Dimethyl sulfoxide (DMSO)-based preparation method for perovskite material and perovskite solar cell using same
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2025-09-24
- Publication Date
- 2026-08-13
Smart Images
Figure KR2025014953_13082026_PF_FP_ABST
Abstract
Description
Method for manufacturing a dimethyl sulfoxide (DMSO)-based perovskite material and a perovskite solar cell utilizing the same
[0001] The present invention relates to a method for producing a perovskite material that does not form a complex with a lead halide by adding an organic acid to dimethyl sulfoxide (DMSO), and to a perovskite solar cell comprising the perovskite material produced by the said method.
[0002]
[0003] Perovskite solar cells are attracting attention as next-generation solar cells because they can be mass-produced relatively easily and inexpensively by coating a solution onto a substrate. Fabricating perovskite solar cells requires a process of dissolving two or more types of materials in a solvent. Highly toxic solvents, such as dimethylformamide (DMF), have primarily been used for this purpose, but there is a problem in that large amounts of dimethylformamide can be released during the manufacturing process.
[0004] Meanwhile, dimethyl sulfoxide (DMSO) is an eco-friendly solvent and is a substance found in small quantities in frequently consumed foods such as milk and vegetables. Perovskite material (FAPbI3) can be produced by mixing a halide (FAI) and a lead halide (PbI2) and dissolving them in the solvent dimethyl sulfoxide (DMSO). At this time, it is known that the solvent dimethyl sulfoxide (DMSO) forms a complex with the lead halide (PbI2) as shown in Reaction Scheme 1 below, making it difficult to remove.
[0005] [Reaction Equation 1]
[0006] FAI + PbI2+ DMSO → FAI + PbI2-DMSO complex
[0007] The double bond between S and O in dimethyl sulfoxide (DMSO) is very weak because efficient overlap does not occur due to the difference in p-orbital sizes, and due to the strong electronegativity of oxygen, polarization of S(+)-O(-) occurs, forming a strong bond with lead halide (PbI2). The PbI2-DMSO complex can be viewed as being composed of Lewis acid-base bonds, and lead halide (PbI2) can act as an acid or a base depending on the conditions of the system. Accordingly, the reaction of Scheme 2 below can be induced by adding an appropriate organic acid, and a perovskite material (FAPbI3) can be prepared by adding an anti-solvent.
[0008] [Reaction Equation 2]
[0009] FAI + PbI2 + DMSO → FA + + PbI3 - + DMSO
[0010] Accordingly, the present invention aims to provide a method for manufacturing a perovskite material that does not form a PbI2-DMSO complex.
[0011]
[0012] The present invention provides a method for producing a perovskite material by adding a suitable organic acid based on dimethyl sulfoxide (DMSO).
[0013] In addition, the present invention provides a perovskite solar cell comprising a perovskite material manufactured using the above method.
[0014]
[0015] A method for manufacturing a perovskite material according to the present invention may comprise: S1) a step of preparing a perovskite precursor solution by dissolving a halide and a lead halide in dimethyl sulfoxide; S2) a step of adding an organic acid to the perovskite precursor solution and stirring until it becomes transparent; and S3) a step of obtaining a perovskite material by washing the transparent perovskite precursor solution with an antisolvent.
[0016] The perovskite material according to one embodiment may be a compound represented by the following chemical formula 1.
[0017] [Chemical Formula 1]
[0018] ABX3
[0019] (A is a monovalent cation, and B is a divalent lead cation (Pb 2+ ) and X is a halogen anion.)
[0020] According to one embodiment, the molar ratio of the halide and the lead halide may be 0.5 to 3:1.
[0021] The halogen according to one embodiment may include one or more selected from organic halogens including formamidinium (FA) and phenethylammonium (PEA); and metal halogens including cesium (Cs) and rubidium (Rb).
[0022] The lead halide according to one embodiment may include a halogen ion of the same type as the halide.
[0023] In step S1) according to one embodiment, the dimethyl sulfoxide (DMSO) may be 1 to 50 mL per 5 g of total halides including the halides and lead halides.
[0024] According to one embodiment, step S2) may add the organic acid until the pH of the perovskite precursor solution reaches a range of 1 to 6.
[0025] According to one embodiment, the organic acid may be a monoprotic acid that is in a liquid state at room temperature.
[0026] According to one embodiment, the pKa of the organic acid may be -1 to 7.
[0027] According to one embodiment, the antisolvent may comprise one or more selected from alcohols including ethanol, isopropanol, butanol, pentanol, and heptanol; and organic solvents including ethyl acetate, diethyl ether, dibutyl ether, toluene, chlorobenzene, dichloromethane, hexane, cyclohexane, benzene, ethylbenzene, chlorobenzene, and chloroform.
[0028] According to one embodiment, the antisolvent may be a mixture of alcohol and ethyl acetate in a volume ratio of 1:0 to 5.
[0029] According to one embodiment, step S3) may dry the perovskite precursor solution washed with the antisolvent at 70 to 200°C.
[0030] In step S1) according to one embodiment, the step of adding and stirring 10 to 100 mL of the antisolvent per 5 g of total halide, including the halide and lead halide, in the perovskite precursor solution may be further included.
[0031] The yield of the perovskite material according to one embodiment may be 60 to 99%.
[0032] According to one embodiment, the bandgap of the perovskite material may be 1 to 3 eV.
[0033] In addition, the perovskite solar cell according to the present invention comprises a first electrode stacked on a substrate; a perovskite material stacked on the first electrode; and a second electrode stacked on the perovskite material; wherein the perovskite material can be manufactured by a method for manufacturing the perovskite material.
[0034] The photoelectric conversion efficiency of the perovskite solar cell according to one embodiment may be 15 to 25%.
