CN111129197B - Gallium arsenide and perovskite heterojunction solar cell and manufacturing method thereof - Google Patents
Gallium arsenide and perovskite heterojunction solar cell and manufacturing method thereof Download PDFInfo
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Abstract
The invention provides a gallium arsenide and perovskite heterojunction solar cell and a manufacturing method thereof. The cell comprises an N-type gallium arsenide half cell and a P-type perovskite half cell positioned above the N-type gallium arsenide half cell, wherein the N-type gallium arsenide half cell sequentially comprises a substrate, an N-type gallium arsenide layer and a gallium arsenide absorption layer from bottom to top; the P-type perovskite half cell sequentially comprises a perovskite absorption layer, a hole transport layer and an electrode layer from bottom to top. The structure of the cell eliminates the growth step of the P-type semiconductor layer of the gallium arsenide solar cell in the manufacturing process, reduces the difficulty of the cell production process and improves the product yield. Meanwhile, the P-type perovskite solar half cell has the advantages of strong light absorption coefficient, long carrier migration distance, high cell voltage and the like, and can further improve the photoelectric conversion efficiency of the gallium arsenide solar cell.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a gallium arsenide and perovskite heterojunction solar cell and a manufacturing method thereof.
Background
Gallium arsenide solar cells are solar cells with highest photoelectric conversion efficiency at present, gallium arsenide is used as a semiconductor material with direct band gap, and the band gap width is 1.43 eV. The multijunction gallium arsenide solar cell is formed by connecting sub-cells with different forbidden band widths in series, the forbidden band widths of the sub-cells are sequentially reduced from top to bottom, and the absorption range of sunlight is widened and the photoelectric conversion efficiency is improved by mainly utilizing the different forbidden band widths of the sub-cells made of different materials and different solar energy absorption ranges.
In recent years, perovskite solar cells are the most rapidly developed solar cells, the perovskite solar cells are simple in preparation method and low in production cost, the forbidden bandwidth of perovskite materials is 1.2-2.3eV, the absorption coefficient of light is strong, the migration distance of carriers is long, and the photoelectric conversion efficiency of the perovskite solar cells is increased from 3.8% to 22.1% in short years.
Patent CN107046027A proposes a method for connecting perovskite solar cells in series on a multijunction gallium arsenide solar cell by using metal bonding technology, and the principle is equivalent to the series mode between cells. However, the GaAs solar cell is generally manufactured by performing epitaxial deposition in Metal Organic Chemical Vapor Deposition (MOCVD) or Molecular Beam Epitaxy (MBE), and during the epitaxial growth process, the p-type GaAs semiconductor layer is generally doped with C element or Zn element, which is difficult to grow, and the p-type heavily doped GaAs is more difficult to manufacture. For the reasons, the problems of high production difficulty and low product yield exist when the perovskite solar cell and the gallium arsenide solar cell are integrated at present.
Disclosure of Invention
The invention mainly aims to provide a gallium arsenide and perovskite heterojunction solar cell and a manufacturing method thereof, and aims to solve the problems of high production difficulty and low product yield when integrating a perovskite solar cell and a gallium arsenide solar cell in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a gallium arsenide and perovskite heterojunction solar cell, comprising an N-type gallium arsenide half cell and a P-type perovskite half cell located above the N-type gallium arsenide half cell, wherein the N-type gallium arsenide half cell comprises, in order from bottom to top, a substrate, an N-type gallium arsenide layer and a gallium arsenide absorption layer; the P-type perovskite half cell sequentially comprises a perovskite absorption layer, a hole transport layer and an electrode layer from bottom to top.
Furthermore, the surface of one side of the gallium arsenide absorbing layer, which is far away from the substrate, is a rough surface or a concave-convex surface, and the surface of the perovskite absorbing layer, which is in contact with the gallium arsenide absorbing layer, is a rough surface or a concave-convex surface matched with the perovskite absorbing layer; preferably, the surface of the gallium arsenide absorbing layer on the side far away from the substrate is a sawtooth-shaped concave-convex surface or a T-shaped concave-convex surface, and the surface of the perovskite absorbing layer in contact with the gallium arsenide absorbing layer is a sawtooth-shaped concave-convex surface or a T-shaped concave-convex surface matched with the surface.
