Patent Application
20240166943
The present invention refers to a process for the synthesis of metal halide-based nanoparticles endowed with optoelectronic activity and to the nanoparticles obtained through the process.
Metal halide perovskite nanocrystals have emerged as promising materials for optoelectronic applications including, to name just some, solar cells, light emission technologies, photodetectors and lasers. Nanocrystals are usually referred to in the field with the abbreviation NCs, that will be used in the rest of the description.
Metal halide perovskite NCs have general formula AMX3, where A is a monovalent cation selected between Rb+, Cs+, CH3NH3+, CH2(NH2)2+, M is a divalent cation, usually selected among Pb2+ and Sn2+, and X is selected among F−, CF−, Br− and I−. The properties of light emission or absorption of these materials can be modulated by varying the specific composition. For instance, a desired emission wavelength (from 400 nm to 700 nm or even beyond, in the near infrared region) can be achieved by adjusting the halide composition, either directly during their synthesis, or through a post-synthesis partial/complete halide exchange reaction, or even through the addition of dopants, during or post-synthesis. The interest in this field, and the related technological applications, have extended beyond the AMX3 composition and the perovskite crystal structure, to encompass metal halide NCs of other compositions and crystal structures as well. This broader class of materials is referred to in the description that follows as “optoelectronic metal halide NCs”, or with the abbreviation OMR NCs.
These materials can be conveniently prepared by known chemical synthesis approaches; the control of crystal growth and the obtainment of nanosized materials is achieved during the synthesis by the ratio between non-linear block copolymers, acting as templates for NCs growth, and the precursors of the NCs. Polymeric micelles have also been used in the past decades as templates to synthesize various types of inorganic NCs. This approach is highly desirable as it enables the synthesis of NCs with low polydispersity. The NCs, as delivered from the synthesis, are coated with a layer made of organic molecules. These molecules have a functional head group, by which they are anchored to the surface of the NCs, and one or more aliphatic chains (usually 6-18 nm long) which help to stabilize the NCs in non-polar or moderately polar organic solvents.
One problem encountered with these materials is that when OMH NCs of different compositions are deposited together in solid films or mixed together in a colloidal suspension, for example with the scope of combining together different emission colors and obtain white emission, the NCs undergo rapid halide ion exchange, such that at steady state each individual NC in the sample reaches the same average halide composition; this in turn leads to a film (or a colloidal suspension) emitting in a single color, dictated by the relative abundance of the various halide ions present in the sample. Such color instability limits the use of OMH NCs as multicolor emitters in displays. In addition to the color instability, OMH NCs have poor stability against moisture, polar solvents, and long-time exposure to high flux irradiation. All these agents cause a quick degradation of the optoelectronic properties of the NCs.
Various strategies have been designed to stabilize OMH NCs against these agents and preserve color stability. Such strategies include the encapsulation of NCs in matrixes made of metal oxides (e.g. SiO2, TiO2, Al2O3), inorganic salts (SrBr2), metal organic hybrids (e.g. metal organic frameworks) and polymers or polymeric micelles; polymers and polymeric micelles allow obtaining a stable surface coating of NCs. NCs coated with organic molecules and/or polymers will be referred to in the rest of the description as nanoparticles, or with the abbreviation NPs; similarly, the term “optoelectronic metal halide NPs” and the abbreviation OMH NPs will be used.
The coating of NCs with polymers has been described for instance in patent application US 2013/0030120 A1, which discloses a star-like polymeric unit produced derivatizing a β-cyclodextrin with several polymeric branches and the functionalizing of the branches with groups capable of binding on the NCs surface. This document describes numerous compositions and structures of polymers for NCs encapsulation, as well as numerous kinds of NPs with different compositions and uses, not limited to optoelectronic functionalities, and does not report any data allowing assessing a degree of stabilization achieved with the disclosed polymeric compounds.
Further studies have shown that polymers with hydrophobic characteristics, such as poly (methyl methacrylate), polyimide, poly (lauryl methacrylate), polystyrene (PS) and their derivatives are suitable choices to protect OMH NCs from polar solvents and they have been widely tested in this regard.