[0035]
[0036] According to the present invention, the ratio of the perovskite composition can be freely adjusted, and using this characteristic, perovskite materials with a bandgap of 1 to 3 eV can be manufactured. In addition, the production equipment can be simplified by manufacturing perovskite materials based on dimethyl sulfoxide (DMSO), an eco-friendly solvent.
[0037] In addition, a perovskite solar cell comprising a dimethyl sulfoxide (DMSO)-based perovskite material according to the present invention exhibits a photoelectric conversion efficiency similar to that of commercially available solar cells.
[0038]
[0039] Figure 1 shows a perovskite material (FAPbI3) prepared as a black powder according to one embodiment of the present invention.
[0040] Figure 2 shows the X-ray diffraction peaks of the perovskite material (FAPbI3) prepared in Examples 1 and 6, measured using X-ray diffraction (XRD).
[0041] Figure 3 shows a perovskite material (FAPbI3) according to the type of organic acid of the present invention.
[0042] Figure 4 shows a current density-voltage graph of a perovskite solar cell according to Experimental Example 3 of the present invention.
[0043] Figure 5 shows a current density-voltage graph of a perovskite solar cell according to Experimental Example 4 of the present invention.
[0044] Figure 6 shows a current density-voltage graph of a perovskite solar cell according to Experimental Example 5 of the present invention.
[0045] FIG. 7 is a perovskite material (FA) according to the perovskite composition of the present invention. 1-x Cs x Pb(I 1-x Br x It represents )3).
[0046] Figure 8 shows the absorbance and photoluminescence of a perovskite material according to Experimental Example 6 of the present invention.
[0047]
[0048] The embodiments described in this specification may be modified in various different forms, and the technology according to one embodiment is not limited to the embodiments described below. Furthermore, the embodiments of one embodiment are provided to more fully explain the present disclosure to those with average knowledge in the relevant technical field. Unless otherwise defined, technical and scientific terms used herein have the meanings commonly understood by those with ordinary knowledge in the technical field to which this invention pertains, and descriptions of known functions and configurations that could unnecessarily obscure the essence of the present invention are omitted in the following description and accompanying drawings.
[0049] Additionally, the singular form used in this specification and the appended claims may be intended to include the plural form unless specifically indicated otherwise in the context.
[0050] Furthermore, in this specification and the appended claims, terms such as "first," "second," etc. are used not in a limiting sense, but for the purpose of distinguishing one component from another.
[0051] Furthermore, in this specification and the appended claims, when a part such as a film (layer), region, or component is described as being located "on," "on top," "on the upper," "under," "on the lower," or "on the lower" of another part, this includes not only cases where a part is in contact with another part, but also cases where another part exists between the two parts.
[0052] Furthermore, terms such as "approximately" and "substantially" as used in this specification and the appended claims are used to mean at or near the stated value when inherent manufacturing and material tolerances are presented in the said meaning, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure in which precise or absolute values are mentioned to aid in understanding this specification and the appended claims.
[0053] Additionally, numeric ranges used in this specification include lower and upper limits and all values within the range, increments logically derived from the shape and width of the defined range, all of which are limited values, and all possible combinations of upper and lower limits of numeric ranges limited in different forms.
[0054] Furthermore, in this specification and the appended claims, terms such as "comprising" or "having" mean that the features or components described in the specification exist, and unless specifically limited, do not preclude the possibility that one or more other features or components may be added.
[0055] Hereinafter, the method for manufacturing a dimethyl sulfoxide (DMSO)-based perovskite material according to the present invention and a perovskite solar cell utilizing the same will be described in detail with reference to the attached drawings.
[0056]
[0057] A method for manufacturing a perovskite material based on dimethyl sulfoxide (DMSO) according to the present invention may comprise: S1) a step of preparing a perovskite precursor solution by dissolving a halide and a lead halide in dimethyl sulfoxide; S2) a step of adding an organic acid to the perovskite precursor solution and stirring until it becomes transparent; and S3) a step of obtaining a perovskite material by washing the transparent perovskite precursor solution with an antisolvent.
[0058] As one example, the perovskite material may be a compound represented by the following chemical formula 1.
[0059] [Chemical Formula 1]
[0060] ABX3
[0061] (A is a monovalent cation, and B is a divalent lead cation (Pb 2+ ) and X is a halogen anion.)
[0062] As one embodiment, the perovskite material can realize various colors depending on the composition of A, B, and X in Chemical Formula 1. For example, the perovskite material of the composition FAPbI3 may be a black powder, but is not limited thereto.
[0063] Step S1) above is a step of preparing a perovskite precursor solution by dissolving halides and lead halides in the solvent dimethyl sulfoxide (DMSO).
[0064] In one embodiment, the molar ratio of the halide and the lead halide may be 2:1 as an upper limit and 0.5:1 as a lower limit, and may be within a range between any two values among 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, or any two values listed herein. For example, it may be 0.5 to 3:1, 0.5 to 2:1, or 0.5 to 1.5:1, but is not limited thereto.
[0065] In one embodiment, the halide may comprise one or more selected from organic halides including formamidinium (FA) and phenethylammonium (PEA); and metal halides including cesium (Cs) and rubidium (Rb). Preferably, it may be formamidinium iodide (FAI), but is not limited thereto. Additionally, organic halides including methylammonium (MA) cannot be used because they form an amide through a side reaction with an organic acid in step S2) described later.
[0066] In one embodiment, the lead halide may include a halogen ion of the same type as the halide, although it is not particularly limited. Preferably, it may be lead iodide (PbI2), but is not limited thereto.
