CN110880552B - Perovskite solution and surfactant step-by-step coating device and method - Google Patents
Perovskite solution and surfactant step-by-step coating device and method Download PDFInfo
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Abstract
本发明涉及一种钙钛矿溶液与表面活性剂分步涂布设备，包括后处理装置、涂布平台以及传送装置，在传送装置的前部设置两组涂布装置，每组涂布装置包括涂布模头、模头升降台、注射泵以及原料瓶，涂布模头通过导管与注射泵接通，注射泵通过管路与原料瓶接通，在两个原料瓶中分别装有钙钛矿溶液和表面活性剂溶液；在传送装置的驱动下，模头升降台与涂布平台之间产生相对移动，放置在涂布平台上的待涂布的基底分别先后被两个涂布模头涂布后被传送装置输送到后处理装置处进行后处理。本发明还公开该涂布设备的使用方法及其应用。本发明提高涂膜的覆盖率和涂膜表面的平整度，得到膜厚分布更加均匀的钙钛矿薄膜。
The present invention relates to a perovskite solution and surfactant step-by-step coating device, comprising a post-processing device, a coating platform and a conveying device. Two groups of coating devices are arranged in front of the conveying device, each group of coating devices comprises a coating die head, a die head lifting platform, an injection pump and a raw material bottle, the coating die head is connected to the injection pump through a conduit, the injection pump is connected to the raw material bottle through a pipeline, and the two raw material bottles are respectively filled with a perovskite solution and a surfactant solution; under the drive of the conveying device, a relative movement is generated between the die head lifting platform and the coating platform, and the substrate to be coated placed on the coating platform is successively coated by the two coating die heads and then transported by the conveying device to the post-processing device for post-processing. The present invention also discloses a method for using the coating device and its application. The present invention improves the coverage of the coating film and the flatness of the coating film surface, and obtains a perovskite film with a more uniform film thickness distribution.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cell preparation, and particularly relates to perovskite solution and surfactant step-by-step coating equipment and a method thereof.
Background
Currently, perovskite solar cells are manufactured in large areas by spraying, knife coating, slot coating, ink printing, ink jet printing, and the like. Slit Coating (Slot Die Coating) is one of the most convenient methods for industrially preparing perovskite solar cells in large area, and has the advantages of short preparation process period, raw material saving, simple process operation and the like. However, the conventional slit coating method for preparing the perovskite solar cell has the defects of more holes, serious uneven film thickness and the like, which severely restricts the slit coating method to be used for large-area preparation and commercial application of the perovskite solar cell.
In China patent with publication number of CN105647530A and patent name of a preparation method of metal halide inorganic perovskite quantum dots, the morphology of the metal halide inorganic perovskite quantum dots is changed by using different surfactants and reaction solvents, and the battery performance is regulated and controlled. Although the method can effectively regulate and control the morphology of the perovskite quantum dots, the method cannot regulate and control the flatness of the film surface, the defects of holes and the like of the perovskite solution coated film.
As shown in fig. 1, which is a schematic view of the cross section of each layer of a conventional perovskite solution coated battery, wherein 11 is a substrate, a lipophilic electron/hole transport layer 12-2 is prepared on the conductive layer 11, and the lipophilic electron/hole transport layer 12-2 is prepared from any one of poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA) and poly (3-hexylthiophene-2, 5-diyl) (P3 HT) as a raw material. Reference numeral 16 denotes a coating layer of a perovskite solution. Under the normal coating condition, the perovskite solution is hydrophilic, so that the electron/hole transport layer with lipophilicity is difficult to infiltrate, the surface of the electron/hole transport layer cannot be paved, and a plurality of necking is easy to generate after the perovskite solution is coated. If at higher preparation temperatures, for example: many pinholes are easily generated at 100-180 ℃, which not only seriously affect the quality of the perovskite battery, but also reduce the conversion efficiency of the perovskite battery.
Disclosure of Invention
The invention aims to solve the technical problem of providing perovskite solution and surfactant step-by-step coating equipment and a method thereof, which can improve the coverage rate of a coating film and the flatness of the surface of the coating film, and obtain a perovskite film with more uniform film thickness distribution.
The invention is realized by providing a perovskite solution and surfactant step-by-step coating device, which comprises a coating platform, a coating device, a conveying device and a post-treatment device, wherein the coating device is provided with two groups, the two groups of coating devices are mutually independent, the post-treatment device is arranged at the rear part of the conveying device and above the coating platform, the two groups of coating devices are arranged at the front part of the conveying device, each group of coating devices comprises a coating die head, a die head lifting table, an injection pump and a raw material bottle, the coating die head is arranged on the corresponding die head lifting table and above the coating platform, the die head lifting table is used for adjusting the height between the coating die head and a substrate to be coated, the coating die head is communicated with the injection pump through a conduit, the injection pump is communicated with the raw material bottle through a pipeline, and the perovskite solution and the surfactant solution are respectively contained in the two raw material bottles; and under the drive of the conveying device, the two groups of die head lifting tables and the coating platform move relatively, and substrates to be coated placed on the coating platform are respectively coated by the two coating die heads in sequence and then conveyed to a post-treatment device by the conveying device for post-treatment.
The invention is realized in such a way that a method for using the perovskite solution and surfactant step-by-step coating equipment is provided, which comprises the following steps:
The method comprises the steps of firstly, pouring prepared surfactant solution and perovskite solution into different raw material bottles respectively, wherein the perovskite solution is contained in the raw material bottle of one group of the first group of coating devices positioned in front, and the surfactant solution is contained in the raw material bottle of the second group of coating devices positioned in rear;
secondly, placing a substrate to be coated on a coating platform, starting a group of injection pumps of a first group of coating devices, starting a conveying device, conveying perovskite solution to a group of coating die heads through a group of guide pipes, and generating relative movement between a group of die head lifting tables and the coating platform under the driving of the conveying device, wherein the first coating is carried out on the surface of the substrate by the group of coating die heads;
Thirdly, starting a second group of injection pumps of a second group of coating devices, conveying the surfactant solution to the second group of coating die heads through the second group of guide pipes, starting a conveying device to convey the substrate coated with the perovskite solution to the second group of coating die heads, and simultaneously, under the driving of the conveying device, generating relative movement between the second group of die head lifting tables and the coating platform, wherein the second group of coating die heads carry out second coating on the surface of the substrate, and the surface of the substrate is sequentially coated with wet films of the perovskite solution and the surfactant solution;
and fourthly, starting a post-treatment device, conveying the substrate coated with the wet film to the post-treatment device by a conveying device for post-treatment, and enabling solvent components in the wet film to be further volatilized to obtain a dry film, so that a perovskite film layer is prepared on the surface of the substrate.