Further, the N-type gallium arsenide layer is a Si doped layer, and the Si doping concentration in the N-type gallium arsenide layer is preferably 1 × 10 17 ～1×10 19 cm -3 (ii) a Preferably, the material of the N-type gallium arsenide layer is Al x Ga 1-x As or (Al) y Ga 1-y ) Z In 1-z P, wherein x is in the range of 0-0.5, y is in the range of 0-0.5, and z is in the range of 0.4-E0.6。
Furthermore, the GaAs absorption layer is made of GaAs and doped with Si with a doping concentration lower than 1 × 10 22 。
Further, the substrate is a Ge substrate, a Si substrate or a GaAs substrate; preferably, the thickness of the N-type gallium arsenide layer is 50-500 nm, the thickness of the gallium arsenide absorption layer is 500-5000 nm, and the thickness of the substrate is 270-1000 um.
Further, the material of the perovskite absorption layer is one or more ABX 3 Materials wherein a is NH ═ CHNH 3 、CH 3 NH 3 Or Cs, B is Pb or Sn, and X is a halogen element; preferably, the material of the perovskite absorption layer is CH 3 NH 3 PbI 3 (ii) a Preferably, the material of the hole transport layer is one or more of Spiro-OMeTAD, P3HT, PEDOT, PSS and PTAA; preferably, the electrode layer is an ITO electrode layer; preferably, the thickness of the perovskite absorption layer is 200-700 nm, and the thickness of the hole transport layer is 10-200 nm.
According to another aspect of the present invention, there is provided a method for fabricating a gallium arsenide and perovskite heterojunction solar cell, comprising the steps of: providing a substrate; forming an N-type gallium arsenide layer on the surface of one side of the substrate; forming a gallium arsenide absorption layer on the surface of one side of the N-type gallium arsenide layer, which is far away from the substrate; growing a perovskite absorption layer on the surface of one side of the gallium arsenide absorption layer, which is far away from the substrate; growing a hole transport layer on the surface of one side, far away from the substrate, of the perovskite absorption layer; and forming an electrode layer on the surface of one side of the hole transport layer, which is far away from the substrate, so as to form the gallium arsenide and perovskite heterojunction solar cell.
Further, before the step of growing the P-type perovskite half cell on the surface of the gallium arsenide absorption layer on the side far away from the substrate, the manufacturing method further comprises the following steps: carrying out surface roughening treatment on the surface of one side, far away from the substrate, of the gallium arsenide absorption layer, or polishing the surface of one side, far away from the substrate, of the gallium arsenide absorption layer into a concave-convex surface; preferably, a chemical etching method is adopted for surface roughening treatment, and more preferably, the chemical etching method is hydrofluoric acid and hydrogen peroxide for co-corrosion; preferably, the mechanical polishing is performed by a physical mechanical method, and more preferably, the surface of the side of the gallium arsenide absorption layer away from the substrate is polished to be a sawtooth-shaped concave-convex surface or a T-shaped concave-convex surface.
Furthermore, the method for forming the N-type gallium arsenide layer and the gallium arsenide absorption layer is a metal organic chemical vapor deposition method, a molecular beam epitaxy method, a vapor phase epitaxy method or a physical vapor deposition method.
Further, the perovskite absorption layer and the hole transport layer are grown by spin coating, spray coating, blade coating, screen printing or ink-jet printing; preferably, the electrode layer is formed by evaporation.
The invention provides a gallium arsenide and perovskite heterojunction solar cell, which is a solar cell with a heterostructure formed by combining an N-type gallium arsenide half cell and a P-type perovskite half cell, wherein the N-type gallium arsenide half cell sequentially comprises a substrate, an N-type gallium arsenide layer and a gallium arsenide absorption layer from bottom to top; the P-type perovskite half cell sequentially comprises a perovskite absorption layer, a hole transport layer and an electrode layer from bottom to top. When the gallium arsenide and perovskite heterojunction solar cell is manufactured, the step of growing the P-type semiconductor layer of the gallium arsenide solar cell is eliminated, the difficulty of the production process of the cell is reduced, and the yield of the product is improved. Meanwhile, the P-type perovskite solar half cell has the advantages of strong light absorption coefficient, long carrier migration distance, high cell voltage and the like, and can further improve the photoelectric conversion efficiency of the gallium arsenide solar cell.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
figure 1 shows a schematic structural diagram of a gallium arsenide and perovskite heterojunction solar cell according to an embodiment of the invention;
FIG. 2 shows a schematic structural diagram of a gallium arsenide and perovskite heterojunction solar cell according to another embodiment of the invention;
figure 3 shows a schematic structural diagram of a gallium arsenide and perovskite heterojunction solar cell according to yet another embodiment of the present invention.
