NL2021912B1 - Organically engineered solar cells - Google Patents

Organically engineered solar cells Download PDF

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Publication number
NL2021912B1
NL2021912B1 NL2021912A NL2021912A NL2021912B1 NL 2021912 B1 NL2021912 B1 NL 2021912B1 NL 2021912 A NL2021912 A NL 2021912A NL 2021912 A NL2021912 A NL 2021912A NL 2021912 B1 NL2021912 B1 NL 2021912B1
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layer
solar cell
anatase
transport layer
substrate
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NL2021912A
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Dutch (nl)
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George Glenn Mcmillan Duncan
Wilhelmus Henricus Eijt Stephanus
Van Amelrooij Edward
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Univ Delft Tech
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Priority to NL2021912A priority Critical patent/NL2021912B1/en
Priority to PCT/NL2019/050698 priority patent/WO2020091593A2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Hybrid Cells (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

The present invention is in the field of a method for producing organically engineered solar cells, and a solar cell obtained by said method. In the method readily available raw material is used wherein an active layer of the solar is de— posited by biomineralization and further treated. As condi— tions of the present method are modest, the method can be per— formed practically anywhere.

Description

Organically engineered solar cells
FIELD OF THE INVENTION
The present invention is in the field of a method for producing organically engineered solar cells, and a solar cell obtained by said method. In the method readily available raw material is used wherein an active layer of the solar cell is deposited by biomineralization and further treated. As conditions of the present method are modest, the method can be performed practically anywhere.
BACKGROUND OF THE INVENTION
The present invention is in the field of solar cells. Conventional typically silicon-based solar cells are fragile and require a complex and costly production process. A promising alternative to these solar cells is a dye-sensitized solar cell (DSSC), since in principle it is robust, lightweight, low-cost and made of abundant materials. However, a drawback of these cells is that their efficiency is significantly lower than that of the silicon based cells. The efficiency depends mostly on the absorption of sunlight by the dye and the carrier transport by the electron and hole conducting materials. These components are therefore intensively studied resulting in alternative materials, morphology's and production techniques. The research in the dye and the hole conduction materials mostly focuses on finding better alternative materials to the traditional ones while the research in the electron conducting material is confined to optimization of a material which is already widely used in DSSCs, titania (T1O2) .
In crystalline form titania may be found as rutile, which is the most common natural form, as brookite, and as anatase. Anatase is a mineral form of titanium dioxide (T1O2) . It has space group I4i/amd, a unit cell with a = 3.7845, c = 9.5143 [A]; and Z = 4. The mineral is almost always encountered as a black solid, although the pure material is colourless or white. Anatase is always found as small, isolated and sharply developed crystals, and like rutile, it crystallizes in as tetragonal crystals. There are also important differences between the physical characters of anatase and rutile: the former is less hard (5.5-6 vs. 6-6.5 Mohs) and less dense (specific gravity about 3.9 gr/cm3 vs. 4.2 gr/cm3) . Also, anatase is optically negative whereas rutile is positive.
In view of its potential application as a semiconductor material, anatase is often prepared synthetically. Crystalline anatase can be prepared in laboratories by chemical methods such as a sol-gel method. Examples include controlled hydrolysis of titanium tetrachloride (T1CI4) or titanium ethoxide. Often dopants are included in such synthesis processes to control the morphology, electronic structure, and surface chemistry of anatase.
Typically thin films, such as silicon nitride films, and similarly SiC films, are deposited directly on wafer substrates using a number of deposition techniques including sputtering, evaporating, plasma-enhanced chemical vapor deposition (PECVD), or low-pressure chemical vapor deposition (LPCVD). A nanostructure is defined by etching a desired pattern, such as into the silicon nitride film. Typically a wet or dry etchant, such as potassium hydroxide (KOH), tetramethylammonium hydroxide (TMAH) or ethylene di-amine pyro-catechol (EDP), is used to remove surplus material, which selectively etches away said material. These methods typically require a high temperature, a high vacuum, involve a toxic environment in view of chemicals used, and are often only accessible in limited facilities. To improve the feasibility of solar cell production technologies there is therefore a need for a cheap and scalable fabrication method to produce functional thin films, while operating in non-toxic and low-temperature environments. In search for alternative production methods, several techniques have been explored regarding the formation of inorganic crystals from aqueous solutions using for example small molecules, short polypeptides, adhesive proteins and carbohydrates .
The present invention therefore relates to an improved method for forming organic solar cells, and solar cells and further products obtained by said method, which solve one or more of the above problems and drawbacks of the prior art, providing reliable results, without jeopardizing functionality and advantages.
SUMMARY OF THE INVENTION
It is an object of the invention to overcome one or more limitations of the methods and devices of the prior art and at the very least to provide an alternative thereto. In the present method naturally occurring biomineralization is used for forming at least one thin film layer of anatase. Therein an enzyme of the cysteine protease super-family, such as papain, is found to provide a strong mineralization of titania when immersed in a titania precursor solution, such as lactate titania. The cysteine protease solution and Ti comprising solution are typically provided in alternating mode. A layer containing anatase and rutile T1O2 is formed comprising nanoparticles thereof as well as hydrolysed lactate species as a further, organic, fraction. It is found that the enzyme, such as papain, is adsorbed into thin layers of the titania, which typically is deposited on a substrate, such as on oxide comprising surface. During deposition the enzyme is found to maintain its ability to catalyse the mineralization of titania. It is found that that titania deposition of a first layer may be repeated to deposit another enzyme comprising layer on top of the previous one. This deposition can be applied and integrated such as into a repeatable dip-coating procedure resulting in a simple and flexible mechanism to create hybrid enzyme/titania thin films. In a further step the deposited films can be annealed at relatively low temperature for short duration to remove most of the organic material in the films and obtain a more refined titania thin film. With the present method titania thin films can be produced with a tuneable thickness at a low temperature, in non-vacuum and non-toxic environments and without a requirement for expensive technologies. Relevant details of the present method and products obtained thereby can be found in a master thesis of one of the inventors (E. van Amelrooij) with title Characterization of Enzymatically Synthesized Titania Thin Films using Positron Annihilation Spectroscopy and the development of organically engineered solar cells. and a to be published article of the present inventors, which documents and their contents are incorporated by reference thereto. The anatase is typically deposited on a substrate. The Ti is dissolved in a solution, typically an aqueous solution, further comprising a cysteine protease as enzyme. Ti may also be provided as a complex, such as titania lactate. It is considered that the cysteine protease may be immobilized on the substrate surface, and as immobilized material forms (catalyses) anatase on the surface. The layer of titanium oxide is mesoporous and typically not in mineral form, i.e. typically in amorphous form. If crystalline material is present, dimensions of such material are < 5 nm,
i.e. below a practical limit of detection. It comprises the cysteine protease as part of the layer. The mineralization can occur at ambient temperature, or slightly higher and lower temperatures, so no energy source is required. Higher temperatures can be applied, but there is no need thereto. To obtain at least one layer suited as a solar cell layer the temperature is increased to 100-500 °C and mesoporous 93-99.5 wt. , % anatase is formed thereby. A remainder of the layer may be largely rutile. The protease is removed from the layer by increasing the temperature. Therewith a solar cell 1 comprising in a stack a substrate 11, a first optically transparent electrode layer 22, acting as an anode or cathode, a second electrode layer 22, acting as a cathode or anode, and between the electrode layers a stack of layer, the stack comprising (i) a light absorbing layer 31, (ii) a hole transport layer 41, and (ill) an electron transport layer 51, the hole transport layer being at one side of the light absorbing layer between the first or second electrode layer and the light absorbing layer, the electron transport layer being at another side of the light absorbing layer between the second or first electrode layer and the light absorbing layer, characterized in that the electron transport layer is at least one mesoporous T1O2 layer, the mesoporous layer comprising 93-99.5 wt. % anatase and having a density of < 1 gr/cm3. It is not quite clear why mainly anatase would be formed. It is noted that the obtained density of < 1 gr/cm3 is far lower than the crystalline density of 3.9 gr/cm3, or that of a typical cysteine protease used (papain with 1.2 gr/cm3) reflecting the mesoporous character of the layer formed after annealing. The density may easily be <0.8 gr/cm3, such as 0.4-0.7 gr/cm3. What is also surprising is that more than one anatase layer is formed the density remains within the above ranges for all layers individually. If depositing more layers it is for instance found that the efficiency and operating voltage increase, which is advantageous .
