CN116836072A - Halogen ammonium salt for passivating perovskite defects, perovskite solar cell, preparation method and application - Google Patents
Halogen ammonium salt for passivating perovskite defects, perovskite solar cell, preparation method and application Download PDFInfo
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- -1 Halogen ammonium salt Chemical class 0.000 title claims abstract description 39
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 29
- 230000007547 defect Effects 0.000 title abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 57
- 239000002243 precursor Substances 0.000 claims description 36
- 238000012986 modification Methods 0.000 claims description 35
- 230000004048 modification Effects 0.000 claims description 35
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000004528 spin coating Methods 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 31
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 238000001704 evaporation Methods 0.000 claims description 19
- 230000005525 hole transport Effects 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 15
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- VOWZMDUIGSNERP-UHFFFAOYSA-N carbamimidoyl iodide Chemical compound NC(I)=N VOWZMDUIGSNERP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- QWVSXPISPLPZQU-UHFFFAOYSA-N bromomethanamine Chemical compound NCBr QWVSXPISPLPZQU-UHFFFAOYSA-N 0.000 claims description 11
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- 238000007747 plating Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000007740 vapor deposition Methods 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000013040 bath agent Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 2
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229940102396 methyl bromide Drugs 0.000 claims description 2
- 229940050176 methyl chloride Drugs 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 43
- 239000010408 film Substances 0.000 description 26
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 9
- 239000012296 anti-solvent Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 6
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- 239000012043 crude product Substances 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 229910052774 Proactinium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- FLEYLGCAQDCGHN-UHFFFAOYSA-N n-methyl-α-β-dehydroalanine Chemical compound CNC(=C)C(O)=O FLEYLGCAQDCGHN-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a halogen ammonium salt which can be used in a Perovskite Solar Cell (PSC) to passivate perovskite Pb-I halide defects and the perovskite solar cell thereof. After the halogen ammonium salt is applied to interface regulation of perovskite, the defects of the perovskite are reduced, the photoelectric conversion efficiency and stability of the device are improved, and the halogen ammonium salt belongs to the sustainable green energy field. Based on the PSC prepared by the method, the photoelectric conversion efficiency is as high as 20% or more, and after 1700h of storage in holes with the relative humidity of 40% -50% at 25 ℃, the battery efficiency can be maintained to be 80% or more of the initial efficiency.
Description
Technical Field
The invention belongs to the field of green sustainable energy, and particularly relates to a halogen ammonium salt for passivating perovskite defects, a perovskite solar cell, a preparation method and application thereof.
Background
Since the first report in 2009, organic-inorganic hybrid PSC photoelectric conversion efficiency has rapidly risen; meanwhile, PSC shows great advantages in both manufacturing process and cost control compared to commercial silicon-based solar cells, thereby drawing a wide attention from the scientific community and commercial community. Since perovskite materials have a relatively low defect formation energy, high density defects are easily formed during their preparation, mainly including Pb with insufficient coordination and positive charge 2+ Negatively charged Pb-I inversion defect and under-coordinated halide ion X - Defects. These defects can cause recombination of photogenerated charges, induce ion migration, and degradation of the perovskite. These factors become one of the main reasons for further improvement of PCE and stability affecting PSCs.
Interface modification materials reported in the literature to passivate perovskite surface defects can be categorized into two broad categories: (1) Organic compounds containing negatively charged lewis bases such as thiophenes, pyridines, phosphates, halides, and the like; such compounds can effectively deactivate positively charged under-coordinated Pb by coordination or electrostatic interactions 2+ Defects. (2) Containing negatively charged lewis acid organic compounds such as fullerenes and the like. The compounds can effectively passivate negatively chargedPb-I inversion defects and under-coordinated halide ion defects. The result shows that the perovskite can reduce defects and improve the long-term stability of the battery after being subjected to surface passivation. However, the materials reported to passivate perovskite all have lower mobility and the passivated perovskite is not level matched with the interfacial layer material, thereby reducing the optoelectronic performance of PSC (Zheng, x.; chen, b.; dai, j.; fang, y.; bai, y.; lin, y.; wei, h.; zeng, x.c.; huang, j.; defect passivation in hybrid perovskite solar cells using quaternary ammonium halide anions and treatments Nature Energy 2017,2 (7), 1-9.).
Disclosure of Invention
The invention provides a halogen ammonium salt M (X) which can be used in a Perovskite Solar Cell (PSC) to passivate perovskite Pb-I halide defects, and the halogen ammonium salt can reduce the perovskite defects after being applied to interface regulation of perovskite, so that the material is applied to the Perovskite Solar Cell (PSC) to improve the photoelectric conversion efficiency and stability of corresponding devices.