The invention is realized in such a way that a preparation method of a perovskite solar cell is provided, and perovskite solution and surfactant step-by-step coating equipment are used in the process of preparing the perovskite solar cell, and the preparation method comprises the following steps:
S1, pouring prepared surfactant solution and perovskite solution into different raw material bottles respectively, wherein the perovskite solution is contained in the raw material bottle of one group of the first group of coating devices positioned in front, and the surfactant solution is contained in the raw material bottle of the second group of coating devices positioned in rear;
s2, placing a substrate with a conductive layer and an electron/hole transport layer on the surface on a coating platform, starting a group of injection pumps of a first group of coating devices, starting a conveying device, conveying perovskite solution to a group of coating die heads through a group of guide pipes, and generating relative movement between a group of die head lifting tables and the coating platform under the driving of the conveying device, wherein the first coating is carried out on the surface of the substrate by the group of coating die heads;
S3, starting a second group of injection pumps of a second group of coating devices, conveying the surfactant solution to the second group of coating die heads through the second group of guide pipes, starting a conveying device to convey the substrate coated with the perovskite solution to the second group of coating die heads, and simultaneously, under the driving of the conveying device, generating relative movement between the second group of die head lifting tables and the coating platform, wherein the second group of coating die heads carry out second coating on the surface of the substrate, and the surface of the substrate is sequentially coated with wet films of the perovskite solution and the surfactant solution;
s4, starting a post-treatment device, conveying the substrate coated with the wet film to the post-treatment device by a conveying device for post-treatment, and enabling the solvent in the wet film to be further volatilized to obtain a dry film, so that a perovskite film layer is prepared on the electron/hole transport layer of the substrate;
S5, continuously preparing a hole/electron transport layer and a back electrode layer on the surface of the perovskite thin film layer of the substrate until the perovskite solar cell is prepared.
The invention is achieved by providing a perovskite solar cell comprising a perovskite thin film layer prepared by using a perovskite solution and surfactant step-coating device as described above, or by using a perovskite solar cell preparation method as described above.
Compared with the prior art, the perovskite solution and surfactant stepwise coating equipment and the method thereof independently separate and stepwise coat the perovskite solution and the surfactant solution when the perovskite film layer is coated and prepared. The surfactant of the coating method is uniformly distributed at the interface between the perovskite layer and the transmission layer, which is beneficial to passivating the interface defect between the perovskite layer and the transmission layer, and does not influence the migration of carriers in the perovskite layer. In addition, the coating method can effectively avoid the problem that partial surfactant is indissolvable in perovskite solution to cause unstable solution and is not suitable for storage. The surfactant solution and the perovskite solution are respectively coated by two independent coating dies, so that the mutual pollution between the surfactant solution and the perovskite solution is avoided, and the adjustment and optimization of the components of the surfactant solution and the perovskite solution are facilitated. Therefore, the process method widens the solution system and the coating process of the surfactant, and is beneficial to adjusting the perovskite film forming performance and optimizing the uniformity of perovskite film forming. The coating equipment and the method thereof are not only applied to the technical field of perovskite solar cells, but also widely applied to the technical fields of organic solar cells, dye sensitized solar cells and quantum dot solar cells.
Drawings
FIG. 1 is a schematic cross-sectional view of a perovskite thin film layer of the prior art after coating;
FIG. 2 is a schematic cross-sectional structure of a conventional perovskite solar cell;
FIG. 3 is a schematic perspective view of a preferred embodiment of a step-wise perovskite solution and surfactant coating apparatus of the invention;
FIG. 4 is a schematic diagram of the morphology of a perovskite thin film layer prepared using prior art methods;
FIG. 5 is a schematic cross-sectional view of a perovskite thin film layer made by the perovskite solution and surfactant solution profile coating of the invention;
FIG. 6 is a schematic diagram of the morphology of a perovskite thin film layer prepared by using the perovskite solution and surfactant step-by-step coating equipment of the present invention;
Fig. 7 is a graph showing the comparison of the efficiency of perovskite solar cell according to example one and example two of the present invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Fig. 2 is a schematic cross-sectional structure of a conventional perovskite solar cell. On the substrate, a conductive layer 11, an electron/hole transport layer 12, a perovskite thin film layer 13, a hole/electron transport layer 14, and a back electrode layer 15 are sequentially prepared, wherein the preparation of the perovskite thin film layer 13 is the most critical.
The present invention first discloses a coating apparatus for preparing a perovskite thin film layer 13, which is used for coating a perovskite solution containing a surfactant on an electron/hole transport layer 12 to prepare the perovskite thin film layer 13.
Referring to fig. 3, a preferred embodiment of the perovskite solution and surfactant step-by-step coating apparatus of the present invention includes a coating platform 16, a coating device, a conveyor 107 and a post-treatment device 105, wherein the coating device has two sets of coating devices, and the two sets of coating devices are independent of each other. The post-treatment device 105 is arranged at the rear of the conveyor 107 above the coating platform 106.
The two sets of coating devices are arranged in front of the conveying device 107, the first set of coating devices in front comprises a set of coating dies 101, a set of die lifting tables 102, a set of guide pipes 103, a set of injection pumps 104, a set of raw material bottles 109 and a set of pipelines 110, and the second set of coating devices in back comprises a set of coating dies 201, a set of die lifting tables 202, a set of guide pipes 203, a set of injection pumps 204, a set of raw material bottles 209 and a set of pipelines 210.
