CN111081878A - Perovskite/silicon-based heterojunction laminated solar cell and preparation method thereof - Google Patents
Perovskite/silicon-based heterojunction laminated solar cell and preparation method thereof Download PDFInfo
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- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 16
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- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
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- H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
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Abstract
The invention discloses a perovskite/silicon-based heterojunction tandem solar cell and a preparation method thereof, and particularly relates to the perovskite/silicon-based heterojunction tandem solar cell which comprises a perovskite cell, a silicon-based heterojunction cell and a tunneling junction between the perovskite cell and the silicon-based heterojunction cell, wherein an anode is arranged on a perovskite cell layer, a cathode is arranged below the silicon-based heterojunction cell layer, and the perovskite cell is in the light incidence direction. The anode of the tandem solar cell is close to the incident position of light, so that the distance from the hole to the anode of the solar cell is effectively reduced, the carrier collection efficiency of the tandem solar cell is improved, and the performance of the solar cell is improved.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a perovskite/silicon-based heterojunction tandem solar cell and a preparation method thereof.
Background
Perovskite solar cells are the most promising solar cells and the research hotspots due to the outstanding advantages of high photoelectric conversion efficiency, low cost, simple manufacture and the like. The perovskite absorption layer with wide band gap is very favorable for forming a double-junction battery with the crystalline silicon solar battery, and has high photoelectric conversion efficiency and better stability than a perovskite single-junction battery.
Currently studied perovskite/Silicon-based heterojunction (SHJ) tandem solar cells generally adopt a structure that light enters from the negative electrode, that is, light is incident from the negative electrode of the perovskite/SHJ tandem solar cell. Specifically, as shown in fig. 1, after light irradiates the solar cell, the light enters the perovskite/SHJ tandem solar cell in the order of an electron transport layer 112, a perovskite absorption layer 111, a hole transport layer 110, a tunnel junction nano-silicon p layer 109, a tunnel junction nano-silicon n layer 108 of the perovskite solar cell, an amorphous silicon n layer 107 of the SHJ cell (i.e. a negative electrode of the SHJ cell), a first intrinsic amorphous silicon layer 106 of the SHJ cell, an SHJ absorption layer silicon wafer 105, a second intrinsic amorphous silicon layer 104 of the SHJ cell, and an amorphous silicon p layer 103 of the SHJ cell (i.e. a positive electrode of the SHJ cell), electrons of the stacked solar cell move to and are collected by the front transparent conductive layer 113 and the front conductive grid line 114, the front conductive grid line 114 serves as a negative electrode of the stacked solar cell, holes of the stacked solar cell move to and are collected by the back transparent conductive layer 102 and the back conductive grid line 101, and the back conductive grid line 101 serves as a positive electrode of the stacked solar cell. In such a structure, the efficiency of the solar cell still has a large difference from the theoretical efficiency, and further optimization of the cell structure and optimization of the device design are one of the working key points for improving the efficiency of the solar cell in the future.
Disclosure of Invention
In view of the above, the present invention is directed to a perovskite/silicon-based heterojunction tandem solar cell, which improves the conversion efficiency of the solar cell.
The perovskite/silicon-based heterojunction tandem solar cell provided by the invention comprises a perovskite cell, a silicon-based heterojunction cell and a tunneling junction between the perovskite cell and the silicon-based heterojunction cell, wherein an anode is arranged on a perovskite cell layer, a cathode is arranged below a silicon-based heterojunction cell layer, and the perovskite cell is in a light incidence direction.
Further, the tunnel junction is a metal oxide layer.
Further, the material of the metal oxide layer is selected from SnO2ZnO or TiO2。
Further, the perovskite battery comprises an electron transport layer, an absorption layer and a hole transport layer which are sequentially arranged on the tunneling junction.
Further, the silicon-based heterojunction cell comprises an amorphous silicon p layer, a first intrinsic amorphous silicon layer, a crystalline silicon wafer, a second intrinsic amorphous silicon layer and an amorphous silicon n layer which are sequentially arranged below the tunnel junction.
Further, the tunneling junction and the electron transport layer are the same layer and made of metal oxide.
Further, the thickness of the tunneling junction is 10nm to 200 nm.
Furthermore, the device also comprises a front transparent conducting layer arranged on the hole transport layer and a back transparent conducting layer arranged below the amorphous silicon n layer.
Further, the positive electrode is arranged on the front transparent conductive layer, and the negative electrode is arranged below the back transparent conductive layer.
The invention also provides a preparation method of the laminated solar cell, which comprises the steps of respectively depositing a first intrinsic amorphous silicon layer and a second intrinsic amorphous silicon layer on two sides of a silicon wafer, sequentially depositing an amorphous silicon p layer, a metal oxide layer, an absorption layer, a hole transmission layer and a front transparent conducting layer on the first intrinsic amorphous silicon layer, sequentially depositing an amorphous silicon n layer and a back transparent conducting layer on the second intrinsic amorphous silicon layer, and respectively preparing a front conductive grid line and a back conductive grid line on the front transparent conducting layer and the back transparent conducting layer.
Further, the metal oxide layer is manufactured by a magnetron sputtering method, a reactive plasma deposition method or a chemical vapor deposition method.
Further, the chemical vapor deposition method is selected from plasma enhanced chemical vapor deposition, atomic layer deposition, low pressure chemical vapor deposition or metal organic chemical vapor deposition.