[0067] In one embodiment, in step S1), dimethyl sulfoxide (DMSO) may be used in an amount of 1 mL or more, 2 mL or more, 3 mL or more, 50 mL or less, 40 mL or less, 30 mL or less, 20 mL or less, 10 mL or less, or within a range between any two of the values listed herein, per 5 g of total halides including the halides and lead halides. For example, it may be 1 to 50 mL, 2 to 30 mL, or 3 to 10 mL per 5 g of total halides, but is not limited thereto.
[0068] Step S2) above is a step of adding an organic acid to the perovskite precursor solution and stirring until the perovskite precursor solution becomes transparent.
[0069] In one embodiment, step S2) may involve adding an organic acid until the pH of the perovskite precursor solution reaches a range of 1 or higher, 2 or higher, 3 or higher, 6 or lower, 5 or lower, 4 or lower, or between any two values listed herein. For example, the pH may be 1 to 6, 2 to 5, or 3 to 4, but is not limited thereto. Accordingly, a reaction to form the perovskite material of Reaction Scheme 2 can be induced.
[0070] As an example, the organic acid is not particularly limited as long as it achieves the purpose and effect of the present invention. Preferably, it may be a single protic acid in a liquid state at room temperature, but is not limited thereto.
[0071] In addition, as one embodiment, the pKa of the organic acid may be -1 or higher, 1 or higher, 2 or higher, 3 or higher, 7 or lower, 6 or lower, 5 or lower, or within a range between any two of the values listed herein. For example, it may be -1 to 7, 1 to 6, or 3 to 5, but is not limited thereto. Preferably, it may be acetic acid (pKa 4.75), formic acid (pKa 3.74), or a mixture thereof, which are monoprotic acids in a liquid state at room temperature, but is not limited thereto.
[0072] Step S3) above is a step of obtaining a perovskite material by washing the cleared perovskite precursor solution with an antisolvent and drying it.
[0073] An anti-solvent refers to a solvent with opposite properties used to remove solvent components from a perovskite precursor solution and grow solid-phase perovskites. By adding an anti-solvent to a solution containing dissolved perovskite components, only the solvent is evaporated, thereby yielding a perovskite material suitable for use as a photoactive layer.
[0074] In one embodiment, the antisolvent is not particularly limited as long as it is an alcohol or organic solvent that does not dissolve the perovskite material. For example, it may include one or more selected from alcohols including ethanol, isopropanol, butanol, pentanol, and heptanol; and organic solvents including ethyl acetate, diethyl ether, dibutyl ether, toluene, chlorobenzene, dichloromethane, hexane, cyclohexane, benzene, ethylbenzene, chlorobenzene, and chloroform. Preferably, alcohol and ethyl acetate may be mixed in a volume ratio of 1:0 to 5, 1:0.5 to 4.5, or 1:1 to 4, but are not limited thereto.
[0075] In one embodiment, the antisolvent washing may be performed one or more times, two or more times, ten or fewer times, nine or fewer times, eight or fewer times, seven or fewer times, six or fewer times, or within a range between any two values listed herein. For example, it may be one or more times, one to ten times, or two to six times, but is not limited thereto.
[0076] In one embodiment, step S3) can obtain a perovskite material by inducing a phase transition while drying the perovskite precursor solution washed with the antisolvent.
[0077] In one embodiment, the drying temperature may be 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 200°C or lower, 190°C or lower, 180°C or lower, 170°C or lower, 160°C or lower, 150°C or lower, or within a range between any two of the values listed herein. For example, it may be 70 to 200°C, 70 to 150°C, or 100 to 150°C, but is not limited thereto.
[0078] In one embodiment, when the perovskite precursor solution is washed with the antisolvent in step S3), perovskite crystals are generated and a precipitate is formed; therefore, the method may further include a step of separating the perovskite precipitate generated in the perovskite precursor solution by vacuum filtration. The vacuum filtration is not particularly limited as long as it is a method capable of separating the perovskite precipitate by applying reduced pressure.
[0079] In addition, as an embodiment, the step of adding the antisolvent to the perovskite precursor solution and stirring may be further included in step S1). The antisolvent may be used in an amount of 10 mL or more, 20 mL or more, 30 mL or more, 100 mL or less, 90 mL or less, 80 mL or less, 70 mL or less, 60 mL or less, 50 mL or less, or within a range between any two of the values listed herein, per 5 g of total halide in the perovskite precursor solution. For example, it may be 10 to 100 mL, 20 to 80 mL, or 30 to 50 mL per 5 g of total halide, but is not limited thereto. Accordingly, the solvent dimethyl sulfoxide (DMSO) can be removed to induce a reaction forming the perovskite material of Reaction Scheme 2, rather than a reaction forming the complex of Reaction Scheme 1.
[0080] As one embodiment, the yield of the perovskite material according to the present invention may be 60% or more, 70% or more, 80% or more, 99% or less, or within a range between any two of the values described herein. For example, it may be 60 to 99%, 70 to 99%, or 80 to 99%, but is not limited thereto.
[0081] In one embodiment, the bandgap of the perovskite material according to the present invention can be controlled according to the ratio of constituent cations and anions. The bandgap may be 1 eV or more, 1.1 eV or more, 1.2 eV or more, 1.3 eV or more, 1.4 eV or more, 3 eV or less, 2.9 eV or less, 2.8 eV or less, 2.7 eV or less, 2.6 eV or less, 2.5 eV or less, 2.4 eV or less, 2.3 eV or less, or within a range between any two of the values described herein. For example, it may be 1 to 3 eV, 1.2 to 2.5 eV, or 1.4 to 2.3 eV, but is not limited thereto.