Similarly, various types of polymeric micelles (e.g. poly(styrene-block-4-vinyl pyridine) have been used as a template to encapsulate in situ individual OMH NCs. The resulting encapsulated NCs exhibited increased stability against polar solvents and photo-irradiation. The paper “Polar organic solvent-tolerant perovskite nanocrystals permanently ligated with polymer hairs via star-like molecular bottlebrush trilobe nanoreactors”, Y. Liu et al., Nano Lett. 2019, 19, pages 9019-9028, describes the capping of NCs with a “trilobe” (i.e., three-branched) polymer comprising a poly(2-hydroxyethyl methacrylate) (PHEMA) backbone onto which are grafted units of a block copolymer of poly(acrylic acid) and partially cross-linked polystyrene. This paper reports stability test of polymer coated CsPbBr3 NPs against polar solvents and shows that the NPs could withstand up to 20% volume of methanol. Furthermore, a photostability test under mild irradiation conditions (365 nm, 400 μW/cm2) shows that the polymer coated CsPbBr3 NPs nearly retain their PL after 35 h of exposure to the UV light. While these results represent an improvement over previously known systems, the synthesis of the trilobe copolymers described in this document requires many consecutive polymerizations along with multiple post-polymerization modification steps and is not suitable for an industrial scale production. Moreover, and most importantly, the assembly of trilobe polymer might not result in symmetric and well-shielded micelles; this, in turn, may create less shielded regions on the surface of the NCs that might enable contact between the solvent molecules and the NCs. The stability of the NCs of this paper against concentrations of polar solvents (e.g. methanol, ethanol, water) higher than 20% and against high flux irradiation is still poor.
Overall, the stability of the OMH NPs available to date under operating conditions that are typical of various fields of applications (high humidity, polar solvents, high flux irradiation, high temperature, etc.) are not yet satisfactory.
It is an object of the present invention to provide a process for the production of OMH NPs of enhanced resistance against moisture, polar solvents and long-time exposure to high flux irradiation, required for the widespread industrial application of these materials.
This object is obtained in the present invention that, in a first aspect thereof refers to a process for the production of optoelectronic metal halide nanoparticles, formed by polymer-coated metal halide nanocrystals, comprising the following steps:
In its second aspect, the invention refers to the stable optoelectronic metal halide nanoparticles obtained according to the process described above.
The present invention is characterized, and distinguished from the known OMH NPs synthesis methods, for the presence of the additive molecules described above during the synthesis of the NPs. The inventors have observed that the modification of the standard encapsulation methods with the addition of these additive molecules leads to a significant increase of stability of the resulting OMH NPs, even with the use of protective block copolymers of relatively simple structure.
The OMH NPs of the invention are composed of a core made of the metallic halide, that is, the NC, the surface of which is covered with an organic coating formed by the additive molecule(s) and the block copolymers.
The OMH NCs of the invention may have a wide variability of composition, comprising the standard composition AMX3, and compositions and structures derived therefrom. In the description that follows, MA+ stands for methylammonium, CH3NH3+, and FA+ stands for formamidinium, CH(NH2)2+.
The simplest composition of OMH NCs according to the invention is the classical perovskite composition AMX3, where A is a monovalent cation selected among Cs+, MA+, FA+, with possible dopants selected among monovalent cations such as K+ and Rb+ and divalent cations such as Mn2+, Cd2+, Zn2+, Sn2+, Ge2+; M is a divalent cation selected among Pb2+ and Sn2+; X is selected among F−, Cr−, Br− and I− or mixtures thereof, so that mixed halide compositions are possible, such as AM(Cl,Br)3 or AM(Br,I)3; the preferred halide ions for the objects of the present invention are Cl−, Br− and I−.
Other possible NCs compositions are:
The process of the invention includes as the first step, a), the preparation of a precursor solution containing the desired halide ion(s) and cation(s), a block copolymer containing one or more polar blocks and one or more non-polar or moderately polar blocks, and one or more additive molecules bearing two or more functional groups, in a solvent selected among dimethyl sulfoxide, N,N-dimethyl acetamide, dimethyl formamide, N-methyl formamide and mixtures of these solvents.
As said above, the OMR NPs may include more than one halogen atom; the salts of the different cations used for a synthesis need not thus to include the same halogen and, just to make an example, the process of the invention could begin with the preparation of a solution containing CsCl and PbBr2 as the halide salts.