The present method may be used in a further aspect to form layers of anatase, such as in a product, wherein the product is selected from a solar cell, a battery, an antifouling layer, a protective coating, and a dielectric layer.
The present invention provides a solution to one or more of the above mentioned problems and overcomes drawbacks of the prior art.
Advantages of the present description are detailed throughout the description.
DETAILED DESCRIPTION OF THE INVENTION
The present substrate may in principle be any substrate, such as glass, silicon, steel, aluminium, a silicon dielectric, such as silicon oxide, and silicon nitride, polymers, and combinations thereof. The substrate thickness is typically in a range of 100 pm-20 mm, such as 200 pm-l mm.
In an exemplary embodiment of the present solar cell the first electrode layer may be selected from tin doped indium oxide (ITO), graphene, and fluorine doped tin oxide (FTO), wherein the first electrode preferably comprises a crystalline material.
In an exemplary embodiment of the present solar cell the second electrode layer may be selected from metals, such as Al, Cu, Mg, Ba, Au, Ag, Pt, and Ca, and conductive oxides or oxides that are made conductive, such as by doping, such as ITO, and ZnO.
In an exemplary embodiment of the present solar cell the light absorbing layer may comprise a dye sensitized layer.
In an exemplary embodiment of the present solar cell the hole transport layer may comprise an electrolyte, such as 0.12 Μ KI/0.01-0.3 M I2 .
In an exemplary embodiment of the present solar cell at least one metal oxide layer is provided on at least one anatase layer, such as an MgO layer. Said layers may have a thickness of 1-10 nm. It is noted that the inventors did not succeed in depositing such further layers using the same method as for the anatase layers, i.e. using the cysteine protease. These layers are found to improve the conversion efficiency, as well as improve (limit) optical absorption.
In an exemplary embodiment of the present solar cell the electron transport layer may comprise 1-500 TiCu layers, typically having a height of about 1 nm/layer, wherein a thickness of the anatase layer may be from 1 nm-5000 nm, such as 2-500 nm, e.g. 10-250 nm.
In the present solar cell the electron transport layer may comprise pores with a length of 10-500 nm, such as 20-300 nm, e.g. 30-100 nm, and a width of 10-500 nm, such as 20-300 nm, e.g. 30-100 nm, and a pore density of 0.1-100 pores/pm2, such as 0.5-20 pores/pm2, e.g. 2-7 pores/pm2.
In an exemplary embodiment of the present solar cell the electron transport layer may have a surface roughness Ra of 0.1-1.0, e.g. 0.2-0.5, i.e. relatively rough. Such may be due to sub-optimal deposition conditions.
In an exemplary embodiment of the present solar cell the electron transport layer is an enzymatically deposited layer and an annealed layer. Such is also detailed in the present method.
In an exemplary embodiment of the present solar cell the electron transport layer is n-doped, such as with 5*10140.5*1019 dopants/cm3, preferably 5*1015-l*1018 dopants/cm3, more preferably 2*1O1S-5*1O17 dopants/cm3, such as 5*1O1S-1*1O17 dopants/cm3 .
In an exemplary embodiment of the present solar cell a doping concentration may preferably be spatially constant.
In an exemplary embodiment of the present solar cell ntype dopants may be selected from P, As, Bi, Sb and Li, preferably Li.
In an exemplary embodiment of the present solar cell the solar cell may be adapted to operate at a current density of 100 μΑ/cm2, an open circuit voltage of 2-500 mV, such as 10100 mV, and a fill factor of 50-80%, such as 60-75%.
In an exemplary embodiment of the present solar cell in the light absorbing layer the dye is selected from natural occurring organic dyes, such as those derived from plants, such as hibiscus, from fruit or vegetable juice, such as pomegranate juice, jackfruit rag, berries, and coumarin, and from bacteria, such as bacteriorhodopsin, and Photosystem I/II, such as comprising anthocyanin.
In an exemplary embodiment the present solar cell may comprise a textured substrate surface, wherein the textured surface has an aspect ratio (height: depth of a textured structure) of 2-10, such as 3-8.
In an exemplary embodiment the present solar cell may comprise at least one hole mobility improver in the hole transport layer, wherein a first hole mobility improver is present in an amount of 0.1-100 mole %, relative to the electrolyte, and optionally wherein the hole transport layer comprises a second hole transport improver in an amount of 0.00120 mole % relative to the electrolyte. The hole mobility improver is typically of p-type. A typical amount of the first hole mobility improver is 0.1-100 mole %, relative to the hole transport molecule, preferably 0.5-50 mole %, more preferably 1-30 mole %, even more preferably 2-20 mole %, such as 3-5 mole's. The hole mobility improver may be considered as a dopant to the hole transport material; it is noted that the concentration of the hole mobility improver is typically much higher than e.g. dopants in semiconductor devices. The hole mobility improver may typically be capable of oxidizing the hole transport material, and/or promote oxidative reaction thereof; in this respect the hole mobility improver may be considered as an oxidant. In principle any such oxidant could be applied in the present invention. Likewise so-called ionic liquids may be used. Hole mobility improvers may be selected from earth alkali metal, monovalent salts, hydrogen salts (or acids), N,N-dimethyl- pyrrolidinium, and N-methyl-N-propyl pyrrolidinium salts of bis(tris-fluoro methyl sulfonyl) imide (TFSI), such as LiTFSI, AgTFSI, HTFSI, and N,N-dimethyl-pyrrolidinium iodide.
In an exemplary embodiment the present solar cell may comprise a protective layer, such as a transparent substrate, such as glass, and/or a counter electrode.
In an exemplary embodiment the present solar cell may comprise a sequence of layers comprising one or more of a 201000 nm first electrode layer, such as ITO, preferably 40-500 nm, more preferably 50-250 nm, such as 100-200 nm, a 10-1000 nm light absorbing layer, preferably 40-500 nm, more preferably 50-250 nm, such as 100-200 nm, a 10-300 nm hole transport layer, preferably 20-200 nm, more preferably 30-150 nm, such as 50-100 nm, an 10-500 nm electron transport layer, preferably 20-200 nm, more preferably 30-150 nm, such as 50-100 nm, and a 20-200 nm second electrode layer, preferably 30-150 nm, more preferably 40-120 nm, such as 50-100 nm.
The present solar cell may comprise microstructures and/or nanostructures. These may be provided by a lithographic process 14, an e-beam process 14, or a combination thereof.