The first set of coating devices is described as assembled and the second set of coating devices is identical thereto. The coating dies 101 of the set are disposed on their corresponding sets of die-lifting tables 102 above the coating platforms 106 of the set, the sets of die-lifting tables 102 adjusting the height between the coating dies 101 of the set and the substrate 208 to be coated. The set of die lifting tables 102 are disposed on either side of the coating platform 106. The coating die 101 of the set is connected to the injection pump 104 of the set through the pipe 103 of the set, and the injection pump 104 of the set is connected to the raw material bottle 109 of the set through the pipe 110 of the set. The perovskite solution and the surfactant solution are respectively contained in the two raw material bottles.
The two groups of die lifting tables and the coating platform 106 are driven by the conveying device 107 to move relatively, and the substrates to be coated 208 placed on the coating platform are respectively coated by the two coating dies in sequence and then conveyed to the post-treatment device 105 by the conveying device 107 for post-treatment.
The conveyor 107 drives the coating platform 106 to move, the two sets of die head lifting tables respectively remain stationary, and each set of die head lifting tables and the coating platform 106 move relatively.
The conveyor 107 drives the two sets of die lifting tables to move simultaneously, the coating platform 106 remains stationary, and relative movement is generated between each set of die lifting tables and the coating platform 106.
A film forming apparatus (not shown) for performing a film forming process on the wet film just coated on the surface of the substrate 208 within 0 to 60s after the end of the coating die of the group is also provided on each of the die lifting stages. The film forming apparatus includes a heater and a blower or blower, or a heater and a vacuum pump.
The aftertreatment device 105 includes a heater, a vacuum pump, and a closed cavity that facilitates opening and closing. The post-treatment device 105 is provided with a drying device that performs a drying treatment of the wet film coated on the surface of the substrate 208 or an annealing device that performs an annealing treatment of the wet film coated on the surface of the substrate.
The concentration of the perovskite solution is 0.5-1.5mol/L, and the perovskite solution comprises perovskite solute and dilution solvent. The perovskite solute is simply called ABX 3, wherein a is at least one of MA +、FA+、Cs+, B is at least one of Pb 2+、Sn2+、Ze2+, and X is at least one of Cl -、Br-、I-; the dilution solvent is at least one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GBL).
The mass ratio of the surfactant solution to the perovskite solution is 0.01-10%, and the surfactant solution comprises an active agent solute and an active agent solvent. The active agent solute is a nonionic, cationic, anionic and amphoteric surfactant, and the active agent solvent is any one of petroleum ether, carbon tetrachloride, trichloroethane, benzene, dichloromethane, chloroform, ethyl acetate and acetone. The active agent solute is polyethylene glycol monooleate, di-coco dimethyl ammonium chloride, di-methyl di-hydrogenated tallow ammonium methosulfate, di-tallow quaternary ammonium salt, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, cetyl dimethyl benzyl ammonium chloride, cetyl pyridinium bromide, cetyl pyridinium chloride, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, polyglycerol fatty acid ester, polyglycerol polyricinoleate, trimethyl soybean oil ammonium chloride, dialkyl dimethyl ammonium chloride, di-methyl di-hydrogenated tallow ammonium chloride, and, Dimethyl cocoyl ammonium chloride, trimethyl tallow ammonium chloride, N-tallow pentamethyl propane diammonium dichloride, L-alpha-phosphatidylcholine, sodium dodecyl sulfate, didodecyl dimethyl ammonium bromide, alkyl polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, linear alcohol polyoxyethylene ether, dioctyl sodium sulfosuccinate, N-octadecyl sulfosuccinamide disodium salt, cocoamidopropyl betaine, ethoxylated sulfosuccinate disodium salt, alkyl ethanolamide sulfosuccinate disodium salt, alkyl sulfosuccinate disodium salt, fatty alcohol sulfate ammonium salt, alkylphenol polyoxyethylene ether sodium salt and ammonium salt, Polyoxyethylene nonylphenol ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan monooleate, polyoxyethylene ether phosphate, polyoxyethylene isooctylphenol ether, polyoxyethylene nonylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty amide, fatty alcohol phosphate, sorbitan monostearate, sorbitan monooleate, tetradecyldimethyl ammonium oxide, hexadecyldimethyl ammonium oxide, octadecyl dimethyl ammonium oxide, C8-18 alkyldimethyl ammonium oxide, hexadecyltrimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, dicococodimethyl ammonium chloride, polyethylene glycol sorbitol laurate, and, Polyoxyethylene sorbitol oleate, polyoxyethylene sorbitol tetraester, polyoxyethylene castor oil, polyoxyethylene propylene glycol monostearate, polyoxyethylene sorbitol ester, polyoxyethylene sorbitol tetraoleate, polyoxyethylene sorbitol hexaoleate, polyoxyethylene stearate, alkylphenol ethoxylates, fatty alcohol ethoxylates, polyoxyethylene fatty amines, coconut oil ethylene oxide adducts, polyoxyethylene castor oil, alkylphenol ethoxylates, fatty alcohol ethoxylates, alkylphenol ethoxylates, alkylaryl ethoxylates, alkyl polyoxyethylene ethers, alkylphenol ethoxylates, fatty alcohol ethoxylates, stearyl alcohol polyoxyethylene ethers, Polyoxyethylene fatty acid ester, polyoxyethylene fatty amine, 2-bromo-2-nitropropane-1, 3-diol, alkyl dimethyl benzyl ammonium chloride, N-tetradecyl dimethyl benzyl ammonium chloride, N-alkyl dimethyl-1-naphthylmethyl ammonium chloride, coconut