Wherein the figures include the following reference numerals:
10. an N-type gallium arsenide half cell; 11. a substrate; 12. an N-type gallium arsenide layer; 13. a gallium arsenide absorbing layer; 20. a P-type perovskite half cell; 21. a perovskite absorption layer; 22. a hole transport layer; 23. and an electrode layer.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
As described in the background of the invention section, the perovskite solar cell and the gallium arsenide solar cell are integrated at present, which has the problems of high production difficulty and low product yield.
In order to solve the above problems, the present invention provides a gallium arsenide and perovskite heterojunction solar cell, as shown in fig. 1, the solar cell includes an N-type gallium arsenide half cell 10 and a P-type perovskite half cell 20 located above the N-type gallium arsenide half cell 10, the N-type gallium arsenide half cell 10 includes, from bottom to top, a substrate 11, an N-type gallium arsenide layer 12 and a gallium arsenide absorption layer 13 in sequence; the P-type perovskite half cell 20 sequentially comprises a perovskite absorption layer 21, a hole transport layer 22 and an electrode layer 23 from bottom to top. When the gallium arsenide and perovskite heterojunction solar cell is manufactured, the step of growing the P-type semiconductor layer of the gallium arsenide solar cell is eliminated, the difficulty of the production process of the cell is reduced, and the yield of the product is improved. Meanwhile, the P-type perovskite solar half cell has the advantages of strong light absorption coefficient, long carrier migration distance, high cell voltage and the like, and can further improve the photoelectric conversion efficiency of the gallium arsenide solar cell.
The N-type gaas half cell 10 includes a substrate 11, an N-type gaas layer 12, and a gaas absorption layer 13, and each layer functions as follows: the substrate 11 is matched with the crystal lattice of the epitaxial layer, and provides a place and a supporting function for epitaxial crystal stacking; the N-type gallium arsenide layer 12 forms a hole barrier in a valence band, so that the holes are prevented from migrating to the contact layer, and the efficiency of the battery is improved; the gallium arsenide absorption layer 13 absorbs photons to generate electron-hole pairs; the electrons migrate to the N-gaas layer 12 and the holes migrate to the P-hole transport layer under the action of the built-in electric field. The P-type perovskite half cell 20 comprises a perovskite absorption layer 21, a hole transport layer 22 and an electrode layer 23, and each layer has the following functions: the perovskite absorption layer 21 is used for absorbing photons to generate electron-hole pairs; the electrons migrate to the N-type gaas layer 12, and the holes migrate to the P-type hole transport layer under the action of the built-in electric field; the hole transport layer 22 prevents electrons from migrating to the P-type electrode and prevents the metal of the electrode layer from diffusing; the electrode layer 23 serves as a current collector for current collection.
In a preferred embodiment, the surface of the gallium arsenide absorption layer 13 on the side away from the substrate 11 is a rough surface or a concave-convex surface, and the surface of the perovskite absorption layer 21 in contact with the gallium arsenide absorption layer 13 is a rough surface or a concave-convex surface adapted to the rough surface or the concave-convex surface. The interface bonding force between the N-type gallium arsenide half cell 10 and the P-type perovskite half cell 20 positioned above the N-type gallium arsenide half cell can be effectively improved by utilizing the rough surface and the concave-convex surface, so that the stability of the solar cell can be effectively improved.
Preferably, the surface of the gallium arsenide absorbing layer 13 on the side away from the substrate 11 is a sawtooth concave-convex surface (as shown in fig. 1) or a T-shaped concave-convex surface (as shown in fig. 2 and 3), and the surface of the perovskite absorbing layer 21 in contact with the gallium arsenide absorbing layer 13 is a sawtooth concave-convex surface or a T-shaped concave-convex surface matched with the surface.
In order to further improve the photoelectric conversion efficiency of the gallium arsenide and perovskite heterojunction solar cell, in a preferred embodiment, the N-type gallium arsenide layer 12 is a Si doped layer, and the Si doping concentration in the N-type gallium arsenide layer 12 is preferably 1 × 10 17 ～1×10 19 cm -3 . More preferably, the material of the N-type GaAs layer 12 is Al x Ga 1-x As or Al y Ga 1-yZ In 1-z P, wherein the value range of x is 0-0.5, the value range of y is 0-0.5, and the value range of z is 0.4-0.6.