In an exemplary embodiment the present method of forming a mesoporous T1O2 layer may comprise providing a substrate, providing a solution comprising a cysteine protease and a solution comprising dissolved Ti ions or a dissolved Ti comprising complex, such as Ti4+, preferably immobilizing said cysteine protease, mineralizing a layer of mesoporous titanium oxide preferably at a temperature of 15-40 °C, such as at room temperature, at least partly incorporating said cysteine protease in the layer, and increasing the temperature to 100-500 °C and forming mesoporous anatase, such as 93-99.5 wt. % anatase. The deposition rate of anatase in the present process is around 0.01-1 nm/min, typically 0.02-0.1 nm/min.
In an exemplary embodiment of the present method a protease concentration may be from 0.05-10 mH, preferably 0.1-5 mN, such as 1-2 mN.
In an exemplary embodiment of the present method the titanium concentration may be from 1-500 mN, preferably 5 -250 mH, such as 20-50 mN.
In an exemplary embodiment of the present method the titanium may be provided as a mono- or di-carboxylate, such as a C1-C5 carboxylate, such as lactate, such as Titanium(IV) bis(ammonium lactato) dihydroxide (BALDH) .
In an exemplary embodiment of the present method the solution comprises a buffer for maintaining the pH in a range of 5-11, such as 8-10, such as 4-Morpholinepropanesulfonic acid (MOPS), 2-(N-morpholino) ethane sulfonic acid (MES) (CAS Number: 4432-31-9, chemical formula: C6H13NO4S), and (4-(2 hydroxyethyl)-1-piperazineethanesulfonic acid) (HEPES) (CAS Number: 7365-45-9 C8H18N2O4S), preferably 1-500 mM, such as 20100 mM.
In an exemplary embodiment of the present method the substrate may be precleaned.
In an exemplary embodiment of the present method the increasing of temperature results in annealing of anatase.
In an exemplary embodiment of the present method 1-50 pg/cm2 cysteine protease may be deposited, such as 2-20 pg/cm2.
In an exemplary embodiment of the present method 1-50 pg/cm2 anatase may be deposited, such as 2-20 pg/cm2.
In an exemplary embodiment of the present method a density of the combined cysteine protease/anatase layer may be < 1 gr/cm3, such as 0.4-0.8 gr/cm3.
In an exemplary embodiment of the present method a density of the annealed anatase layer may be < 1 gr/cm3, such as 0.5-0.9 gr/cm3 .
In an exemplary embodiment of the present method a thickness of the annealed layer may be decreased by 20-50% relative to the un-annealed layer, such as by 30-40%.
In an exemplary embodiment of the present method after increasing the temperature, the temperature may be maintained in said temperature range for a period of 1-4 hours, such as 1.5-3 hours .
In the present method during the step of depositing titanium oxide the substrate may be immersed during 0.5-10 minutes in the titanium comprising solution, such as during 1.5-5 minutes. It has been found that unexpectedly if longer periods of deposition are taken the deposited titanium oxide is actually being destroyed.
In an exemplary embodiment of the present method the step of depositing titanium oxide is repeated 2-100 times, such as 5-10 times.
In an exemplary embodiment of the present method before the step of depositing titanium oxide the substrate may be immersed during 0.5-10 minutes in the cysteine protease comprising solution, such as during 1.5-5 minutes.
In an exemplary embodiment of the present method the cysteine protease may be selected from fruit proteases, such as papain.
In an exemplary embodiment of the present method the cysteine protease may be selected from MEROPS classification super families CA, such as Cl, C2, C6, CIO, C12, C16, C19, C28, C31, C32, C33, C39, C47, C51, C54, C58, C64, C65, 066, C67, C70, C71, C76, C78, C83, C85, C86, C87, C93, C96, C98, C101, such as Papain (Carica papaya) , Actinidain (Actinidia deliciosa), bromelain (Ananas comosus), cathepsin K (liverwort) and calpain (Homo sapiens), CD, such as Cll, C13, C14, C25, C50, C80, C84, such as Caspase-1 (Rattus norvegicus) and separase (Saccharomyces cerevisiae) , CE, such as C5, C48, C55, C57, C63, C79, such as Adenain (human adenovirus type 2), CF, such as C15, such as Pyroglutamyl-peptidase I (Bacillus amyloliquefaciens), CL, such as C60, C82, such as Sortase A (Staphylococcus aureus), CM, such as C18, such as Hepatitis C virus peptidase 2 (hepatitis C virus), CN, such as C9, such as Sindbis virus-type nsP2 peptidase (sindbis virus), CO, such as C40, such as Dipeptidyl-peptidase VI (Lysinibacillus sphaericus), CP, such as C97, such as DeSI-1 peptidase (Mus musculus), PA , such as C3, C4, C24, C30, C37, C62, C74, C99, such as TEV protease (Tobacco etch virus), PB, such as C44, C45, C59, 069, C89, C95, such as Amidophosphoribosyltransferase precursor (Homo sapiens), PC, such as C26, C56, such as Gammaglutamyl hydrolase (Rattus norvegicus), PD, such as C46, such as Hedgehog protein (Drosophila melanogaster), and PE, such as Pl, such as DmpA aminopeptidase (Ochrobactrum anthropi).
In an exemplary embodiment of the present method the substrate may comprise an optically transparent conducting layer, such as ITO, wherein the enzyme is immobilized on said optically transparent layer, and titanium oxide is mineralized on said transparent conducting layer.
In an exemplary embodiment of the present method a lightabsorbing layer may be deposited on the mesoporous anatase layer, and wherein preferably the light absorbing layer is at least partly incorporated in the anatase layer.
In an exemplary embodiment of the present method at least one of a 20-1000 nm first electrode layer, such as ITO, a 10
1000 nm light absorbing layer, a 10-300 nm hole transport layer, an 10-500 nm mesoporous anatase electron transport layer, and a 20-200 nm second electrode layer may be provided.
The invention will hereafter be further elucidated through the following examples that are exemplary and explanatory of nature and are not intended to be considered limiting of the invention. To the person skilled in the art it may be clear that many variants, being obvious or not, may be conceivable falling within the scope of protection, defined by the present claims.
SUMMARY OF THE FIGURES
Figures la-b show exemplary embodiments of the present solar cell.
Fig. 2 shows operation of a solar cell schematically.
Figs. 3a-h show SEM measurements, 8000x and 35000x.
Figure 4 shows a schematic solar cell.
Figs. 5a,b show SEM images.
DETAILED DESCRIPTION OF FIGURES
In the figures:
I Solar cell (cross section)
II substrate anode/cathode metal layer light absorbing layer hole transport layer intermediate layer glass + ITO coating papain titania layer adhered dye layer electrolyte conducting layer glass + ITO coating load
Two stacks of layers are considered specifically, relating to a so-called inverted and standard devices (see fig. 4a-
b) . The substrate 11 therein is typically glass. In the inverted device the anode 21 is an optically transparent electrode, such as FTO, in contact with the substrate. In contact with the anode and the light absorbing layer 31 is the present hole transport layer 41. A metal layer 22 (such as Al) acts as second electrode. Typically an intermediate layer 51, such as a fullerene, is present between the cathode and light absorbing layer. The light absorbing layer may be organic, such as a dye sensitized layer, and an inorganic light absorbing layer. In the standard light absorbing layer device the cathode 21, such as FTO is on the substrate 11, such as glass. A metal layer (such as Au) acts as second electrode 22. In contact with the cathode and light absorbing layer 31 is an intermediate layer 51, such as T1O2. In contact with the anode 22 and the light absorbing layer 31 is the present hole transport layer 41.
