CN112103393B - Plasmon structure and perovskite photoelectric device - Google Patents
Plasmon structure and perovskite photoelectric device Download PDFInfo
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Abstract
The invention provides a plasmon structure and a perovskite photoelectric device, and relates to the technical field of photoelectricity. The plasmonic structure includes: the nano metal particle comprises a nano metal particle core, an outer shell layer wrapping the nano metal particle core and passivation modification molecules positioned outside the outer shell layer; passivation modifying molecules include: the shell layer passivation end, the passivation molecular carbon chain and the perovskite passivation end are connected to the shell layer; the passivated molecular carbon chain is connected with the outer shell layer passivated end and the perovskite passivated end; the envelope layer passivation end includes: at least one of an amine group, a phosphine group, a carboxyl group, a sulfo group, and a mercapto group; the perovskite passivation end includes: at least one functional group containing a lone pair of electrons. The amine group, the phosphine group, the carboxyl group, the sulfo group and the sulfhydryl group are combined with dangling bonds on the surface of the shell layer, so that defects of the shell layer are passivated, a passivated molecular carbon chain stabilizes 'core-shell plasmons', and lone pair electrons are combined with halogen vacancies, halogen dangling bonds and the like at the grain boundary and the interface of the perovskite, so that the efficiency of the perovskite photoelectric device is improved.
Description
Technical Field
The invention relates to the technical field of photoelectricity, in particular to a plasmon structure and a perovskite photoelectric device.
Background
The plasmon structure can promote the absorption effect on photons, and can promote the photoelectric conversion efficiency when applied to photoelectric products, so that the plasmon structure has wide application prospect.
However, the plasmonic structure in the prior art is easy to introduce more defects into the perovskite photoelectric device, and conversely, the efficiency of the perovskite photoelectric device is reduced.
Disclosure of Invention
The invention provides a plasmonic structure and a perovskite photoelectric device, and aims to solve the problem that the plasmonic structure introduces more defects in the perovskite photoelectric device.
According to a first aspect of the present invention, there is provided a plasmonic structure comprising: a nano metal particle inner core, an outer shell layer wrapping the nano metal particle inner core, and passivation modification molecules positioned outside the outer shell layer;
the material of the outer shell layer is selected from dielectric materials and/or wide bandgap semiconductor materials;
the passivation modifying molecule comprises: the shell layer passivation end, the passivation molecular carbon chain and the perovskite passivation end are connected to the shell layer; the passivation molecular carbon chain is connected with the passivation end of the shell layer and the perovskite passivation end; the shell layer passivation end comprises: at least one passivating functional group, the passivating functional group comprising: at least one of an amine group, a phosphine group, a carboxyl group, a sulfo group, and a mercapto group; the perovskite passivation end comprises: at least one functional group containing a lone pair of electrons.
The nano metal particle inner core in the plasmon structure generates surface plasmon resonance under illumination, so that the effects of trapping light and enhancing photon absorption are realized. The material of the outer shell layer is selected from dielectric materials and/or wide-bandgap semiconductor materials, and the outer shell layer wrapping the nano metal particle inner core can avoid the reaction of metal and perovskite and the electric leakage caused by the metal. The passivation functional group of at least one of amino, phosphino, carboxyl, sulfo and sulfhydryl in the passivation end of the outer shell layer is combined with dangling bonds on the surface of the outer shell layer to passivate the defects on the surface of the outer shell layer, and the aggregation growth of plasmons of a core-shell structure is avoided, so that the stability of the plasmons is enhanced. The passivated molecular carbon chain can fully stabilize the core-shell plasmon polariton, so that the polariton cannot be agglomerated, and a good plasmon resonance effect is maintained. The lone pair electrons in the passivation end of the perovskite are combined with halogen vacancies, halogen dangling bonds and the like at the crystal boundary and the interface of the perovskite, so that the defects of ion vacancies, dangling bonds and the like at the crystal boundary and the interface of the perovskite are passivated, the composite center of the photo-generated carriers is filled, electrons and holes generated by illumination are not captured by the defects when being transmitted to the vicinity of the defects, and the carrier transmission is facilitated. In summary, the plasmon structure in the embodiment of the invention passivates defects in the perovskite photoelectric device and improves the efficiency of the perovskite photoelectric device on the basis of realizing light trapping and photon absorption enhancement.
