CN116828873A - Solar cell and manufacturing method thereof - Google Patents
Solar cell and manufacturing method thereof Download PDFInfo
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- CN116828873A CN116828873A CN202310700674.1A CN202310700674A CN116828873A CN 116828873 A CN116828873 A CN 116828873A CN 202310700674 A CN202310700674 A CN 202310700674A CN 116828873 A CN116828873 A CN 116828873A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000003446 ligand Substances 0.000 claims abstract description 127
- 230000005540 biological transmission Effects 0.000 claims abstract description 70
- 230000005525 hole transport Effects 0.000 claims abstract description 44
- 230000007480 spreading Effects 0.000 claims abstract description 6
- 238000003892 spreading Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 672
- 239000000463 material Substances 0.000 claims description 61
- 230000031700 light absorption Effects 0.000 claims description 36
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 230000005641 tunneling Effects 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 11
- 239000002094 self assembled monolayer Substances 0.000 claims description 11
- 239000013545 self-assembled monolayer Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 9
- 238000005215 recombination Methods 0.000 claims description 8
- 230000006798 recombination Effects 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
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- 229910001195 gallium oxide Inorganic materials 0.000 claims description 7
- BDVZHDCXCXJPSO-UHFFFAOYSA-N indium(3+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[In+3] BDVZHDCXCXJPSO-UHFFFAOYSA-N 0.000 claims description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 7
- ATFCOADKYSRZES-UHFFFAOYSA-N indium;oxotungsten Chemical compound [In].[W]=O ATFCOADKYSRZES-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229930192474 thiophene Natural products 0.000 claims description 5
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000000969 carrier Substances 0.000 description 15
- ZROZRIKRPGMZBK-UHFFFAOYSA-N 2-iodo-1h-benzimidazole Chemical compound C1=CC=C2NC(I)=NC2=C1 ZROZRIKRPGMZBK-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- CWCKRNKYWPNOAZ-UHFFFAOYSA-N 2,3,5,6-tetrabromothieno[3,2-b]thiophene Chemical compound BrC1=C(Br)SC2=C1SC(Br)=C2Br CWCKRNKYWPNOAZ-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
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- -1 2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl Chemical group 0.000 description 5
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- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 4
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- KIMPAVBWSFLENS-UHFFFAOYSA-N 2-carbazol-9-ylethylphosphonic acid Chemical compound C1=CC=CC=2C3=CC=CC=C3N(C1=2)CCP(O)(O)=O KIMPAVBWSFLENS-UHFFFAOYSA-N 0.000 description 2
- YECSLYXTXWSKBO-UHFFFAOYSA-N 2-nonyl-1h-benzimidazole Chemical compound C1=CC=C2NC(CCCCCCCCC)=NC2=C1 YECSLYXTXWSKBO-UHFFFAOYSA-N 0.000 description 2
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 2
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
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- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
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- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
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- 238000004528 spin coating Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- APDAUBNBDJUQGW-UHFFFAOYSA-N 2,5-dibromothieno[3,2-b]thiophene Chemical compound S1C(Br)=CC2=C1C=C(Br)S2 APDAUBNBDJUQGW-UHFFFAOYSA-N 0.000 description 1
- DWPMHGKBWNDQQO-UHFFFAOYSA-N 2,5-dichlorothieno[3,2-b]thiophene Chemical compound S1C(Cl)=CC2=C1C=C(Cl)S2 DWPMHGKBWNDQQO-UHFFFAOYSA-N 0.000 description 1
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 1
- IUUMHORDQCAXQU-UHFFFAOYSA-N 3-heptylthiophene Chemical compound CCCCCCCC=1C=CSC=1 IUUMHORDQCAXQU-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- BXNFVPMHMPQBRO-UHFFFAOYSA-N magnesium nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Mg++].[Ni++] BXNFVPMHMPQBRO-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses a solar cell and a manufacturing method thereof, and relates to the technical field of photovoltaics, wherein a first carrier transmission layer is uniformly spread on a transparent conductive layer through a conductive ligand layer, so that the first carrier transmission layer has excellent transmission performance, and the photoelectric conversion efficiency of the solar cell is improved. The solar cell includes: a transparent conductive layer, and a conductive ligand layer, a first carrier transport layer, a light absorbing layer, and a second carrier transport layer sequentially stacked on the transparent conductive layer. One of the first carrier transport layer and the second carrier transport layer is a hole transport layer, and the other is an electron transport layer. The conductive ligand layer is used for uniformly spreading the first carrier transport layer on the transparent conductive layer. The manufacturing method of the solar cell is used for manufacturing the solar cell.
Description
Technical Field
The invention relates to the technical field of photovoltaics, in particular to a solar cell and a manufacturing method thereof.
Background
A solar cell is a device that converts solar energy into electric energy using the photoelectric effect of semiconductor materials. In particular, solar cells generally include a light absorbing layer, an electron transporting layer, a hole transporting layer, and a transparent conductive layer. The electron transport layer and the hole transport layer are respectively positioned on two sides of the light absorption layer along the thickness direction. The transparent conductive layer is positioned on one side of the electron transmission layer and/or the hole transmission layer, which is away from the light absorption layer, so as to improve the transverse transport of carriers of corresponding conductivity types and reduce the carrier recombination rate.
However, in the existing solar cell, the material of the transparent conductive layer has a large surface tension with the material of the electron transport layer and the hole transport layer, so that the electron transport layer or the hole transport layer directly manufactured on the transparent conductive layer is difficult to uniformly spread, thereby affecting the transport performance of the electron transport layer or the hole transport layer, and being unfavorable for improving the photoelectric conversion efficiency of the solar cell.
Disclosure of Invention
The invention aims to provide a solar cell and a manufacturing method thereof, so that a first carrier transmission layer is uniformly spread on a transparent conductive layer through a conductive ligand layer, and further the first carrier transmission layer has excellent transmission performance, which is beneficial to improving the photoelectric conversion efficiency of the solar cell.
In order to achieve the above object, in a first aspect, the present invention provides a solar cell comprising: a transparent conductive layer, and a conductive ligand layer, a first carrier transport layer, a light absorbing layer, and a second carrier transport layer sequentially stacked on the transparent conductive layer. One of the first carrier transport layer and the second carrier transport layer is a hole transport layer, and the other is an electron transport layer. The conductive ligand layer is used for uniformly spreading the first carrier transport layer on the transparent conductive layer.
Under the condition of adopting the technical scheme, the conductive ligand layer, the first carrier transmission layer, the light absorption layer and the second carrier transmission layer are sequentially stacked on the transparent conductive layer. One of the first carrier transport layer and the second carrier transport layer is a hole transport layer, and the other is an electron transport layer. Based on the above, when the solar cell is in an operating state, the electron and hole pairs generated by the photon absorption of the light absorption layer can be separated under the action of the first carrier transmission layer and the second carrier transmission layer and collected by the first carrier transmission layer and the second carrier transmission layer respectively. In addition, a transparent conductive layer is arranged on one side, away from the light absorption layer, of the first carrier transmission layer, and has excellent carrier transverse transmission rate, so that the collection rate of carriers is accelerated, the carrier recombination rate of the light absorption layer on one side, close to the first carrier transmission layer, is reduced, and the photoelectric conversion efficiency of the solar cell is improved. And, a conductive ligand layer having superior anchoring characteristics is further formed between the transparent conductive layer and the first carrier transport layer, so that the first carrier transport layer is uniformly spread on the transparent conductive layer. At this time, the thicknesses of the portions of the first carrier transport layer in the direction parallel to the surface of the light absorbing layer are the same or substantially the same, so that the portions of the first carrier transport layer in the direction parallel to the surface of the light absorbing layer can effectively collect carriers of the respective conductivity types. Meanwhile, the electric leakage and even short circuit caused by the fact that the first carrier transmission layer cannot be uniformly spread on the transparent conductive layer to enable the transparent conductive layer to be in direct contact with part of the light absorption layer can be prevented, only carriers of corresponding conductivity types and more in quantity can be led out through the first carrier transmission layer, the conductive ligand layer and the transparent conductive layer in sequence, and the photoelectric conversion efficiency of the solar cell is further improved.