Figure 2 shows a schematic illustration of a dye-sensitized solar cell. Therein a photon excites an electron in a dye layer, which may be a monolayer. The electron is provided in a typically n-type conductor, such as the present anatase. Electrons typically move to a front contact which is then negatively charged. Dye molecules are regenerated by injecting a hole into the electrolyte. Positively charged ions in the electrolyte diffuse to the counter electrode on a back-contact. A charge difference between front and back contact may generate an electric current.
Figs. 3a-h show SEM measurements, 8000x and 35000x. Two magnifications of different P-T layers. Annealing is done at 400°C for 4h.
Fig. 4 shows schematics of solar cell fabrication. Therein, from top to bottom, a glass with ITO coating facing downward, a deposited and annealed papain-titania layer, an adhered dye-layer from pomegranate juice, a liquid electrolyte (I~/l3~) (Lugols solution 5%), a graphite layer, and a glass with ITO coating facing upward, are shown.
Figure 5(a) Surface of single annealed PT-layer on ITO and (b) Reference of SEM measurement of a blank ITO film.
Examples
In an example papain is used as cysteine protease, such as a papaya fruit papain. Papain is found to self-assemble into monolayers on oxide and polymer surfaces as well as breaking down TiBALDH to catalyse the surface mineralization of crystalline T1O2 nanoparticles at room temperature. Papain fruit extract in powder form was purchased from Shaanxi Sangherb Bio-Tech Inc. (CAS: 9001-73-4). TiBALDH from Sigma Aldrich (CAS: 65104-06-5) and Mg-Lactate from Sigma Aldrich (CAS: 1220086-24-7) has been used in experiments.
Samples were thoroughly cleaned before dip coating. The samples were immersed in distilled water with 0.05 SDS detergent and sonicated for 10 minutes. Then gloves were used to softly rub the samples and afterwards they are washed with distilled water. In a fume hood, 5g KOH was dissolved in lOOmL ethanol. Then the samples were again sonicated for 10 minutes in this solution, and sonicated three times in distilled deionized water while refreshing the water every time.
4.7 g of the papain (powder from Papaya latex) was dissolved in 200 mL of lOOmM 3-(N-morpholino) propane sulfonic acid (MOPS) pH 7.0 to get a in a range of 0.5-40 mM, such as ImM solution. Afterwards, 200 mL of lOOmM MOPS buffer of pH7.0 was magnetically stirred until all the powder was dissolved and a yellow-green solution is achieved. 2mL (in a range of 10-50 mM, such as 20 mM) of TiBALDH was added to 200 mL distilled de-ionized water and stirred. A wash solution was distilled de-ionized water.
Tweezers or a scoop is used to put the (ITO)glass substrate in the papain solution where it is left for 5 minutes. Subsequently the remaining liquid is removed from the sample by shaking before putting the sample in the first beaker with water for 30 seconds whilst slowly stirring. Then the sample is put into the TiBALDH solution for 2 minutes. This procedure can be reiterated as often as desired to produce multi-layered layers. After more than 7 iterations the papain solution can become cloudy and may be refreshed. Every ten cycles the solutions may be refreshed if necessary. The above samples were put in an oven at 450 °C for 4 hours after which the oven slowly cooled down to room temperature for annealing.
As a natural sensitized dye pomegranates were extracted to obtain a clear purple pomegranate juice. The dye molecules therein are used to slowly adhere to immersed titania films. Immersion may take up 24 hours. It may be carried out at room temperature preferably in low-light conditions to prevent the dye from destabilizing. Afterwards the slide is rinsed with ethanol and dried.
A very simple solar cell fabrication process is used, as an example. A conductive ITO glass as a substrate was used to deposit papain-titania layers. In order to connect a cable some space is left free. The papain-titania layers were annealed as described above. Then the annealed film was immersed in the above filtered pomegranate juice for 24 hours. A second glass substrate was coated with a small amount of conductive material, such as graphite from a pencil by colouring in the glass. Again space was left free for connecting the other cable. A small drop of electrolyte (Lugols Solution 5%) comprising IM KI and 0. IM I2 in water is put on the substrate with the titania layer. The substrate with the graphite is put on top of the slide with the side with the counter electrode facing the dye-sensitized titania layer (see fig. 4). The two substrates were pressed together to spread out the electrolyte. Then they are fixed together using clamps. Now the cables were connected to the clean sides of the glass and performance was measured with a multimeter. It is noted that the obtained solar cell is extremely simple and low tech in design .
Papain concentrations have been varied from 10 μΜ, to 100 μΜ and 1 mM, TiBALDH concentrations from 20 mM to 200 mM, MOPS concentration from 20 mM to 100 mM, and a pH from 6.0 to 7.0 and 8.0, to study deposition. A higher papain concentration results in faster deposition, and subsequent layers deposited are typically deposited faster compared to previous layers. Subsequent layers are typically also thicker, at the same boundary conditions ([papain], [Ti], pH, T, t). Also a surface roughness is found to increase for subsequent layers. For the concentration of Ti the effect of a higher concentration is limited. For annealing a higher temperature typically results in shorter annealing times. Annealing preferably removes most (>80%) or all of the cysteine protease. As a result the anatase layers typically decrease in thickness. A thickness decrease is typically > 25%, such as 50-75%, relative to an initial thickness including the protease.
Obtained cells and layers were analysed, such as with positron annihilation spectroscopy, with Doppler broadening spectroscopy, with a profilometer (Dektak 8 of Veeco/Bruker), with X-rays diffraction, scanning electron microscopy (FEI Helios G4 CX), with Energy Dispersive X-ray spectroscopy, and using a Tao-Eldrup model for matching lifetime with pore size in so far as applicable.
A simple multimeter was used to establish photovoltaic activity. On a sunny day in broad daylight the triple layer showed a maximum open circuit voltage (Voc and tlayers) of Voc,3 = 3.2 mV, the nonalayer Voc,9 =13.1 mV and the 15-layer Voc,15 = 35.1 mV. These voltages decreased by half when the cells were put in the shadow. The maximum measured current Im was in the order of 1 μΑ/cm2. Inventors estimate the efficiency of this initial solar cell assuming a low current density of 100 μΑ/cm2 and a modest fill factor of FF = 0.7 as η = 0.003%.
For the sake of searching the following section is added.
1. Solar cell (1) comprising in a stack a substrate (11), a first optically transparent electrode layer (22), a second electrode layer (22), and between the electrode layers a stack of layers, the stack comprising (i) a light absorbing layer (31), (ii) a hole transport layer (41), and (iii) an electron transport layer (51), the hole transport layer being at one side of the light absorbing layer between the first or second electrode layer and the light absorbing layer, the electron transport layer being at another side of the light absorbing layer between the second or first electrode layer and the light absorbing layer, characterized in that the electron transport layer is at least one mesoporous T1O2 layer, the mesoporous layer comprising 93-99.5 wt. % anatase and having a density of < 1 gr/cm3, wherein the electron transport layer comprises pores with a length of
10-500 nm, and a width of 10-500 nm, and a pore density of 0.1-100 pores/pm2.