According to a second aspect of the present invention there is provided a perovskite optoelectronic device comprising a layer of perovskite material, the plasmonic structure of any one of the preceding claims being located at the interface of the layer of perovskite material with the other functional layer, at the surface of the layer of perovskite material or within the layer of perovskite material.
The perovskite photoelectric device has the same or similar beneficial effects as the plasmon structure.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments of the present invention will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a schematic structural diagram of a plasmonic structure in an embodiment of the invention;
fig. 2 shows a schematic structure of a solar cell according to an embodiment of the present invention.
Description of the drawings:
the structure comprises a 1-plasmon structure, a 11-nano metal particle inner core, a 12-outer shell layer, a 13-passivation modification molecule, a 131-outer shell layer passivation end, a 132-passivation molecular carbon chain, a 133-perovskite passivation end, a 2-first carrier transmission layer, a 3-perovskite layer, a 31-perovskite crystal grain, a 32-crystal boundary, a 4-second carrier transmission layer, a 5-back electrode layer and a 6-front electrode layer.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The inventor finds that the plasmon structure in the prior art is easy to introduce more defects into the perovskite photoelectric device, but the efficiency of the perovskite photoelectric device is reduced due to the fact that: in the prior art, the plasmon structure is incompatible with the structure of the perovskite material no matter the plasmon structure is a metal nano particle or the nano metal particle is wrapped to form a core-shell structure, and the plasmon structure is concentrated at the positions of a crystal boundary and an interface to become the defect of the perovskite absorption layer. However, in perovskite photovoltaic devices, defects at grain boundaries and interfaces lead to a large extent to a loss of efficiency of the perovskite photovoltaic device.
Fig. 1 shows a schematic structural diagram of a plasmonic structure in an embodiment of the invention. Referring to fig. 1, plasmonic structure 1 includes: the nano-metal particle comprises a nano-metal particle inner core 11, an outer shell layer 12 wrapping the nano-metal particle inner core 11 and passivation modification molecules 13 positioned outside the outer shell layer 12. The nano metal particle core 11 generates surface plasmon resonance under illumination, so that light trapping and photon absorption enhancement are realized. The material of the outer shell layer 12 is selected from dielectric materials and/or wide bandgap semiconductor materials, and the outer shell layer 12 wrapping the inner core 11 of the nano-metal particles can avoid the reaction of metal with perovskite and the electric leakage caused by metal.
Passivation modifying molecule 13 includes: a shell layer passivated end 131 attached to the shell layer 12, a passivated molecular carbon chain 132, and a perovskite passivated end 133. The passivated molecular carbon chain 132 connects the outer shell passivated end 131 and the perovskite passivated end 133.
The outer shell layer passivation end 131 includes: at least one passivating functional group. The number of passivation functional groups included in the outer shell layer passivation end 131 is not particularly limited. For example, the outer shell layer blunt end 131 includes 1 blunt functional group or 2 blunt functional groups. The passivating functional group includes: at least one of amino, phosphino, carboxyl, sulfo and sulfhydryl, the passivation functional group can be combined with broken bonds or dangling bonds on the outer surface of the outer shell layer 12 to passivate the defect on the surface of the outer shell layer 12, and avoid the agglomeration growth of plasmons of the core-shell structure and enhance the stability of the plasmons.
The passivated molecular carbon chain 132 can play a role in sufficiently stabilizing the core-shell plasmons so that the plasmons are not agglomerated and a good plasmon resonance effect is maintained.
Perovskite passivation end 133 includes: at least one functional group containing a lone pair of electrons. The number of lone pair electrons included in the perovskite passivation end 133 is not particularly limited. For example, perovskite passivation end 133 includes 1 lone pair or 2 lone pairs. The lone pair electrons in the perovskite passivation end 133 are combined with halogen vacancies (such as defects caused by the deletion of Cl, br and I) or halogen dangling bonds (such as chemical bonds without bonds formed by Cl, br and I) at the crystal boundary and interface of the perovskite, so that the defects of ion vacancies, dangling bonds and the like at the crystal boundary and interface of the perovskite are passivated, the "recombination centers" of the photo-generated carriers are filled, and electrons and holes generated by illumination are not captured by the defects when transmitted to the vicinity of the defects, thereby being beneficial to the carrier transmission.