In a preferred embodiment, gallium arsenide absorptionThe material of layer 13 is GaAs, doped in Si type with a doping concentration lower than 1X 10 22 . The substrate 11 may be a substrate commonly used in the field of gallium arsenide solar cells, such as: the substrate 11 includes, but is not limited to, a Ge substrate, a Si substrate, or a GaAs substrate.
In order to further improve the photoelectric conversion efficiency, in a preferred embodiment, the thickness of the N-type gallium arsenide layer 12 is 50 to 500nm, the thickness of the gallium arsenide absorption layer 13 is 500 to 5000nm, and the thickness of the substrate 11 is 270 to 1000 μm.
In a preferred embodiment, the material of the perovskite absorption layer 21 is one or more ABX 3 Materials wherein a is NH ═ CHNH 3 、CH 3 NH 3 Or Cs, B is Pb or Sn, and X is a halogen element. The perovskite absorption layer 21 formed by the material has better light absorption coefficient and carrier migration distance, and is beneficial to further improving the battery performance. Meanwhile, the perovskite absorption layer 21 formed by the material has better bonding performance with the N-type gallium arsenide half cell 10, and the stability of the cell is improved. More preferably, the material of the perovskite absorption layer 21 is CH 3 NH 3 PbI 3 。
In a preferred embodiment, the hole transport layer 22 is made of one or more of Spiro-MeOTAD, P3HT, PEDOT: PSS, and PTAA. The hole transport layer 22 formed by these materials has stronger hole transport capability, thereby being beneficial to further improving the battery performance. Preferably, the electrode layer 23 is an ITO electrode layer.
In order to further improve the battery performance, in a preferred embodiment, the thickness of the perovskite absorption layer 21 is 200 to 700nm, and the thickness of the hole transport layer 22 is 10 to 200 nm.
According to another aspect of the present invention, there is also provided a method for manufacturing the above gallium arsenide and perovskite heterojunction solar cell, which includes the following steps: and growing a P-type perovskite half cell 20 on the N-type gallium arsenide half cell 10 and the position above the N-type gallium arsenide half cell 10, and further obtaining the gallium arsenide and perovskite heterojunction solar cell. When the gallium arsenide and perovskite heterojunction solar cell is manufactured, the step of growing the P-type semiconductor layer of the gallium arsenide solar cell is eliminated, the difficulty of the production process of the cell is reduced, and the yield of the product is improved. Meanwhile, the P-type perovskite solar half cell has the advantages of strong light absorption coefficient, long carrier migration distance, high cell voltage and the like, and can further improve the photoelectric conversion efficiency of the gallium arsenide solar cell.
In a preferred embodiment, the N-type gallium arsenide half cell 10 is made by: providing a substrate 11; forming an N-type gallium arsenide layer 12 on one side surface of a substrate 11; a gallium arsenide absorption layer 13 is formed on the surface of the N-type gallium arsenide layer 12 on the side away from the substrate 11, and a P-type perovskite half cell 20 is grown on the surface of the gallium arsenide absorption layer 13 on the side away from the substrate 11. The above-mentioned layers can be made by the conventional process in the art, and preferably, the method for forming the N-type gallium arsenide layer 12 and the gallium arsenide absorbing layer 13 is metal organic chemical vapor deposition, molecular beam epitaxy, vapor phase epitaxy or physical vapor deposition.
More preferably, the growth temperature of the N-type GaAs layer 12 is 600-1100 deg.C, and the growth temperature of the GaAs absorption layer 13 is 400-1000 deg.C.
In a preferred embodiment, the P-type perovskite half cell 20 is made by: growing a perovskite absorption layer 21 on the surface of one side of the gallium arsenide absorption layer 13 far away from the substrate 11; growing a hole transport layer 22 on the surface of the perovskite absorption layer 21 on the side far away from the substrate 11; an electrode layer 23 is formed on the surface of the hole transport layer 22 on the side away from the substrate 11.
Preferably, the method for growing the perovskite absorption layer 21 and the hole transport layer 22 is spin coating, spray coating, blade coating, screen printing or ink jet printing; preferably, the electrode layer 23 is formed by evaporation.
In order to further improve the interfacial bonding force between the N-type gallium arsenide half cell 10 and the P-type perovskite half cell 20, in a preferred embodiment, before the step of growing the P-type perovskite half cell 20 on the surface of the gallium arsenide absorption layer 13 on the side far from the substrate 11, the manufacturing method further comprises: the surface of the side of the gallium arsenide absorption layer 13 far away from the substrate 11 is subjected to surface roughening treatment, or the surface of the side of the gallium arsenide absorption layer 13 far away from the substrate 11 is polished to a concave-convex surface.