2. Solar cell according to embodiment 1, wherein the substrate is selected from glass, silicon, steel, aluminum, a silicon dielectric, such as silicon oxide, and silicon nitride, polymers, and combinations thereof, and/or wherein the first electrode layer is selected from tin doped indium oxide (ITO), graphene, and fluorine doped tin oxide (FTO), wherein the first electrode preferably comprises a crystalline material, and/or wherein the second electrode layer is selected from metals, such as Al, Cu, Mg, Ba, Au, Ag, Pt, and Ca, and conductive oxides or oxides that are made conductive, such as ZnO, and ITO,
3. Solar cell according to any of embodiments 1-2, wherein the light absorbing layer comprises a dye sensitized layer, and/or wherein the hole transport layer comprises an electrolyte, such as 0.1-2 M KI/0.01-0.3 Μ I2, and/or wherein at least one metal oxide layer is provided on at least one anatase layer.
4. Solar cell according to any of embodiments 1-3, wherein the electron transport layer comprises 1-500 T1O2 layers, wherein a thickness of the anatase layer is from 1 nm5000 nm, such as 2-500 nm, e.g. 10-250 nm.
5. Solar cell according to any of embodiments 1-4, wherein the electron transport layer is an enzymatically deposited layer and an annealed layer.
6. Solar cell according to any of embodiments 1-5, wherein the electron transport layer is n-doped, such as with 5* 1014-0.5*1019 dopants/cm3, preferably 5* 1015-l* 1018 dopants/cm3, more preferably 2*1016-5*1017 dopants/cm3, such as 5*1016-l*1017 dopants/cm3, wherein a doping concentration is preferably spatially constant, and/or wherein ntype dopants are selected from P, As, Bi, Sb and Li, preferably Li.
7. Solar cell according to any of embodiments 1-6, wherein the solar cell is adapted to operate at a current density of 100 μΑ/cm2, an open circuit voltage of 2-500 mV and a fill factor of 50-80%.
8. Solar cell according to any of embodiments 1-7, wherein in the light absorbing layer the dye is selected from natural occurring organic dyes, such as those derived from plants, such as hibiscus, from fruit or vegetable juice, such as pomegranate juice, jackfruit rag, berries, and coumarin, and from bacteria, such as bacteriorhodopsin, and Photosystem I/II, such as comprising anthocyanin .
9. Solar cell according to any of embodiments 1-8, comprising a textured substrate surface, wherein the textured surface has an aspect ratio (height: depth of a textured structure) of 2-10.
10. Solar cell according to any of embodiments 1-9, comprising at least one hole mobility improver in the hole transport layer, wherein a first hole mobility improver is present in an amount of 0.1-100 mole %, relative to the electrolyte, and optionally wherein the hole transport layer comprises a second hole transport improver in an amount of 0.001-20 mole % relative to the electrolyte .
11. Solar cell according to any of embodiments 1-10, comprising a protective layer, such as a transparent substrate, such as glass, and/or a counter electrode.
12. Solar cell according to any of embodiments 1-11, comprising a sequence of layers comprising one or more of a 20-1000 nm first electrode layer, such as ITO, a 10-1000 nm light absorbing layer, a 10-300 nm hole transport layer, an 10-500 nm electron transport layer, and a 20-200 nm second electrode layer.
13. Method of forming a mesoporous T1O2 layer comprising providing a substrate, providing a solution comprising a cysteine protease and a solution comprising dissolved Ti ions or a dissolved Ti comprising complex, such as Ti4+, preferably immobilizing said cysteine protease, mineralizing a layer of mesoporous titanium oxide preferably at a temperature of 15-40 °C, such as at room temperature, at least partly incorporating said cysteine protease in the layer, wherein during the step of depositing titanium oxide the substrate is immersed during 0.5-10 minutes in the titanium comprising solution, such as during 1.5-5 minutes, and increasing the temperature to 100-500 °C and forming a mesoporous layer comprising 93-99.5 wt.% anatase and having a density of < 1 gr/cm3, wherein the anatase layer comprises pores with a length of 10-500 nm, and a width of 10-500 nm, and a pore density of 0.1-100 pores/pm2.
14. Method according to embodiment 13, wherein the cysteine protease solution and Ti comprising solution are provided in alternating mode, and/or wherein a protease concentration is from 0.05-10 mM, preferably 0.1-5 mM, and/or wherein the titanium concentration is from 1-500 mM, preferably 5 -250 mM, and/or wherein the titanium is provided as a mono- or di-carboxylate, such as a C1-C5 carboxylate, such as lactate, such as Titanium(IV) bis(ammonium lactato) dihydroxide (BALDH), and/or wherein the solution comprises a buffer for maintaining the pH in a range of 5-11, such as 8-10, such as 4-Morpholinepropanesulfonic acid (MOPS), 2-(N-morpholino)ethane sulfonic acid (MES), (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid) (HEPES) such as 1-500 mM, and/or wherein the substrate is precleaned, and/or wherein the increasing of temperature results in annealing of anatase, and/or wherein 1-50 pg/cm2 cysteine protease is deposited, such as 2-20 pg/cm2, and/or wherein 1-50 pg/cm2 anatase is deposited, such as 2-20 pg/cm2, and/or wherein a density of the combined cysteine protease/anatase layer is < 1 gr/cm3, such as 0.4-0.8 gr/cm3, and/or wherein a density of the annealed anatase layer is < 1 gr/cm3, such as 0.5-0.9 gr/cm3, and/or wherein a thickness of the annealed layer is decreased by 20-50% relative to the un-annealed layer.
15. Method of according to embodiment 13 or 14, wherein after increasing the temperature, the temperature is maintained in said temperature range for a period of 1-4 hours, such as 1.5-3 hours .
16. Method according to any of embodiments 13-15, wherein the step of depositing titanium oxide is repeated
2-100 times.
17. Method according to any of embodiments 13-16, wherein before the step of depositing titanium oxide the substrate is immersed during 0.5-10 minutes in the cysteine protease comprising solution, such as during 1.5-5 minutes, and/or wherein the cysteine protease is selected from fruit proteases, such as papain.
18. Method according to any of embodiments 13-17, wherein the cysteine protease is selected from
MEROPS classification super families CA, such as Cl, C2, C6, C10, C12, C16, C19, C28, C31, C32, C33, C39, C47, C51, C54, C58, C64, C65, C66, C67, C70, C71, C76, C78, C83, C85, C86, C87, C93, C96, C98, C101, such as Papain (Carica papaya), Actinidain (Actinidia deliciosa), bromelain (Ananas comosus), cathepsin K (liverwort) and calpain (Homo sapiens), CD, such as Cll, C13, C14, C25, C50, C80, C84, such as Caspase-1 (Rattus norvegicus) and separase (Saccharomyces cerevisiae), CE, such as C5, C48, C55, C57, C63, C79, such as Adenain (human adenovirus type 2), CF, such as C15, such as Pyroglutamyl-peptidase I (Bacillus amyloliquefaciens), CL, such as C60, C82, such as Sortase A (Staphylococcus aureus), CM, such as C18, such as Hepatitis C virus peptidase 2 (hepatitis C virus), CN, such as C9, such as Sindbis virus-type nsP2 peptidase (sindbis virus), CO, such as C40, such as Dipeptidyl-peptidase VI (Lysinibacillus sphaericus), CP, such as C97, such as DeSI-1 peptidase (Mus musculus), PA, such as C3, C4, C24, C30, C37, C62, C74, C99, such as TEV protease (Tobacco etch virus), PB, such as C44, C45, C59, C69, C89, C95, such as Amidophosphoribosyltransferase precursor (Homo sapiens), PC, such as C26, C56, such as Gamma-glutamyl hydrolase (Rattus norvegicus), PD, such as C46, such as Hedgehog protein (Drosophila melanogaster), and PE, such as Pl, such as DmpA aminopeptidase (Ochrobactrum anthropi).