Optionally, perovskite passivated end 133 is an amine group and/or a guanidine group; the nitrogen atom in the amine group and the guanidine group has a lone pair of electrons, and the lone pair of electrons in the above group is easily bonded to a halogen vacancy, a halogen dangling bond, or the like at the grain boundary and interface of the perovskite.
Optionally, the passivation molecular carbon chain 132 has 4-20 carbon atoms, and the length of the passivation molecular carbon chain 132 is suitable, so that the passivation molecular carbon chain 132 is not too long, and the resistances of the perovskite layer, the perovskite layer/electron transport layer interface and the perovskite layer/hole transport layer interface are smaller, thereby being beneficial to carrier transport in perovskite products. Meanwhile, the passivated molecular carbon chain 132 is not too short, so that the effect of 'core-shell plasmons' can be sufficiently stabilized, the plasmons cannot be agglomerated, and a good plasmon resonance effect is maintained. Preferred passivated molecular carbon chains 132 have 6-15 carbon atoms.
Optionally, 1-4 carbon atoms in the passivation molecular carbon chain 132 are replaced by oxygen atoms, specifically, the lone pair electrons in the perovskite passivation end 133 are easily combined with MA (methamidamide) and FA (formamidine) plasmas in the perovskite to form hydrogen bonds, so that the lone pair electrons of defects such as ion vacancies and dangling bonds at the crystal boundary and interface of the passivation perovskite in the perovskite passivation end 133 are reduced, 1-4 carbon atoms in the passivation molecular carbon chain 132 are replaced by oxygen atoms, and the replaced passivation molecular carbon chain 132 has the capability of weakening the combination of the lone pair electrons in the perovskite passivation end 133 with MA and FA plasmas in the perovskite to form hydrogen bonds, so that the lone pair electrons of defects such as ion vacancies and dangling bonds at the crystal boundary and interface of the passivation perovskite are increased, and the passivation effect is enhanced.
Optionally, 1-2 benzene rings are connected to carbon atoms in the passivated molecular carbon chain 132, and pi electrons on the benzene rings can improve the conductivity of the modified molecule. The above number of benzene rings not only makes the steric hindrance smaller when the passivation modification molecule 13 is connected to the surface of the core-shell plasmon, but also facilitates the stabilization of the passivation modification molecule on the plasmon. If the number of the connected benzene rings is more than 2, the steric hindrance is larger when the passivation modification molecule 13 is connected to the surface of the core-shell plasmon, and the stabilization of the plasmon by the passivation modification molecule is not facilitated.
Optionally, the material of the nano metal particles 11 is at least one selected from gold, silver, copper, aluminum, nickel, tin, indium and gallium, and the nano metal particles 11 of the material have excellent surface plasmon resonance performance and strong light trapping and photon absorption enhancing effects.
Optionally, the shape of the nano metal particles 11 is one of a sphere, a hemisphere, a spheroid, a cylinder, a cone, a cube and a cuboid, and the nano metal particles 11 with the shape have excellent surface plasmon resonance performance and strong light trapping and photon absorption enhancing effects.
Optionally, the size of the nano metal particles 11 is 1-50nm, and the nano metal particles 11 with the size have excellent surface plasmon resonance performance and strong light trapping and photon absorption enhancement effects. More preferably, the size of the nano-metal particles 11 is 1-20nm.
Optionally, the material of the shell layer 12 is selected from a dielectric material and/or a wide bandgap semiconductor material, where the dielectric material has a dielectric constant of 1.2-200, and the wide bandgap semiconductor material has a bandgap width greater than or equal to 2.3eV, and the shell layer 12 of the above material can sufficiently avoid the reaction between metal and perovskite and the electric leakage caused by the metal.