The block copolymer has amphiphilic properties, due to the presence in the polymer chain of hydrophilic and hydrophobic moieties. The hydrophilic moieties of the block copolymer are preferably selected between poly acrylic acid (PAA) and poly methacrylic acid (PMA); the hydrophobic moieties are preferably selected among poly(alkyl methacrylate)s with length of the alkyl chain(s) ranging from 1 to 12 carbon atoms, polyesters (particularly polylactide, polyglycolide and polycaprolactone) and, more preferably, polystyrene (PS). A typical block copolymer suitable for the objects of the invention has the general formula shown below:
wherein m can range between 14 and 14000 and n can range between 10 and 5200, and Y typically is a nitrile functional group, or a radical bearing a nitrile functional group.
The synthesis of these block copolymers is well known to those skilled in the art. These copolymers are also commercially available.
The use of an additive molecule in the synthesis of the OMH NCs is the key feature of the present invention; these additive molecules likely act improving the compatibility between the surface of the NCs and the block copolymer. Said additive molecules are characterized by containing two or more functional groups, in particular carboxylic, phosphonic, amino and combinations of these, and one or more aliphatic, cycloaliphatic or aromatic chains, preferably with a chain length comprised between 4 and 12 carbon atoms. Examples of additive molecules that have proven suitable for the aims of the invention are succinic acid (two carboxylic groups, C4 aliphatic chain), γ-aminobutyric acid (one carboxylic group and one primary amino group, C4 aliphatic chain), 5-aminovaleric acid (one carboxylic group and one primary amino group, C5 aliphatic chain), 3-aminopropylphosphonic acid (one phosphonic group and one primary amino group, C3 aliphatic chain), L-valine (one carboxylic group and one primary amino group, branched-05 aliphatic chain), L-proline (one secondary amino group in a 5-membered ring and one carboxylic group, C5 aliphatic chain), L-glutamic acid (one amino group and two carboxylic groups, CS aliphatic chain) and 2-aminoterephthalic acid (one amino group and two carboxylic groups, aromatic chain).
The amounts of the various components added in the precursor solution are calculated based on the amount of M, M′ or M″ cation, or on the sum of M′ and M″ cations when the desired NC composition is of the kind A2M′M″X6.
Known the amount of cations M, M′ and M″ in the precursor solution, the required amount of A cation(s) is easily calculated from the stoichiometry of the specific NC to be produced. The amount of block copolymer is such that the molar ratio between the monomers of the polar blocks and the M, M′ or M″ cation(s) is between 10 and 20. Finally, the amount of additive molecules is such that the molar ratio M, M′ or M″ cation(s) to said additive molecules is between 20 and 30.
The concentration of the M, M′ or M″ cation(s) in the precursor solution is conveniently chosen in the range from 10 to 100 mM/l (millimolar); the concentrations of the other components of the precursor solution are calculated as a consequence from the ratios to M, M′ or M″ cation(s) defined above.
The precursor solution can be prepared in various ways. It is possible to prepare separate stock solutions of the various components (halide salts of the useful cations, block copolymers, additive molecules) and then mixing them in suitable ratios to obtain the desired overall composition. Alternatively, it is possible to prepare the precursor solution adding all the components in the correct amounts to one of the solvents indicated above. Intermediate methods are also possible: for instance, it could be possible to prepare a solution containing the block copolymer and the additive molecules in the correct ratio as a stock solution, and to add the halide salts to this intermediate solution. Any other order of addition of components can be followed, as will be evident to the skilled person.
The preparation of the precursor solution, or of the intermediate stock solutions, takes place under agitation or stirring, to obtain a uniform composition of the same. Once prepared, this precursor solution is stable indefinitely; if it has been prepared long before its use, it is better re-agitated prior to its use in step b), to re-homogenize its components.
In step b) of the process of the invention, the precursor solution prepared in step a) is added dropwise to a solvent which is selective for the non-polar or moderately polar blocks of the block copolymer, selected among toluene, xylene, mesitylene, ethyl acetate, anisole and mixtures thereof. The addition of the precursor solution to said solvent takes place under ambient conditions (typically, a temperature between 20 and 25° C. and a pressure between 9.8·104 and 1.04·105 Pa) and under agitation. The reaction of formation of OMH NPs takes place nearly immediately and is indicated by the change of color of the formed suspension.
When the addition of the precursor solution to the solvent is concluded, the reaction is quenched in step c) by addition of an excess of a solvent selected among pentane, hexane, heptane, diethyl ether and their mixtures. By “an excess” it is meant a volume of quenching solvent of at least 1.5 times the volume of suspension prepared in step b).
