cells, without adding additional costs and using abundant materials. In the present invention, a method for manufacturing a composite hybrid material with pedot: pss and conductive transparent oxide nanostructures is proposed, obtaining the passivation of the silicon surface by using a thin composite film with a thickness of less than 200 nm. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2650213A1
    申请号:ES201600562
    申请日:2016-07-11
    公开日:2018-01-17
    发明作者:Miguel GARCÍA TECEDOR；Geraldo Cristian VÁSQUEZ VILLANUEVA；María TAEÑO GONZÁLEZ；David MAESTRE VAREA；Ana Isabel CREMADES RODRÍGUEZ；Julio RAMÍREZ CASTELLANOS；Francisco Javier PIQUERAS DE NORIEGA；José María GONZÁLEZ CALBET；Smagul Karazhanov；Halvard HAUG；Chang CHUAN YOU；Erik S. MARSTEIN
    申请人:Institute For Energy Tech；Institute For Energy Technology；Universidad Complutense de Madrid；
    IPC主号:
    专利说明:

    Organic-inorganic hybrid material and silicon surface passivation method.
    Technique SectorThe invention falls within the field of semiconductor devices and functional coatings. More specifically, it refers to a method of manufacturing a composite material consisting of an organic conductor and semiconductor nanostructures (nanoparticles and / or nanowires) for application as a silicon surface electronic passivation layer in solar cells and other electronic devices. .
    State of the art
    One of the most relevant aspects in the field of photovoltaic technology is the passivation of surfaces in order to obtain good performances from solar devices (Y. Cao et al., "The role of surface passivation for efficient and photostable PbS quantum dots solar cells ", Nature Energy 1, 16035 (2016); AH lp Y col.," Hybrid passivated col / oidal quantum dot solids ", Nature Nanotechnology 7, 577-582 (2012); BG Lee et al," Excel! ent passivation and low reflectivity with atomic layer deposited bilayer coatings for n-type silicon solar cel / s ", Thin Solid Films 550, 541-544 (2014); Y. Li Y col," Ultrathin flexible planar crystalline-siliconlpolymer hybrid solar cel! with 5.68% efficiency by effective passivation ", Applied Surface Science 366, 494-498 (2016». As an example, the advances in passivation achieved during the 80s, allowed us to manufacture the first crystalline silicon-based solar cells with efficiencies greater than 20 %. The fact that l he electronic and optoelectronic devices use increasingly thin sheets as active components, making the passivation of both the front and rear surfaces of the Si increasingly relevant. Currently, SiNx, Ab03 or Si02 are some of the materials that are successfully used in passivation of the Si surface. However, the deposition of these materials generally requires processes carried out at elevated temperatures and pretreatments of the Si surface with, for example, hydrofluoric acid (HF), which usually entails high costs and undesirable laboratory working conditions. Therefore, it is necessary to develop passivation materials and techniques that require lower temperatures, easier procedures and less cost. One of the materials that can meet these needs is polymers. Polymers can be deposited at room temperature and can maintain their functionality if the processing temperatures are low (D. Biro et al., "Low temperature passivation of silicon surfaces by polymer films",
    Solar Energy and Solar Cells 7, 369-374, (2002 ”. The most frequently used conductive polymer so far is poly (3,4-ethylenedioxythiophene) / poly- (styrene sulfonate) (PEDOT: PSS), which has a high p-type electrical conductivity, behavior as anti-reflective coating, as well as good chemical stability, optical transparency in the visible range and can be easily processed in aqueous solution (as for example described in patents KR101548612, and CNI04934540). Some works (L. He et al., "High efficiency planar Si / organic helerojunclion hybrid solar cells", Applied Physics Letters 100, 073503 (2012 ») indicate that the use of PEDOT: PSS generates poor passivation on the surface of the Si used in Si / organic solar cells that reach efficiencies of 10.6%. Other works (R. Yang, et al. "Organic Vapor Passivalion of Silicon to Room Temperalure", Advanced Malerials 25, 