As one possible implementation, in the case where the first carrier transport layer is a hole transport layer, the hole transport layer is a self-assembled monolayer having a phosphate group, and the conductive ligand layer is a pyridine-based conductive ligand layer.
Under the condition of adopting the technical scheme, the material of the conductive ligand layer is exemplified by 2-iodobenzimidazole: the main functional group of the self-assembled monolayer having phosphate groups is p=o. On this account, after the first carrier transport layer is formed on the conductive ligand layer, C in the five-membered ring and I connected thereto, which are possessed by 2-iodobenzimidazole, have strong dipole moment between the whole molecules, so that p=o is provided at an additional bonding site, and a chemical bond having a stronger bond strength and a larger bond energy such as p=o-I or p=o-N can be formed. Compared with a bond such as p=o-In or p=o-Sn formed by directly forming the first carrier transport layer on the transparent conductive layer, the chemical bond can remarkably enhance the coverage rate of the first carrier transport layer above the transparent conductive layer along the portions parallel to the surface of the conductive ligand layer, ensure that the first carrier transport layer serving as a hole transport layer can be uniformly spread above the transparent battery layer, further enable the first carrier transport layer to have excellent transport performance along the portions parallel to the surface of the conductive ligand layer, and further improve the photoelectric conversion efficiency of the solar battery. The mechanism of action of the other pyridine conductive ligand layers except the material of 2-iodobenzimidazole is similar to that of the conductive ligand layer of 2-iodobenzimidazole, and p=o is provided for an additional bonding site through the conductive ligand layer, which is not described herein.
As one possible implementation, in the case where the first carrier transport layer is a hole transport layer, the material of the conductive ligand layer is a benzimidazole-based bidentate ligand compound containing pyridine.
Under the condition of adopting the technical scheme, the transparent conductive film is directly transparent conductive with the prior artCompared with a solar cell with a first carrier transmission layer formed on the layer, when the solar cell comprises a conductive ligand layer made of benzimidazole bidentate ligand compound containing pyridine, various electrical parameters of the conductive ligand layer are improved well, and especially the short-circuit current density of the solar cell can be improved from 17.21mA/cm -2 Lifting to 19.36mA/cm -2 So that the solar cell has excellent working performance.
As one possible implementation, in the case where the first carrier transport layer is an electron transport layer, the electron transport layer is an N-type semiconductor layer having a conjugated cage-like carbon molecular structure, and the conductive ligand layer is a thiophene conductive ligand layer.
Under the condition of adopting the technical scheme, the conductive ligand layer is made of 2,3,5, 6-tetrabromothieno [3,2-b ] thiophene: thiophene ring is a heterocyclic compound, based on which, after forming a first carrier transport layer on a conductive ligand layer, the thiophene ring interacts with benzene rings on a carbon cage to form a large conjugate plane after contacting with an electron transport layer of a conjugated cage-shaped carbon molecular structure because S on a five-membered ring of 2 pairs of lone electrons and 2 C=C double bonds of 2,3,5, 6-tetrabromothieno [3,2-b ] thiophene has, thereby improving the coverage rate of the first carrier transport layer above the transparent conductive layer along parts parallel to the surface of the conductive ligand layer and improving the carrier transport; on the other hand, the thiophene ring of the small molecule can play a role of filling the cage-shaped carbon molecules, so that the stacking degree of the carbon cages is improved, and the carrier transmission is smoother; meanwhile, S also has stronger electronegativity, so the thiophene ring has strong electron-withdrawing characteristic, and the electron cloud density on the benzene ring can be changed, thereby improving the energy level of PCBM, enabling the energy level to be aligned, further enabling carriers to be fully led out, and playing a role in improving the open-circuit voltage of the device. The mechanism of action of the rest of the thiophene conductive ligand layers except the material 2,3,5, 6-tetrabromothieno [3,2-b ] thiophene is similar to that of the material 2,3,5, 6-tetrabromothieno [3,2-b ] thiophene, and is not repeated here.
As a possible implementation, the thickness of the conductive ligand layer is 1nm to 10nm.
Under the condition of adopting the technical scheme, the thickness of the conductive ligand layer is in the range, so that the possibility of direct contact between the first carrier transmission layer and the transparent conductive layer can be prevented from being increased due to the small thickness of the conductive ligand layer, and the first carrier transmission layer can be ensured to be uniformly spread above the transparent conductive layer through the conductive ligand layer. Meanwhile, the problem that the transmission path of carriers of the corresponding conductivity type is long and is unfavorable for transmission due to the fact that the thickness of the conductive ligand layer is large can be avoided, the transmission resistance of the conductive ligand layer is reduced, and the photoelectric conversion efficiency of the solar cell is further improved.
As one possible implementation, the thickness of the first carrier transport layer is 10nm to 20nm.
Under the condition of adopting the technical scheme, the thickness of the first carrier transmission layer is in the range, and carriers of corresponding conductivity types can be effectively extracted from the light absorption layer to the electrode structure through charge tunneling effect, so that the working performance of the solar cell is improved.
As a possible implementation manner, the solar cell is a perovskite solar cell, and the light absorbing layer is a perovskite absorbing layer. Under the condition, the solar cell provided by the invention has the advantages of high conversion efficiency, low exciton binding energy, flexible and adjustable band gap, simple manufacturing process, low cost and the like.
As a possible implementation manner, the solar cell is a stacked solar cell, and the stacked solar cell includes a bottom cell, a transparent conductive layer, and a top cell that are sequentially disposed. The bottom cell and the top cell are connected in series through the transparent conductive layer. The top cell includes a conductive ligand layer, a first carrier transport layer, a light absorbing layer, and a second carrier transport layer.
Under the condition that the technical scheme is adopted, under the working state of the solar cell, sunlight with shorter wavelength can be utilized by the top cell positioned above, sunlight with longer wavelength can be transmitted into the bottom cell through the top cell and utilized by the bottom cell, so that the solar cell provided by the invention can utilize a wider wavelength range of sunlight, and the light energy utilization rate of the solar cell is further improved.
As a possible implementation manner, the light-facing surface of the bottom cell is a suede surface. And, the transparent conductive layer, the conductive ligand layer, the first carrier transport layer, the light absorbing layer, and the second carrier transport layer are sequentially conformally formed on the textured surface.