Finally, in the last step of the process of the invention, d), the OMH NPs are recovered from the suspension. The preferred method is by centrifugation, but also alternative methods could be used, for instance it is possible to use in step c) a great excess of quenching solvent, causing an immediate precipitation of the OMH NPs, which thereafter can be collected by simply decanting the solvents. In case of centrifugation, after discarding the supernatant the precipitate is preferably redispersed in the solvent of step b) followed by another round of centrifugation and redispersion.
The OMH NPs suspension thus obtained can be used as such for characterization or for their intended uses. Additionally, the emission color of the NCs can be tuned towards red or blue by introducing appropriate halide precursors (CF, BC and ions) in such suspension (as explained in detail below).
In its second aspect, the invention refers to the OMH NPs obtained according to the process described above. Although difficult to observe directly, the inventors believe that these NPs comprise a layer of additive molecules in direct contact with the surface of the OMH NC, forming an intermediate layer between the core and the outer shell made of the block copolymer. An indirect evidence of the presence of the additive molecule(s) in the final product is provided by the enhanced stability of the OMH NPs of the invention compared to similar NPs of the prior art. In fact, the inventors have observed that mixing together dry powders or colloidal suspensions (in polar solvents), or yet preparing films of multiple samples of OMH NPs emitting at different wavelengths, results in a final emission spectrum that is the weighted sum of the emission spectra of the individual NC components, and importantly, the emission intensity remains stable for months of storage under air. This unique feature enables the preparation of multicolor emissive samples that retain their spectral features.
Another unique feature of the OMH NPs of the invention is the possibility to reversibly turn on/off the anion exchange reaction. When the OMH NCs are dispersed in a polar solvent, in which the hydrophobic component of the block copolymer is not soluble, the polymer shell is closed (“globule state”), anion exchange reactions are prevented, and the pristine emission color of the NCs is preserved. The opposite is observed in solvents or mixtures of solvents (toluene or toluene plus methanol) in which the hydrophobic component of the block copolymer is soluble: in these conditions, the copolymer shell is partially or completely open (“coil state”), anion exchange is allowed and the emission color of the NCs can be tuned across the entire visible spectrum by dosing the appropriate amount of halide precursors.
This is indeed confirmed by the excellent stability of the NCs against polar solvents (such as methanol, ethanol and water) and by the inhibition of anion exchange reactions, even at high temperatures (70° C.) in these solvents. In comparison, the polymer encapsulated perovskite NCs described in the paper of Liu et al. discussed above could not withstand more than 20% volume of the same polar solvents.
The invention will be further illustrated by the examples that follow.
Instruments and Methods
Structural characterization: Structural analysis was performed on a PANanalytical Empyrean X-ray diffractometer, equipped with a 1.8 kW CuKα ceramic X-ray tube, operating at 45 kV and 40 mA, and a PIXcel3D2×2 area detector. Colloidal dispersion of corresponding NCs was drop-cast on zero-diffraction silicon substrate. All the diffraction patterns reported in this work were collected at room temperature under ambient conditions using parallel beam geometry and symmetric reflection mode. Post-acquisition XR data analysis was carried out using the HighScore 4.1 software from PANalytical.
Morphological characterization: TEM images of the NC samples were acquired with a JEOL-1100 transmission electron microscope operating at an acceleration voltage of 100 kV. Samples were prepared by drop casting diluted solutions of NCs onto carbon film-coated 200 mesh copper grids.
Spectroscopic measurements. Optical absorption spectra were recorded using a Varian Cary 300 UV-VIS absorption spectrophotometer. The PL spectra were measured on a Varian Cary Eclipse spectrophotometer using an excitation wavelength (λex) of 350 nm for all the samples. Samples were prepared by diluting NC solutions in toluene, in quartz cuvettes with a path length of 1 cm. Absolute Photoluminescence quantum yields of NC samples were measured using an Edinburgh FLS900 fluorescence spectrometer equipped with a Xenon lamp, a monochromator for steady-state PL excitation, and a time-correlated single photon counting unit coupled with a pulsed laser diode (λex=405 nm, pulse width=50 ps) for time-resolved PL. The PLQY was measured using a calibrated integrating sphere (λex=350 nm for all samples). For the PLQY measurements, all the NC dispersions were diluted to an optical density of 0.1±0.02 at the corresponding excitation wavelength in order to minimize the amount of fluorophore being reabsorbed.