One of the purposes of the present invention is to provide a halogen ammonium salt, which has the following structural general formula:
wherein R is saturated or unsaturated alkyl with at least one of carbonyl, ester and mercapto; x is halogen, preferably, R is saturated or unsaturated alkyl with at least one of carbonyl, ester and sulfhydryl with 2-20 carbon atoms, preferably, saturated or unsaturated alkyl with at least one of carbonyl, ester and sulfhydryl with 4-12 carbon atoms, and X is preferably selected from one of Cl, br and I.
According to an embodiment of the invention, the haloammonium salt is obtained by reacting a haloalkane with an amine-based compound.
The second object of the present invention is to provide a method for preparing the above-mentioned haloammonium salt, comprising: dissolving halogenated alkane in a solvent, adding an amino compound, and heating to react to obtain the halogenated ammonium salt.
Specifically, in the preparation method:
wherein the halogenated alkane is selected from halogenated alkanes with the carbon number of 1-6, preferably at least one of methyl iodide, methyl chloride and methyl bromide;
the amino compound is at least one of amino fatty acid or a derivative thereof, preferably at least one of dimethylaminoethyl methacrylate, urethane dimethacrylate, diethylaminoethyl methacrylate and amino methacrylate;
the molar ratio of the halogenated alkane to the amino compound is 1.5:1-10:1, preferably 2.5:1-6:1;
the solvent is selected from organic solvents, can be marked as an organic solvent S1, and is preferably selected from at least one of dichloromethane, diethyl ether and tetrahydrofuran;
the volume ratio of the halogenated alkane to the solvent is 1:0.1-1:10, preferably 1:1-1:5;
the heating reaction temperature is 40-100 ℃, and the heating reaction time is 5-24 hours; preferably, the heating reaction temperature is 45-80 ℃, and the heating reaction time is 12-16 h;
the heating reaction is carried out in inert atmosphere;
the haloammonium salt obtained by the heating reaction also needs to be recrystallized, the solution obtained by the heating reaction is cooled, the solvent is removed, and the obtained crude product adopts a common recrystallization process to obtain the white solid haloammonium salt.
The invention also provides the application of the halogen ammonium salt or the halogen ammonium salt obtained by the preparation method to perovskite solar cells.
The fourth object of the present invention is to provide a perovskite solar cell comprising the above-mentioned haloammonium salt or the haloammonium salt obtained by the above-mentioned production method. Preferably, the perovskite solar cell sequentially comprises: the cathode comprises a cathode substrate, a hole transport layer, a photoactive layer, an interface modification layer containing the halogen ammonium salt, an electron transport layer and a metal anode.
In a preferred embodiment of the invention:
the cathode substrate is ITO glass;
the hole transport layer is a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] layer;
the thickness of the hole transport layer is 5-20 nm, preferably 10-15 nm;
the photoactive layer is a perovskite photoactive layer; the perovskite photoactive layer can be selected from various perovskite photoactive layers existing in perovskite solar cells in the prior art;
the thickness of the photoactive layer is 200-500 nm, preferably 300-400 nm;
the thickness of the interface modification layer is 1-10 nm, preferably 2-5 nm;
the electron transport layer comprises C 60 An electron transport layer and a copper bath layer, preferably the C 60 The thickness of the electron transport layer is 10-50 nm, and the thickness of the copper bath agent is 5-10 nm; more preferably, said C 60 The thickness of the electron transport layer is 20-30 nm, and the thickness of the copper bath agent is 6-8 nm;
the metal anode is selected from at least one of Ag and Cu;
the thickness of the metal anode is 50-200 nm, preferably 80-100 nm.
The fifth object of the present invention is to provide a method for preparing the perovskite solar cell, comprising the steps of preparing an interface modification layer from components including the halogen ammonium salt, evaporating an electron transport layer and a metal electrode to obtain the perovskite solar cell, wherein the preparation method specifically comprises the following steps:
step one, preparing a precursor solution:
(a) Adding poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] Powder (PTAA) into an organic solvent, marking as an organic solvent S2, selecting a common toluene solvent, and stirring to obtain a hole transport precursor solution;
(b) Dissolving lead iodide, lead bromide, bromomethylamine, iodoformamidine and cesium iodide in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide to obtain a perovskite precursor solution;
(c) Dissolving ammonium halide salt in organic solvent, and marking as organic solvent S3, and selecting common Trifluoroethanol (TFE) to obtain ammonium halide salt solution;
spin-coating a hole transport precursor solution on indium tin oxide, and annealing to obtain an ITO/HTL film coated with a hole transport layer;
step three, spin-coating the perovskite precursor solution on the ITO/HTL film obtained in the step two, and drying to obtain the ITO/HTL/perovskite film coated with the perovskite photoactive layer;
spin-coating an ammonium halide salt solution on the ITO/HTL/perovskite film obtained in the step three to obtain an ITO/HTL/perovskite film covered with an interface modification layer;
step five, vapor deposition C 60 An electron transport layer, vapor plating bath copper;
and step six, evaporating the metal electrode.