2078-83, (2013 »report a high passivation surface quality e of Si, reaching values of surface recombination speed below 10 cm / s, however, in this case, requiring the use of vapor phase deposition techniques. In addition to PEDOT: PSS, some authors have considered the use of other polymers in the passivation of the Si surface. For example, D Biro et al. ("Low lemperalure passivation of silicon surfaces by polymer films", Solar Energy Malerials and Solar Cells 71, 369-374 (2002 »manage to achieve Si surface recombination rates of 30 cm / s using the Nafion ® (DuPont) polymer based on poly-tetrafluoroethylene. FF Zhang et al., ("Methyl / Allyl Monolayer on Silicon: Efficienl Surface Passivation for Silicon-Conjugated Polymer Hybrid Solar Cells", ACS Applied Malerials and Interfaces 5, 4678-84 (2013 »also achieve good results in Si passivation in hybrid solar cells, reaching a conversion efficiency of 10.2%. There are also studies on the functionalization of PEDOT: PSS with different organic surfactants that allow increasing the dispersion of the polymer on the Si surface. For example, JP Thomas et al., ("Interfacial micropore defectformation in PEDOT: PSSSi hybrid solar cells probed by TOF-SIMS 3D chemical imaging", Analylical Chemistry 85, 6840-45, (2013 »employ Triton-X 00, while B. Fan et al., ("Novel ways to significantly enhance the conductivity of transparenl PEDOT: PSS", Proc. SPIE 7415, Organic Light Emitting Malerials and Devices XIII, 74151Q doi: 10.1117 / 12.826009 (2009 »added cationic and anionic surfactants. In search of an improvement in polymer properties, other authors added ethylene glycol and dimethyl sulfoxide to PEDOT: PSS for improve their electrical conductivity by minimizing defects, thus achieving an efficiency of 13.3% (JP Thomas et al., "Defect-minimized PEDOT: PSS / planar-Si solar cel! with very high efficincy, Advanced Functional Materials 24, 4978- 4985 (2014 ». In other works (p. Yu and cO.," 13% Efficiency Hybrid Organic / Silicon Nanowire Helerojunction
    Solcar Cell via Interface Engineering ", ACS Nano 7, 10780-10787 (2013)) considers the possibility of engineering the interface by controlling the energy differences of the band structure known by its English name, energy offset, to increase the lifetime values of charge carriers. On the other hand, Y. Li Y col., ("Ultrathin
    flexible planar crystalline-siliconlpolymer hybrid solar cel! with 5.68% efficiency by effective passivation ", Applied Surface Science 366,494-498 (2016)) use amorphous silicon between PEDOT: PSS and Si to passivate the silicon surface in ultra-flat and flexible Si-based solar cells. In other works, has reported the formation of an inversion layer between Si nanowires and PEDOT: PSS capable of reducing the recombination of charge carriers (X. Yu et al., "High efficiency organic / silicon nanowire hybrid solar cel / s: significance ofstrong inversion layer ", Scientific Reports S, 17371 (2015). In the case of J. Sheng et al., (" Ideal rear contact formed via emp / oying a conjugated po / ymer for SilP EDOT: PSS hybrid solar cells " , RSC Advances 6, 16010 (2016)) employ an alcohol soluble polymer (PFN) to improve the Si / Al interface. In addition, PEDOT: PSS and inorganic nanostructures have also recently been manufactured for different purposes. and patented on manufacturing PEDOT-based composites: PSS and noble metal nanoparticles, mainly gold and silver, (for example, Patents KR20140071986, KR20140007082, KR20140132191, CNI02875978, JP2012248635, and CNI02875978), to enhance the plasmonic effect and obtain an improvement in conductivity . In addition to metallic nanoparticles, semiconductor nanoparticles have also been used in the manufacture of composite material. In the reference s.