Alternatively, the dielectric material may be at least one selected from titanium oxide, silicon oxide, aluminum oxide, silicon nitride, tantalum oxide, and aluminum nitride. The wide bandgap semiconductor material may be at least one selected from silicon carbide, gallium nitride, gallium oxide, zinc oxide. The shell layer 12 of the above material can further avoid the reaction of metal with perovskite and the leakage of electricity caused by metal.
The thickness of the shell layer 12 is 1-20nm, the shell layer 12 with the thickness can sufficiently avoid the reaction of metal and perovskite and electric leakage caused by the metal, and the space occupied by the shell layer 12 is small. Preferably, the thickness of the outer shell layer 12 may be 1-5nm.
The embodiment of the invention also provides a production method of the plasmon structure, which comprises the following steps:
step S1, providing a plasmonic dispersion.
The plasmonic dispersion is used to prepare the nano-metal particle core 11 and the outer shell layer 12 surrounding the nano-metal particle core 11. In the step S1, a nanoparticle dispersion liquid may be prepared, and then the nanoparticle dispersion liquid may be further processed.
For example, if the inner core 11 of the nano-metal particles and the outer shell 12 surrounding the inner core of the nano-metal particles form Au@TiO 2 Wherein Au is the material of the nano metal particle core 11, and the material of the shell layer 12 is TiO 2 . The preparation method of the corresponding plasmon dispersion liquid comprises the following steps: 2ml of HAuCl at 50mM concentration 4 The (tetrachloroauric acid) solution was added to 98ml of deionized water, heated to boiling in an oil bath at 135 ℃ with stirring, and 10ml of 35mM sodium citrate solution was added rapidly. After heating and stirring for 30 minutes, naturally cooling to room temperature. Centrifuging the solution, and removing supernatant to obtain Au nano-particles. After the above-mentioned Au nanoparticles can be washed three times with ethanol "redispersion-centrifugation", the Au nanoparticles are dispersed in isopropanol to obtain Au nanoparticle dispersion liquid of about 15 to 25 nm. The Au nanoparticle dispersion was further processed: 18ml of 12wt% ammonia water was added to the Au nanoparticle dispersion, and the mixture was stirred for 30 minutes and then stirred at a high speedAfter 30. Mu.l of titanium tetraisopropoxide was added dropwise, stirring was continued for 24 hours. Centrifuging the solution, and removing supernatant to obtain Au@TiO 2 A core-shell structure. Then the mixture is washed three times by ethanol redispersion and centrifugation, and then dispersed in isopropanol to obtain Au@TiO 2 Isopropanol dispersion of (a). Au@TiO 2 The isopropanol dispersion liquid is the plasmon dispersion liquid. The method can coat TiO of 2-10nm on the Au nano-particle outer layer 2 A shell layer.
And S2, adding passivation modification molecules into the plasmon dispersion liquid to obtain mixed liquid.
As for the above example, the passivation modification molecule is added to Au@TiO 2 In the isopropanol dispersion of (2) to obtain a mixed liquid.
And step S3, stirring the mixed liquid at the temperature of 20-50 ℃ to obtain the plasmonic structure solution.
The temperature of 20-50 ℃ is usually room temperature, namely, the mixed liquid is stirred at room temperature, so as to obtain the plasmonic structure solution. For example, for the above example, the passivation modification molecule described above is added to Au@TiO 2 In the isopropanol dispersion liquid of (2), a mixed liquid is obtained, and the mixed liquid is stirred for 24 hours at room temperature, so that the passivation modification molecules and plasmons are fully combined, and HSCH is obtained 2 (CH 2 ) 4 CH 2 NH 2 (6-amino-n-hexanethiol) modified Au@TiO 2 Core-shell plasmonic structure solution, which is marked as' P-Au@TiO 2 "(P stands for passion, passivation).
And S4, performing heat treatment on the plasmonic structure solution to obtain the plasmonic structure.
The heat treatment may be performed together after the plasmonic structure solution and the perovskite layer solution are mixed, or may be performed separately. In the embodiment of the present invention, this is not particularly limited.