Specifically, the preparation method comprises the following steps:
the concentration of the hole-transporting precursor solution is 0.1-5 mg/mL, preferably 0.5-2.0 mg/mL;
the dimethyl sulfoxide in the step b accounts for 1-20% of the total volume of the mixed solvent, preferably 5-10% by volume percent;
the perovskite precursor solution is filtered by a polytetrafluoroethylene filter head with the aperture of 0.45 mu m for later use;
in the perovskite precursor solution, calculated by taking 1mL of mixed solvent, 400-700 mg of lead iodide, 60-120 mg of lead bromide, 5-50 mg of bromomethylamine, 100-250 mg of iodoformamidine and 5-30 mg of cesium iodide are calculated; preferably, the mixed solvent is 1mL, the lead iodide is 450-600 mg, the lead bromide is 70-100 mg, the bromomethylamine is 10-30 mg, the iodoformamidine is 150-210 mg, and the cesium iodide is 10-20 mg;
the concentration of the halogen ammonium salt solution is 0.1-5.0 mg/mL, preferably 0.1-1.0 mg/mL;
the annealing temperature in the second step is 65-120 ℃, and the annealing time is 5-20 min; preferably, the annealing temperature is 80-100 ℃ and the annealing time is 5-10 min;
the drying temperature in the third step is 80-150 ℃, preferably 90-120 ℃;
evaporating C in the fifth step 60 The electron transport layer and the vapor plating bath copper can be obtained by vapor plating using common vacuum vapor plating method and process conditions, for example, in one embodiment of the invention, the electron transport layer and the vapor plating bath copper are formed by vapor plating in a range of less than 1×10 -5 Under Pa vacuum degree, C 60 After being heatedSlowly evaporating the film obtained in the step four to form a compact layer with a certain thickness, and evaporating a layer of Bath Copper (BCP);
the evaporation electrode in the step six can be obtained by adopting common electrode evaporation process conditions, and the metal electrode is selected from at least one of Ag and Cu. In one embodiment of the invention, the pressure of the vacuum chamber pressure during evaporation is kept to be less than 1×10 -4 Pa, in order toAg was evaporated at a rate of (c).
The invention provides a halogen ammonium salt M (X) ionization interface modification material with strong electric dipole moment, wherein the halogen ammonium salt compound has a carbonyl group, an ester group and other functional groups with lone pair electron pairs, and can passivate the defects of noncoordinating Pb in perovskite; meanwhile, the material has longer alkyl chain, has certain hydrophobicity and can improve the humidity stability of the device. The material can not only passivate the defects on the surface of perovskite and reduce the probability of charge recombination in a defect state, but also improve the charge transmission and collection of PSC, thereby greatly improving the Photoelectric Conversion Efficiency (PCE) and stability of PSC. After M (X) interface passivation, PCE of PSC is obviously improved by more than 20%, and stability of the device is also obviously improved. After 1700h of storage in holes with a relative humidity of 40% -50% at 25 ℃, the initial efficiency is still maintained to be more than 80%.
The invention has the beneficial effects that:
1. the highest PCE of PSC prepared after M (X) interface modification was 20.4%, while the highest PCE of PSC without interface modification was 18.8%, corresponding J-V curves are shown in fig. 2;
2. the device efficiency prepared based on M (X) interface modification is obviously higher than that of a control group, because after M (X) interface modification, the transmission resistance is reduced, good charge transfer and lower recombination (as shown in figure 3) are realized, and the photovoltaic performance of the device can be improved;
3. unencapsulated PSCs prepared based on M (X) interface modification exhibited excellent humidity stability. PSC devices based on M (X) interface modification can still maintain more than 80% of initial efficiency (i.e., T) when placed for 1700h under atmospheric conditions with humidity of 40% -50% and temperature of 25deg.C 80 ＝1700h)。
Drawings
FIG. 1 is a J-V curve of PSC prepared in accordance with the present invention, wherein a is the J-V curve of PSC obtained in example 3 and b is the J-V curve of PSC obtained in comparative example 1;
FIG. 2 is an electrochemical impedance spectrum test of PSC prepared in accordance with the present invention, wherein a is an electrochemical impedance spectrum curve of PSC obtained in example 3, and b is an electrochemical impedance spectrum curve of PSC obtained in comparative example 1;
FIG. 3 is a graph showing the humidity stability test of PSC prepared in accordance with the present invention, wherein a is the humidity stability test curve of PSC obtained in example 3, and b is the humidity stability test curve of PSC obtained in comparative example 1.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The test instruments and test conditions used in the examples are as follows:
the J-V curve is thatMeasurement under specific light and temperature. According to the world-accepted standard test condition requirement of the ground photovoltaic module, the atmospheric mass is AM1.5, and the irradiation intensity of the sunlight of the standard battery is 1000 W.m -2 The test temperature was 25 ℃. We used the XES-70S1 solar simulator of Japan to provide radiation, keithley 2400 of Keithley Instruments, U.S. to record the output of current and voltage to obtain the J-V curve of the cell. The illumination area of the active layer fixed by the mask plate is 0.1cm during the test 2 。
Thickness measurement: spectroscopic ellipsometry (M-2000V,J.A.Woollam Co., lincoln, NE, USA).