Laser Irradiation Stability Test:
Stability tests were carried out using a continuous wave laser diode for excitation (λex=445 nm, Oxxius LBX-445-650-HPE-PP, max power 715 mW) coupled with an iris to reduce the circular excitation spot to a diameter of 1 mm (spot size was determined with Thorlabs BP209-VIS/M beam profiler). The excitation power was measured after the iris using a Thorlabs PM100D Digital Optical Power meter interfaced with a Thorlabs S121C photodiode. Samples for the stability test were prepared by blending the NCs dispersion with polystyrene (20-30 mg/mL) in toluene. Thereafter, the solution was precipitated by adding 12 mL of hexane followed by overnight drying in vacuum oven at 40° C. Then, the powder was grounded by using mortar pestle and placed inside a glass cell. The emission was monitored via a collimator/optical fiber/filter holder/optical fiber assembly coupled with an Ocean Optics HR4000 spectrometer. The collection optics was placed at 45° with the respect to the excitation beam and a long pass filter (λcut-off=450 nm, Thorlabs FEL0450) was placed in the fiber coupled filter holder. The emission was collected every 60 seconds using the Ocean View software.
This example refers to the synthesis of copolymer encapsulated APbBr3 NCs, where A may be Cs+, the monovalent formamidine ion (FA+), or a mixture of the two.
As the block copolymer, a polystyrene-block-poly(acrylic acid) copolymer sold by Sigma-Aldrich with catalog number 746991, referred to in the following as PAA-b-PS, has been used; in this product, the PAA blocks have average molar mass of 5000 g/mol and the PS blocks have average molar mass of 28000 g/mol.
Solutions of metal bromide salts (CsBr, FABr and PbBr2), of 5-aminovaleric acid (AVAc) as an additive molecule and of PAA-b-PS block copolymer were prepared separately by dissolving the compounds in DMF; the solutions had concentration 10 mM each in case of the halide salts, 17 mM in case of AVAc and 110 mg/mL in case of PAA-b-PS.
Then, a precursor solution obtained by mixing 100 μL of the ABr solutions, 100 μL of the PbBr2 solution, 4 μL of the AVAc solution and 75 μL of the PAA-b-PS solution was injected dropwise into a 20 mL vial containing toluene (8 mL) under vigorous stirring at room temperature in air. The preparation was carried out three times, the first time with CsBr only obtaining CsPbBr3 NPs, the second time with FABr only obtaining FAPbBr3 NPs and the third time with a ABr solution comprising CsBr and FABr in a 1:1 molar ratio obtaining Cs0.5FA0.5PbBr3 NPs. In all cases the color of the solution immediately turned green indicating the formation of perovskite NPs.
After about 20 seconds, the reaction was quenched by adding 12 ml of hexane and the NPs were collected by centrifugation. The supernatant was discarded, and the precipitate was re-dispersed in toluene, the system was centrifuged again, the supernatant eliminated, and the collected NPs redispersed in toluene.
The suspensions thus obtained are Sample 1 (CsPbBr3 NPs), Sample 2 (FAPbBr3 NPs) and Sample 3 (Cs0.5FA0.5PbBr3 NPs).
This example refers to morphological, structural and optical characterizations of Samples 1-3 obtained in Example 1.
Specimens of the three samples were drop-cast on carbon coated copper grids and zero diffraction silicon wafer for morphological and structural characterization, respectively.
Morphological characterization of the dried samples by using transmission electron microscopy (TEM) has revealed the presence of nearly cubic shaped NCs in all three samples. The obtained micrographs are reproduced in
UV-Vis optical absorption and photoluminescence (PL) spectra recorded in toluene dispersions are reported in
The structural characterization by X-ray diffraction (XRD) reported in
This example refers to test to assess the stability of the OMH NPs of the invention against polar solvents.
Specimens of Sample 1 were added dropwise to methanol at the volume ratio of 1 to 10 (toluene to methanol) at 25° C. in air. After about 30 s, 12 ml hexane was added and the NPs suspension was centrifuged. The supernatant was discarded, and the precipitate was re-dispersed in the selected test polar solvent (methanol, ethanol or water). Finally, the NPs suspensions in polar solvents were store at 25° C. in air to examine the PL stability over ageing. The PL spectra recorded over time for the NPs of Sample 1 dispersed in various solvents are reported in
This example demonstrates the possibility of controlling the composition, and as a consequence the optoelectronic properties, of the OMR NPs of the invention.