19. Method according to any of embodiments 13-18, wherein the substrate comprises an optically transparent conducting layer, such as ITO, wherein the enzyme is immobilized on said optically transparent layer, and titanium oxide is mineralized on said transparent conducting layer.
20. Method according to any of embodiments 13-19, wherein a light absorbing layer is deposited on the mesoporous anatase layer, and wherein preferably the light absorbing layer is at least partly incorporated in the anatase layer .
21. Method according to any of embodiments 13-20, wherein at least one of a 20-1000 nm first electrode layer, such as ITO, a 10-1000 nm light absorbing layer, a 10-300 nm hole transport layer, an 10-500 nm mesoporous anatase electron transport layer, and a 20-200 nm second electrode layer is provided.
22. Product obtained by a method according to any of embodi- ments 13-21, wherein the product is selected from a solar cell, a battery, an anti-fouling layer, a protective coating, and a dielectric layer.

Claims (22)

1. Zonnecel (1) omvattende in een stapel een substraat (11), een eerste optisch transparante elektrodelaag (22), een tweede elektrodelaag (22), en tussen de elektrodelagen een stapel lagen, waarbij de stapel omvat (i) een lichtabsorberende laag (31), (ii) een gaten-transportlaag (41), en (iii) een elektronentransportlaag (51), waarbij de gatentransportlaag zich aan één zijde van de lichtabsorberende laag bevindt tussen de eerste of tweede elektrodelaag en de lichtabsorberende laag, waarbij de elektronentransportlaag zich aan een andere zijde van de lichtabsorberende laag bevindt tussen de tweede of eerste elektrode laag en de lichtabsorberende laag, met het kenmerk dat de elektronentransportlaag ten minste één mesoporeuze T1O2laag is, waarbij de mesoporeuze laag 93-99,5 gew.% anataas omvat en een dichtheid van <1 gr/cm3 heeft, waarbij de elektronentransportlaag poriën met een lengte van 10-500 nm omvat, en een breedte van 10-500 nm, en een poriëndichtheid van 0,1-100 poriën/pm2.A solar cell (1) comprising in a stack a substrate (11), a first optically transparent electrode layer (22), a second electrode layer (22), and a stack of layers between the electrode layers, the stack comprising (i) a light-absorbing layer (31), (ii) a hole transport layer (41), and (iii) an electron transport layer (51), the hole transport layer being on one side of the light absorbing layer between the first or second electrode layer and the light absorbing layer, the electron transport layer located on another side of the light absorbing layer between the second or first electrode layer and the light absorbing layer, characterized in that the electron transport layer is at least one mesoporous T1O2 layer, the mesoporous layer comprising 93-99.5 wt% anatase and has a density of <1 g / cm 3 , wherein the electron transport layer comprises pores 10-500 nm in length, 10-500 nm in width, and a pore density of 0.1-100 pores / µm 2 . 2. Zonnecel volgens conclusie 1, waarbij het substraat is gekozen uit glas, silicium, staal, aluminium, een siliciumdielektricum, zoals siliciumoxide, en siliciumnitride, polymeren, en combinaties daarvan, en/of waarbij de eerste elektrodelaag is gekozen uit met tin gedoteerd indiumoxide (ITO), grafeen, en met fluor gedoteerd tinoxide (FTO), waarbij de eerste elektrode bij voorkeur een kristallijn materiaal omvat, en/of waarbij de tweede elektrodelaag is gekozen uit metalen, zoals Al, Cu, Mg, Ba, Au, Ag, Pt en Ca, en geleidende oxiden of oxiden die geleidend zijn gemaakt, zoals ZnO en ITO,The solar cell of claim 1, wherein the substrate is selected from glass, silicon, steel, aluminum, a silicon dielectric, such as silicon oxide, and silicon nitride, polymers, and combinations thereof, and / or wherein the first electrode layer is selected from tin-doped indium oxide (ITO), graphene, and fluorine-doped tin oxide (FTO), the first electrode preferably comprising a crystalline material, and / or wherein the second electrode layer is selected from metals such as Al, Cu, Mg, Ba, Au, Ag , Pt and Ca, and conductive oxides or oxides made conductive, such as ZnO and ITO, 3. Zonnecel volgens een der conclusies 1-2, waarbij de lichtabsorberende laag een door kleurstof gesensibiliseerde laag omvat en/of waarbij de gatentransportlaag een elektrolyt omvat, zoals 0,12 M KI/0,01-0,3 M I2, en/of waarbij ten minste één metaaloxidelaag op ten minste één anataas-laag is verschaft.Solar cell according to any one of claims 1-2, wherein the light-absorbing layer comprises a dye-sensitized layer and / or wherein the hole transport layer comprises an electrolyte, such as 0.12 M KI / 0.01-0.3 MI 2 , and / or wherein at least one metal oxide layer is provided on at least one anatase layer. 4. Zonnecel volgens een van de conclusies 1-3, waarbij de elektronentransportlaag 1-500 Ti02-lagen omvat, waarbij een dikte van de anataaslaag 1 nm-5000 nm, zoals 2-500 nm, e.g. 10-250 nm.The solar cell of any one of claims 1-3, wherein the electron transport layer comprises 1-500 TiO2 layers, wherein the anatase layer thickness is 1 nm-5000 nm, such as 2-500 nm, e.g. 10-250 nm. 5. Zonnecel volgens een der conclusies 1-4, waarbij de elektronentransportlaag een enzymatisch afgezette laag en een uitgegloeide laag is.Solar cell according to any one of claims 1-4, wherein the electron transport layer is an enzymatically deposited layer and an annealed layer. 6. Zonnecel volgens een der conclusies 1-5, waarbij de elektronentransportlaag n-gedoteerd is, zoals met 5*10140,5*1019 dopants/cm3, bij voorkeur 5*1015-l*1018 dopants/cm3, liever 2* 1016-5* 1017 dopants/cm3, zoals 5*10ie-l* 1017 dopants/cm3, waarbij een doteringsconcentratie bij voorkeur ruimtelijk constant is, en/of waarbij n-type doponats zijn gekozen uit P, As, Bi, Sb, en Li, bij voorkeur Li.Solar cell according to any one of claims 1-5, wherein the electron transport layer is n-doped, such as with 5 * 10 14 0.5 * 10 19 dopants / cm 3 , preferably 5 * 10 15 -1 * 10 18 dopants / cm 3 , more preferably 2 * 10 16 -5 * 10 17 dopants / cm 3 , such as 5 * 10 ie -l * 10 17 dopants / cm 3 , where a doping concentration is preferably spatially constant, and / or where n-type doponats are selected from P, As, Bi, Sb, and Li, preferably Li. 7. Zonnecel volgens een van de conclusies 1-6, waarbij de zonnecel is ingericht om te werken bij een stroomdichtheid van 100 μΑ/cm2, een nullastspanning van 2-500 mV en een vulfactor van 50-80%.Solar cell according to any one of claims 1-6, wherein the solar cell is adapted to operate at a current density of 100 μΑ / cm 2 , a no-load voltage of 2-500 mV and a filling factor of 50-80%. 