The sources of the raw materials used in the examples are as follows:
the ITO used in the experiment has a thickness of 1.2mm, a transmittance of >80%, and a sheet resistance of 10Ω/sq, and is purchased from Shenen glass Co.
The other raw materials are as follows:
| reagent(s) | Purity of | Source |
| Acetone (acetone) | Analytical grade | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Absolute ethyl alcohol | Analytical grade | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Isopropyl alcohol | Analytical grade | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| DMF | 99.8%, ultra-dry | Beijing Enoka technology Co.Ltd |
| DMSO | 99.8%, ultra-dry | Beijing Enoka technology Co.Ltd |
| Toluene (toluene) | 99.9%, ultra-dry | Sigma Aldrich Co Ltd |
| 2, 2-trifluoroethanol | 99％ | BEIJING J&K SCIENTIFIC Ltd. |
| PTAA | 99％ | Seanbao Lai SpA |
| Lead iodide | 99.999％ | Seanbao Lai SpA |
| Lead bromide | 99.999％ | Seanbao Lai SpA |
| Cesium iodide | 99.999％ | Seanbao Lai SpA |
| Iodoformamidine | 99％ | Seanbao Lai SpA |
| Bromomethylamine | 99.9％ | Seanbao Lai SpA |
| C 60 | 99％ | Seanbao Lai SpA |
| BCP | 99％ | Seanbao Lai SpA |
| Silver (Ag), copper (Cu) | 99.999％ | Minodyn science and technology Co Ltd |
Example 1
Preparation of ITO/PTAA/Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 /M(Cl)/C 60 PSC of/BCP/Ag.
(a) Synthesis of interface modification material M (Cl)
Into a 50mL two-necked flask, 10mL of methylene chloride solvent was added, 5mL of dimethylaminoethyl methacrylate was added under an inert atmosphere, and then 5mL of chloromethane was added dropwise. The reaction was heated to reflux 12h at 45 ℃. After cooling, the solvent was removed and the crude product was recrystallized to give M (Cl) as a white solid.
(b)ITO/PTAA/Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 /M(Cl)/C 60 Preparation of/BCP/Ag perovskite solar cell
Step one, preparing a precursor solution:
0.5mg of PTAA was weighed, dissolved in 1mL of toluene, and stirred overnight to give a hole transporting precursor solution.
Preparing Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 Perovskite precursor solution. Lead iodide (PbI) 2 ) 470.7 mg lead bromide (PbBr) 2 ) 71.1mg, 18.9mg of bromomethylamine (MABr), 169.2 mg of iodoformamidine (FAI) mg, 16.2mg of cesium iodide (CsI) are dissolved in 1mL of a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), wherein DMF: DMSO volume ratio of 95:5, obtaining perovskite precursor solution, and placing the perovskite precursor solution on a room temperature hot bench for stirring overnight.
1mg of M (Cl) was weighed, dissolved in 1mL of TFE, and stirred overnight to give an M (Cl) solution.
Step two, ITO/HTL film preparation
The ITO transparent substrate is sequentially washed by deionized water, acetone, ethanol and isopropanol for 20 minutes in an ultrasonic mode, is treated by ozone plasma for 15 minutes after being dried by nitrogen, and is placed in a nitrogen glove box to prepare the device. Firstly, 30 mu L of toluene solution of PTAA is spin-coated on an ITO substrate by adopting a spin-coating method, the rotating speed is 3000 revolutions per minute, the time is 30s, and after spin-coating is finished, the film is annealed on a hot table at 90 ℃ for 5 minutes to obtain a compact hole transport layer film, and the thickness is 14nm.