HSCH 2 (CH 2 ) 4 CH 2 NH 2 (6-amino-n-hexanethiol) modifiedAu@TiO 2 HS-functional groups of the core-shell plasmon structure can be combined with Au@TiO 2 The surface defect and dangling bond are combined, so that the molecule can serve as a stable plasmon to prevent agglomeration while the surface defect is passivated. passivating-NH in modified molecules 2 The lone pair of electrons on the N atom in the functional group can passivate defects in the perovskite.
The production method of the plasmonic structure and the content of the plasmonic structure can be mutually referred, and the same or similar beneficial effects can be achieved.
The perovskite photoelectric device comprises a perovskite material layer, wherein the plasmon structure of any one of the above is positioned at the interface of the perovskite material layer and other functional layers, at the surface of the perovskite material layer or in the perovskite material layer, the content of the perovskite photoelectric device and the content of the plasmon structure can be referred to each other, and the same or similar beneficial effects can be achieved.
The interface between the perovskite material layer and the other functional layers is specifically: interfaces between the perovskite material layer and other functional layers. At the surface of the perovskite material layer may be a light facing surface or a backlight surface of the perovskite material layer, as in a perovskite optoelectronic device, if the perovskite material layer is the uppermost layer, the light facing surface of the perovskite material layer may have a plasmonic structure as described in any of the foregoing. Or, if part of the surface of the perovskite is exposed at the uppermost layer in the perovskite photovoltaic device, the surface of the part of the perovskite exposed at the light-facing surface may have a plasmonic structure as described in any one of the foregoing. The perovskite material layer may be any location within the perovskite material layer that has a defect.
The embodiment of the invention also provides application of any plasmon structure in perovskite light-emitting diodes and perovskite photodetectors, which can refer to relevant records in the embodiment of the plasmon light-trapping structure and can achieve the same or similar beneficial effects, and in order to avoid repetition, the description is omitted here.
Fig. 2 shows a schematic structure of a solar cell according to an embodiment of the present invention. Referring to fig. 2, the solar cell includes a first carrier transport layer 2, a perovskite layer 3, and a second carrier transport layer 4, which are stacked in this order. The first carrier transport layer 2 is of opposite type to the second carrier transport layer 4. One of the first carrier transport layer 2 and the second carrier transport layer 4 is an electron transport layer, and the other is a hole transport layer. If the first carrier transport layer 2 is a hole transport layer, the second carrier transport layer 4 is an electron transport layer. The electron transport layer is used for transporting electrons, and the hole transport layer is used for transporting holes. In fig. 2, 6 is a front electrode layer, and 5 is a back electrode layer. The back electrode layer 5 may be a transparent conductive substrate, which refers to a rigid substrate or a flexible substrate plated with a transparent conductive film. The rigid substrate is predominantly glass. The flexible substrate is mainly PET (polyethylene terephthalate) or PEN (polyethylene naphthalate). The transparent conductive film plated on the substrate mainly includes ITO (Indium Tin Oxide), FTO (Fluorine Tin Oxide, fluorine doped Tin Oxide), AZO (Aluminum Zinc Oxide, aluminum doped zinc Oxide). The front electrode layer 6 may be made of a transparent conductive material ITO, FTO, AZO, a metal material such as gold, silver, or aluminum, or a carbon material.
Perovskite layer 3 includes perovskite grains 31 and grain boundaries 32 between perovskite grains 31, and plasmonic structure 1 as described in any of the foregoing is located at least one of the first interface, the second interface, and grain boundaries 32. The first interface is the interface between the first carrier transport layer 2 and the perovskite layer 3. The second interface is the interface between the second carrier transport layer 4 and the perovskite layer 3. The plasmon structure 1 is not particularly limited, and may be located at one or more of the three. In the solar cell shown in fig. 2, plasmonic structure 1 is located in both the first interface, the second interface, and the grain boundary 32.
Plasmonic structure 1 located at the first interface passivates defects at the first interface while serving as a light trapping function. Plasmonic structure 1 located at the second interface passivates defects at the second interface while serving as a light trapping function. Plasmonic structure 1 located at grain boundary 32 passivates defects at grain boundary 32 while serving as a light trapping function.
The embodiment of the invention also provides a production method of the solar cell, which is used for producing the solar cell. The method mainly comprises a one-step method, a two-step method, front passivation and rear passivation.