Under the condition of adopting the technical scheme, compared with a plane, the suede has good light trapping effect. Based on the above, when the light-facing surface of the bottom cell is a suede surface, more sunlight can be transmitted into the bottom cell from the backlight surface of the transparent conductive layer, and the photoelectric conversion efficiency of the bottom cell is improved. In addition, after the transparent conductive layer and the conductive ligand layer are sequentially and conformally formed on the suede of the bottom cell, the conductive ligand layer can enable the first carrier transmission layer to be uniformly spread on the suede with the rugged top surface through anchoring characteristics, so that the problem that the first carrier transmission layer is directly separated from the top of the suede structure under the action of gravity due to the fact that the first carrier transmission layer is directly formed on the top surface of the transparent conductive layer with the suede characteristic in the existing solar cell, the part, which is located at the top of the suede structure, of the transparent conductive layer is directly contacted with the light absorption layer, leakage is reduced, open-circuit voltage of the solar cell is improved, and short circuit of the solar cell is prevented.
As one possible implementation, the bottom cell is a silicon heterojunction cell and the top cell is a perovskite cell. Alternatively, both the bottom and top cells are perovskite cells. Under the condition, the bottom cell is provided with two selection schemes, namely a silicon heterojunction cell and a perovskite cell, so that a proper scheme can be conveniently selected according to practical application scenes, and the application range of the solar cell provided by the invention can be enlarged.
As one possible implementation, the solar cell is a stacked solar cell, where the stacked solar cell includes a top cell and a bottom cell connected in series, and a tunneling recombination layer between the bottom cell and the top cell. In this case, the bottom cell includes a transparent conductive layer, a conductive ligand layer, a first carrier transport layer, a light absorbing layer, and a second carrier transport layer, which are sequentially stacked in the direction from the bottom cell to the top cell. The tunneling composite layer is formed on a side of the second carrier transport layer facing away from the light absorbing layer.
Under the condition of adopting the technical scheme, the battery at least comprising the conductive ligand layer, the first carrier transmission layer, the light absorption layer and the second carrier transmission layer can be used as a top battery of the laminated solar battery as described above and can also be used as a bottom battery of the laminated solar battery, so that another possible implementation scheme is provided for the solar battery provided by the invention, and the applicability of the solar battery provided by the invention under different application scenes is improved.
As one possible implementation manner, the material of the transparent conductive layer includes: at least one of indium tin oxide, indium zinc oxide, indium titanium oxide, indium tungsten oxide, zinc gallium oxide, and zinc aluminum oxide.
In a second aspect, the present invention also provides a method for manufacturing a solar cell, the method comprising: forming a transparent conductive layer. Next, a conductive ligand layer, a first carrier transport layer, a light absorbing layer, and a second carrier transport layer, which are stacked in this order, are formed on the transparent conductive layer. One of the first carrier transport layer and the second carrier transport layer is a hole transport layer, and the other is an electron transport layer. The conductive ligand layer is used for uniformly spreading the first carrier transport layer on the transparent conductive layer.
As a possible implementation manner, before the forming of the transparent conductive layer, the method for manufacturing a solar cell further includes: forming a bottom cell. The solar cell is a laminated solar cell, and the laminated solar cell comprises a bottom cell, a transparent conductive layer and a top cell which are sequentially arranged. The bottom cell and the top cell are connected in series through the transparent conductive layer. The top cell includes a conductive ligand layer, a first carrier transport layer, a light absorbing layer, and a second carrier transport layer.
As one possible implementation manner, in the case where the solar cell is a stacked solar cell, after sequentially forming the conductive ligand layer, the first carrier transport layer, the light absorption layer, and the second carrier transport layer, which are stacked on the transparent conductive layer, the method for manufacturing a solar cell further includes: a tunneling composite layer is formed on a side of the second carrier transport layer facing away from the light absorbing layer. Next, a top cell is formed on the tunneling composite. The laminated solar cell comprises a top cell and a bottom cell which are connected in series through a tunneling composite layer. Along the direction of bottom battery to top battery, the bottom battery includes transparent conducting layer, electrically conductive ligand layer, first carrier transport layer, light absorption layer and the second carrier transport layer of range upon range of setting in proper order.
The advantages of the second aspect and various implementations of the present invention may be referred to for analysis of the advantages of the first aspect and various implementations of the first aspect, which are not described here in detail.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention. In the drawings:
Fig. 1 is a schematic longitudinal sectional view of one structure of a solar cell in the related art;
fig. 2 is a schematic longitudinal sectional view of another structure of a solar cell in the related art;
fig. 3 is a schematic longitudinal sectional view of a first solar cell according to an embodiment of the present invention;
fig. 4 is a schematic longitudinal sectional view of a second solar cell according to an embodiment of the present invention;
fig. 5 is a schematic view illustrating a longitudinal cross-section of a third solar cell according to an embodiment of the present invention;
fig. 6 is a schematic view of a longitudinal cross-section of a fourth solar cell according to an embodiment of the present invention;
fig. 7 is a graph showing the relationship between time and device efficiency of solar cells according to comparative examples and examples 1 to 4, respectively, provided in examples of the present invention, when the solar cells were exposed to an environment having a humidity of about 30% to 50% without any package;
fig. 8 is a schematic cross-sectional view of a solar cell according to an embodiment of the present invention during a manufacturing process;
fig. 9 is a schematic diagram showing a cross-sectional structure of a solar cell in a manufacturing process according to an embodiment of the present invention;
fig. 10 is a schematic diagram showing a cross-sectional structure of a solar cell in a manufacturing process according to an embodiment of the present invention;
Fig. 11 is a schematic cross-sectional view of a solar cell according to an embodiment of the present invention during a manufacturing process;
fig. 12 is a schematic cross-sectional view of a solar cell according to an embodiment of the present invention in a manufacturing process.
Reference numerals: 11 is a transparent conductive layer, 12 is a conductive ligand layer, 13 is a first carrier transport layer, 14 is a light absorbing layer, 15 is a second carrier transport layer, 16 is a bottom cell, 17 is a top cell, and 18 is a tunneling composite layer.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. It should be understood that the description is only exemplary and is not intended to limit the scope of the present disclosure. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the concepts of the present disclosure.
Various structural schematic diagrams according to embodiments of the present disclosure are shown in the drawings. The figures are not drawn to scale, wherein certain details are exaggerated for clarity of presentation and may have been omitted. The shapes of the various regions, layers and relative sizes, positional relationships between them shown in the drawings are merely exemplary, may in practice deviate due to manufacturing tolerances or technical limitations, and one skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions as actually required.
In the context of the present disclosure, when a layer/element is referred to as being "on" another layer/element, it can be directly on the other layer/element or intervening layers/elements may be present therebetween. In addition, if one layer/element is located "on" another layer/element in one orientation, that layer/element may be located "under" the other layer/element when the orientation is turned. In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise. The meaning of "a number" is one or more than one unless specifically defined otherwise.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
A solar cell is a device that converts solar energy into electric energy using the photoelectric effect of semiconductor materials. Specifically, a solar cell generally includes a light absorbing layer, an electron transporting layer and a hole transporting layer located at both sides of the light absorbing layer. When the solar cell is in a working state, after the electron and hole pairs generated by photon absorption of the light absorption layer are separated under the action of the electron transmission layer and the hole transmission layer, the electrons are guided out through the electron transmission layer, and the holes are guided out through the hole transmission layer.
The electron transport layer and the hole transport layer have poor transverse electric transport rate, and transport of transverse carriers is seriously hindered. To address this problem, a transparent conductive layer is typically provided on the side of the electron transport layer and the hole transport layer facing away from the light absorbing layer. The transparent conductive layer has excellent carrier transverse transmission performance, and can improve the carrier transmission rate.