fatty acid diethanolamide sodium alkylaryl sulfonate, sodium linear alkylbenzenesulfonate, propylene glycol fatty acid monoester, carboxyl polymethyl compound, linear alcohol polyoxyethylene ether, ammonium laureth sulfate, sodium laureth sulfate, nonylphenol polyoxyethylene ether, dodecyl alcohol polyoxyethylene ether, N, N-dimethylhydroxyethyl octadecyl amino ammonium nitrate, N-dimethylhydroxyethyl octadecyl amino ammonium phosphate, polyether, glucosyl amino propyl dimethyl-2-hydroxyethyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium bromide, fatty alcohol polyoxyethylene ether, propylene glycol and synthetic acid, polyethylene glycol stearate, polyoxyethylene castor oil, polyoxyethylene nonylphenol ether, polyoxyethylene stearate, polyoxyethylene nonylphenol ether, fatty alcohol polyoxyethylene ether, sodium alkyl naphthalene sulfonate, potassium alkyl naphthalene sulfonate, monoalkali aryl sulfonate, monocalcium salt, Tridecylsiloxysilicate, nonylphenol polyoxyethylene ether, C10-13 fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, sodium alkylbenzenesulfonate, polyoxyethylene alkylamine, coconut fatty acid polyoxyethylene ester, propylene glycol polyoxypropylene polyoxyethylene ether, alkylphenol polyether, sucrose fatty acid ester, nonylphenol polyoxyethylene ether, sodium dodecyl diphenyl ether disulfonate, sodium N-decyl diphenyl ether disulfonate, 4-dodecyl-2, 3-oxo-disodium bisphenesulfonate, propylene oxide ethylene oxide block copolymer, sodium alkylbenzenesulfonate, cocoyl-1, 3-propylenediamine diacetate, N-tallow-1, 3-propylenediamine diacetate, N-coco-1, 3-propanediol, N-tallow-1, 3-propanediol, diethanolamine lauryl sulfate, alkylpolyglycol ether, sodium fatty acid alkyl amide sulfosuccinate monoester, sodium fatty alcohol polyoxyethylene ether sulfosuccinate monoester, sodium polyoxyethylene fatty acid alkanolamide sulfosuccinate monoester, sodium fatty alcohol phosphate, sodium alkyl polyoxyethylene ether phosphate, alkylaryl polyoxyethylene ether, sodium alkyl phosphate, disodium sulfosuccinate, dialkylsuccinates, alkylaryl sulfonate, alkyl dimethyl betaine, tertiary amine alkyl oxide, polyoxyethylene oleate, polyethylene glycol fatty acid ester, alkylpolyglycol ether, Polyoxyethylene fatty amines, fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, trideceth polyoxyethylene ethanol, fatty alcohol polyoxyethylene ethers, oleic polyoxyethylene esters, fatty alcohol polyoxyethylene ethers, stearic polyoxyethylene esters, polyoxyethylene castor oil, alpha-alkenyl sulfonates, polyoxyethylene coconut oil amides, polyoxyethylene oleamides, nonylphenol polyoxyethylene ethers, propylene glycol polyoxypropylene polyoxyethylene ethers, polyoxyethylene fatty amines, modified alkylphenol polyoxyethylene ethers, nonylphenol polyethylene glycol ethers, fatty alcohol polyethylene glycol ethers, octadecyl pyridinium chloride, cetyl pyridinium bromide, tetradecyl pyridinium bromide, cetyl trimethyl ammonium bromide, propylene glycol monoricinoleate, glycerol monoricinoleate, ethylene glycol monoricinoleate, ammonium perfluoroalkylsulfonate, potassium fluoroalkylcarboxylate, fluoroalkyl quaternary ammonium sulfonate character, ammonium perfluoroalkylcarboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl alkoxylate, perfluoroalkyl polyoxyethylene polyoxypropylene ether, polyoxyethylene sorbitol hexaoleate, polyoxyethylene glycerol fatty acid ester, polyoxyethylene polyoxypropylene monostearate, polyoxyethylene coconut fatty amine, alkyl dimethyl ammonium chloride, sodium alkyl polyethylene glycol ether sulfate, propylene glycol polyoxyethylene polyoxypropylene ether, imidazolidinyl urea, Polyoxyethylene methyl glucoside sesquistearate, fatty alcohol phosphate, mixed organic phosphate, alpha-olefin sodium sulfonate, sodium secondary alkane sulfonate, fatty alcohol polyoxyethylene ether, polyoxyethylene diisobutyl phenoxy ethyl dimethyl benzyl ammonium chloride, linear fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, dinonylphenol polyoxyethylene ether, dodecylphenol polyoxyethylene ether, sodium oleoyl ethanesulfonate, sodium N-palmitoyl-N-cyclohexyl taurine, sodium N-methyl-N-oleoyl sulfonate, fatty alcohol polyoxyethylene ether, 3-trifluoromethyl-4, 4' -dichloro-N, N-diphenyl urea, Polypropylene glycol, polyethylene glycol, N-alkyl trimethyl ammonium chloride, polyethylene glycol fatty acid ester, organosilicone, polyoxyethylene fatty amine, fatty acid polyethylene glycol ester, alkylphenol polyglycol ether, cocoyl alkyl betaine, cocoyl hydrolyzed animal protein potassium salt, propylene glycol fatty acid ester and potassium salt thereof, polyoxyethylene castor oil, nonylphenol polyoxyethylene ether, oleyl polyoxyethylene ether, polyoxyethylene stearate, polyoxyethylene tall oil, sodium oleoyl aminobenzenesulfonate, nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, dodecyl alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, saponin, alkyl benzene sulfonic acid alkanolamine salt, alkyl phenol polyoxyethylene ether sulfate sodium salt, cationic modified polyoxyethylene fatty acid esters, carboxymethylcellulose, polyethylene glycol stearates, nonylphenol polyoxyethylene ethers, alkyl alcohol polyoxyethylene ethers, polyquaternised vinyl alcohols, monocarboxylated coconut imidazoline derivatives, fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene esters, fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, mixtures of sodium alkylbenzenesulfonate and fatty acid polyethylene glycol esters, alkylphenol polyethers, sodium alkylnaphthalene sulfonates, secondary alcohol polyoxyethylene ethers, C13-15 secondary alcohol polyoxyethylene ethers, secondary alcohol polyoxyethylene ether sulfate salts, sorbitan stearates, and, Polyoxyethylene sorbitan stearate, nonylphenol polyoxyethylene ether, cetyl alcohol polyoxyethylene ether, sodium salt of C8 fatty alcohol polyoxyethylene