Preferably, a chemical etching method is adopted for surface roughening treatment, and more preferably, the chemical etching method is hydrofluoric acid and hydrogen peroxide for co-corrosion; preferably, the mechanical polishing is performed by a physical mechanical method, and more preferably, the surface of the side of the gallium arsenide absorption layer 13 away from the substrate 11 is polished to a sawtooth concave-convex surface (as shown in fig. 1) or a T-shaped concave-convex surface (as shown in fig. 2 and 3).
The beneficial effects of the present invention are further illustrated by the following examples:
example 1
The gallium arsenide and perovskite heterojunction solar cell is manufactured by the embodiment through the following specific process:
transferring the GaAs substrate into MOCVD equipment, and introducing H 2 Raising the temperature of the gas to carry out high-temperature cleaning on the substrate, wherein the temperature range is 1000 ℃;
as shown in FIG. 1, a Si-doped N-type GaAs layer Al is grown on a GaAs substrate 0.2 Ga 0.8 As with a doping concentration of 1X 10 17 cm -3 The thickness range is 500nm, and the growth temperature is 1100 ℃;
growing Si-doped GaAs material layer as GaAs absorption layer on the N-type GaAs layer with doping concentration of 1 × 10 15 cm -3 The thickness range is 5000nm, and the growth temperature is 1000 ℃;
cooling the temperature to room temperature, and taking out the device;
roughening the surface of the gallium arsenide absorption layer by using hydrofluoric acid and hydrogen peroxide;
taking PbI 2 Spin coating DMF solution on the surface of GaAs absorption layer, air drying, and collecting CH 3 NH 3 I isopropanol solution, spin-coated on air-dried PbI 2 Then annealed at 120 ℃ for 30min to form CH with a thickness of 700nm 3 NH 3 PbI 3 A perovskite absorption layer;
dissolving 50000g/mol of P3HT with the weight-average molecular weight and the regularity of more than 95% in a 1, 2-dichlorobenzene solution with the solution concentration of 5mg/ml, spin-coating the solution on a perovskite absorption layer, and drying to form a P3HT hole transport layer with the thickness of 200 nm;
and evaporating an ITO electrode layer on the surface of the hole transport layer to form the gallium arsenide and perovskite heterojunction solar cell, wherein the photoelectric conversion efficiency of the gallium arsenide and perovskite heterojunction solar cell is 25.1% through detection.
Example 2
The gallium arsenide and perovskite heterojunction solar cell is manufactured by the embodiment through the following specific process:
conveying the Si substrate into MOCVD equipment, and introducing H 2 Raising the temperature of the gas to carry out high-temperature cleaning on the substrate, wherein the temperature range is 200 ℃;
as shown in FIG. 1, Si-doped N-type GaAs layer Al is grown on Si substrate 0.2 Ga 0.8 As with a doping concentration of 1X 10 19 cm -3 The thickness range is 50nm, and the growth temperature is 600 ℃;
growing Si-doped GaAs material layer as GaAs absorption layer on the N-type GaAs layer with doping concentration of 1 × 10 18 cm -3 The thickness range is 500nm, and the growth temperature is 400 ℃;
cooling the temperature to room temperature, and taking out the device;
roughening the surface of the gallium arsenide absorption layer by using hydrofluoric acid and hydrogen peroxide;
taking PbI 2 The DMF solution is coated on the surface of the gallium arsenide absorption layer in a spinning way, and is naturally dried, and then a certain amount of CH is taken 3 NH 3 I isopropanol solution, spin-coated with air-dried PbI 2 Then annealed at 120 ℃ for 30min to form CH with a thickness of 200nm 3 NH 3 PbI 3 A perovskite absorption layer;
dissolving 50000g/mol of P3HT with the weight-average molecular weight and the regularity of more than 95% in a 1, 2-dichlorobenzene solution with the solution concentration of 5mg/ml, spin-coating the solution on a perovskite absorption layer, and drying to form a P3HT hole transport layer with the thickness of 10 nm;
and evaporating an ITO electrode layer on the surface of the hole transport layer to form the gallium arsenide and perovskite heterojunction solar cell, wherein the photoelectric conversion efficiency of the gallium arsenide and perovskite heterojunction solar cell is 23.3% through detection.