The following describes a one-step process: the perovskite precursor solution contains all the raw materials of the perovskite material. The perovskite precursor solution is mainly MAPbI 3 、FAPbI 3 、CsPbI 3 The perovskite precursor is dissolved in a polar solvent such as DMF (dimethyl formamide, N, N-Dimethylformamide), DMSO (Dimethyl sulfoxide ), NMP (N-Methyl-2-pyrrosidone, N-methylpyrrolidone). The perovskite precursor solution is coated on the back electrode layer at one time, and the perovskite film is obtained through heat treatment. In the one-time coating process, an anti-solvent for perovskite is usually added to accelerate the evaporation of the solvent in the perovskite wet film and the crystallization of perovskite. The antisolvent is mainly a solvent that accelerates the crystallization of the perovskite thin film, specifically a weakly polar or nonpolar solvent. Typical antisolvents are chlorobenzene, toluene, ethyl acetate, diethyl ether, and the like. In one-step preparation of perovskite, plasmonic structure solutions may: a-is added in advance in the perovskite precursor solution, or b-is added in the antisolvent.
In the one-step process, the plasmonic structure is mainly in the grain boundaries of the perovskite layer. The plasmon structure can enhance the light absorption of the perovskite battery, has a light trapping effect, and can passivate defects at the grain boundary of the perovskite layer.
The two-step process is described as follows: the two-step process refers to the dissolution of the perovskite starting material in different solvents, respectively, to form two different perovskite precursor solutions. When preparing the perovskite layer, firstly, coating a first perovskite precursor solution on the back electrode layer, and drying; then a second perovskite precursor solution is applied, and when the second perovskite precursor solution is applied, the second perovskite precursor solutionChemical reaction with the first perovskite precursor solution that has been applied, followed by heat treatment, results in a perovskite layer. The first perovskite precursor solution being essentially the first material for the perovskite, e.g. PbI 2 ，PbBr 2 And a solution of a lead halide. The second perovskite precursor solution is primarily a solution of a monovalent cation halide such as CsI, FAI, MAI of the second starting material for the perovskite.
In the two-step process for preparing perovskite, the plasmonic structure solution may: a-in the first perovskite precursor solution, or b-in the second perovskite precursor solution. In the two-step process, the plasmonic structure is mainly in the grain boundaries of the perovskite layer.
The one-step method and the two-step method specifically prepare the plasmonic structure while adding the plasmonic structure solution into the perovskite precursor solution to prepare the perovskite layer.
The pre-passivation and post-passivation are described as follows: the pre-passivation may passivate defects of the second interface between the second carrier transport layer and the perovskite layer. Post passivation may passivate defects of perovskite grain boundaries, defects of a first interface between the first carrier transport layer and the perovskite layer. In pre-passivation, the plasmonic structure is primarily at the second interface between the second carrier transport layer and the perovskite layer. In post passivation, the plasmonic structure is mainly at the first interface between the first carrier transport layer and the perovskite layer, and some of the plasmons may also penetrate into the grain boundaries of the perovskite layer.
The production method of the perovskite battery is explained below with several examples.
Example 1: first, P-Au@TiO is prepared according to the example described in the production method of the above-mentioned ion excimer trapping structure 2 . The preparation can then be continued in a one-step process, in particular by reacting P-Au@TiO 2 Added to the perovskite precursor solution.
Cleaning: after the FTO substrate is respectively ultrasonically cleaned in cleaning agent, water, acetone and ethanol for 15 minutes, drying air is dried, and ultraviolet ozone treatment is carried out for 15 minutes.
Electron transport layer: spin-coating 2.67wt% SnO at 4000rpm 2 The solution was then annealed at 150℃for 30 minutes.