However, in the conventional solar cell, the material of the transparent conductive layer 11 (such as indium tin oxide, indium zinc oxide, indium titanium oxide, indium tungsten oxide, zinc gallium oxide, zinc aluminum oxide, etc.) is different from the material of the electron transport layer (such as [6,6 ]]Phenyl C60 methyl butyrate (abbreviated as PC 60 BM)、[6,6]Phenyl C70 methyl butyrate PC 70 BM and [6,6 ]]Phenyl C80 methyl butyrate (abbreviated as PC 80 BM)、[6,6]Phenyl C82 methyl butyrate (abbreviated as PC 82 BM), etc.) and a hole transport layer (e.g., (2- (9H-carbazol-9-yl) ethyl) phosphonic acid) (abbreviated as 2 PACz), (4- (9H-carbazol-9-yl) ethyl) phosphonic acid) (abbreviated as 4 PACz), (2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl)]Phosphonic acid (abbreviated as MeO-2 PACz), [4- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ]]Phosphonic acid (abbreviated as MeO-4 PACz), [2- (3, 6-dimethyl-9H-carbazol-9-yl) ethyl ]]Phosphonic acid (abbreviated as Me-2 PACz), [4- (3, 6-dimethyl-9H-carbazol-9-yl) ethyl ]]Phosphonic acid (abbreviated as Me-4 PACz), and [4- (3, 6-dibromo-9H-carbazol-9-yl) butyl ]](abbreviated as 2Br-4 PACz) and the like), which results in difficulty in uniform spreading of the electron transport layer or the hole transport layer directly fabricated on the transparent conductive layer 11 (see fig. 1 and 2), thereby easily affecting the collection of carriers due to the non-uniformity of the thickness of each portion of the electron transport layer or the hole transport layer in a direction parallel to the surface of the light absorption layer 14, and causing electric leakage due to direct contact of the transparent conductive layer 11 with a portion of the light absorption layer 14, thereby affecting the transport performance of the electron transport layer or the hole transport layer, and being disadvantageous in improving the photoelectric conversion efficiency of the solar cell.
In order to solve the technical problems described above, in a first aspect, an embodiment of the present invention provides a solar cell. As shown in fig. 3 to 6, the solar cell includes: the transparent conductive layer 11 includes a conductive ligand layer 12, a first carrier transport layer 13, a light absorbing layer 14, and a second carrier transport layer 15, which are sequentially stacked on the transparent conductive layer 11. One of the first carrier transport layer 13 and the second carrier transport layer 15 is a hole transport layer, and the other is an electron transport layer. The conductive ligand layer 12 serves to uniformly spread the first carrier transport layer 13 on the transparent conductive layer 11.
In an actual application process, in the working state of the solar cell provided by the embodiment of the invention, electron and hole pairs generated by photon absorption of the light absorption layer can be separated under the action of the first carrier transmission layer and the second carrier transmission layer and collected by the first carrier transmission layer and the second carrier transmission layer respectively. In addition, as shown in fig. 3 to 6, a transparent conductive layer 11 is disposed on a side of the first carrier transmission layer 13 away from the light absorption layer 14, and the transparent conductive layer 11 has an excellent carrier lateral transmission rate, which is beneficial to accelerating the collection rate of carriers, reducing the carrier recombination rate of the side of the light absorption layer 14 close to the first carrier transmission layer 13, and further beneficial to improving the photoelectric conversion efficiency of the solar cell. Also, a conductive ligand layer 12 is formed between the transparent conductive layer 11 and the first carrier transport layer 13, and the conductive ligand layer 12 has superior anchoring characteristics such that the first carrier transport layer 13 is uniformly spread on the transparent conductive layer 11. At this time, the thicknesses of the portions of the first carrier transport layer 13 in the direction parallel to the surface of the light absorbing layer 14 are the same or substantially the same, so that the portions of the first carrier transport layer 13 in the direction parallel to the surface of the light absorbing layer 14 can effectively collect carriers of the respective conductivity types. Meanwhile, electric leakage and even short circuit caused by the fact that the first carrier transmission layer 13 cannot be uniformly spread on the transparent conductive layer 11 to enable the transparent conductive layer 11 to be in direct contact with part of the light absorption layer 14 can be prevented, so that only carriers with corresponding conductivity types and more quantity can be guided out through the first carrier transmission layer 13, the conductive ligand layer 12 and the transparent conductive layer 11 in sequence, and the photoelectric conversion efficiency of the solar cell is further improved.
In terms of structure, as shown in fig. 3, the solar cell provided in the embodiment of the invention may be a single-layer solar cell. Alternatively, as shown in fig. 4 to 6, the solar cell may be a stacked solar cell.
In terms of materials, when the solar cell is a single-layer solar cell, the solar cell may be a cell having a transparent conductive layer, such as a perovskite cell or an organic solar cell, and it is necessary to provide a first carrier transport layer and a second carrier transport layer on both sides of the light absorbing layer.
When the solar cell is a stacked solar cell, the stacked solar cell includes a bottom cell and a top cell connected together in series. Specifically, in this case, as shown in fig. 4 and 5, the top cell 17 may include the above-described conductive ligand layer 12, first carrier transport layer 13, light absorbing layer 14, and second carrier transport layer 15. The bottom cell 16 and the top cell 17 are connected in series through the transparent conductive layer 11. In this case, when the solar cell is in a working state, the solar light with a shorter wavelength can be utilized by the top cell 17 positioned above, and the solar light with a longer wavelength can be transmitted into the bottom cell 16 through the top cell 17 and utilized by the bottom cell 16, so that the solar cell provided by the embodiment of the invention can utilize a wider wavelength range of the solar light, and further improve the light energy utilization rate of the solar cell.
In this case, as shown in fig. 4 and 5, the bottom cell 16 may be any solar cell such as a silicon-based solar cell (e.g., a silicon heterojunction cell), a perovskite solar cell, an organic solar cell, etc., as long as the bottom cell can be applied to the solar cell provided in the embodiment of the present invention. The types of the top cell 17 may be referred to as the types of the single-layer solar cell described above, and will not be described here.
In the above case, as shown in fig. 4, the light-facing surface of the bottom cell 16 may be a flat surface. Alternatively, as shown in fig. 5, the light-facing surface of the bottom cell 16 may be textured. And, the transparent conductive layer 11, the conductive ligand layer 12, the first carrier transport layer 13, the light absorbing layer 14, and the second carrier transport layer 15 are sequentially conformally formed on the textured surface. In this case, the pile surface has a good light trapping effect compared to the plane surface. Based on this, when the light-facing surface of the bottom cell 16 is a textured surface, more sunlight can be transmitted into the bottom cell 16 from the backlight surface of the transparent conductive layer 11, and the photoelectric conversion efficiency of the bottom cell 16 can be improved. In addition, after the transparent conductive layer 11 and the conductive ligand layer 12 are sequentially conformally formed on the textured surface of the bottom cell 16, the conductive ligand layer 12 can uniformly spread the first carrier transmission layer 13 on the textured surface with the rugged top surface through the anchoring property, so that the problem that the first carrier transmission layer 13 is directly formed on the textured top surface of the transparent conductive layer 11 to separate from the top of the textured structure under the action of gravity, so that the part of the transparent conductive layer 11 positioned on the top of the textured structure is directly contacted with the light absorption layer 14 in the existing solar cell can be solved, the electric leakage is reduced, the open circuit voltage of the solar cell is improved, and the short circuit of the solar cell is prevented.