Example 3
Introducing Ge substrate into MOCVD equipment, and introducing H 2 Raising the temperature of the gas to carry out high-temperature cleaning on the substrate, wherein the temperature range is 1000 ℃;
as shown in FIG. 1, a Si-doped N-type GaAs layer Al is grown on a Ge substrate 0.2 Ga 0.8 As with a doping concentration of 1X 10 17 cm -3 The thickness range is 500nm, and the growth temperature is 1100 ℃;
growing Si-doped GaAs material layer as GaAs absorption layer on the N-type GaAs layer with doping concentration of 1 × 10 17 cm -3 The thickness range is 5000nm, and the growth temperature is 1000 ℃;
cooling the temperature to room temperature, and taking out the device;
polishing the surface of the gallium arsenide absorption layer into a serrated concave-convex surface as shown in fig. 1 by using a mechanical polishing mode;
taking PbI 2 The DMF solution is coated on the surface of the gallium arsenide absorption layer in a spinning way, and is naturally dried, and then a certain amount of CH is taken 3 NH 3 I isopropanol solution, spin-coated on air-dried PbI 2 Then annealed at 120 ℃ for 30min to form CH with a thickness of 700nm 3 NH 3 PbI 3 A perovskite absorption layer;
dissolving 50000g/mol of P3HT with the weight-average molecular weight and the regularity of more than 95% in a 1, 2-dichlorobenzene solution with the solution concentration of 5mg/ml, spin-coating the solution on a perovskite absorption layer, and drying to form a P3HT hole transport layer with the thickness of 200 nm;
and evaporating an ITO electrode layer on the surface of the hole transport layer to form the gallium arsenide and perovskite heterojunction solar cell, wherein the photoelectric conversion efficiency of the gallium arsenide and perovskite heterojunction solar cell is 24.9% through detection.
Example 4
The gallium arsenide and perovskite heterojunction solar cell is manufactured by the embodiment through the following specific process:
introducing Ge substrate into MOCVD equipment, and introducing H 2 Raising the temperature of the gas to carry out high-temperature cleaning on the substrate, wherein the temperature range is 1000 ℃;
as shown in FIG. 1, a Si-doped N-type GaAs layer Al is grown on a Ge substrate 0.2 Ga 0.8 As with a doping concentration of 1X 10 16 cm -3 The thickness range is 500nm, and the growth temperature is 1100 ℃;
growing Si-doped GaAs material layer as GaAs absorption layer on the N-type GaAs layer with doping concentration of 1 × 10 16 cm -3 The thickness range is 5000nm, and the growth temperature is 1000 ℃;
cooling the temperature to room temperature, and taking out the device;
roughening the surface of the gallium arsenide absorption layer by using hydrofluoric acid and hydrogen peroxide;
taking PbI 2 The DMF solution is coated on the surface of the gallium arsenide absorption layer in a spinning way, and is naturally dried, and then a certain amount of CH is taken 3 NH 3 I isopropanol solution, spin-coated on air-dried PbI 2 Then annealed at 120 ℃ for 30min to form CH with a thickness of 400nm 3 NH 3 PbI 3 A perovskite absorption layer;
dissolving 50000g/mol of P3HT with the weight-average molecular weight and the regularity of more than 95% in a 1, 2-dichlorobenzene solution with the solution concentration of 5mg/ml, spin-coating the solution on a perovskite absorption layer, and drying to form a P3HT hole transport layer with the thickness of 200 nm;
and evaporating an ITO electrode layer on the surface of the hole transport layer to form the gallium arsenide and perovskite heterojunction solar cell, wherein the photoelectric conversion efficiency of the gallium arsenide and perovskite heterojunction solar cell is 24.7% through detection.
Example 5
The gallium arsenide and perovskite heterojunction solar cell is manufactured by the embodiment through the following specific process:
introducing Ge substrate into MOCVD equipment, and introducing H 2 Raising the temperature of the gas to carry out high-temperature cleaning on the substrate, wherein the temperature range is 1000 ℃;
as shown in FIG. 1, a Si-doped N-type GaAs layer Al is grown on a Ge substrate 0.2 Ga 0.8 As with a doping concentration of 1X 10 17 cm -3 The thickness range is 500nm, and the growth temperature is 1100 ℃;
growing Si-doped GaAs material layer as GaAs absorption layer on the N-type GaAs layer with doping concentration of 1 × 10 17 cm -3 The thickness range is 5000nm, and the growth temperature is 1000 ℃;
cooling the temperature to room temperature, and taking out the device;
roughening the surface of the gallium arsenide absorption layer by using hydrofluoric acid and hydrogen peroxide;
taking PbI 2 The DMF solution is coated on the surface of the gallium arsenide absorption layer in a spinning way, and is naturally dried, and then a certain amount of CH is taken 3 NH 3 I isopropanol solution, spin-coated on air-dried PbI 2 Then annealed at 120 ℃ for 30min to form CH with a thickness of 700nm 3 NH 3 PbI 3 A perovskite absorption layer;
spin-coating a chlorobenzene solution of Spiro-MeOTAD with the concentration of 80mg/mL on the perovskite absorption layer, and drying to form a Spiro-OMeTAD hole transport layer with the thickness of 200 nm;
and evaporating an ITO electrode layer on the surface of the hole transport layer to form the gallium arsenide and perovskite heterojunction solar cell, wherein the photoelectric conversion efficiency of the gallium arsenide and perovskite heterojunction solar cell is 24.5% through detection.