Perovskite layer: in FTO/SnO 2 Spin-on coating containing P-Au@TiO 2 Is (FA 0.83 MA 0.17 ) 0.95 Cs 0.05 Pb(I 0.83 Br 0.17 ) 3 Perovskite, solvent is DMF, DMSO=4:1 mixed solvent, concentration is 1.2M, P-Au@TiO 2 The concentration of (2) is 1-10%. The spin coating process is 500rpm,10 seconds, 5000rpm,30 seconds, and at the 10 th second of reciprocal, 150 microliters of chlorobenzene anti-solvent is rapidly added dropwise, and then annealing is carried out at 150 ℃ for 60 minutes;
hole transport layer: spin-coating 72.3mg/ml of a solution of Spiro-OMeTAD (2, 2', 7' -Tetrakis-9,9' -spirobifluorene,2, 7-Tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene) in chlorobenzene, spin-coating at 3000rpm for 30 seconds;
front electrode layer: molybdenum oxide 7nm thick and gold 80nm thick were evaporated as the front electrode layer.
P-Au@TiO 2 May also be added to the anti-solvent, in the above embodiment, the perovskite precursor does not contain P-Au@TiO 2 But is dissolved in chlorobenzene anti-solvent at a concentration of 1-10wt% with the same conditions.
Example 2: first, P-Au@TiO is prepared according to the example described in the production method of the above-mentioned ion excimer trapping structure 2 . Then can be prepared continuously by adopting a two-step method, in particular to P-Au@TiO 2 Adding to the first perovskite precursor solution: pbI of 1.5M 2 1-10wt% of P-Au@TiO is added to the DMF solution 2 The method comprises the steps of carrying out a first treatment on the surface of the The second perovskite precursor solution was 90mg/ml of an isopropanol solution of FAI; the cleaning, electron transport layer step, hole transport layer, front electrode layer were the same as in example 1.
Spin coating of a first perovskite precursor solution: spin-coating at 2000rpm for 30 seconds, and drying at 70 ℃ for 1 minute;
spin coating of the second perovskite precursor solution, spin coating at 1500rpm for 30 seconds, spin coating at 150 ℃ for 60 minutes.
P-Au@TiO 2 Can also be added into the second perovskite precursor solution, P-Au@TiO 2 The concentrations were 1-10 wt.%, the remaining steps were the same as in example 1.
Example 3: first, P-Au@TiO is prepared according to the example described in the production method of the above-mentioned ion excimer trapping structure 2 . The preparation can then be continued by means of pre-passivation. In particular, the method comprises the steps of,
cleaning: after the FTO substrate is respectively ultrasonically cleaned in cleaning agent, water, acetone and ethanol for 15 minutes, drying air is dried, and ultraviolet ozone treatment is carried out for 15 minutes.
Electron transport layer: spin-coating 2.67wt% SnO at 4000rpm 2 The solution was then annealed at 150℃for 30 minutes.
Front passivation: in FTO/SnO 2 P-Au@TiO with spin-on concentration of 1-10wt% 2 After the isopropanol solution of (2), the mixture was dried at 100℃for 10 minutes.
Perovskite layer: perovskite precursor solution (solute is (FA 0.83 MA 0.17 ） 0.95 Cs 0.05 Pb（I 0.83 Br 0.17 ） 3 Perovskite, solvent is DMF: DMSO=4:1 mixed solvent, concentration is 1.2M, spin coating process is 500rpm,10 seconds, 5000rpm,30 seconds, at the last 10 seconds, quick dropwise add 150 microliter chlorobenzene antisolvent, then 150 ℃ annealing 60 minutes.
Hole transport layer: 72.3mg/ml of a solution of Spiro-OMeTAD in chlorobenzene was spin-coated for 30 seconds at 3000 rpm.
Front electrode layer: molybdenum oxide 7nm thick and gold 80nm thick were evaporated as electrodes.
Example 4: first, P-Au@TiO is prepared according to the example described in the production method of the above-mentioned ion excimer trapping structure 2 . The preparation can then be continued by means of post-passivation. In particular, the method comprises the steps of,
cleaning: after the FTO substrate is respectively ultrasonically cleaned in cleaning agent, water, acetone and ethanol for 15 minutes, drying air is dried, and ultraviolet ozone treatment is carried out for 15 minutes.