Alternatively, as shown in fig. 6, in the stacked solar cell, the bottom cell 16 may include a transparent conductive layer 11, a conductive ligand layer 12, a first carrier transport layer 13, a light absorption layer 14, and a second carrier transport layer 15. At this time, the stacked solar cell further includes a tunneling clad layer 18, the tunneling clad layer 18 is formed on a side of the second carrier transporting layer 15 facing away from the light absorbing layer 14, and the bottom cell 16 and the top cell 17 are connected in series through the tunneling clad layer 18. In this case, the cell including at least the conductive ligand layer 12, the first carrier transport layer 13, the light absorbing layer 14 and the second carrier transport layer 15 may be used not only as the top cell 17 of the stacked solar cell, as described above, but also as the bottom cell 16 of the stacked solar cell, so as to provide another possible implementation scheme for the solar cell provided by the embodiment of the present invention, which is beneficial to improving the applicability of the solar cell provided by the embodiment of the present invention in different application scenarios.
In this case, the types of the bottom cells may be referred to as the types of the single-layer solar cells described above, and will not be described herein. The top cell may be any solar cell such as a silicon-based solar cell, a perovskite solar cell, or an organic solar cell, so long as the top cell can be applied to the solar cell provided in the embodiment of the present invention.
For the transparent conductive layer, the material and thickness of the transparent conductive layer may be set according to the actual application scenario, so long as the transparent conductive layer can be applied to the solar cell provided by the embodiment of the present invention.
Illustratively, the material of the transparent conductive layer may include: at least one of indium tin oxide, indium zinc oxide, indium titanium oxide, indium tungsten oxide, zinc gallium oxide, and zinc aluminum oxide. For example: the material of the transparent conductive layer can be indium tin oxide, indium zinc oxide, indium titanium oxide, indium tungsten oxide, zinc gallium oxide or zinc aluminum oxide. Also for example: the material of the transparent conductive layer may include: any two or three of indium tin oxide, indium zinc oxide, indium titanium oxide, indium tungsten oxide, zinc gallium oxide, and zinc aluminum oxide. In the above-mentioned case, indium tin oxide, indium zinc oxide, indium titanium oxide, indium tungsten oxide, zinc gallium oxide and zinc aluminum oxide are common transparent conductive materials, so that in at least one of the above materials for the transparent conductive layer, the difficulty in manufacturing the solar cell can be reduced, and the application range of the solar cell can be enlarged.
The thickness of the transparent conductive layer may be, for example, 5nm to 30nm. For example: the thickness of the transparent conductive layer may be 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, or the like.
As for the first carrier transport layer and the second carrier transport layer described above, the first carrier transport layer may be a hole transport layer in terms of conductivity type, and the second carrier transport layer is an electron transport layer. And, along the thickness direction of the transparent conductive layer, the hole transport layer, the light absorption layer and the electron transport layer are sequentially laminated on the transparent conductive layer. The hole transport layer is in direct contact with the transparent conductive layer.
Alternatively, the first carrier transport layer may be an electron transport layer, in which case the second carrier transport layer is a hole transport layer. And, along the thickness direction of the transparent conductive layer, the electron transport layer, the light absorption layer and the hole transport layer are sequentially laminated on the transparent conductive layer. The electron transport layer is in direct contact with the transparent conductive layer.
As for the materials of the first carrier transport layer and the second carrier transport layer described above, determination can be made according to the conductivity types of both.
Illustratively, at the first carrierIn the case where the electron transport layer is a hole transport layer, the hole transport layer may be a self-assembled monolayer having a phosphate group. The specific type of the self-assembled monolayer having a phosphate group may be determined according to actual requirements, and is not particularly limited herein. For example: the material of the self-assembled monolayer having phosphate groups may include at least one of 2PACz, 4PACz, meO-2PACz, meO-4PACz, me-2PACz, me4-2PACz, and 2Br-4 PACz. In addition, in the above case, the second carrier transport layer is an electron transport layer, and the material of the electron transport layer may be PC 61 BM、BCP、C 60 、ZnO、TiO 2 Or SnO 2 And the like can be applied to the electron transport material in the embodiment of the present invention.
In an exemplary embodiment, in the case where the first carrier transport layer is an electron transport layer, the electron transport layer is an N-type semiconductor layer having a conjugated cage-like carbon molecular structure. The specific type of the N-type semiconductor layer having the conjugated cage-like carbon molecular structure may be determined according to actual requirements, and is not particularly limited herein. For example: the material of the N-type semiconductor layer with the conjugated cage-shaped carbon molecular structure can comprise PC 60 BM、PC 61 BM、PC 70BM and PC71 At least one of the BMs. In addition, in the above case, the second carrier transport layer is a hole transport layer, and the material of the hole transport layer may be 2,2', 7' -tetrakis (N, N-di-P-methoxyphenylamine)) 9,9 '-spirobifluorene (abbreviated as Sprio-OMeTAD), 2',7 '-tetrakis (di-P-tolylamino) spiro-9, 9' -bifluorene (abbreviated as Sprio-TTB), poly-3 hexylthiophene (abbreviated as P3 HT), nickel magnesium oxide (abbreviated as NiMgO x ) Vanadium pentoxide (abbreviated as V 2 O 5 ) Molybdenum oxide (abbreviated as MoO x ) Or nickel oxide (may be abbreviated as NiO x ) And the like can be applied to the hole transport material in the embodiment of the present invention.
In addition, the thicknesses of the first carrier transport layer and the second carrier transport layer are not particularly limited in the embodiment of the present invention.
The first carrier transport layer may have a thickness of 10nm to 20nm, for example. For example: the thickness of the first carrier transport layer may be 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, or the like. In this case, the thickness of the first carrier transport layer is within the above range, and carriers of the corresponding conductivity type can be effectively extracted from the light absorbing layer to the electrode structure by the charge tunneling effect, which is advantageous for improving the working performance of the solar cell.
The absolute value of the difference in thickness of each portion of the first carrier transport layer in the direction parallel to the surface of the light absorbing layer is 0 or more and 2nm or less, and the first carrier transport layer can be considered to be uniformly spread on the transparent conductive layer.
The thickness of the second carrier transport layer may be, for example, 10nm to 30nm. For example: the thickness of the second carrier transport layer may be 10nm, 14nm, 16nm, 18nm, 22nm, 26nm, 28nm, 30nm, or the like.
For the above-described light absorbing layer, the material and thickness of the light absorbing layer may be determined according to the type of solar cell. For example: in the case where the cell including the light absorbing layer is a perovskite solar cell, the light absorbing layer is a perovskite absorbing layer. The molecular general formula of the perovskite absorption layer material is ABX 3 . Wherein A, B is a cation of different sizes and X is an anion bonded to both. And the cation B and the anion X coordinate to form a regular octahedral symmetry structure, the cation A is positioned at the center of eight regular octahedrons, and the cation B is positioned at the center of the regular octahedrons. Specifically, the perovskite absorbing layer may contain an inorganic perovskite material, an organic perovskite material, or an organic-inorganic hybrid perovskite material. For example: the perovskite absorption layer may contain CsPbI as material 2 Br、MAPbBr 3 、FAPbI 3 Or Cs 1-y- z FA y MA z PbI 3-x Br x (wherein FA is methyl ether, MA is methylamine, x is 0.ltoreq.3, y is 0.ltoreq.1, z is 0.ltoreq.1, and y+z is 0.ltoreq.1). Under the condition, the solar cell provided by the embodiment of the invention has the advantages of high conversion efficiency, low exciton binding energy, flexible and adjustable band gap, simple manufacturing process, low cost and the like.