[0082] According to the present invention, FA + , Cs + A site and I of etc. - , Br - The ratio of X sites can be freely controlled, and using this characteristic, perovskite materials with a bandgap of 1 to 3 eV can be manufactured. In addition, the production equipment can be simplified by manufacturing perovskite materials based on dimethyl sulfoxide (DMSO), an eco-friendly solvent.
[0083] In addition, the perovskite solar cell according to the present invention comprises a first electrode stacked on a substrate; a perovskite material stacked on the first electrode; and a second electrode stacked on the perovskite material; wherein the perovskite material can be manufactured by the method for manufacturing a perovskite material based on dimethyl sulfoxide (DMSO) described above.
[0084] As an example, the substrate is not particularly limited as long as it is one commonly used in the art. For example, it may comprise one or more selected from glass, plastic, metal, or composites thereof. Preferably, it may be a glass substrate, but is not limited thereto.
[0085] In one embodiment, the first electrode is not particularly limited as long as it is commonly used in the art. For example, as a transparent conductive electrode, it may include one or more selected from the group comprising indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), and carbon (C). Preferably, it may be indium-doped tin oxide (ITO), but is not limited thereto.
[0086] In one embodiment, the second electrode is not particularly limited as long as it is commonly used in the art. For example, it may include one or more selected from the group comprising gold (Au), silver (Ag), platinum (Pt), palladium (Pd), copper (Cu), aluminum (Al), and carbon (C). Preferably, it may be a gold (Au) electrode, but is not limited thereto.
[0087] In one embodiment, the perovskite solar cell may further include an electron transport layer or a hole transport layer on top of each component to improve the performance of the perovskite solar cell.
[0088] As an example, the electron transport layer is not particularly limited as long as it is one commonly used in the art. For example, titanium oxide, tin oxide, zinc oxide, PCBM (Phenyl-C61-Butyric Acid Methyl Ester), PCDTBT (Poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4,7-di-2-thienyl-2,1,3-benzothiadiazole)]), and Fullerene (C 60 It may include one or more selected from the group including ). Preferably, it may be tin oxide (SnO2), but is not limited thereto.
[0089] As an example, the hole transport layer is not particularly limited as long as it is one commonly used in the art. For example, it may include one or more selected from the group comprising PTAA (poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]), Spiro-OMeTAD (2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene), P3HT (poly(3-hexylthiophene)), CuPc (copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine), and PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate). Preferably, it may be Spiro-OMeTAD, but is not limited thereto.
[0090] In one embodiment, the perovskite material may be surface-treated to improve the efficiency and stability of the perovskite solar cell. For example, the surface treatment may be performed using a solution containing one or more selected from the group comprising MeO-PEAI (4-methoxy-phenethylammonium iodide), MABr (Methylammonium bromide), MACl (Methylammonium Chloride), Meo-4PACz ((4-(3,6-Dimethoxy-9H-carbazol-9-yl)butyl)phosphonic acid) and BCP (Bathocuproine). Preferably, it may be MeO-PEAI, but is not limited thereto.
[0091] The photoelectric conversion efficiency of the perovskite solar cell according to the present invention may be 15% or more, 16% or more, 17% or more, 18% or more, 25% or less, 24% or less, 23% or less, 22% or less, 21% or less, or within a range between any two of the values described herein. For example, it may be 15 to 25%, 17 to 23%, or 18 to 21%, but is not limited thereto.
[0092]
[0093] Examples and experimental examples are described below with specific examples. However, the examples and experimental examples described below are merely illustrative of some aspects, and the technology described in this specification is not limited thereto.
[0094]
[0095] <Example 1>
[0096] 2.72 g (15.8 mmol) of FAI, 7.28 g (15.8 mmol) of PbI2, and 8 mL of DMSO were mixed and stirred at room temperature for about 20 minutes until all of the PbI2 was dissolved. To the above solution, 80 mL of a solution of EtOH and EA mixed in a 1:1 volume ratio was added, and 12 mL of acetic acid was added as an organic acid and stirred until the solution became clear. The above solution was washed twice with a solution of EtOH and EA mixed in a 1:1 volume ratio, and then dried at 150 °C to produce 9.45 g (yield 94.5%) of perovskite material (FAPbI3).
[0097]
[0098] <Example 2>
[0099] 9.05 g (yield 90.5%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 10 mL of acetic acid was added.
[0100]
[0101] <Example 3>
[0102] 8.73 g (yield 87.3%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 8 mL of acetic acid was added.
[0103]
[0104] <Example 4>
[0105] 8.26 g (yield 82.6%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 6 mL of acetic acid was added.
[0106]
[0107] <Example 5>
[0108] 8.05 g (yield 80.5%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 4 mL of acetic acid was added.
[0109]
[0110] <Example 6>
[0111] 7.57 g (yield 75.7%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 2 mL of acetic acid was added.
[0112]
[0113] <Experimental Example 1>
[0114] The perovskite material (FAPbI3) prepared according to one embodiment of the present invention is a black powder. The perovskite materials (FAPbI3) prepared in Examples 1 to 6 were compared according to the amount of acetic acid added. Figure 1 shows the perovskite material (FAPbI3) prepared as a black powder according to one embodiment of the present invention.
[0115]
[0116] Amount Added (mL) pH Before Addition pH After Addition Whether Synthesis Example 1 1 27.2 3.00 Example 2 1 0 7.5 3.50 Example 3 8 7.2 3.20 Example 4 6 7.5 3.60 Example 5 4 7.3 3.7X Example 6 2 7.4 3.9X
[0117]
[0118] Table 1 shows whether perovskite materials were synthesized according to the amount of acetic acid added in Examples 1 to 6. In Examples 1 to 4, the perovskite materials were produced as black powders. However, in Examples 5 and 6, perovskite materials were not produced as a result of forming a PbI2-DMSO complex. This was confirmed to be because the amount of acetic acid added in Examples 5 and 6 was insufficient, which failed to induce the reaction to form perovskite materials.