ether sulfate, propylene oxide-ethylene oxide block copolymer, cetyl alcohol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, oleyl alcohol polyoxyethylene ether, and polyoxyethylene ether fatty alcohol polyoxyethylene ether diphosphate, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, sucrose monolaurate, sucrose monooleate, sucrose monopalmitate, sucrose distearate, sucrose mono-distearate, polyethylene glycol distearate, nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, sucrose monopalmitate, sucrose distearate, polyethylene glycol distearate, and, Oleyl alcohol/cetyl alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, oleyl alcohol polyoxyethylene ether, oleic polyoxyethylene ester, oleyl alcohol polyoxyethylene ether, eicosyl acid polyoxyethylene ester, 4-tert-butyl-4' -methoxydibenzoylmethane, 2-ethylhexyl p-methoxylaurate, fatty alcohol polyoxyethylene ether, alkyl methyl polyoxyethylene ether quaternary ammonium salt, dimethylpolysiloxane polyether, methyl hydroxybenzoate, propyl hydroxybenzoate and potassium alkyl phosphate of ethanol monophenyl ether, potassium alkyl phosphate, propylene glycol polyoxyethylene polyoxypropylene ether, propylene glycol polyoxypropylene polyoxyethylene ether, ethylenediamine polyoxypropylene polyoxyethylene vinyl ether, Stearyl alcohol polyoxyethylene ether and stearyl alcohol complex, glycerol polyoxypropylene ethylene ether, quaternary amino ether of ethoxylated cellulose, polyoxyethylene sorbitan fatty acid ester, C16-20 fatty acid polyoxyethylene ester, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, ethylenediamine polyoxyethylene polyoxypropylene ether, petroleum sulfonate, quaternized shan imidazoline, sodium stearyl lactate, nonylphenol polyethylene ether, laureth sulfate sodium salt, derivative of lanolin sterol, sodium dodecylbenzenesulfonate, diisopropyl dimer acid, alkylamine oxide, alkyl diethanolamide, polyoxyethylene nonionic surfactant, polyoxyethylene type nonionic surfactant, and process for preparing the same, Propylene glycol propylene oxide ethylene oxide block copolymers, alkyl phenolic polyethers, dimethyl siloxane, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, cetyl polyoxyethylene ether, triethanolamine laurate, sodium laureth sulfate, polyoxyethylene synthetic fatty acid monoethanolamides, primary alcohol polyoxyethylene ethers, alkyl polyoxyethylene ethers, fatty alcohol polyvinyl ether mixtures, quaternary ammonium salts, dimethyl distearyl chloride amine, polyoxyethylene fatty amides, polyoxyethylene stearates, neutral lecithin, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, At least one of sorbitan monooleate, sorbitan trioleate, coconut diethanolamide, lauric acid diethanolamide, imidazole derivatives, fatty acid polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecyl benzene sulfonate, alkylbenzene sulfonate, sodium secondary alkyl sulfate, nonylphenol polyoxyethylene ether, ethylenediamine polyoxypropylene polyoxyethylene ether, tridecyl alcohol polyoxyethylene ether sulfate sodium salt, laurinol diethanolamide, alkylphenol polyoxyethylene ether, fatty alcohol polyoxypropylene polyoxyethylene ether, and fatty alcohol polyoxypropylene polyoxyethylene ether succinate.
After the perovskite solution and a certain amount of surfactant solution are coated step by step, the hydrophilicity of the surface of the electron/hole transport layer during coating is improved, the flatness of the surface contacted with air after the perovskite solution is formed into a film is regulated, and the volatilization speed of a solvent in the perovskite solution is regulated, so that defects such as shrinkage cavity, pinholes, uneven film thickness and the like caused during coating are reduced. After the complete solar cell is prepared, interface defects between the perovskite layer and the transmission layer and internal defects of the perovskite layer can be passivated, so that the carrier transmission performance of the perovskite solar cell is effectively improved, and the recombination of electron-hole carrier pairs is inhibited, so that the efficiency of the perovskite solar cell is improved.
In the slit coating process by using the coating equipment, the surfactant plays a role in leveling the perovskite solution, so that the defects of uneven film thickness and holes of the formed perovskite film are reduced, and the efficiency of the manufactured perovskite solar cell is improved. Compared with the prior art, the invention also relates to the functions of emulsifying, solubilizing and suspending the surfactant in the perovskite solution.
The invention also discloses a using method of the perovskite solution and surfactant step-by-step coating equipment, which comprises the following steps:
In the first step, the prepared surfactant solution and perovskite solution are poured into different raw material bottles respectively, and the perovskite solution is contained in the raw material bottle 109 of one group of the first coating device positioned in front, and the surfactant solution is contained in the raw material bottle 209 of the second group of the second coating device positioned in rear.
In a second step, the substrate 208 to be coated is placed on the coating platform 106. First, the injection pump 104 of one of the first group of coating devices is turned on, the transfer device 107 is turned on, and the perovskite solution is transported to the coating die 101 of one group through the conduit 103 of one group. The set of die lifting tables 102 and the coating platform 106 are driven by the conveying device 107 to move relatively, the height between the set of coating dies 101 and the substrate 208 to be coated is adjusted by the set of die lifting tables 102, and the set of coating dies 101 performs first coating on the surface of the substrate 208 to be coated placed on the coating platform 106.