Also for example: in the case where the cell comprising the light absorbing layer is an organic solar cell, the material of the light absorbing layer comprises an electron donor material (such as poly-3-hexylthiophene, etc.) and an electron acceptor material (such as [6,6] -phenyl-C61-butyric acid, etc.).
The thickness of the light absorbing layer may be 300nm to 800nm, for example. For example: the thickness of the light absorbing layer may be 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, or the like.
For the above-described conductive ligand layer, the material of the conductive ligand layer may be determined according to the material of the first carrier transport layer.
Illustratively, in the case where the first carrier transport layer is a hole transport layer and the hole transport layer is a self-assembled monolayer having phosphate groups, the conductive ligand layer is a pyridine-based conductive ligand layer. For example: in the case where the first carrier transport layer is a hole transport layer and the hole transport layer is a self-assembled monolayer having a phosphate group, the material of the conductive ligand layer may include at least one of benzimidazole, 2-nonylbenzimidazole, 2-iodobenzimidazole, and ethylenediamine tetraacetic acid. In this case, the material of the conductive ligand layer is exemplified by 2-iodobenzimidazole: the main functional group of the self-assembled monolayer having phosphate groups is p=o. On this account, after the first carrier transport layer is formed on the conductive ligand layer, C in the five-membered ring and I connected thereto, which are possessed by 2-iodobenzimidazole, have strong dipole moment between the whole molecules, so that p=o is provided at an additional bonding site, and a chemical bond having a stronger bond strength and a larger bond energy such as p=o-I or p=o-N can be formed. Compared with the bond such as P=O-In or P=O-Sn formed by directly forming the first carrier transport layer on the transparent conductive layer, the chemical bond can remarkably enhance the coverage rate of the first carrier transport layer above the transparent conductive layer along the parts parallel to the surface of the conductive ligand layer, ensure that the first carrier transport layer serving as a hole transport layer can be uniformly spread above the transparent battery layer, further ensure that the first carrier transport layer has excellent transport performance along the parts parallel to the surface of the conductive ligand layer, and further improve the photoelectric conversion efficiency of the solar battery. The mechanism of action of the other pyridine conductive ligand layers except the material of 2-iodobenzimidazole is similar to that of the conductive ligand layer of 2-iodobenzimidazole, and p=o is provided for an additional bonding site through the conductive ligand layer, which is not described herein.
Preferably, in the case where the first carrier transport layer is a hole transport layer and the hole transport layer is a self-assembled monolayer having a phosphate group, the material of the conductive ligand layer is a benzimidazole-based bidentate ligand compound containing pyridine. For example: in the case where the first carrier transport layer is a hole transport layer and the hole transport layer is a self-assembled monolayer having phosphate groups, the material of the conductive ligand layer includes 2-iodobenzimidazole. In this case, when the solar cell includes the conductive ligand layer made of the benzimidazole-based bidentate ligand compound containing pyridine, various electrical parameters are improved well, and particularly, the short-circuit current density of the solar cell can be improved from 17.21mA/cm, compared with the conventional solar cell in which the first carrier transport layer is directly formed on the transparent conductive layer -2 Lifting to 19.36mA/cm -2 So that the solar cell has excellent working performance.
Illustratively, in the case where the first carrier transport layer is an electron transport layer and the electron transport layer is an N-type semiconductor layer having a conjugated cage-like carbon molecular structure, the conductive ligand layer is a thiophene-based conductive ligand layer. For example: in the case where the first carrier transport layer is an electron transport layer and the electron transport layer is an N-type semiconductor layer having a conjugated cage-like carbon molecular structure, the conductive ligand layer may include at least one of 3-bromothiophene, 3-heptylthiophene, 2, 5-dichlorothieno [3,2-b ] thiophene, 2, 5-dibromothieno [3,2-b ] thiophene, 2,3,5, 6-tetrabromothieno [3,2-b ] thiophene, and diethylenetriamine pentaacetic acid. In this case, the material of the conductive ligand layer is 2,3,5, 6-tetrabromothieno [3,2-b ] thiophene: thiophene ring is a heterocyclic compound, based on which, after forming a first carrier transport layer on a conductive ligand layer, the thiophene ring interacts with benzene rings on a carbon cage to form a large conjugate plane after contacting with an electron transport layer of a conjugated cage-shaped carbon molecular structure because S on a five-membered ring of 2 pairs of lone electrons and 2 C=C double bonds of 2,3,5, 6-tetrabromothieno [3,2-b ] thiophene has, thereby improving the coverage rate of the first carrier transport layer above the transparent conductive layer along parts parallel to the surface of the conductive ligand layer and improving the carrier transport; on the other hand, the thiophene ring of the small molecule can play a role of filling the cage-shaped carbon molecules, so that the stacking degree of the carbon cages is improved, and the carrier transmission is smoother; meanwhile, S also has stronger electronegativity, so the thiophene ring has strong electron-withdrawing characteristic, and the electron cloud density on the benzene ring can be changed, thereby improving the energy level of PCBM, enabling the energy level to be aligned, further enabling carriers to be fully led out, and playing a role in improving the open-circuit voltage of the device. The mechanism of action of the rest of the thiophene conductive ligand layers except the material 2,3,5, 6-tetrabromothieno [3,2-b ] thiophene is similar to that of the material 2,3,5, 6-tetrabromothieno [3,2-b ] thiophene, and is not repeated here.
The thickness of the conductive ligand layer may be determined according to the practical application, and is not particularly limited herein.
The thickness of the conductive ligand layer may be 1nm to 10nm, for example. For example: the thickness of the conductive ligand layer may be 1nm, 3nm, 6nm, 9nm, 10nm, or the like. In this case, the thickness of the conductive ligand layer is within the above range, so that the possibility of direct contact of the first carrier transport layer with the transparent conductive layer due to the small thickness of the conductive ligand layer can be prevented from increasing, ensuring that the first carrier transport layer can be uniformly spread over the transparent conductive layer through the conductive ligand layer. Meanwhile, the problem that the transmission path of carriers of the corresponding conductivity type is long and is unfavorable for transmission due to the fact that the thickness of the conductive ligand layer is large can be avoided, the transmission resistance of the conductive ligand layer is reduced, and the photoelectric conversion efficiency of the solar cell is further improved.
The solar cell provided by the embodiment of the invention can further comprise another transparent conductive layer positioned on one side of the second carrier transmission layer away from the light absorption layer. The material and thickness of the transparent conductive layer in contact with the second carrier may be referred to as the material and thickness of the transparent conductive layer in contact with the conductive ligand layer described above, and will not be described here.
The solar cell provided by the embodiment of the invention can further comprise a buffer layer positioned between the second carrier transmission layer and the other transparent conductive layer, so as to improve the problems of energy band mismatch, carrier recombination, chemical reaction and the like between interfaces. The material of the buffer layer may comprise TiO 2 、SnO 2 、SiO 2 、Al 2 O 3 、Fe 2 O 3 、Cu 2 O, alZnO, etc.
As for the thickness of the buffer layer, it may be determined according to the actual application scenario. For example: the thickness of the buffer layer may be 10nm to 30nm.