[0119] Figure 2 shows the X-ray diffraction peaks of the perovskite material (FAPbI3) prepared in Examples 1 and 6, measured using X-ray diffraction (XRD). The XRD peak at 2θ = 10 ± 0.5° corresponds to the PbI2-DMSO complex. The XRD peak at 2θ = 11.8 ± 0.5° corresponds to the δ phase of the perovskite. The perovskite δ phase has a non-perovskite trigonal crystal structure, and the higher the δ phase contained in the perovskite, the lower the photoelectric conversion efficiency of the perovskite device. The XRD peak at 2θ = 13.8 ± 0.5° corresponds to the α phase of the perovskite. The α-phase of the perovskite is a perovskite with a cubic crystal structure, and the more α-phase there is, the higher the photoelectric conversion efficiency of the perovskite and the higher the stability from the external environment.
[0120] In Example 1, the peak corresponding to the PbI2-DMSO complex and the δ phase is significantly low, and the peak corresponding to the α phase is large, indicating that it has a cubic crystal structure. However, in Example 6, the peak corresponding to the PbI2-DMSO complex and the δ phase is large, indicating that it has a PbI2-DMSO complex and a trigonal crystal structure. Accordingly, it was confirmed that high-quality perovskite materials can be synthesized by suppressing the formation of the PbI2-DMSO complex upon the addition of acetic acid.
[0121]
[0122] <Example 7>
[0123] 9.37 g (yield 93.7%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 12 mL of Formic acid was added as the organic acid.
[0124]
[0125] <Example 8>
[0126] 8.90 g (yield 89.0%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 16 mL of propanoic acid was added as the organic acid.
[0127]
[0128] <Example 9>
[0129] 8.86 g (yield 88.6%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 12 mL of valeric acid was added as the organic acid.
[0130]
[0131] <Example 10>
[0132] 6.70 g (yield 67.0%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 12 mL of Pivalic acid was added as the organic acid.
[0133]
[0134] <Example 11>
[0135] 6.74 g of perovskite material (FAPbI3) (yield 67.4%) was prepared by carrying out the same procedure as in Example 1 above, except that 8 mL of citric acid was added as the organic acid.
[0136]
[0137] <Example 12>
[0138] 6.44 g (yield 64.4%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 12 mL of oxalic acid was added as the organic acid.
[0139]
[0140] <Example 13>
[0141] 6.64 g (yield 66.4%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 12 mL of Benzoic acid was added as the organic acid.
[0142]
[0143] <Example 14>
[0144] 5.90 g (yield 59.0%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 8 mL of hypo-phosphorous acid was added as the organic acid.
[0145]
[0146] <Example 15>
[0147] 5.37 g (yield 53.7%) of perovskite material (FAPbI3) was prepared by carrying out the same procedure as in Example 1 above, except that 4 mL of phosphorous acid was added as the organic acid.
[0148]
[0149] <Experimental Example 2>
[0150] Perovskite materials (FAPbI3) prepared in Examples 1, 7 to 15 were compared according to the type of organic acid. Figure 3 shows the perovskite materials (FAPbI3) according to the type of organic acid of the present invention.
[0151]
[0152] Organic Acid Type State pKa Amount Added (mL) Synthesis Status Example 1 Acetic acid Monoprotonic acid Liquid 4.75 12 O Example 7 Formic acid Monoprotonic acid Liquid 3.74 12 O Example 8 Propanoic acid Monoprotonic acid Liquid 4.88 16 O Example 9 Valeric acid Monoprotonic acid Liquid 4.82 12 O Example 10 Pivalic acid Monoprotonic acid Solid 5.01 12 X Example 11 Citric acid Polyprotonic acid Solid 3.13 8 X Example 12 Oxalic acid Diprotonic acid Solid pKa1= 1.27, pKa2= 4.27 12 X Example 13 Benzoic acid Monoprotonic acid Solid 4.2 12 X Example 14 Hypo-phosphorous acid Monoprotonic acid Solid 2.28 X 15 Phosphorous acid, a diprotic solid, pKa1= 1.3, pKa2= 6.74X
[0153]
[0154] Table 2 shows whether perovskite materials were synthesized according to the type of organic acid in Examples 1, 7 to 15. In Examples 1, 7 to 9, the perovskite materials were produced as black powder. However, in Examples 10 and 15, impurities remained, so the perovskite materials were not produced as black powder.
[0155]
[0156] <Example 16>
[0157] 2.5×2.5 cm 2 After forming a first electrode by depositing indium tin oxide (ITO) on a glass substrate using a sputtering method, it was completely cleaned through ultrasonic treatment using isopropyl alcohol (IPA) and subsequent argon (Ar) plasma treatment.
[0158] 300 μL of an aqueous solution of SnO2 nanoparticles at a concentration of 10 mmol / mL was spin-coated onto the first electrode at 3000 rpm for 30 seconds, and then heat-treated at 150 ℃ for 10 minutes to form an electron transport layer.
[0159] A perovskite precursor solution was prepared by dissolving the perovskite material (FAPbI3) prepared in Example 1 above in a solvent mixed with dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 8:1. 70 μL of the perovskite precursor solution was spin-coated onto the electron transport layer at 5000 rpm for 30 seconds, and at the 10-second mark, 0.6 mL of diethyl ether was dropped onto a substrate rotating at 5000 rpm, and heat-treated at 100 ℃ for 1 hour to form a perovskite layer.