-J Wang and H-H Park, Journalof Electroceramics 18, 161 (200 7), the manufacture of a compound of PEDOT: PSS and tin oxide nanoparticles on glass is reported for application as an anode. Due to the high amount of nanoparticles (up to 50% by weight of the PEDOT: PSS solution), the low speed of rotation during the centrifugal coating process (400 rpm), and thermal processing to remove water and other used additives, a thick granular sheet, several microns thick, is obtained, made up of the percolation of tin oxide particles with n-type conductivity, which reduces the resistivity of the film and correspondingly displaces the maximum of the valence band and the Fermi level from the PEDOT: PSS eigenvalues to those of tin oxide. On the other hand, in the reference Y Liu et al., ("Enhanced dispersion of Ti02 nanoparticles in a TiOyPEDOT: PSS hybris nanocomposite via plasma-liquid inteactions", Scientific Reports S, 15765 (2015)) describes a manufacturing technique of Compound nanoparticles with TiOz nucleus in 25 nm anatase phase and PEDOT: PSS shell, using a
    processed with plasma in aqueous solution. In this case, the agglomeration of the nanoparticles during the manufacture of the composite is reduced due to the state of charge of the plasma-induced nanoparticle surfaces. However, continuous and homogeneous thin sheets, such as those proposed in this invention, which are also more easily processable, are not obtained by this method. K.H. Yoo et al., ("The Ti02 nanoparticle effect on the performance of a conducting polymer Schottky diode", Nanolechnology 19, 505202 (2008)), have also used Ti02 nanoparticles undoped with PEDOT: PSS to form
    a composite material. In this case, the nanoparticles are less than 40nm and are dispersed in PEDOT: PSS in high concentrations, up to 20% by weight, to form a Schottky diode structure between aluminum and gold contacts, with final film thicknesses Composed of PEDOT: PSS and 1 micron nanoparticles. Said film presents nano-and micro-cracks depending on the final treatment. None of the works mentioned report data on the performance as a passivating layer of a composite sheet such as that described in the present invention. Other related concepts can be found in the use of a multilayer system such as that published in CN Patent! 04867678, which reports the manufacture of a trilayer containing PEDOT: PSS, porous nanometric zinc oxide and a compact zinc oxide film for application in dye solar cells. Similarly, one can mention the layer-by-layer arrangement of two types of components, an n-type inorganic semiconductor (Ti02 nanoparticle film) and a p-type polymeric conductor (PEDOT: PSS) such as those published by N. Sakai et al. ., ("Layer-by-layer assembled Ti02 nanoparticlelPEDOT: PSS composite films for switching of electric conductivity in response lo ultraviolet and visible light", Chemistry of Materials 18, 3596-3598, (2006)) or in Patents KR20 150084702 Y CN20121390201, in which they make different solar cells using a hole transport film that contains PEDOT: PSS and tungsten oxide.
    In the present invention, a method is proposed to manufacture a composite material with PEDOT: PSS and nanoparticles and / or nanowires obtaining the passivation of the silicon surface, by using economical materials and techniques, which avoid techniques that operate in vacuum and complex pre-treatments of the silicon surface. For the formation of the composite material, the nanostructures of transparent conductive oxides (TCO), in particular tin and / or titanium oxide in low concentrations, are considered. The use of limited concentrations of nanoparticles (less than 10% by weight with respect to the PEDOT: PSS solution) is a crucial point of the invention since it prevents percolation of the same and the change in the p-type character of the conductivity PEDOT: PSS, maintaining its transparency, and allowing the proper passivation of the surface of n-type silicon in silicon by means of a thin composite film with a thickness of less than 200 nm. The possibility of creating multilayers based on this composite material with varying concentrations, types of nanostructures, materials and dops throughout the multilayer structure expands the applications and design on demand of a functional coating with bespoke properties. The development of rapid procedures and with low associated economic costs, such as those described in this invention, will facilitate the implementation and optimization of devices based on solar cells. Detailed description of the invention
    Organic-inorganic hybrid material and silicon surface passivation method.