For example, in the case where the solar cell provided by the embodiment of the present invention is a single-layer solar cell, or where the solar cell provided by the embodiment of the present invention is a stacked solar cell and the top cell includes a light absorbing layer or other layer, the solar cell may further include an antireflection layer located on a light facing surface side. Specifically, when the second carrier transport layer is located on the light-facing surface side of the light absorption layer, the antireflection layer is formed on the side of the second carrier transport layer facing away from the light absorption layer. When the first carrier transmission layer is positioned on the light facing surface side of the light absorption layer, the anti-reflection layer is formed on one side of the transparent conductive layer contacting with the first carrier transmission layer, which is away from the light absorption layer.
The material of the anti-reflection layer may be silicon nitride or aluminum oxide. The thickness of the anti-reflection layer may be 100nm to 200nm or the like.
The solar cell provided by the embodiment of the invention can further comprise a first electrode and a second electrode. The first electrode is in ohmic contact with the first carrier transport layer through at least two film layers, a transparent conductive layer and a conductive ligand layer. The second electrode is in ohmic contact with the second carrier layer. The materials of the first electrode and the second electrode can be silver, copper, aluminum or gold. The thickness of the first electrode and the second electrode may be 100nm to 1000nm or the like.
The embodiment of the invention also provides a comparative example and four embodiments for explaining the working performance of the solar cell provided by the embodiment of the invention.
As shown in fig. 2, the solar cell provided in the comparative example is a stacked solar cell. The stacked solar cell comprises a silicon heterojunction bottom cell, a transparent conductive layer 11 and a top cell. The silicon heterojunction bottom cell is connected in series with the top cell through the transparent conductive layer 11. And, the top cell includes a first carrier transport layer 13, a light absorbing layer 14, and a second carrier transport layer 15.
As shown in fig. 5, the solar cells provided in example 1, example 2, example 3 and example 4 are all stacked solar cells. The stacked solar cell comprises a silicon heterojunction bottom cell, a transparent conductive layer 11 and a top cell 17. The silicon heterojunction bottom cell is connected in series with the top cell 17 through the transparent conductive layer 11. Also, the top cell 17 includes a conductive ligand layer 12, a first carrier transport layer 13, a light absorbing layer 14, and a second carrier transport layer 15. In contrast, the material of the conductive ligand layer 12 in example 1 was benzimidazole, the material of the conductive ligand layer 12 in example 2 was 2-nonylbenzimidazole, the material of the conductive ligand layer 12 in example 3 was 2-iodobenzimidazole, and the material of the conductive ligand layer 12 in example 4 was ethylenediamine tetraacetic acid.
Specifically, the information of the materials and thicknesses of the silicon heterojunction bottom cell, the transparent conductive layer, the first carrier transport layer, the light-absorbing layer, and the second carrier transport layer in the comparative example, and in examples 1 to 4 are the same. Table 1 tests were performed on the solar cells corresponding to the above comparative examples and examples 1 to 4, and parameters of the above five solar cells were compared.
Table 1: comparative example, and comparative examples 1 to 4 for respective parameters of solar cells
Since the solar cells according to embodiments 1 to 4 include the conductive ligand layer between the transparent conductive layer and the first carrier transport layer, the first carrier transport layer can be uniformly spread over the transparent conductive layer. And the conductive ligand layer can react with the first carrier transmission layer to form a carrier transmission channel, and the carrier transmission channel has carrier extraction effects of different degrees, so that the carrier recombination rate of the light absorption layer on the side close to the first carrier transmission layer can be reduced. Secondly, the conductive ligand layer also has a good refraction buffer effect, so that more light rays can be projected into the bottom cell, and the short-circuit current density of the solar cell can be effectively improved. Based on this, as can be seen from the various data shown in table 1, the short-circuit current density, the open-circuit voltage, the fill factor, and the conversion efficiency of the solar cells corresponding to examples 1 to 4 were all higher than the respective parameter values of the solar cells corresponding to the comparative examples, i.e., the operation performance of the solar cells corresponding to examples 1 to 4 was superior to that of the solar cells corresponding to the comparative examples.
It should be further noted that, the conductive ligand layers made of conductive ligand materials with high anchoring property and different chain lengths have different degrees of hydrophobicity, so that the solar cell provided by the embodiment of the invention can reduce the influence degree of the external environment humidity on the working performance of the solar cell and improve the operation stability of devices in the external environment of the solar cell under the condition that the conductive ligand layers are included. As shown in fig. 7, the device efficiency of the solar cells corresponding to examples 1 to 4 was higher than that of the solar cells corresponding to the comparative examples. And, the solar cells corresponding to examples 1 to 4 were placed in an environment having a humidity of about 30% to 50% without any packaging over 90 days, and maintained 90% or more of the initial efficiency.
In a second aspect, the embodiment of the invention also provides a manufacturing method of the solar cell. For the specific structure of the solar cell, reference may be made to the solar cell provided in the foregoing first aspect and various implementation manners thereof, which are not described herein again.
Hereinafter, the manufacturing process will be described with reference to fig. 3 to 6, and cross-sectional views of the operations shown in fig. 8 to 12. Specifically, the method for manufacturing the solar cell comprises the following steps:
First, as shown in fig. 9, a transparent conductive layer 11 is formed.
In the practical application process, if the manufactured solar cell is a single-layer solar cell or a stacked solar cell, and the bottom cell in the stacked solar cell includes the transparent conductive layer … … and the second carrier transport layer that are stacked, the transparent conductive layer may be formed on the corresponding substrate by one or more of radio frequency magnetron sputtering, vacuum evaporation deposition, sol-gel, chemical vapor deposition, and the like.
If the solar cell being fabricated is a stacked solar cell and the top cell in the stacked solar cell includes the conductive ligand layer … … and the second carrier transporting layer, as shown in fig. 8, the bottom cell 16 is first formed. Then, the transparent conductive layer 11 may be formed on the light-facing surface of the bottom cell 16 in the above-described manner. It should be noted that, in this case, reference may be made to conventional technical solutions in the art, which are not important to the present invention, and the present invention is not described in detail herein.
Next, as shown in fig. 3 to 6, the conductive ligand layer 12, the first carrier transport layer 13, the light absorbing layer 14, and the second carrier transport layer 15, which are stacked, are sequentially formed on the transparent conductive layer 11. One of the first carrier transport layer 13 and the second carrier transport layer 15 is a hole transport layer, and the other is an electron transport layer. The conductive ligand layer 12 serves to uniformly spread the first carrier transport layer 13 on the transparent conductive layer 11.
In an actual manufacturing process, as shown in fig. 10, the conductive ligand layer 12 may be formed on the transparent conductive layer 11 according to the material of the conductive ligand layer 12 and by one or more of dipping, knife coating, spin coating, radio frequency magnetron sputtering, atomic layer deposition, thermal evaporation, organic evaporation, and the like. Next, as shown in fig. 11, the first carrier transport layer 13 may be formed on the conductive ligand layer 12 according to a material of the first carrier transport layer 13 and by one or more of radio frequency magnetron sputtering, atomic layer deposition, evaporation, and the like. Next, the light absorbing layer 14 is formed on the first carrier transporting layer 13 according to the material of the light absorbing layer 14 by one or more of knife coating, spin coating, ultrasonic spraying, slot coating, vapor deposition, and the like. Then, as shown in fig. 12, the second carrier transport layer 15 is formed on the light absorbing layer 14 according to the material of the second carrier transport layer 15 and by one or more of sol-gel, atomic layer deposition, thermal evaporation, and the like.