[0160] In addition, 200 μL of an isopropyl alcohol (IPA) solution containing 4-methoxyphenethylammonium iodide (4MeO-PEAI) dissolved at a concentration of 10 mM was spin-coated onto the perovskite layer at 5000 rpm for 30 seconds, and then heat-treated at 100 ℃ for 5 minutes to surface-treat the perovskite layer.
[0161] A hole transport layer was formed by spin-coating 70 μL of spiro-OMeTAD solution onto the surface-treated perovskite layer at 3000 rpm for 30 seconds.
[0162] A perovskite solar cell was fabricated by depositing gold (Au) to a thickness of 70 nm as a second electrode on the hole transport layer using thermal evaporation equipment.
[0163]
[0164] <Example 17>
[0165] A perovskite solar cell was manufactured by carrying out the same procedure as in Example 16 above, except that the perovskite material (FAPbI3) of Example 7 above was used.
[0166]
[0167] <Example 18>
[0168] A perovskite solar cell was manufactured by carrying out the same procedure as in Example 16 above, except that the perovskite material (FAPbI3) of Example 8 above was used.
[0169]
[0170] <Example 19>
[0171] A perovskite solar cell was manufactured by carrying out the same procedure as in Example 16 above, except that the perovskite material (FAPbI3) of Example 9 above was used.
[0172]
[0173] <Comparative Example 1>
[0174] 2.72 g (15.8 mmol) of FAI, 7.28 g (15.8 mmol) of PbI2, and 8 mL of 2ME (2-Methoxyethanol) were mixed and stirred at room temperature for about 20 minutes until all of the PbI2 was dissolved. The solution was placed in an oil bath at 100 °C and stirred for 20 minutes to precipitate FAPbI3. Afterward, the supernatant of the solution was discarded, and the lower layer was washed twice with EA. The washed lower layer was dried at 100 °C to produce 9.63 g (yield 96.3%) of perovskite material (FAPbI3). Subsequently, a perovskite solar cell was prepared by proceeding in the same manner as in Example 16, except that the perovskite material (FAPbI3) was used.
[0175]
[0176] <Experimental Example 3>
[0177] A perovskite solar cell containing the perovskite material (FAPbI3) of Examples 1, 7 to 9, prepared as a black powder in Experimental Example 2 above was prepared and compared with the perovskite solar cell of Comparative Example 1, prepared using 2ME, which is used in conventional perovskite manufacturing, as a solvent. Figure 4 shows the current density-voltage graph of the perovskite solar cell according to Experimental Example 3 of the present invention.
[0178]
[0179] ReverseV OC (V)J SC (mA / cm 2 )FF (%) PCE (%) Example 16 (Acetic acid) 1.17 23.9 17 9.5 22.36 Example 17 (Formic acid) 1.16 23.5 0 76.6 20.91 Example 18 (Propanoic acid) 1.19 23.8 17 7.7 22.04 Example 19 (Valeric acid) 1.14 23.5 6 78.1 21.11 Comparative Example 1 (2ME) 1.12 24.0 27 5.7 20.44
[0180]
[0181] Table 3 shows the open-circuit voltages (V) of Examples 16 to 19 and Comparative Example 1. OC ), short-circuit current density (J SC This shows the filling factor (FF) and photoelectric conversion efficiency (PCE). Examples 16 to 19 showed photoelectric conversion efficiencies similar to Comparative Example 1. Therefore, it was confirmed that the photoelectric conversion efficiency of a perovskite solar cell prepared using DMSO as a solvent and a perovskite solar cell prepared using the conventional solvent 2ME is almost similar, regardless of the type of organic acid used in the preparation of the perovskite material.
[0182]
[0183] <Example 20>
[0184] 2.72 g (15.8 mmol) of FAI from greatcell solar, 7.28 g (15.8 mmol) of PbI2 from TCI, and 8 mL of DMSO were mixed and heated to 70 °C while stirring for about 20 minutes until all the PbI2 was dissolved. To the above solution, 80 mL of a solution of EtOH and EA mixed in a 1:1 volume ratio was added, and 12 mL of acetic acid was added and stirred until the solution became transparent. The above solution was washed twice with a solution of EtOH and EA mixed in a 1:1 volume ratio, and then dried at 150 °C to produce 9.37 g (yield 93.7%) of perovskite material (FAPbI3). Subsequently, a perovskite solar cell was prepared by proceeding in the same manner as in Example 16, except that the above perovskite material (FAPbI3) was used.
[0185]
[0186] <Example 21>
[0187] Synthetic PbI2 was prepared by mixing a solution of 243.1 g of Pb(NO3) dissolved in 61 mL of distilled water with a solution of 51.84 g of KI dissolved in 42 mL of distilled water, stirring at 100 °C for 1 hour, washing with distilled water, ethanol (EtOH), and ether, and drying at 150 °C. Subsequently, a perovskite material was prepared by carrying out the same procedure as in Example 20, except that 9.15 g (yield 91.5%) of perovskite material (FAPbI3) was prepared using the synthesized PbI2.
[0188]
[0189] <Example 22>
[0190] 17 mL of HI no stabilizer was added to 50 mL of an aqueous solution containing 12.1 g of FA acetate using a pipette pump, and the mixture was concentrated under reduced pressure at 80 °C for 1 hour. 30 mL of ethanol (EtOH) was added to the concentrated material to dissolve it, and then ether was added to precipitate the solution until it became clear. The precipitated material was washed with distilled water, ethanol (EtOH), and ether, and dried at 75 °C to produce synthetic FAI. Subsequently, a perovskite material was prepared by proceeding in the same manner as in Example 20, except that 9.27 g (yield 92.7%) of perovskite material (FAPbI3) was prepared using the synthetic FAI.