Step three, perovskite active layer preparation
Then spin-coating perovskite precursor solution on the ITO/PTAA film by adopting an anti-solvent method, and spin-coating 60 mu L of DMF solution at a rotation speed of 5000 revolutions per minute for 20 seconds to increase the wettability of PTAA. Then spin-coating 60uL of Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 Slowly dripping 120 mu L of anti-solvent toluene 3s before spin coating is finished at the rotating speed of 3000 revolutions per minute for 28s, and annealing the solution on a hot table at 90 ℃ for 10 minutes after spin coating is finished to obtain compactIs 330 a/nm a.
Step four, preparation of interface modification layer
Subsequently, an interface modification layer was spin-coated, and 50. Mu.L of a TFE solution of M (Cl) was spin-coated on the perovskite thin film at 4000 revolutions per minute for 50s, with an interface modification layer thickness of 4nm.
Step five, vapor deposition C 60 Electronic transmission layer, vapor plating bath copper agent
Then transferring into a vacuum evaporator to sequentially evaporate an electron transport layer C with the thickness of about 20nm 60 8nm electrode modification layer Bathocuproine (BCP). At less than 1X 10 -5 Under Pa vacuum degree, C 60 After being heatedAnd (3) slowly evaporating the film obtained in the step four to form a compact layer with a certain thickness, and then evaporating a layer of Bath Copper (BCP).
Step six, evaporating metal electrode
The pressure of the vacuum chamber pressure in vapor deposition is kept to be less than 1 multiplied by 10 -4 Pa, in order toAg electrode of 100nm.
Example 2
Preparation of ITO/PTAA/Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 /M(Br)/C 60 BCP/Ag perovskite solar cell.
(a) Synthesis of interface modification material M (Br)
Into a 50mL two-necked flask, 10mL of a tetrahydrofuran solvent was charged, 5mL of dimethylaminoethyl ethacrylate was added under an inert atmosphere, and then 5mL of bromomethane was added dropwise. The reaction was heated to reflux 16h at 60 ℃. After cooling, the solvent was removed and the crude product was recrystallized to give M (Br) as a white solid. After cooling, the solvent was removed and the crude product was recrystallized to give M (Br) as a white solid.
(b)ITO/PTAA/Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 /M(Br)/C 60 Preparation of/BCP/Ag perovskite solar cell
Step one, preparing a precursor solution:
1mg of PTAA was weighed, dissolved in 1mL of toluene, and stirred overnight to give a hole transporting precursor solution.
Preparing Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 Perovskite precursor solution. Lead iodide (PbI) 2 ) 575.3 mg lead bromide (PbBr) 2 ) 86.9mg, bromomethylamine (MABr) 23.1mg, iodoformamidine (FAI) 206.8 mg, cesium iodide (CsI) 19.8mg were dissolved in 1mL of a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), DMF: DMSO volume ratio 90: the perovskite precursor solution was obtained and placed on a room temperature hot bench and stirred overnight.
0.5mg of M (Br) was weighed, dissolved in 1mL of TFE, and stirred overnight to give an M (Br) solution.
Step two, ITO/HTL film preparation
The ITO transparent substrate is sequentially washed by deionized water, acetone, ethanol and isopropanol for 20 minutes in an ultrasonic mode, is treated by ozone plasma for 15 minutes after being dried by nitrogen, and is placed in a nitrogen glove box to prepare the device. Firstly, 30 mu L of toluene solution of PTAA is spin-coated on an ITO substrate by adopting a spin-coating method, the rotating speed is 4000 revolutions per minute, the time is 30s, and after spin-coating is finished, the film is annealed on a 95 ℃ hot table for 5 minutes to obtain a compact hole transport layer film, and the thickness of the film is 12nm.
Step three, perovskite active layer preparation
Then spin-coating perovskite precursor solution on the ITO/PTAA film by adopting an anti-solvent method, and spin-coating 60 mu L of DMF solution at a rotation speed of 5000 revolutions per minute for 20 seconds to increase the wettability of PTAA. Then spin-coating 60uL of Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 The solution, the rotation speed is 5000 revolutions per minute, the time is 28s, 140 mu L of anti-solvent toluene is slowly dripped 3s before the spin coating is finished, and the solution is placed on a 95 ℃ hot table for annealing for 10 minutes after the spin coating is finished, so that a compact perovskite active layer with the thickness of 300 nm is obtained.
Step four, preparation of interface modification layer
Subsequently, an interface modification layer was spin-coated, 50. Mu.L of a solution of M (Br) TFE was spin-coated on the perovskite film at a rotation speed of 5000 revolutions per minute for 50s, and the thickness of the interface modification layer was 3nm.