For example, if the manufactured solar cell is a stacked solar cell, and the bottom cell in the stacked solar cell includes the transparent conductive layer … … and the second carrier transporting layer that are stacked, the method for manufacturing a solar cell further includes the steps of: the tunneling composite layer may be formed on a side of the second carrier transport layer facing away from the light absorbing layer by atomic layer deposition, thermal evaporation, or the like. Next, as shown in fig. 6, a top cell 17 is formed on the tunneling composite 18. In this case, how to form the top battery may refer to conventional technical schemes in the art, which are not important to the present invention, and the present invention is not described in detail herein.
In some cases, in the case where the solar cell provided by the embodiment of the present invention is a single-layer solar cell, or where the solar cell provided by the embodiment of the present invention is a stacked solar cell and the top cell includes a layer such as a light absorption layer, after forming the second carrier transport layer, the method for manufacturing the solar cell may further include: and forming a buffer layer, a transparent conductive layer and an antireflection layer on the second carrier transmission layer in sequence by adopting chemical vapor deposition and other processes.
In some cases, after forming the second carrier transporting layer, or after forming the antireflection layer, the method for manufacturing a solar cell further includes the steps of: and a first electrode is formed on one side of the first carrier transmission layer, which is away from the light absorption layer, and a second electrode is formed on one side of the second carrier transmission layer, which is away from the light absorption layer, by adopting screen printing, thermal evaporation or other modes. The first electrode is in ohmic contact with the first carrier transport layer through at least two film layers, namely a transparent conductive layer and a conductive ligand layer. The second electrode is in ohmic contact with the second carrier layer.
The beneficial effects of the second aspect and various implementations of the embodiments of the present invention may refer to the beneficial effect analysis in the first aspect and various implementations of the first aspect, which are not described herein.
In the above description, technical details of patterning, etching, and the like of each layer are not described in detail. Those skilled in the art will appreciate that layers, regions, etc. of the desired shape may be formed by a variety of techniques. In addition, to form the same structure, those skilled in the art can also devise methods that are not exactly the same as those described above. In addition, although the embodiments are described above separately, this does not mean that the measures in the embodiments cannot be used advantageously in combination.
The embodiments of the present disclosure are described above. However, these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. The scope of the disclosure is defined by the appended claims and equivalents thereof. Various alternatives and modifications can be made by those skilled in the art without departing from the scope of the disclosure, and such alternatives and modifications are intended to fall within the scope of the disclosure.
Claims (14)
1. A solar cell, comprising: a transparent conductive layer is provided on the transparent conductive layer,
and a conductive ligand layer, a first carrier transport layer, a light absorbing layer, and a second carrier transport layer, which are sequentially stacked on the transparent conductive layer; wherein one of the first carrier transport layer and the second carrier transport layer is a hole transport layer, and the other is an electron transport layer; the conductive ligand layer is used for uniformly spreading the first carrier transport layer on the transparent conductive layer.
2. The solar cell according to claim 1, wherein in the case where the first carrier transport layer is a hole transport layer, the hole transport layer is a self-assembled monolayer having a phosphate group, and the conductive ligand layer is a pyridine-based conductive ligand layer.
3. The solar cell according to claim 2, wherein in the case where the first carrier transport layer is a hole transport layer, the material of the conductive ligand layer is a benzimidazole-based bidentate ligand compound containing pyridine.
4. The solar cell according to claim 1, wherein in the case where the first carrier transport layer is an electron transport layer, the electron transport layer is an N-type semiconductor layer having a conjugated cage-like carbon molecular structure, and the conductive ligand layer is a thiophene-based conductive ligand layer.
5. The solar cell according to claim 1, wherein the thickness of the conductive ligand layer is 1nm to 10nm; and/or the number of the groups of groups,
the first carrier transport layer has a thickness of 10nm to 20nm.
6. The solar cell according to any one of claims 1 to 5, wherein the solar cell is a perovskite solar cell and the light absorbing layer is a perovskite absorbing layer.
7. The solar cell according to any one of claims 1 to 4, wherein the solar cell is a stacked solar cell comprising a bottom cell, the transparent conductive layer and a top cell arranged in that order;
the bottom cell and the top cell are connected in series through the transparent conductive layer; the top cell includes the conductive ligand layer, the first carrier transport layer, the light absorbing layer, and the second carrier transport layer.
8. The solar cell of claim 7, wherein the light-facing surface of the bottom cell is a textured surface;
the transparent conductive layer, the conductive ligand layer, the first carrier transport layer, the light absorbing layer, and the second carrier transport layer are sequentially conformally formed on the pile face.
9. The solar cell of claim 7, wherein the bottom cell is a silicon heterojunction cell and the top cell is a perovskite cell;
or, the bottom cell and the top cell are both perovskite cells.
10. The solar cell of any one of claims 1-4, wherein the solar cell is a stacked solar cell comprising a top cell and a bottom cell connected together in series, and a tunneling recombination layer between the bottom cell and the top cell;
The bottom cell comprises the transparent conductive layer, the conductive ligand layer, the first carrier transmission layer, the light absorption layer and the second carrier transmission layer which are sequentially stacked along the direction from the bottom cell to the top cell; the tunneling composite layer is formed on a side of the second carrier transport layer facing away from the light absorbing layer.
11. The solar cell according to any one of claims 1 to 5, wherein the material of the transparent conductive layer comprises: at least one of indium tin oxide, indium zinc oxide, indium titanium oxide, indium tungsten oxide, zinc gallium oxide, and zinc aluminum oxide.
12. A method for manufacturing a solar cell, comprising:
forming a transparent conductive layer;
sequentially forming a conductive ligand layer, a first carrier transmission layer, a light absorption layer and a second carrier transmission layer which are stacked on the transparent conductive layer; wherein one of the first carrier transport layer and the second carrier transport layer is a hole transport layer, and the other is an electron transport layer; the conductive ligand layer is used for uniformly spreading the first carrier transport layer on the transparent conductive layer.
13. The method of manufacturing a solar cell according to claim 12, wherein before the forming of the transparent conductive layer, the method further comprises: forming a bottom cell; wherein,
The solar cell is a laminated solar cell, and the laminated solar cell comprises a bottom cell, the transparent conductive layer and a top cell which are sequentially arranged; the bottom cell and the top cell are connected in series through the transparent conductive layer; the top cell includes the conductive ligand layer, the first carrier transport layer, the light absorbing layer, and the second carrier transport layer.
14. The method according to claim 12, wherein when the solar cell is a stacked solar cell, after sequentially forming the conductive ligand layer, the first carrier transport layer, the light absorption layer, and the second carrier transport layer, which are stacked on the transparent conductive layer, the method further comprises:
forming a tunneling composite layer on a side of the second carrier transport layer facing away from the light absorbing layer;
forming a top cell on the tunneling composite layer; wherein,
the stacked solar cell includes the top and bottom cells connected together in series by the tunneling recombination layer; the bottom cell comprises the transparent conductive layer, the conductive ligand layer, the first carrier transmission layer, the light absorption layer and the second carrier transmission layer which are sequentially stacked along the direction from the bottom cell to the top cell.
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| CN117156875B (en) * | 2023-10-31 | 2024-01-23 | 电子科技大学 | High-performance solar cell based on non-contact passivation |
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