8. Zonnecel volgens een van de conclusies 1-7, waarbij in de lichtabsorberende laag de kleurstof is gekozen uit natuurlijk voorkomende organische kleurstoffen, zoals die welke zijn afgeleid van planten, zoals hibiscus, uit fruit- of groentesap, zoals granaatappelsap, nangka-vod, bessen, en coumarine, en van bacteriën, zoals bacteriorodopsine, en Fotosysteem I/II, zoals anthocyanine.Solar cell according to any one of claims 1-7, wherein in the light-absorbing layer the dye is selected from naturally occurring organic dyes, such as those derived from plants, such as hibiscus, from fruit or vegetable juice, such as pomegranate juice, nangka rag , berries, and coumarin, and from bacteria, such as bacteriorodopsine, and Photosystem I / II, such as anthocyanin. 9. Zonnecel volgens één der conclusies 1-8, omvattende een gestructureerd substraatoppervlak, waarbij het gestructureerde oppervlak een aspectverhouding (hoogte:diepte van een gestructureerde structuur) van 2-10 heeft.Solar cell according to any one of claims 1-8, comprising a structured substrate surface, the structured surface having an aspect ratio (height: depth of a structured structure) of 2-10. 10. Zonnecel volgens een van de conclusies 1-9, omvattende ten minste één gatenmobiliteitverbeteraar in de gaten transportlaag, waarbij een eerste gatenmobiliteitverbeteraar aanwezig is in een hoeveelheid van 0,1-100 mol% ten opzichte van het elektrolyt, en waarbij de gatentransportlaag een tweede gatentransportverbeteraar omvat in een hoeveelheid van 0,001-20 molt ten opzichte van het elektrolyt.Solar cell according to any one of claims 1-9, comprising at least one hole mobility improver in the hole transport layer, wherein a first hole mobility improver is present in an amount of 0.1-100 mol% with respect to the electrolyte, and wherein the hole transport layer second hole transport improver in an amount of 0.001-20 mols to the electrolyte. 11. Zonnecel volgens één van de conclusies 1-10, omvattende een beschermende laag, zoals een transparant substraat, zoals glas, en/of een tegenelektrode.Solar cell according to any one of claims 1-10, comprising a protective layer, such as a transparent substrate, such as glass, and / or a counter electrode. 12. Zonnecel volgens een van de conclusies 1-11, omvattende een reeks lagen omvattende één of meer van een eerste elektrodelaag van 20-1000 nm, zoals ITO, een lichtabsorberende laag van 10-1000 nm, een 10-300 nm gatentransportlaag, een 10-500 nm elektronentransportlaag, en een elektrodelaag van 20-200 nm.A solar cell according to any one of claims 1-11, comprising a series of layers comprising one or more of a first electrode layer of 20-1000 nm, such as ITO, a light-absorbing layer of 10-1000 nm, a 10-300 nm hole transport layer, a 10-500 nm electron transport layer, and an electrode layer of 20-200 nm. 13. Werkwijze voor het vormen van een mesoporeuze T1O2laag omvattende het verschaffen van een substraat, het verschaffen van een oplossing omvattende een cysteineprotease en een oplossing omvattende opgeloste Ti-ionen of een opgelost Ti omvattende complex, zoals Ti4+, bij voorkeur het immobiliseren van het cysteïneprotease, het mineraliseren van een laag mesoporeus titaanoxide bij voorkeur bij een temperatuur van 15-40 °C, zoals bij kamertemperatuur, het ten minste gedeeltelijk opnemen van genoemd cysteïneprotease in de laag, waarbij tijdens de stap van het afzetten van titaniumoxide het substraat wordt ondergedompeld gedurende 0,5-10 minuten in de titanium omvattende oplossing, zoals gedurende 1,5-5 minuten, en het verhogen van de temperatuur tot 100-500 °C en het vormen van mesoporeus, omvattende 93-99,5 gew.% anatase en met een dichtheid van <1 gr/cm3, waarbij de anataaslaag poriën omvat met een lengte van 10-500 nm, en een breedte van 10-500 nm en een poriëndichtheid van 0,1-100 poriën/pm2.A method of forming a mesoporous T102 layer comprising providing a substrate, providing a solution comprising a cysteine protease and a solution comprising dissolved Ti ions or a dissolved Ti complex, such as Ti 4+ , preferably immobilizing the cysteine protease, mineralizing a layer of mesoporous titanium oxide preferably at a temperature of 15-40 ° C, such as at room temperature, at least partially incorporating said cysteine protease into the layer, the substrate being deposited during the step of depositing titanium oxide immersed in the titanium-containing solution for 0.5-10 minutes, such as for 1.5-5 minutes, and raising the temperature to 100-500 ° C and forming mesoporous, comprising 93-99.5 wt% anatase and with a density of <1 gr / cm 3 , the anatase layer comprising pores with a length of 10-500 nm, a width of 10-500 nm and a pore density of 0.1-10 0 pores / pm 2 . 14. Werkwijze volgens conclusie 13, waarbij de cysteïneproteaseoplossing en Ti-omvattende oplossing worden verschaft in alternerende modus, en/of waarbij een proteaseconcentratie 0,05-10 mM, bij voorkeur 0,15 mM en/of is waarbij de titaniumconcentratie 1-500 mM is, bij voorkeur 5250 mM, en/ofThe method of claim 13, wherein the cysteine protease solution and Ti-containing solution are provided in alternating mode, and / or wherein a protease concentration is 0.05-10 mM, preferably 0.15 mM and / or wherein the titanium concentration is 1-500 mM is preferably 5250 mM, and / or 2 4 waarbij het titanium wordt verschaft als een mono- of di-carboxylaat, zoals een C1-C5 carboxylaat, zoals lactaat, zoals Titanium (IV) bis (ammoniumlactaat) dihydroxide (BALDH), en/of waarbij de oplossing een buffer omvat voor het handhaven van de pH in een bereik van 5-11, zoals 8-10, zoals 4-morfolinepropaansulfonzuur (MOPS), 2-(N-morfolino)ethaansulfonzuur (MES), (4-(2-hydroxyethyl)-1-piperazineethaansulfonzuur) (HEPES), zoals 1-500 mM, en/of waarbij het substraat wordt voorgereinigd en/of waarbij het verhogen van de temperatuur leidt tot uitgloeien van anataas, en/of waarbij 1-50 pg/cm2 cysteïneprotease wordt afgezet, zoals 2-20 pg/cm2, en/of waarbij 1-50 pg/cm2 anataas wordt afgezet, zoals 2-20 pg/cm2, en/of waarbij een dichtheid van de gecombineerde cysteïneprotease/anataaslaag <1 gr/cm3 is, zoals 0,4-0,8 gr/cm3, en/of waarbij een dichtheid van de uitgegloeide anataaslaag <1 gr/cm3 is, zoals 0,5-0,9 g/cm3, en/of waarbij een dikte van de uitgegloeide laag wordt verminderd met 20-50% ten opzichte van de niet-uitgegloeide laag.2 wherein the titanium is provided as a mono- or di-carboxylate, such as a C1-C5 carboxylate, such as lactate, such as Titanium (IV) bis (ammonium lactate) dihydroxide (BALDH), and / or wherein the solution comprises a buffer for maintaining the pH in a range of 5-11, such as 8-10, such as 4-morpholine propanesulfonic acid (MOPS), 2- (N-morpholino) ethanesulfonic acid (MES), (4- (2-hydroxyethyl) -1-piperazinethanesulfonic acid ) (HEPES), such as 1-500 mM, and / or wherein the substrate is pre-cleaned and / or where increasing the temperature results in annealing of anatase, and / or depositing 1-50 µg / cm 2 of cysteine protease, such as 2-20 pg / cm 2 , and / or wherein 1-50 pg / cm 2 anatase is deposited, such as 2-20 pg / cm 2 , and / or where a density of the combined cysteine protease / anatase layer is <1 gr / cm 3 is, such as 0.4-0.8 g / cm 3 , and / or wherein a density of the annealed anatase layer is <1 g / cm 3 , such as 0.5-0.9 g / cm 3 , and / or a thickness of the annealed layer is consumed reduced by 20-50% relative to the non-annealed layer. 