Step five, vapor deposition C 60 Electronic transmission layer, vapor plating bath copper agent
Then transferring into a vacuum evaporator to sequentially evaporate an electron transport layer C with the thickness of about 25nm 60 7nm electrode modification layer Bath Copper (BCP) below 1×10 -5 Under Pa vacuum degree, C 60 After being heatedAnd (3) slowly evaporating the film obtained in the step four to form a compact layer with a certain thickness, and then evaporating a layer of Bath Copper (BCP).
Step six, evaporating metal electrode
The pressure of the vacuum chamber pressure in vapor deposition is kept to be less than 1 multiplied by 10 -4 Pa, in order toIs evaporated at a rate of 90 nm.
Example 3
Preparation of ITO/PTAA/Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 /M(I)/C 60 BCP/Ag perovskite solar cell.
(a) Synthesis of interface modification material M (I)
In a 50mL two-necked flask, 5mL of a mixed solvent of methylene chloride and 5mL of methyl iodide was added, and 5mL of methylaminoacrylic acid was added under an inert atmosphere. The reaction was heated to reflux at 80℃for 12h. After cooling, the solvent was removed and the crude product was recrystallized to give white solid M (I).
(b)ITO/PTAA/Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 /M(I)/C 60 Preparation of/BCP/Ag perovskite solar cell
Step one, preparing a precursor solution:
2mg of PTAA was weighed, dissolved in 1mL of toluene, and stirred overnight to give a hole transporting precursor solution.
Preparing Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 Perovskite precursor solution. Lead iodide (PbI) 2 ) 523mg, lead bromide (PbBr) 2 ) 79mg, 21mg of bromomethylamine (MABr), 188mg of iodoformamidine (FAI), 18mg of cesium iodide (CsI) are dissolved in 1mL of a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), DMF: DMSO volume ratio of 95:5, obtaining perovskite precursor solution, and placing the perovskite precursor solution on a room temperature hot bench for stirring overnight.
0.1mg of M (I) was weighed, dissolved in 1mL of TFE, and stirred overnight to give a solution of M (I).
Step two, ITO/HTL film preparation
The ITO transparent substrate is sequentially washed by deionized water, acetone, ethanol and isopropanol for 20 minutes in an ultrasonic mode, is treated by ozone plasma for 15 minutes after being dried by nitrogen, and is placed in a nitrogen glove box to prepare the device. Firstly, 30 mu L of toluene solution of PTAA is spin-coated on an ITO substrate by adopting a spin-coating method, the rotating speed is 5000 revolutions per minute, the time is 30s, and after spin-coating is finished, the film is annealed on a hot table at 100 ℃ for 5 minutes to obtain a compact hole transport layer film, and the thickness of the film is 10nm.
Step three, perovskite active layer preparation
Then spin-coating perovskite precursor solution on the ITO/PTAA film by adopting an anti-solvent method, and spin-coating 60 mu L of DMF solution at a rotation speed of 5000 revolutions per minute for 20 seconds to increase the wettability of PTAA. Then spin-coating 60uL of Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 The solution, the rotation speed is 4000 rpm, the time is 28s, 130 mu L of anti-solvent toluene is slowly dripped 3s before the spin coating is finished, and the solution is placed on a 100 ℃ hot table for annealing for 10 minutes after the spin coating is finished, so that a compact perovskite active layer with the thickness of 320 nm is obtained.
Step four, preparation of interface modification layer
Subsequently, an interface modification layer was spin-coated, and 50. Mu.L of a TFE solution of M (I) was spin-coated on the perovskite thin film at 6000 rpm for 50s, with an interface modification layer thickness of 2nm.
Step five, vapor deposition C 60 Electronic transmission layer, vapor plating bath copper agent
Then transferring into a vacuum evaporator to sequentially evaporate an electron transport layer C with the thickness of about 30nm 60 6nm electrode modification layer Bath Copper (BCP) below 1×10 -5 Under Pa vacuum degree, C 60 After being heatedAnd (3) slowly evaporating the film obtained in the step four to form a compact layer with a certain thickness, and then evaporating a layer of Bath Copper (BCP).
Step six, evaporating metal electrode
The pressure of the vacuum chamber pressure in vapor deposition is kept to be less than 1 multiplied by 10 -4 Pa, in order toAn Ag electrode of 80nm was vapor deposited at a rate.