    The present invention is focused on the manufacture of a thin sheet composed of an organic and inorganic hybrid material that comprises an organic conductor as matrix and nanostructures of transparent conductive oxides as filler and that can be used for passivation of the silicon surface in devices based on silicon, particularly in solar cells, as well as towards the development of a hybrid foil deposition method. The deposition process employed in this invention is fast and economical compared to other methods currently employed, such as chemical vapor phase deposition (CVD) or plasma enhanced CVD (PECVD). In the examples presented below, the deposit by spin-coating of a thin sheet up to 200 nm thick is described, formed by the combination of transparent conductive oxide (TCO) nanostructures, such as Sn02 and Ti02 (in rutile and / or anatase phase ) with a p-type organic semiconductor (PEDOT: PSS). If necessary, these nanostructures could also be replaced by other nanostructures such as carbon nanotubes, Si or Ah03 nanoparticles or nanowires, and SiN "nanoparticles or nanowires. And even a mixture of several of these nanostructures. The thin sheet of the composite material including nanoparticles improves the passivation properties of the Si surface, increasing the lifetime of the charge carriers and the conductivity of the sheet with a slight modification in light absorption, compared to the response of a thin sheet formed only by PEDOT: PSS, as described in Example l.
    Various techniques can be used in the manufacture of the Sn02 and Ti02 nanoparticles, such as hydrolysis (using SnCIz · 2H20 or Ti (OBu) 4 and I-butanol as precursors for the manufacture of tin and titanium oxide nanoparticles, respectively), or a variant of
    Pechini method (as followed in patent ES201400759). The dimensions of the
    nanoparticles used in this invention are between 5 and 50 nm. In addition to
    nanoparticles, Sn02 and Ti02 nanowires can also be used in the manufacture of the
    Composite material as described in Example 2. These nanowires have been manufactured
    S by means of the vapor-solid method that does not require the use of catalysts or external substrates.
    Sn02 and Ti02 nanowires have been synthesized using metallic Sn or TiN as
    precursors and temperatures of 800 and 900 ° C respectively. The dimensions of the
    nanowires used can reach lengths of hundreds of nm and sections of tens of
    nm. In the case of Ti02 nanostructures, these can consist of anatase and / or rutile phase,
    10 while the tin oxide nanostructures have a rutile structure. Further,
    Sn02 and Ti02 nanostructures doped with Cr, Al or Li can be used, which will act as
    you will accept for Sn02 and Ti02. Concentrations have been used in the present invention
    of dopant of 10, 20 and 30% cationic.
    1 S EIPEDOT: PSS, which must be dispersed in water (1.3% v / v), has a sheet resistance
    below 100 nlsq and can reach conductivity values of up to cr = 1 000 S / cm.
    In addition, various additives can be added to the polymer for different purposes, such as
    It is described in Example 3. In the case of adding ethylene glycol (EG), the
    PEDOT electrical conductivity: PSS due to alignment of polymer chains. The
    twenty The use of EG as an additive also presents another interesting property as a dispersant,
    highly useful in the present invention by avoiding the agglomeration of nanostructures during
    spin-coating process. It is also of great interest to use isopropanol (IPA) before
    spin-coating process, because this compound facilitates the deposit on Si-H,
    especially after cleaning the substrate with HF, resulting in increased
    2S homogeneity of the sheets thus deposited thanks to the improvement of the hydrophilic character of the
    silicon surface, as described in example 3.
    In the manufacture of the composite material used in the present invention the
    nanostructures must be dispersed in PEDOT: PSS in a composition between 0.25 and 5% in
    30 weight, although it is expected that the composite material will also show good results with
    a greater concentration range (0.1-10% by weight). Example 1 describes how the
    lifetime values of carriers vary depending on the content of nanostructures in
    the composite material, so special attention should be paid to this parameter when
    use this material as a passivation layer.
    The dispersion of PEDOT: PSS and nanostructures has been carried out by ultrasonication in the desired concentrations. Once the PEDOT: PSS dispersions and the nanostructures were made in the chosen concentrations, the deposition process was carried out using the spin-coating technique. The process has been carried out at room temperature and at atmospheric pressure. The spin-coaling method used consists of three stages: start (500
    r.p.m. for 2 s), coating (3000 r.p.m. for 30 s) and drying (4000 r.p.m. for 40 s). Once these stages are completed, annealing is carried out at 120 oC for 20 minutes to evaporate the water in which the PEDOT: PSS is diluted. In this way, it is finally possible to deposit a thin and homogeneous sheet of the composite material on the silicon substrate. Similarly, bilayers can also be manufactured, by depositing a new sheet on the previously deposited composite sheet, or by repeating the process several times, multilayers would be obtained, as described in Example 4.