15. Werkwijze volgens conclusie 13 of 14, waarbij na het verhogen van de temperatuur, de temperatuur in genoemd temperatuurbereik wordt gehandhaafd gedurende een periode van 1-4 uur, zoals 1,5-3 uur.A method according to claim 13 or 14, wherein after increasing the temperature, the temperature in said temperature range is maintained for a period of 1-4 hours, such as 1.5-3 hours. 16. Werkwijze volgens een der conclusies 13-15, waarbij de stap van het afzetten van titaniumoxide 2-100 keer wordt herhaald.The method of any one of claims 13-15, wherein the step of depositing titanium oxide is repeated 2-100 times. 17. Werkwijze volgens een van de conclusies 13-16, waarbij voorafgaand aan de stap van het afzetten van titaniumoxide het substraat gedurende 0,5-10 minuten ondergedompeld wordt in de cysteine protease omvattende oplossing, zoals gedurende 1,5-5 minuten, en/of waarbij het cysteïneprotease wordt gekozen uit fruitproteasen, zoals papaïne.The method of any one of claims 13-16, wherein prior to the step of depositing titanium oxide, the substrate is immersed in the cysteine protease-containing solution for 0.5-10 minutes, such as for 1.5-5 minutes, and / or wherein the cysteine protease is selected from fruit proteases, such as papain. 18. Werkwijze volgens een van de conclusies 13-17, waarbij het cysteïneprotease wordt gekozen uit MEROPS-classificatie superfamilies CA, zoals Cl, C2, C6, C10, C12, C16, C19, C28, C31, C32, C33, C39, C47, C51, C54, C58, C64, C65, C66,The method of any one of claims 13-17, wherein the cysteine protease is selected from MEROPS classification superfamilies CA, such as Cl, C2, C6, C10, C12, C16, C19, C28, C31, C32, C33, C39, C47 , C51, C54, C58, C64, C65, C66, C67, C70, C71, C76, C78, C83, C85, C86, C87, C93, C96, C98, C101, zoals Papaïne (Carica papaya), Actinidain (Actinidia deliciosa), bromelaïne (Ananas comosus), cathepsine K (levermos) en calpaïne (Homo sapiens), CD, zoals Cll, C13, C14, C25, C50, C80, C84, zoals Caspase-1 (Rattus norvegicus) en separase (Saccharomyces cerevisiae) , CE, zoals C5, C48, C55, C57, C63, C79, zoals Adenain (humaan adenovirus type 2), CF, zoals C15, zoals Pyroglutamyl-peptidase I (Bacillus amyloliquefaciens) ,C67, C70, C71, C76, C78, C83, C85, C86, C87, C93, C96, C98, C101, such as Papain (Carica papaya), Actinidain (Actinidia deliciosa), Bromelain (Pineapple comosus), Cathepsin K (liverwort) and calpain (Homo sapiens), CD, such as Cll, C13, C14, C25, C50, C80, C84, such as Caspase-1 (Rattus norvegicus) and separase (Saccharomyces cerevisiae), CE, such as C5, C48, C55, C57, C63, C79, such as Adenain (human adenovirus type 2), CF, such as C15, such as Pyroglutamyl peptidase I (Bacillus amyloliquefaciens), CL, zoals C60, C82, zoals Sortase A (Staphylococcus aureus),CL, such as C60, C82, such as Sortase A (Staphylococcus aureus), CM, zoals C18, zoals Hepatitis C-virus peptidase 2 (hepatitis C-virus), CN, zoals C9, zoals Sindbis-virustype nsP2-peptidase (sindbis-virus), CO, zoals 040, zoals Dipeptidyl-peptidase VI (Lysinibacillus sphaericus), CP, zoals C97, zoals DeSI-1 peptidase (Mus musculus), PA, zoals C3, C4, C24, C30, C37, 062, C74, C99, zoals TEV-protease (Tobacco ets virus), PB, zoals C44, 045, C59, C69, C89, 095, zoals Amidophosphoribosyltransferase precursor (Homo sapiens), PC, zoals C26, C56, zoals Gamma-glutamylhydrolase (Rattus norvegicus), PD, zoals C46, zoals Hedgehog-eiwit (Drosophila melanogaster), en PE, zoals PI, zoals DmpA-aminopeptidase (Ochrobactrum anthropi).CM, such as C18, such as Hepatitis C virus peptidase 2 (hepatitis C virus), CN, such as C9, such as Sindbis virus type nsP2 peptidase (sindbis virus), CO, such as 040, such as Dipeptidyl peptidase VI (Lysinibacillus sphaericus ), CP, such as C97, such as DeSI-1 peptidase (Mus musculus), PA, such as C3, C4, C24, C30, C37, 062, C74, C99, such as TEV protease (Tobacco etching virus), PB, such as C44 .045, C59, C69, C89, 095, such as Amidophosphoribosyltransferase precursor (Homo sapiens), PC, such as C26, C56, such as Gamma-glutamylhydrolase (Rattus norvegicus), PD, such as C46, such as Hedgehog protein (Drosophila melanogaster), and PE, such as PI, such as DmpA aminopeptidase (Ochrobactrum anthropi). 19. Werkwijze volgens een der conclusies 13-18, waarbij het substraat een optisch transparante geleidende laag omvat, zoals ITO, waarbij het enzym op de optisch transparante laag wordt geïmmobiliseerd, en titaniumoxide op de transparante geleidende laag wordt gemineraliseerd.The method of any one of claims 13-18, wherein the substrate comprises an optically transparent conductive layer, such as ITO, wherein the enzyme is immobilized on the optically transparent layer, and titanium oxide is mineralized on the transparent conductive layer. 20. Werkwijze volgens een van de conclusies 13-19, waarbij een lichtabsorberende laag op de mesoporeuze anataaslaag wordt afgezet, en waarbij bij voorkeur de lichtabsorberende laag ten minste gedeeltelijk in de anataaslaag wordt opgenomen .A method according to any one of claims 13-19, wherein a light absorbing layer is deposited on the mesoporous anatase layer, and preferably the light absorbing layer is at least partially incorporated in the anatase layer. 21. Werkwijze volgens een van de conclusies 13-20, waarbij ten minste één van een eerste elektrodelaag van 20-1000 nm, zoals ITO, een lichtabsorberende laag van 10-1000 nm, een gatentransportlaag van 10-300 nm, een 10 -500 nm mesoporeuze anataas elektronentransportlaag, en een 20-200 nm tweede elektrodelaag wordt verschaft.The method of any one of claims 13-20, wherein at least one of a first electrode layer of 20-1000 nm, such as ITO, a light-absorbing layer of 10-1000 nm, a hole transport layer of 10-300 nm, a 10-500 nm mesoporous anatase electron transport layer, and a 20-200 nm second electrode layer is provided. 22. Product verkregen door een werkwijze volgens één van de conclusies 13-21, waarbij het product is gekozen uit een zonnecel, een batterij, een aangroeiwerende laag, een beschermende bekleding, en een diëlektrische laag.The product obtained by a method according to any one of claims 13-21, wherein the product is selected from a solar cell, a battery, an anti-fouling layer, a protective coating, and a dielectric layer.
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