Example 6
The gallium arsenide and perovskite heterojunction solar cell is manufactured by the embodiment through the following specific process:
introducing Ge substrate into MOCVD equipment, and introducing H 2 Raising the temperature of the gas to carry out high-temperature cleaning on the substrate, wherein the temperature range is 1000 ℃;
as shown in FIG. 1, a Si-doped N-type GaAs layer Al is grown on a Ge substrate 0.2 Ga 0.8 As with a doping concentration of 1X 10 17 cm -3 The thickness range is 500nm, and the growth temperature is 1100 ℃;
growing Si-doped GaAs material layer as GaAs absorption layer on the N-type GaAs layer with doping concentration of 1 × 10 17 cm -3 The thickness range is 5000nm, and the growth temperature is 1000 ℃;
cooling the temperature to room temperature, and taking out the device;
roughening the surface of the gallium arsenide absorption layer by using hydrofluoric acid and hydrogen peroxide;
taking SnF 2 Spin coating DMF solution on GaAsDrying the surface of the absorbing layer naturally, and taking a certain amount of CH 3 NH 3 I isopropanol solution, spin-coated onto air-dried SnF 2 Then annealed at 120 ℃ for 30min to form CH with a thickness of 700nm 3 NH 3 SnF 3 A perovskite absorption layer;
dissolving 50000g/mol of P3HT with the weight-average molecular weight and the regularity of more than 95% in a 1, 2-dichlorobenzene solution with the solution concentration of 5mg/ml, spin-coating the solution on a perovskite absorption layer, and drying to form a P3HT hole transport layer with the thickness of 200 nm;
and evaporating an ITO electrode layer on the surface of the hole transport layer to form the gallium arsenide and perovskite heterojunction solar cell, wherein the photoelectric conversion efficiency of the gallium arsenide and perovskite heterojunction solar cell is 24.3% through detection.
Comparative example 1
Transferring the GaAs substrate into MOCVD equipment, and introducing H 2 Raising the temperature of the gas to carry out high-temperature cleaning on the substrate, wherein the temperature range is 1000 ℃;
as shown in FIG. 1, a Si-doped N-type GaAs layer Al is grown on a GaAs substrate 0.2 Ga 0.8 As with a doping concentration of 1X 10 17 cm -3 The thickness range is 500nm, and the growth temperature is 1100 ℃;
growing Si-doped GaAs absorption layer on N-type GaAs layer with doping concentration of 1 × 10 17 cm -3 The thickness range is 5000nm, and the growth temperature is 1000 ℃;
growing a C-doped P-type GaAs layer on the GaAs absorption layer, Al 0.2 Ga 0.8 As, doping concentration 1X 10 17 cm -3 The thickness range is 500nm, and the growth temperature is 750 ℃;
growing a heavily C-doped metal contact layer on the P-type GaAs layer with a doping concentration range of 1 × 10 20 cm -3 The thickness range is 100nm, and the growth temperature is 750 ℃;
the gallium arsenide solar cell is assembled by the vapor deposition top electrode, and the photoelectric conversion efficiency is 22.7% through detection.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The gallium arsenide and perovskite heterojunction solar cell is characterized by comprising an N-type gallium arsenide half cell (10) and a P-type perovskite half cell (20) positioned above the N-type gallium arsenide half cell (10), wherein the N-type gallium arsenide half cell (10) sequentially comprises a substrate (11), an N-type gallium arsenide layer (12) and a gallium arsenide absorption layer (13) from bottom to top; the P-type perovskite half cell (20) sequentially comprises a perovskite absorption layer (21), a hole transport layer (22) and an electrode layer (23) from bottom to top;
wherein the content of the first and second substances,
the N-type gallium arsenide layer (12) is made of Al x Ga 1-x As or (Al) y Ga 1-y ) Z In 1-z P, wherein the value range of x is 0-0.5, the value range of y is 0-0.5, and the value range of z is 0.4-0.6;
the gallium arsenide absorption layer (13) is made of GaAs;
the perovskite absorption layer (21) is made of one or more ABX3 materials, wherein A is NH (CHNH) 3 、CH 3 NH 3 Or Cs, B is Pb or Sn, and X is a halogen element.