In a third step, the second set of injection pumps 204 of the second set of coating devices are then turned on and the surfactant solution is delivered to the second set of coating dies 201 through the second set of conduits 203. The conveyor 107 is turned on to deliver the substrate 208 coated with the perovskite solution to the coating dies 201 of the two groups of the second group of coating devices. Simultaneously, the two sets of die lifting tables 202 and the coating platform 106 are driven by the conveying device 107 to move relatively, the two sets of die lifting tables 202 are used for adjusting the height between the two sets of coating dies 201 and the substrate 208 to be coated, the two sets of coating dies 201 are used for coating the surface of the substrate 208 which is placed on the coating platform 106 and is coated with the perovskite solution for the second time, and the surface of the substrate 208 is coated with a wet film of the perovskite solution and the surfactant solution in sequence.
Fourth, the post-treatment device 105 is started, the substrate 208 coated with the wet film is conveyed to the post-treatment device 105 by the conveying device 107 for post-treatment, and solvent components in the wet film are further volatilized to obtain a dry film, so that a perovskite thin film layer is prepared on the surface of the substrate 208.
Specifically, in the third step, the two-group coating die 201 is to coat the surfactant solution in a state where the perovskite solution wet film coated by the first-group coating device on the surface of the substrate 208 is in a semi-solidified and semi-flowing state. The semi-solidification and semi-flowing state refers to that part of the solvent of the perovskite solution volatilizes and solute crystallization is started to be separated out, a solute deposition layer is formed on the surface of the substrate visually, and a flowable perovskite solution is still arranged on the solute deposition layer. The aim of coating a surface active agent layer under the state that the perovskite solution wet film is semi-solidified and semi-flowing is to reduce the surface tension of the perovskite solution, so that the perovskite solution is leveled and dried to form a relatively uniform perovskite film layer. The surfactant prevents the volatilization of the solvent in the perovskite solution after being paved on the surface of the perovskite solution, so that the surfactant also plays a role in regulating and controlling the film formation of the perovskite solution in the film formation process of the perovskite solution.
Specifically, in the fourth step, the wet film on the surface of the substrate 208 is in a leveling state before the post-treatment device 105 is turned on.
Specifically, in the first step, the perovskite solution and the surfactant solution are placed in the order that they are interchanged as needed, and the coating order and the number of coating times of the perovskite solution and the surfactant solution in the second step and the third step are also adjusted as needed.
In practical use, the process and sequence of solution coating should be determined according to the wettability of the perovskite solution to the substrate. For hydrophilic substrates, a layer of surfactant layer solution is immediately coated after perovskite solution is coated, and after the surfactant layer solution is further leveled on the substrate, the substrate is dried to form a flat perovskite film layer. For lipophilic substrates, the perovskite solution with hydrophilicity has a tendency to shrink after being directly coated because the cohesion of the perovskite solution is greater than the adhesion force of the surface of the contact part with the substrate, thereby causing shrinkage defects. Therefore, before the perovskite solution is coated on the lipophilic substrate, a layer of surfactant solution is coated, then the perovskite solution is coated, finally a layer of surfactant solution is coated, and after the surfactant solution is further leveled on the substrate, the perovskite film layer is obtained after drying and film forming.
The hydrophilic substrate includes: at least one of copper oxide, nickel oxide, molybdenum oxide and zinc oxide.
The lipophilic base includes: PTAA (poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ]), P3HT (poly (3-hexylthiophene-2, 5-diyl)), PCBM ([ 6.6] -phenyl-C61-butanoic acid methyl ester), graphene.
Specifically, in the first step, the concentration of the perovskite solution is 0.5-1.5mol/L, the perovskite solution comprises perovskite solute and a dilution solvent, the perovskite solute is simply called ABX 3, wherein A is at least one of MA +、FA+、Cs+, B is at least one of Pb 2+、Sn2+、Ze2+, and X is at least one of Cl -、Br-、I-. The dilution solvent is at least one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GBL). The mass ratio of the surfactant solution to the perovskite solution is 0.01-10%, the surfactant solution comprises an active agent solute and an active agent solvent, the active agent solute is a nonionic, cationic, anionic or amphoteric surfactant, and the active agent solvent is at least one of petroleum ether, carbon tetrachloride, trichloroethane, benzene, dichloromethane, chloroform, ethyl acetate and acetone.
Specifically, in the second and third steps, the conditions of the operation setting parameters of the two sets of the coating dies are: the width of the slit is 20-300um, the coating liquid amount is 0.2-2ul/cm 2, the coating speed is 0.5-50cm/s, the liquid outlet temperature of the coating die head is 25-180 ℃, and the coating temperature is 25-180 ℃. The two groups of coating dies also met the following environmental conditions when coated: the ambient temperature is 15-30 ℃, the ambient humidity is 0-50% RH, and the environment is in a common atmosphere or an inert protective atmosphere. The coating parameters and coating positions of the coating dies 101 of one group and the coating dies 201 of two groups are set independently of each other.
Specifically, a film forming apparatus (not shown) that performs a film forming process on the wet film just coated on the surface of the substrate 208 within 0 to 60s after the end of the coating die of the group is also provided on each of the die lifting tables. The film forming apparatus of each set includes a heater and a blower or blower, or a heater and a vacuum pump.
Specifically, the film forming treatment includes a heat treatment or a drying treatment. The heat treatment is to place the substrate after each coating is finished at the low vacuum pressure of 10 -5-105 Pa and the air temperature of 25-150 ℃ for 10-600s for annealing treatment. The drying treatment is to rapidly dry the wet film on the surface of the substrate after each coating by adopting air convection caused by a blowing or exhausting mode, wherein the air speed of air flowing caused by blowing or exhausting is 0.5-10m/s, and the temperature of flowing air is 25-150 ℃.
Specifically, in the fourth step, the post-processing performed by the post-processing device 105 includes: placing the substrate 208 coated with the wet film of the perovskite solution and the surfactant solution under the action of at least one gas of vacuum, dry air, H 2 O (water), DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), GBL (gamma-butyrolactone) and NMP (N-methylpyrrolidone), wherein the ambient pressure is 10 -5-106 Pa, the ambient temperature is 100-150 ℃, the standing time is 5-120min, and drying the wet film into a dry film, thereby preparing the perovskite thin film layer on the surface of the substrate.