Comparative example 1
Preparation of ITO/PTAA/Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 /C 60 BCP/Ag perovskite solar cell:
weigh 2mg of PTAA, dissolve in 1mL of toluene and stir overnight. Preparing Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 Perovskite precursor solution. Lead iodide (PbI) 2 ) 523mg, lead bromide (PbBr) 2 ) 79mg, 21mg of bromomethylamine (MABr), 188mg of iodoformamidine (FAI), 18mg of cesium iodide (CsI) are dissolved in 1mL of a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), DMF: DMSO volume ratio of 95:5, obtaining perovskite precursor solution, and placing the perovskite precursor solution on a room temperature hot bench for stirring overnight; the ITO transparent substrate is sequentially washed by deionized water, acetone, ethanol and isopropanol for 20 minutes in an ultrasonic mode, is treated by ozone plasma for 15 minutes after being dried by nitrogen, and is placed in a nitrogen glove box to prepare the device. First, 30. Mu.L of PTAA in toluene was applied by spin coatingSpin-coating on an ITO substrate at a rotation speed of 5000 revolutions per minute for 30s, and annealing on a 100 ℃ heat table for 5 minutes after spin-coating to obtain a compact hole transport layer film; then spin-coating perovskite precursor solution on the ITO/PTAA film by adopting an anti-solvent method, and spin-coating 60 mu L of DMF solution at a rotation speed of 5000 revolutions per minute for 20 seconds to increase the wettability of PTAA. Then spin-coating 60uL of Cs 0.05 FA 0.81 MA 0.14 PbI 2.55 Br 0.45 The solution, the rotation speed is 4000 rpm, the time is 28s, 130 mu L of anti-solvent toluene is slowly dripped 3s before the spin coating is finished, and the solution is placed on a 100 ℃ hot table for annealing for 10 minutes after the spin coating is finished, so that a compact perovskite active layer is obtained. Then transferring into a vacuum evaporator to sequentially evaporate an electron transport layer C with the thickness of about 30nm 60 A6 nm electrode modification layer Bathes Copper (BCP) and an 80nm Ag electrode.
The photoelectric conversion efficiency was measured after the device preparation was completed, and the device efficiency obtained in example 3 was 20.4%; the photoelectric conversion efficiency of the device obtained in comparative example 1 was 18.8%, as shown in fig. 1. The photoelectric conversion efficiency of the device of comparative example 1 was 18.8%, which is significantly lower than that of the device modified with M (X) in the present invention. The charge carrier transport and recombination properties of the devices were studied using electrochemical impedance spectroscopy testing (fig. 2). The data shows that the transmission resistance is smaller after M (I) interface modification (example 3), which indicates that the device provided by the invention has good charge transfer and lower recombination; finally, the unpackaged device was placed in a cavity with a humidity of 40% -50% to test the humidity stability of the device (FIG. 3), and the M (I) -interface-based modified device (example 3) was maintained at 80% of the initial efficiency after 1700h, i.e., T 80 =1700 h, therefore, perovskite solar cells prepared based on M (I) interface modification layers open the way for commercialization development.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (12)
1. A haloammonium salt having the general structural formula:
wherein R is saturated or unsaturated alkyl with at least one of carbonyl, ester and mercapto; x is halogen.
2. The haloammonium salt according to claim 1, wherein in the structural formula:
the R is a saturated or unsaturated alkyl group with at least one of carbonyl, ester and sulfhydryl groups with the carbon number of 2-20, preferably a saturated or unsaturated alkyl group with at least one of carbonyl, ester and sulfhydryl groups with the carbon number of 4-12; and/or the number of the groups of groups,
and X is selected from one of Cl, br and I.
3. A process for the preparation of the haloammonium salt of claim 1 or 2 comprising: dissolving halogenated alkane in a solvent, adding an amino compound, and heating to react to obtain the halogenated ammonium salt.
4. A process according to claim 3, wherein,
the halogenated alkane is selected from halogenated alkanes with the carbon number of 1-6, preferably at least one of methyl iodide, methyl chloride and methyl bromide; and/or the number of the groups of groups,
the amino compound is at least one of amino fatty acid or a derivative thereof, preferably at least one of dimethylaminoethyl methacrylate, urethane dimethacrylate, diethylaminoethyl methacrylate and amino methacrylate; and/or the number of the groups of groups,
the molar ratio of the halogenated alkane to the amino compound is 1.5:1-10:1, preferably 2.5:1-6:1; and/or the number of the groups of groups,
the solvent is selected from organic solvents, preferably at least one of dichloromethane, diethyl ether and tetrahydrofuran; and/or the number of the groups of groups,
the volume ratio of the halogenated alkane to the solvent is 1:0.1-1:10, preferably 1:1-1:5; and/or the number of the groups of groups,
the heating reaction temperature is 40-100 ℃, and the heating reaction time is 5-24 hours; preferably, the heating reaction temperature is 45-80 ℃, and the heating reaction time is 12-16 h; and/or the number of the groups of groups,
the heating reaction is carried out in inert atmosphere; and/or the number of the groups of groups,
the haloammonium salt obtained by the heating reaction also needs to be recrystallized.