[0191]
[0192] <Experimental Example 4>
[0193] Perovskite solar cells prepared in Examples 20 to 22 and Comparative Example 1 were compared according to the manufacturers of the halide (FAPbI3) and lead halide (PbI2). Figure 5 shows the current density-voltage graph of the perovskite solar cell according to Experimental Example 4 of the present invention.
[0194]
[0195] ReverseV OC(V)J SC (mA / cm 2 )FF (%) PCE (%) Example 20 (greatcell solar FAI + TCI PbI2, DMSO) 1.05 2.04 8.01 1.86 1 Example 21 (greatcell solar FAI + synthetic PbI2, DMSO) 1.12 2.87 7.97 1.95 1.56 Example 22 (synthetic FAI + TCI PbI2, DMSO) 1.11 2.74 7.96 1.95 1.3 Comparative Example 1 (FAPbI3, 2ME) 1.12 2.03 7.95 1.96 1.5
[0196]
[0197] Table 4 shows the open-circuit voltages (V) of Examples 20 to 22 and Comparative Example 1. OC ), short-circuit current density (J SC This shows the packing factor (FF) and photoelectric conversion efficiency (PCE). Examples 20 to 22 showed photoelectric conversion efficiencies similar to Comparative Example 1. Therefore, it was confirmed that the photoelectric conversion efficiency of a perovskite solar cell prepared using DMSO as a solvent and a perovskite solar cell prepared using the conventional solvent 2ME is almost similar, regardless of the manufacturer of the halide and lead halide used in the preparation of the perovskite material.
[0198]
[0199] <Example 23>
[0200] 2.54 g (20.3 mmol) of FABr, 7.46 g (20.3 mmol) of PbBr2, and 7 mL of DMSO were mixed and stirred at room temperature for about 20 minutes until all of the PbBr2 was dissolved. To the above solution, 80 mL of a solution of EtOH and EA mixed in a 1:1 volume ratio was added, and 12 mL of acetic acid was added and stirred until the solution became clear. The above solution was washed twice with a solution of EtOH and EA mixed in a 1:1 volume ratio, and then dried at 150 °C to produce 8.84 g (yield 88.4%) of perovskite material (FAPbBr3). Subsequently, a perovskite solar cell was prepared by proceeding in the same manner as in Example 16, except that the above perovskite material (FAPbBr3) was used.
[0201]
[0202] <Comparative Example 2>
[0203] A perovskite solar cell was prepared by carrying out the same procedure as in Comparative Example 1 above, except that 9.5 g of perovskite material (FAPbBr3) (yield 95.0%) was prepared using 2.54 g (20.3 mmol) of FABr, 27.46 g (20.3 mmol) of PbBr, and 10 mL of 2ME.
[0204]
[0205] <Experimental Example 5>
[0206] Perovskite solar cells prepared in Example 23 and Comparative Example 2 were compared according to the solvent used in the preparation of the perovskite material. Figure 6 shows the current density-voltage graph of the perovskite solar cell according to Experimental Example 5 of the present invention.
[0207]
[0208] ReverseV OC (V)J SC (mA / cm 2)FF (%) PCE (%) Example 23 (FAPbBr3, DMSO) 1.40 7.737 7.28.33 Comparative Example 2 (FAPbBr3, 2ME) 1.35 7.676 9.47.16
[0209]
[0210] Table 5 shows the open-circuit voltage (V) of Example 23 and Comparative Example 2. OC ), short-circuit current density (J SC This shows the filling factor (FF) and photoelectric conversion efficiency (PCE). Example 23, in which DMSO was used as a solvent when preparing the perovskite material (FAPbI3), showed a photoelectric conversion efficiency similar to that of Comparative Example 2, in which 2ME was used as a solvent. Therefore, it was confirmed that regardless of the type of material used when preparing the perovskite material, the photoelectric conversion efficiency of a perovskite solar cell prepared using DMSO as a solvent and a perovskite solar cell prepared using the conventional solvent 2ME are almost similar.
[0211]
[0212] <Example 24>
[0213] 2.037 g (11.8 mmol) of FAI, 5.465 g (11.8 mmol) of PbI2, 0.84 g (3.95 mmol) of CsBr, 1.45 g (3.95 mmol) of PbBr2, and 8 mL of DMSO were mixed and stirred at room temperature for about 20 minutes until all of PbI2 and PbBr2 dissolved. To the above solution, 80 mL of a solution of EtOH and EA mixed in a 1:1 volume ratio was added, followed by the addition of 12 mL of acetic acid, and the mixture was stirred until the solution became clear. The above solution was washed twice with a solution of EtOH and EA mixed in a 1:1 volume ratio, and then dried at 150 °C to obtain a perovskite material (Cs 0.25 FA 0.75 Pb(I 0.75 Br 0.25 )3) 8.66 g (yield 88.4%) was produced.
[0214]
[0215] <Example 25>
[0216] The above Example 24 was carried out in the same manner as before, except that 1.36 g (7.91 mmol) of FAI, 3.64 g (7.91 mmol) of PbI2, 1.68 g (7.90 mmol) of CsBr, and 22.90 g (7.90 mmol) of PbBr2 were used, and the perovskite material (Cs 0.5 FA 0.5 Pb(I 0.5 Br 0.5 )3) 8.7 g (yield 90.8%) was produced.
[0217]
[0218] <Example 26>
[0219] The above Example 24 was carried out in the same manner as before, except that 0.68 g (3.95 mmol) of FAI, 1.82 g (3.95 mmol) of PbI, 2.52 g (11.8 mmol) of CsBr, and 24.35 g (11.8 mmol) of PbBr were used, and the perovskite material (Cs 0.75 FA 0.25 Pb(I 0.25 Br 0.75 )3) 8.5 g (yield 90.7%) was produced.