The invention also discloses a preparation method of the perovskite solar cell, wherein the perovskite solution and the surfactant step-by-step coating equipment are used in the process of preparing the perovskite solar cell, and the preparation method comprises the following steps of:
S1, pouring the prepared surfactant solution and perovskite solution into different raw material bottles respectively, wherein the perovskite solution is contained in the raw material bottle 109 of one group of the first group of coating devices positioned in front, and the surfactant solution is contained in the raw material bottle 209 of the second group of coating devices positioned in rear.
S2, a substrate 208, on the surface of which a conductive layer and an electron/hole transport layer have been prepared, is placed on the coating stage 106. First, the injection pump 104 of one of the first group of coating devices is turned on, the transfer device 107 is turned on, and the perovskite solution is transported to the coating die 101 of one group through the conduit 103 of one group. The set of die lifting tables 102 and the coating platform 106 are driven by the conveying device 107 to move relatively, the height between the set of coating dies 101 and the substrate 208 to be coated is adjusted by the two sets of die lifting tables 102, and the set of coating dies 101 performs first coating on the surface of the substrate 208 to be coated placed on the coating platform 106.
S3, next, the injection pump 204 of the second group of coating devices is turned on, the surfactant solution is delivered to the coating dies 201 of the second group through the conduit 203 of the second group, and the conveyor 107 is turned on to deliver the substrate 208 coated with the perovskite solution to the coating dies 201 of the second group of coating devices. Simultaneously, the two sets of die lifting tables 202 and the coating platform 106 are driven by the conveying device 107 to move relatively, the two sets of die lifting tables 202 are used for adjusting the height between the two sets of coating dies 201 and the substrate 208 to be coated, the two sets of coating dies 201 are used for coating the surface of the substrate 208 which is placed on the coating platform 106 and is coated with the perovskite solution for the second time, and the surface of the substrate 208 is coated with a wet film of the perovskite solution and the surfactant solution in sequence.
And S4, starting the post-processing device 105, conveying the substrate 208 coated with the wet film to the post-processing device 105 by the conveying device 107 for post-processing, and promoting the solvent in the wet film to be further volatilized to obtain a dry film, so that a perovskite thin film layer is prepared on the electron/hole transport layer of the substrate 208.
And S5, continuously preparing a hole/electron transport layer and a back electrode layer on the surface of the perovskite thin film layer of the substrate 208 until the preparation of the perovskite solar cell is completed.
Specifically, in S3, the two-group coating die 201 is to coat the surfactant solution in a state where the perovskite solution wet film coated by the first-group coating device on the surface of the substrate 208 is in a semi-solidified and semi-flowing state.
Specifically, in S4, before the post-processing device 105 is turned on, the wet film on the surface of the substrate 208 is in a leveling state.
Specifically, in S1, the perovskite solution and the surfactant solution placement order are interchanged as needed, and the coating order and the number of coating times of the perovskite solution and the surfactant solution in S2 and S3 are also adjusted as needed.
Specifically, in S1, the concentration of the perovskite solution is 0.5-1.5mol/L, the perovskite solution includes a perovskite solute and a dilution solvent, the perovskite solute is abbreviated as ABX 3, wherein a is at least one of MA +、FA+、Cs+, B is at least one of Pb 2+、Sn2+、Ze2+, and X is at least one of Cl -、Br-、I-. The dilution solvent is at least one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GBL). The mass ratio of the surfactant solution to the perovskite solution is 0.01-10%, and the surfactant solution comprises an active agent solute and an active agent solvent. The active agent solute is nonionic, cationic, anionic and amphoteric surfactant, and the active agent solvent is at least one of petroleum ether, carbon tetrachloride, trichloroethane, benzene, dichloromethane, chloroform, ethyl acetate and acetone.
Specifically, in S2 and S3, the operation setting parameter conditions of the two sets of the coating dies are: the width of the slit is 20-300um, the coating liquid amount is 0.2-2ul/cm 2, the coating speed is 0.5-50cm/s, the liquid outlet temperature of the coating die head is 25-180 ℃, and the coating temperature is 25-180 ℃. The two groups of coating dies also met the following environmental conditions when coated: the ambient temperature is 15-30 ℃, the ambient humidity is 0-50% RH, and the environment is in a common atmosphere or an inert protective atmosphere. The parameters of the coating die 101 of one set and the coating die 201 of two sets are set independently of each other, and are not necessarily the same.
Specifically, a film forming apparatus (not shown) that performs a film forming process on the wet film just coated on the surface of the substrate 208 within 0 to 60s after the end of the coating die of the group is also provided on each of the die lifting tables. The film forming apparatus includes a heater and a blower or blower, or a heater and a vacuum pump.
Specifically, the film forming treatment includes a heat treatment or a drying treatment. The heat treatment is to place the substrate after each coating is finished at the low vacuum pressure of 10 -5-105 Pa and the air temperature of 25-150 ℃ for 10-600s for annealing treatment. The drying treatment is to rapidly dry the wet film on the surface of the substrate after each coating by adopting air convection caused by a blowing or exhausting mode, wherein the air speed of air flowing caused by blowing or exhausting is 0.5-10m/s, and the temperature of flowing air is 25-150 ℃.
Specifically, in S4, the post-processing performed by the post-processing device 105 includes: placing the substrate 208 coated with the wet film of the perovskite solution and the surfactant solution under the action of at least one gas of vacuum, dry air, nitrogen, H 2 O (water), DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), GBL (gamma-butyrolactone) and NMP (N-methylpyrrolidone), wherein the ambient pressure is 10 -5-106 Pa, the ambient temperature is 100-150 ℃, the standing time is 5-120min, and drying the wet film into a dry film, thereby preparing the perovskite thin film layer on the surface of the substrate.
The invention also discloses a perovskite solar cell, which comprises a perovskite thin film layer, wherein the perovskite thin film layer is prepared by adopting the perovskite solution and surfactant step-by-step coating equipment, or is prepared by adopting the using method of the perovskite solution and surfactant step-by-step coating equipment, or is prepared by adopting the preparation method of the perovskite solar cell.