    Description of the figures
    Figure l. Optical image of a 125 nm thick sheet with good homogeneity deposited by spin-coating on an n-Si substrate (3.5 x 3.5 mm). The sheet is made of a composite material (PEDOT: PSS and Sn02 nanoparticles in a concentration of 0.5% by weight).
    Figure 2. Variation of the life times of the charge carriers as a function of the concentration of Sn02 nanoparticles in the composite material, acquired by illumination from the front surface with the PEDOT: PSS compound and nanoparticles or from the posterior surface with hydrogenated amorphous silicon (a-Si: H).
    Figure 3. Optical image of the composite sheet formed by PEDOT: PSS and Sn02 nanoparticles deposited by spin-coating on an untreated n-Si substrate (a) and another previously treated with IPA (b). In image (b) it can be seen how the use of IPA results in a great homogeneity of the coating due to the improvement in the hydrophilic character of Si induced by the treatment with IPA. (c) Image of the drops of the compound PEDOT: PSS and Sn02 nanoparticles deposited on silicon n-type substrates that have been cleaned (right) or not (left) by means of the RCA procedure, which induces in the first case greater hydrophilicity of the silicon substrate;
    EMBODIMENT OF THE INVENTION The present invention is further illustrated by the following examples, which are not intended to be limiting of its scope. Example 1:
    This first example describes the manufacture of a composite material consisting of PEDOT: PSS combined with doped or undoped tin oxide and / or titanium oxide nanoparticles, in different concentrations. In the case of using nanoparticles in the manufacture of the hybrid composite material, both Sn02 (rutile) and Ti02 have been used, the latter in both the anatase and rutile phases, with different properties depending on the crystalline phase. The Sn02 and Ti02 (rutile) nanoparticles used in this example, with sizes between 5 and 50 nm, have been manufactured by hydrolysis using SnCh · 2H20 or Ti (OBu) 4 and l-butanol, respectively, as precursors. The reduced dimensions of the nanoparticles used facilitate their dispersion and deposition through the spincoating process used in this invention, which results in thin and homogeneous sheets. Figure I shows the optical image of a sheet of a composite material consisting of PEDOT: PSS and 0.5% by weight of Sn02 nanoparticles deposited by spin-coating on a n-type silicon substrate. The spin-coating process has been carried out following the description included in the section "Detailed description of the invention" that includes the following stages: starting, coating and drying. The process ends with a heat treatment at 120 oC for 20 minutes. Different concentrations by weight (0.25 -5%) of the semiconductor oxide nanoparticles have been used in the formation of the composite material, although good results are also expected for a higher concentration range (0.1 -10% by weight). In order to study the passivation degree of these sheets of composite material deposited on n-type silicon, life-time measurements of carriers have been carried out using a photoluminescence imaging system. Specifically, a LIS-Rl photoluminescence imaging equipment from BT Imaging has been used, with a constant illumination of intensity 4.2 x 10-2 W / cm2 and an excitation wavelength of 808 nm. In addition, in this case, a layer of 40nm thick hydrogenated amorphous silicon (a-Si: H) has been deposited by sputtering on the posterior palte of the Si sheet used as a substrate, as a reference passivating layer. The passivating surface of a-Si: H has a low rate of surface recombination (SRV) while the Si sheet has long life times in the massive material of several milliseconds. This allows us to calculate quite accurately the SRV values of the Si front surface passivated with PEDOT: PSS. As an example, Figure 2 shows the lifetime values of carriers as a function of the
    different concentrations of Sn02 nanoparticles used in the manufacture of the composite material. The best passivating behaviors are achieved using concentrations of 0.5% wt, in the case of Sn02 nanoparticles, and l% wt. for Ti02 nanoparticles, obtaining lifetime values of hundreds of Ils. These results confirm 5 that the control of the concentration of nanostructures in the formation of the composite material is a key parameter that determines the passivating behavior of these thin sheets formed by hybrid composite material. In addition to undoped nanoparticles, doped nanoparticles have also been employed in this invention. As an example, in this case Cr, Al or Li have been used in cationic concentrations between 10% and 30% cationic, both
    lOn Sn02 nanoparticles as in Ti02 (anatase). In the choice of these doping elements, the possible p-type character that they can generate in the conductivity of the metal oxide nanoparticles used has been taken into account. Therefore, this example is not limited to the use of Cr, Al or Li, but can be extended to the use of other doping elements.