A specimen of Sample 1, emitting in the green range (515-525 nm), was treated with different halide compounds in different solvents. In detail, two separate suspensions, containing Sample 1, of equal volumes and concentrations, were prepared by dispersing the NPs in methanol. Precursor solutions of halide ions (Cl− and I−) were also prepared. The solution of CF ions was then added to one sample suspension and the solution of I− ions was added to the other sample suspension, in both cases in a large excess, in an attempt to promote anion exchange. In both cases, however, even after several days the PL spectral position and the PL linewidth of the starting bromine-based NPs were retained as shown in
The test was repeated, this time however adding Cl− and I− to specimens of Sample 1 in toluene; in this solvent, the polymeric shell surrounding the NPs core is in the coil state, which allows anion exchange. For tuning the emission color from green to blue, a specimen of Sample 1 in toluene was mixed with a didecyldimethylammonium chloride solution (pre-dissolved in toluene, 25 mM) under continuous stirring. For obtaining red emitting NPs, oleylammonium iodide (prepared separately by reacting molecular iodine with oleylamine; I− concentration 0.4 M) was added to a specimen of Sample 1. Once the desired emission color was obtained, the polymer shell was closed (globule state) by exposing the NPs suspensions to polar solvents, the NPs were precipitated by centrifugation and the resulting precipitates were dried in a vacuum oven at 40° C., yielding a dry powder. The powders were finally grounded in a ceramic crucible. The PL spectra of the NPs obtained are reported in
This example demonstrates the stability of multicolor powders of the invention.
Red and blue emitting specimens were prepared by performing anion exchange reaction on a specimen of Sample 1. Then, the polymer shell for all three materials was closed by adding a mixture of methanol and hexane in 1:3 volume ratio. The resulting mixtures were centrifuged at 6000 rpm for 5 minutes. The supernatant of each suspension was discarded, and the precipitate was dried in vacuum oven at 40° C. The obtained powders were individually ground with a mortar and pestle in a ceramic crucible and then mixed in an appropriate ratio to get a multicolor emitting product. Remarkably, the spectral features of the multicolor powder remained unchanged over months of storage under ambient conditions, as demonstrated by the stable positions of peaks in PL spectra reproduced in
This example is directed to demonstrating the fluorescence stability of OMR NPs of the invention against laser irradiation.
Specimens of Samples 1 to 3 were dried and subjected to a high flux photon irradiation test; the powders were placed between two glass slides and irradiated continuously under a flux of 3.2 W/cm2 for 60 minutes at 445 nm. Notably, these high flux irradiation conditions are nearly ten times harsher than the required industrial standards for the displays (100-400 mW/cm2). For comparison, a CsPbBr3 NPs sample prepared via a standard colloidal approach (reference) was blended with polystyrene and tested in parallel under identical conditions.
The decrease of photoluminescence (PL) spectra for the materials of the invention is shown in
For assessing the role of the bi-functional additive molecules of the invention, the synthesis of Example 2 was repeated with several mono-functional ligands. CsPbBr3 NP samples were prepared coated with Cs-oleate, mixed ligands (Cs-oleate/oleylammonium bromide) and quaternary ammonium bromide (QAB capped). These materials were tested under the harsh conditions of Example 6. All the samples lost their PL instantly upon addition of methanol.
The test of Example 7 was repeated on a specimen of Sample 3 (core of composition Cs0.5FA0.5PbBr3). For comparison, the synthesis of Example 2 was repeated in identical conditions, using however the monovalent ligand phenethylammonium bromide (PEABr, functional group ammonium) in place of AVAc.
The stability of the NPs under high flux irradiation is reported in
Similar trends in stability were observed when the samples were dispersed in methanol:
Several NP compositions according to the invention were prepared following the procedure of Example 1, using FABr as the bromide salt, and various additive molecules different from AVAc. The test of Example 7 was repeated on the NPs thus prepared. The results of the tests are reproduced in
| Number | Date | Country | Kind |
|---|---|---|---|
| 102021000005213 | Mar 2021 | IT | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/055428 | 3/3/2022 | WO |