5. Use of the haloammonium salt according to claim 1 or 2, or obtained according to the preparation method of claim 3 or 4, in perovskite solar cells.
6. A perovskite solar cell comprising the haloammonium salt according to claim 1 or 2 or the haloammonium salt obtained by the production method according to claim 3 or 4.
7. The perovskite solar cell of claim 6, wherein the perovskite solar cell comprises, in order: the cathode comprises a cathode substrate, a hole transport layer, a photoactive layer, an interface modification layer containing the halogen ammonium salt, an electron transport layer and a metal anode.
8. The perovskite solar cell according to claim 7, wherein,
the cathode substrate is ITO glass; and/or the number of the groups of groups,
the hole transport layer is a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] layer; and/or the number of the groups of groups,
the thickness of the hole transport layer is 5-20 nm, preferably 10-15 nm; and/or the number of the groups of groups,
the photoactive layer is a perovskite photoactive layer; and/or the number of the groups of groups,
the thickness of the photoactive layer is 200-500 nm, preferably 300-400 nm; and/or the number of the groups of groups,
the thickness of the interface modification layer is 1-10 nm, preferably 2-5 nm; and/or the number of the groups of groups,
the electron transport layer comprises C 60 An electron transport layer and a bath copper layer, preferably the C 60 The thickness of the electron transport layer is 10-50 nm, and the thickness of the copper bath agent is 5-10 nm; more preferably, the C 60 The thickness of the electron transport layer is 20-30 nm, and the thickness of the copper bath agent is 6-8 nm; and/or the number of the groups of groups,
the metal anode is selected from at least one of Ag and Cu; and/or the number of the groups of groups,
the thickness of the metal anode is 50-200 nm, preferably 80-100 nm.
9. A method for preparing a perovskite solar cell according to any one of claims 6 to 8, comprising preparing an interface modification layer from components containing the halogen ammonium salt, evaporating an electron transport layer and a metal electrode, and obtaining the perovskite solar cell.
10. The preparation method according to claim 9, characterized in that the preparation method specifically comprises the following steps:
step one, preparing a precursor solution:
(a) Adding poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] powder into an organic solvent, and stirring to obtain a hole transport precursor solution;
(b) Dissolving lead iodide, lead bromide, bromomethylamine, iodoformamidine and cesium iodide in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide to obtain a perovskite precursor solution;
(c) Dissolving a halogen ammonium salt in an organic solvent to obtain a halogen ammonium salt solution;
spin-coating a hole transport precursor solution on indium tin oxide, and annealing to obtain an ITO/HTL film coated with a hole transport layer;
step three, spin-coating the perovskite precursor solution on the ITO/HTL film obtained in the step two, and drying to obtain the ITO/HTL/perovskite film coated with the perovskite photoactive layer;
spin-coating an ammonium halide salt solution on the ITO/HTL/perovskite film obtained in the step three to obtain an ITO/HTL/perovskite film covered with an interface modification layer;
step five, vapor deposition C 60 An electron transport layer, vapor plating bath copper;
and step six, evaporating the metal electrode.
11. The method according to claim 10, wherein in the first step:
the concentration of the hole-transporting precursor solution is 0.1-5 mg/mL, preferably 0.5-2.0 mg/mL; and/or the number of the groups of groups,
the dimethyl sulfoxide in the step b accounts for 1-20% of the total volume of the mixed solvent, preferably 5-10% by volume percent; and/or the number of the groups of groups,
in the perovskite precursor solution, calculated by taking 1mL of mixed solvent, 400-700 mg of lead iodide, 60-120 mg of lead bromide, 5-50 mg of bromomethylamine, 100-250 mg of iodoformamidine and 5-30 mg of cesium iodide are calculated; preferably, the mixed solvent is 1mL, the lead iodide is 450-600 mg, the lead bromide is 70-100 mg, the bromomethylamine is 10-30 mg, the iodoformamidine is 150-210 mg, and the cesium iodide is 10-20 mg; and/or the number of the groups of groups,
the concentration of the halogen ammonium salt solution is 0.1-5.0 mg/mL, preferably 0.1-1.0 mg/mL.
12. The method according to claim 10, wherein,
the annealing temperature in the second step is 65-120 ℃, and the annealing time is 5-20 min; preferably, the annealing temperature is 80-100 ℃ and the annealing time is 5-10 min; and/or the number of the groups of groups,
the drying temperature in the third step is 80-150 ℃, preferably 90-120 ℃.
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