Electron transport layer: spin-coating 2.67wt% SnO at 4000rpm 2 The solution was then annealed at 150℃for 30 minutes。
Perovskite layer: perovskite precursor solution (solute is (FA 0.83 MA 0.17 ) 0.95 Cs 0.05 Pb(I 0.83 Br 0.17 ) 3 Perovskite, solvent is DMF: DMSO=4:1 mixed solvent, concentration is 1.2M, spin coating process is 500rpm,10 seconds, 5000rpm,30 seconds, at the last 10 seconds, quick dropwise add 150 microliter chlorobenzene antisolvent, then 150 ℃ annealing 60 minutes.
Post passivation: on the perovskite film, the P-Au@TiO with the concentration of 1-10wt% is spin-coated 2 At 1500rpm for 30 seconds.
Hole transport layer: 72.3mg/ml of a solution of Spiro-OMeTAD in chlorobenzene was spin-coated for 30 seconds at 3000 rpm.
Front electrode layer: molybdenum oxide 7nm thick and gold 80nm thick were evaporated as the front electrode layer.
The embodiment of the invention also provides a photovoltaic module, which comprises any one of the solar cells. The solar cell in the photovoltaic module can refer to the relevant description in the foregoing solar cell embodiments, and can achieve the same or similar beneficial effects, and in order to avoid repetition, the description is omitted here.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and many forms may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the claims, which are to be protected by the present invention.
Claims (10)
1. A plasmonic structure, comprising: a nano metal particle inner core, an outer shell layer wrapping the nano metal particle inner core, and passivation modification molecules positioned outside the outer shell layer;
the material of the outer shell layer is selected from dielectric materials and/or wide bandgap semiconductor materials;
the passivation modifying molecule comprises: the shell layer passivation end, the passivation molecular carbon chain and the perovskite passivation end are connected to the shell layer; the passivation molecular carbon chain is connected with the passivation end of the shell layer and the perovskite passivation end; the shell layer passivation end comprises: at least one passivating functional group, the passivating functional group comprising: at least one of an amine group, a phosphine group, a carboxyl group, a sulfo group, and a mercapto group; the perovskite passivation end comprises: at least one functional group containing a lone pair of electrons;
the nano metal particle inner core and the outer shell layer wrapping the nano metal particle inner core form a plasmon polariton of a core-shell structure; the shell layer passivation end and the passivation molecular carbon chain are provided with: avoiding the effect of plasmonic agglomeration of the core-shell structure.
2. The plasmonic structure of claim 1, wherein the passivated molecular carbon chain has 4-20 carbon atoms.
3. The plasmonic structure of claim 2, wherein the passivated molecular carbon chain has 6-15 carbon atoms.
4. The plasmonic structure of claim 1, wherein 1-4 carbon atoms in the passivated molecular carbon chain are replaced by oxygen atoms.
5. The plasmonic structure of claim 1, wherein 1-2 benzene rings are attached to carbon atoms in the passivated molecular carbon chain.
6. The plasmonic structure of claim 1, wherein the perovskite passivated end is an amine group and/or a guanidine group.
7. The plasmonic structure of any one of claims 1-6, wherein the material of the inner core of the nano-metal particles is selected from at least one of gold, silver, copper, aluminum, nickel, tin, indium, gallium;
the shape of the nano metal particle inner core is one of a sphere, a hemisphere, a spheroid, a cylinder, a cone, a cube and a cuboid;
the size of the nano metal particle core is 1-50nm;
the dielectric constant of the dielectric material is 1.2-200, and the forbidden bandwidth of the wide forbidden bandwidth semiconductor material is more than or equal to 2.3eV; the thickness of the shell layer is 1-20nm.
8. The plasmonic structure of claim 7, wherein the nano-metal particle inner core has a size of 1-20nm; the thickness of the shell layer is 1-5nm.
9. The plasmonic structure of claim 7, wherein the dielectric material is selected from at least one of titanium oxide, silicon oxide, aluminum oxide, silicon nitride, tantalum oxide, aluminum nitride; the wide bandgap semiconductor material is at least one selected from silicon carbide, gallium nitride, gallium oxide and zinc oxide.
10. A perovskite optoelectronic device comprising a layer of perovskite material, wherein the plasmonic structure of any one of claims 1-9 is located at an interface of the perovskite material layer with other functional layers, at a surface of the perovskite material layer, or within the perovskite material layer.
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