2. A gaas and perovskite heterojunction solar cell according to claim 1, characterized in that the surface of the gaas absorber layer (13) on the side remote from the substrate (11) is a concave-convex surface and the surface of the perovskite absorber layer (21) in contact with the gaas absorber layer (13) is a concave-convex surface adapted thereto;
the surface of one side, far away from the substrate (11), of the gallium arsenide absorption layer (13) is a sawtooth-shaped concave-convex surface or a T-shaped concave-convex surface, and the surface, in contact with the gallium arsenide absorption layer (13), of the perovskite absorption layer (21) is a sawtooth-shaped concave-convex surface or a T-shaped concave-convex surface matched with the surface.
3. A gaas and perovskite heterojunction solar cell according to claim 1, characterized in that said N-type gaas layer (12) is a Si doped layer.
4. Gallium arsenide and perovskite heterojunction solar cell according to claim 1, characterized in that the material of the gallium arsenide absorber layer (13) is Si doped GaAs with a doping concentration lower than 1 x 10 22 cm -3 。
5. Gallium arsenide and perovskite heterojunction solar cell according to any of claims 1 to 4, characterized in that said substrate (11) is a Ge, Si or GaAs substrate;
the thickness of N type gallium arsenide layer (12) is 50 ~ 500nm, the thickness of gallium arsenide absorbed layer (13) is 500 ~ 5000nm, the thickness of substrate (11) is 270 ~ 1000 um.
6. The gallium arsenide and perovskite heterojunction solar cell of any of claims 1 to 4,
the perovskite absorption layer (21) is made of CH 3 NH 3 PbI 3 ；
The material of the hole transport layer (22) is one or more of Spiro-OMeTAD, P3HT, PEDOT, PSS and PTAA;
the electrode layer (23) is an ITO electrode layer;
the thickness of the perovskite absorption layer (21) is 200-700 nm, and the thickness of the hole transmission layer (22) is 10-200 nm.
7. A method of fabricating a GaAs and perovskite heterojunction solar cell as claimed in any of claims 1 to 6, comprising the steps of:
providing a substrate (11);
forming an N-type gallium arsenide layer (12) on one side surface of the substrate (11);
forming a gallium arsenide absorption layer (13) on the surface of one side of the N-type gallium arsenide layer (12) far away from the substrate (11);
growing a perovskite absorption layer (21) on the surface of one side of the gallium arsenide absorption layer (13) far away from the substrate (11);
growing a hole transport layer (22) on the surface of the perovskite absorption layer (21) on the side far away from the substrate (11);
and forming an electrode layer (23) on the surface of one side of the hole transport layer (22) far away from the substrate (11), thereby forming the gallium arsenide and perovskite heterojunction solar cell.
8. The fabrication method according to claim 7, characterized in that, before the step of growing the P-type perovskite half cell (20) on the surface of the gallium arsenide absorption layer (13) on the side away from the substrate (11), the fabrication method further comprises:
polishing the surface of one side of the gallium arsenide absorption layer (13) far away from the substrate (11) into a concave-convex surface;
the concave-convex surface is subjected to surface roughening treatment by adopting a chemical etching method, wherein the chemical etching method is hydrofluoric acid and hydrogen peroxide for co-corrosion;
and mechanically polishing by adopting a physical mechanical method, and polishing the surface of one side of the gallium arsenide absorption layer (13) far away from the substrate (11) into a sawtooth-shaped concave-convex surface or a T-shaped concave-convex surface.
9. The method of manufacturing according to claim 7 or 8, wherein the method of forming the N-type gallium arsenide layer (12) and the gallium arsenide absorption layer (13) is a metal organic chemical vapor deposition method, a molecular beam epitaxy method, a vapor phase epitaxy method, or a physical vapor deposition method.
10. A production method according to claim 7 or 8, characterized in that the method of growing the perovskite absorption layer (21) and the hole transport layer (22) is spin coating, spray coating, blade coating, screen printing or ink jet printing; the electrode layer (23) is formed by an evaporation method.
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