    Example 2: In the formation of the composite material, Sn02 and / or Ti02 (rutile) nanowires have also been used. These nanowires have been manufactured using a vapor-solid process and have lengths of hundreds of nanometers and sections of tens of nanometers. In
    In the manufacture of Sn02 nanowires, metallic Sn has been used as the precursor material and heat treatments have been carried out at 800 oC, while in the case of Ti02 nanowires, TiN has been used as precursor and treatments of 900 oC. Nanowires have been added to the PEDOT: PSS dispersion in a concentration between 0.25% and S% by weight, although it is also expected to obtain good results using a range of concentrations.
    25 major (0.1 -10% by weight). In this case, the life time results are lower than those achieved by using nanoparticles. However, due to the characteristic morphology of nanowires, their use may improve some of the relevant optical properties in their use in solar cells, such as absorbance. The sheets deposited using nanowires in the formation of the composite material are not as homogeneous as
    30 deposited using nanoparticles in the composite material. This is mainly due to the difficulty of dispersing the nanowires during the spin-coating deposition process, due to the particular morphology and dimensions of the nanowires used. However, by optimizing the deposition process and using suitable additives, it is also possible to deposit sheets of material
    35 composed with nanowires that have good homogeneity. Thus, employment
    of ethylene glycol (EO) and isopropanol (IPA) hinders the aggregation processes and favors the deposition by spin-coating, as described in example 3. By improving the use of these additives, higher life time values can be achieved . As with the nanoparticles described in Example 1, doped nanowires can also be used in this case.
    In the manufacture of the composite material, mixtures of Sn02rri02 nanoparticles and / or nanowires can also be used, in order to take advantage of the properties of both materials in the design of passivation layers. Example 3:
    In this third example, the use of additives in the organic polymer PEDOT: PSS is described in order to improve its performance. Specifically, the use of Ethylene Glycol (EO) not only improves the electrical conductivity of the polymer, thanks to the alignment of the polymer chains, but also favors the dispersion of nanostructures, which must be taken into account during the deposition process. Agglomeration of nanoparticles (nanowires) can be avoided by using this dispersant (EO) in a concentration range of 3-4.5% by weight during the process of deposition of the composite material by spincoating, which allows to deposit homogeneous sheets of the composite material . The homogeneity of the sheets thus deposited can also be improved using isopropanol (lPA) and / or a standard RCA cleaning process of the silicon substrate (W Kern and D. Puotinen, RCA Rev., 31, 187 (19 70)), prior to the spin-coating process. For lPA cleaning, the Si substrate is placed on the centrifuge deck and IPA covering the silicon surface is deposited for 90 seconds, prior to the PEDOT: PSS deposit. In this way, the sample is dried by the centrifugation process. Using lPA or RCA cleaning, the silicon surface coating improves, as shown in Figure 3, resulting in greater film homogeneity due to improvement in the hydrophilicity of the surface. In this way, the use of EO and / or lPA leads to an improvement in the homogeneity of the deposited sheets, without altering their passivating properties.