[0220]
[0221] <Example 27>
[0222] 9.5 g (yield 95.0%) of perovskite material (CsPbBr3) was prepared by carrying out the same procedure as in Example 24 above, except that 3.67 g (17.2 mmol) of CsBr and 26.33 g (17.2 mmol) of PbBr were used.
[0223]
[0224] <Experimental Example 6>
[0225] FIG. 7 is a perovskite material (FA) according to the perovskite composition of the present invention. 1-x Cs x Pb(I 1-x Br x)3) is shown. The perovskite materials prepared in Examples 1, 24 to 27 were prepared as powders of various colors depending on the composition of the perovskite.
[0226] Figure 8 shows the absorbance and photoluminescence of a perovskite material according to Experimental Example 6 of the present invention. To analyze the optical properties of a perovskite solar cell, UV-Vis absorption spectra and photoluminescence spectra were measured.
[0227] The bandgap of Example 1 was measured to be 1.53 eV in UV-Vis and 1.56 eV in PL, the bandgap of Example 24 was measured to be 1.71 eV in UV-Vis and 1.73 eV in PL, and the bandgap of Example 25 was measured to be 1.92 eV in UV-Vis and 1.94 eV in PL. In addition, the bandgap of Example 26 was measured to be 2.15 eV in UV-Vis and 2.15 eV in PL, and the bandgap of Example 27 was measured to be 2.27 eV in UV-Vis and 2.31 eV in PL. Therefore, as confirmed in UV-Vis and PL, it was confirmed that perovskite materials with bandgaps ranging from 1 to 3 eV can be manufactured depending on the composition of the perovskite.
[0228]
[0229] As described above, the present invention has been explained in this specification by specific details and limited embodiments, but this is provided only to aid in a more comprehensive understanding of the invention, and the invention is not limited to the above embodiments. A person skilled in the art to which the invention pertains can make various modifications and variations from this description. Accordingly, the concept described in this specification should not be limited to the described embodiments, and all things equivalent to or having equivalent variations to the claims set forth below, as well as the claims themselves, shall be considered to fall within the scope of the concept described in this specification.
Claims
1. S1) A step of preparing a perovskite precursor solution by dissolving a halide and a lead halide in dimethyl sulfoxide; S2) a step of adding an organic acid to the perovskite precursor solution and stirring until it becomes transparent; and S3) A step of obtaining a perovskite material by washing the above-mentioned transparent perovskite precursor solution with an antisolvent; A method for manufacturing a perovskite material comprising 2. In Paragraph 1, A method for manufacturing a perovskite material, wherein the perovskite material is a compound represented by the following chemical formula 1. [Chemical Formula 1] ABX3 (A is a monovalent cation, and B is a divalent lead cation (Pb 2+ ) and X is a halogen anion.) 3. In Paragraph 1, A method for manufacturing a perovskite material, wherein the molar ratio of the halide and lead halide is 0.5 to 3:
1.
4. In Paragraph 1, A method for manufacturing a perovskite material, wherein the above-mentioned halide comprises one or more selected from organic halides including formamidinium (FA) and phenethylammonium (PEA); and metal halides including cesium (Cs) and rubidium (Rb).
5. In Paragraph 1, A method for manufacturing a perovskite material in which the lead halide comprises a halogen ion of the same type as the halide.
6. In Paragraph 1, A method for preparing a perovskite material, wherein in step S1) above, dimethyl sulfoxide (DMSO) is 1 to 50 mL per 5 g of total halides including the halides and lead halides.
7. In Paragraph 1, The above step S2) is a method for manufacturing a perovskite material, wherein the organic acid is added until the pH of the perovskite precursor solution reaches a range of 1 to 6.
8. In Paragraph 1, A method for manufacturing a perovskite material, wherein the above organic acid is a monoprotic acid that is in a liquid state at room temperature.
9. In Paragraph 8, A method for manufacturing a perovskite material, wherein the pKa of the organic acid is -1 to 7.
10. In Paragraph 1, A method for manufacturing a perovskite material, wherein the above-mentioned antisolvent comprises one or more selected from alcohols including ethanol, isopropanol, butanol, pentanol, and heptanol; and organic solvents including ethyl acetate, diethyl ether, dibutyl ether, toluene, chlorobenzene, dichloromethane, hexane, cyclohexane, benzene, ethylbenzene, chlorobenzene, and chloroform.
11. In Paragraph 10, A method for manufacturing a perovskite material, wherein the above-mentioned antisolvent is a mixture of alcohol and ethyl acetate in a volume ratio of 1:0 to 5.
12. In Paragraph 1, A method for manufacturing a perovskite material, wherein step S3) above involves drying the perovskite precursor solution washed with the above antisolvent at 70 to 200 ℃.
13. In Paragraph 1, A method for manufacturing a perovskite material, further comprising the step of adding and stirring 10 to 100 mL of the antisolvent per 5 g of the total halide, including the halide and lead halide, in the above step S1).
14. In Paragraph 1, A method for manufacturing a perovskite material, wherein the yield of the perovskite material is 60 to 99%.
15. In Paragraph 1, A method for manufacturing a perovskite material, wherein the bandgap of the perovskite material is 1 to 3 eV.
16. A first electrode laminated on a substrate; A perovskite material stacked on the first electrode; and A second electrode laminated on the above perovskite material; comprising, The above perovskite material is a perovskite solar cell manufactured by the method of any one of claims 1 to 15.
17. In Paragraph 16, A perovskite solar cell having a photoelectric conversion efficiency of 15 to 25%.