The technical scheme of the invention is further described below in combination with specific implementation.
Example 1
The perovskite thin film layer is prepared by adopting the method in the prior art, so that the perovskite solar cell is prepared. And coating 1mol/L of MAPbI 3 perovskite solution on the substrate of the PTAA electron/hole transport layer in a slit coating mode, wherein the dilution solvents contained in the perovskite solution are DMF and DMSO, the volume ratio of DMF to DMSO is 9:1, and then heating and drying the coated substrate to obtain the substrate containing the perovskite film layer.
Wherein, slit coating conditions: the amount of the coating solution was 0.7ul/cm 2 at 25℃and 30% RH, the slit width was 100um, and the coating speed was 5cm/s. Drying conditions after coating: and (3) carrying out hot air drying, wherein the air speed near the surface of the substrate is 2m/s, the temperature near the surface of the substrate is 60 ℃, and annealing the substrate containing the MAPbI 3 film at 100 ℃ for 10min after coating.
Referring to fig. 4, there are many white holes in the perovskite thin film layer, because the hydrophilic MAPbI 3 solution is difficult to infiltrate the surface of the lipophilic PTAA electron/hole transport layer when the MAPbI 3 solution is applied, and the cohesion of the MAPbI 3 solution is greater than the adhesion to the surface of the contact portion of the PTAA electron/hole transport layer, resulting in a tendency of the MAPbI 3 solution to "shrink", thereby causing many holes.
Example two
If a layer of surfactant solution is applied before the perovskite solution is applied, and a layer of surfactant solution is applied after the perovskite solution is applied, a schematic cross-sectional view of the perovskite thin film layer after the perovskite thin film layer is applied is obtained as shown in FIG. 5. The conductive layer 11 and the electron/hole transport layer 12-2 are sequentially prepared on a substrate, a perovskite solution 16 containing a surfactant is coated on the electron/hole transport layer 12-2, and the surface active agent 17 is respectively arranged on the upper and lower surfaces of the perovskite solution 16. In the figure, small dots of the surfactant 17 are hydrophilic groups and curves are lipophilic groups. Hydrophilic groups are distributed on the side near the perovskite solution 16, while lipophilic groups are distributed on the lipophilic electron/hole transport layer 12-2 and the air side of the perovskite solution 16. The addition of the surfactant 17 effectively improves the wettability of the perovskite solution 16 to the lipophilic electron/hole transport layer 12-2, improves the flatness of the surface of the perovskite solution in contact with air, and improves the coverage rate of the perovskite film to the electron/hole transport layer 12-2 and the uniformity of film thickness.
An embodiment of preparing a perovskite thin film layer using the perovskite solution and surfactant step-coating apparatus of the present invention comprises the steps of:
Firstly, preparing a perovskite solution of 1mol/L MAPbI 3 by taking DMF (N, N-dimethylformamide) as a solvent; DMF (N, N-dimethylformamide) is prepared as a solvent, and is mixed with SDS (sodium dodecyl sulfate) surfactant solution with mass fraction of 10% of MAPbI 3 perovskite solution.
Next, SDS surfactant solution and MAPbI 3 perovskite solution were separately filled into two feed bottles.
Then, a layer of SDS surfactant solution is coated on the PTAA electron/hole transport layer substrate in a slit mode by using the perovskite solution and surfactant step-by-step coating equipment, after the PTAA electron/hole transport layer substrate is dried to form a film, a layer of MAPbI 3 perovskite solution is coated, and after the MAPbI 3 perovskite solution is in a semi-solidification semi-flow state, a layer of SDS surfactant solution is coated in a slit mode.
Wherein, the conditions of slot coating of SDS surfactant solution: the coating liquid amount was 0.4ul/cm 2, the slit width was 100um, the coating speed was 5cm/s, the coating temperature was 70℃and the coating was performed under hot air (the wind speed near the surface of the substrate coated with hot air was 2m/s, and the temperature near the surface of the substrate was 60 ℃) at 25℃and 30% RH.
Wherein, slit coating conditions of MAPbI 3 perovskite solution: the coating liquid amount was 0.7ul/cm 2, the slit width was 100um, the coating speed was 5cm/s, the coating temperature was 130℃and the coating was performed under hot air (the wind speed near the surface of the substrate coated with hot air was 2m/s, and the temperature near the surface of the substrate was 60 ℃) at 25℃and 30% RH.
Then, the coated substrate was post-treated with a post-treatment device to obtain a substrate containing a perovskite thin film layer. Wherein, post-treatment conditions: the substrate coated with the MAPbI 3 film was annealed at 100℃under 10 3 Pa and in a dry air atmosphere for 10min.
As shown in fig. 6, it is clear from the figure that, compared with the first embodiment, the defects such as shrinkage cavity are eliminated, the coverage rate of the perovskite thin film layer of the present embodiment on the substrate of the lipophilic PTAA electron/hole transport layer is greatly improved, and the outer surface of the perovskite thin film layer is smoother.
Referring to fig. 7, an efficiency chart of perovskite solar cell is shown after perovskite thin film layers of example one and example two are completely prepared in the same manner. The structure of the prepared perovskite solar cell is as follows: the test effective cell area was 1cm 2 for ITO/hole transport layer/perovskite layer/C 60/BCP/Cu. The test gave the battery efficiencies of example one and example two as follows: 6.5 percent and 17.3 percent.
As can be seen from fig. 7, the perovskite thin film of the first embodiment has a large number of shrinkage cavities, which results in low coverage of the perovskite layer on the electron/hole transport layer substrate, resulting in poor short circuit current density JSC and fill factor FF of the battery. The existence of the holes may also cause leakage of the battery, resulting in poor open circuit voltage VOC.
Compared with the first embodiment, after the surfactant is added in the second embodiment, the coverage rate of the perovskite film on the electron/hole transport layer substrate is obviously and greatly improved, so that the battery efficiency is also greatly improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
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