    Example 4: As a last example, this technique also allows multilayers to be manufactured by repeating the deposition process using spin-coating. In this way, once a homogeneous sheet is deposited by this method, it can be used as a substrate to deposit a next layer on it by means of the same spin-coating process. By repeating this process, different sheets with varying concentrations of TeO nanostructures can be deposited consecutively in PEDOT: PSS, as well as multilayers that have different optical properties depending on the characteristics of each of the layers. As an example, by using dopants and the combination of different materials, you can
    5 achieve the manufacture of multilayers formed by layers with materials of different ranges of prohibited energy. This example extends the functionality of these sheets, maintaining their homogeneity and low production costs. This extends the applicability and performance of this invention in the field of solar cells, as well as other optoelectronic devices.
    权利要求:
    Claims (9)
    [1]
    one. Organic-inorganic hybrid material comprising an organic conductor as matrix and transparent conductive oxide (TeO) nanostructures as filler characterized in that the organic conductor is the PEDOT: PSS polymer and the transparent oxide nanostructures are dispersed in said polymer in a proportion preferably between 0.25 and 5% by weight, although they can also be dispersed in a greater proportion range (0.1 -10% by weight).
    [2]
    2. Organic-inorganic hybrid material, according to claim 1, where the nanostructures are nanoparticles of tin and / or titanium oxide undoped or doped with er, Al, or Li with cationic percentages preferably between 10-30% and sizes between 5 and 50 nm .
    [3]
    3. Inorganic organic hybrid material, according to claim 1, where the nanostructures are un doped or doped with er, Al, or Li tin oxide and / or titanium nanowires with cationic percentages between 10-30% and sections of few tens of nm and lengths hundreds of nm.
    [4]
    Four. Organic-inorganic hybrid material, according to claim 1, where the nanostructures are a percentage controlled mixture of undoped or doped or er, Al, or Li tin and / or titanium oxide nanowires and nanoparticles, described in claims 2 and 3 .
    [5]
    5. Organic-inorganic hybrid material, according to claim 1, where the nanostructures correspond to carbon nanotubes, nanoparticles or nanowires of Si, AbO), SiNx, or a mixture of the above.
    [6]
    6. Organic-inorganic hybrid material, according to previous claims, where EG is added as dispersant to the organic conductor dispersion.
    [7]
    7. Manufacturing method of the claimed organic-inorganic hybrid material that
    It comprises: Preparing an aqueous dispersion of the polymeric conductor. Preparing the conductive transparent oxide nanostructures by techniques such as hydrolysis, variants of the Pechini method or vapor-solid method.
    Add the nanostructures to the aqueous dispersion of the polymeric conductor in a proportion of less than 10% by weight, or in relation to the aqueous dispersion, preferably in a range between 0.25 and 5% by weight, and disperse by means of ul-son. ieae ion.
    1I. Passivation method that involves deposition using the $ pin - (; IJuling dc) technique, one or more sheets of the claimed material on a substrate and, subsequently, removing water.
    Passivation method, according to claim 8, where the water is removed by technical treatment at 120 oC for 20 minutes,
    OR. Paiva ~ ón method, according to claim 8, where the sheet has a thickness less than 200 nm.
    11, Passivation method, according to claims 7 to 10, where the subslrate to p.1sivar is untreated silicon.
    [12]
    12. Passivation method according to claim 11, wherein the substrate to be passivated is silicon covered by a layer of silicon oxide.
    one). Passivation method, according to claims 8 to 12. where the silicon substrate is combined with] PA to increase the hydrophilicity of the substrate.
    [14]
    14. Passivation method. according to claims 8 to 13, where the passivation layer contains two or more composite sheets stacked by spin-coating with a gradient of concentrAtions of nanostructures of different types and materials designed to dem: ndB,
    JO
    - Vl
    :one. 280
    .....
    "'O o 240 ro
    .....
    .....
    or 200
    c .. Q) 160
    "'OR
    ro
    "'O 120
    ':;
    Q) 80
    "'OR
    or
    c .. 40-E
    Q)
    ¡::
    Figure 1
    Maximum values
    ! .-o-Lighting from the PEDOT side: PSS
    ..
    : ', -. Illumination from the a-Si side
    ,.
    ,.
    , I •.
    I,. •I • • ",
    I
    f ~ -,
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    ::! ---::. -----. ----------.
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    .;
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    .
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    Sn0 concentration (% weight)
    Figure 2
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