As can be seen from the above description, according to the perovskite/silicon-based heterojunction tandem solar cell and the preparation method thereof provided by the invention, the positive electrode of the tandem solar cell is arranged on the perovskite cell layer, and the negative electrode is arranged below the silicon-based heterojunction cell layer, so that the holes move to the positive electrode of the tandem solar cell and are collected, and the electrons move to the negative electrode of the tandem solar cell and are collected. After light enters the solar cell absorption layer, most of the light is absorbed near the light incidence position to generate electron-hole pairs, the effective mass of the holes is far larger than that of the electrons, and therefore, the mobility of the holes is far lower than that of the electrons. Compared with the prior art that the cavity needs to move a longer distance to reach the anode of the tandem cell, the tandem solar cell structure has the advantages that the anode of the tandem solar cell is close to the incident position of light, the distance from the cavity to the anode of the solar cell is effectively reduced, the carrier collection efficiency of the tandem solar cell is improved, and the performance of the solar cell is improved.
The perovskite/silicon-based heterojunction tandem solar cell and the preparation method thereof provided by the invention further set the tunneling junction and the electron transport layer of the perovskite cell arranged on the tunneling junction as the same metal oxide layer, and the metal oxide layer is both a tunneling junction and an electron transport layer, so that the tandem solar cell has a simpler structure, reduces the interface loss between the electron transport layer of the perovskite cell close to the SHJ cell and the tunneling junction in the prior art, improves the charge transport performance of the solar cell and the composite efficiency of the tunneling junction, and further improves the open-circuit voltage and the filling factor of the cell; in addition, the preparation steps are reduced, and the production cost is saved.
Drawings
FIG. 1 is a schematic structural view of a prior art perovskite/SHJ tandem solar cell;
fig. 2 is a schematic structural diagram of a perovskite/SHJ tandem solar cell according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
It should be noted that all expressions using "first" and "second" in the embodiments of the present invention are used for distinguishing two entities with the same name but different names or different parameters, and it should be noted that "first" and "second" are merely for convenience of description and should not be construed as limitations of the embodiments of the present invention, and they are not described in any more detail in the following embodiments.
Fig. 2 shows that the present invention provides a perovskite/silicon-based heterojunction tandem solar cell, which comprises a perovskite cell, a silicon-based heterojunction cell, and a tunneling junction between the perovskite cell and the silicon-based heterojunction cell; the perovskite battery layer is provided with an anode, the silicon-based heterojunction battery layer is provided with a cathode, and the perovskite battery is in the light incidence direction. According to the technical scheme, the positive electrode is used as a window layer of the solar cell, most of light is absorbed at a position close to the light incidence position after the light enters the solar cell absorption layer from the perovskite cell, an electron hole pair is generated near the positive electrode accessory of the solar cell, and the effective mass of the hole is far larger than that of the electron and the hole, so that the mobility of the hole is far lower than that of the electron; compared with the prior art that most of electron hole pairs are generated near the cathode of the tandem solar cell, and holes need to migrate to a longer distance to reach the anode of the tandem solar cell, so that the charge collection efficiency of the solar cell is greatly reduced, the structure of the tandem solar cell provided by the invention has the advantages that the holes are collected by the anode of the tandem solar cell close to the light incidence position, the moving distance of the holes is effectively reduced, the carrier collection efficiency of the tandem solar cell is further improved, and the performances of the solar cell in three aspects including open-circuit voltage, filling factors and short-circuit current are improved.
In some embodiments of the present invention, the tunnel junction 208 is a metal oxide layer. Compared with the tunneling junction of the composite layer in the prior art, the metal oxide layer improves the composite efficiency of the tunneling junction.
In some embodiments of the invention, the material of the metal oxide layer is selected from SnO2ZnO or TiO2。
In some embodiments of the present invention, the perovskite cell includes an electron transport layer (not shown in the figures), an absorption layer 209, and a hole transport layer 210 disposed in that order on the tunneling junction 208.
In some embodiments of the present invention, the silicon-based heterojunction cell includes an amorphous silicon p-layer 207, a first intrinsic amorphous silicon layer 206, a crystalline silicon wafer 205, a second intrinsic amorphous silicon layer 204, and an amorphous silicon n-layer 203, which are sequentially disposed under the tunneling junction 208.
In some embodiments of the present invention, the tunneling junction and the electron transport layer are the same layer and the material is a metal oxide. The metal oxide layer is a tunneling junction and an electron transport layer, so that the structure of the laminated solar cell is simpler, the interface loss between the electron transport layer of the perovskite cell and the tunneling junction is reduced, the charge transport performance of the solar cell and the composite efficiency of the tunneling junction are improved, and the open-circuit voltage and the filling factor of the cell are improved; furthermore, the preparation steps are reduced, and the production cost is saved.
In some embodiments of the present invention, the tunnel junction 208 has a thickness of 10nm to 200 nm.
In some embodiments of the invention, the material of the absorber layer 209 is FA1-xCsxPbI3(wherein 0.1)<x<0.3) or FA1-xMAxPbI3(wherein x is more than or equal to 0.05 and less than or equal to 0.5).
Further, the hole transport layer 210 has a thickness of 5nm to 100nm, and the material is selected from organic small molecule materials such as nickel oxide (NiO), cuprous thiocyanate (CuSCN), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine (PTAA), 2',7,7' -tetrakis (di-p-tolylamino) spiro-9, 9' -bifluorene (spiro-TTB), and the like.
Further, the thickness of the amorphous silicon p-layer 207 is 2nm to 100 nm; the thickness of the amorphous silicon n-layer 203 is 2nm to 200 nm.
Further, the thickness of the first intrinsic amorphous silicon layer 206 and the second intrinsic amorphous silicon layer 204 is 2nm to 50 nm.
Further, the thickness of the crystalline silicon wafer 205 is 150 micrometers to 250 micrometers, and is selected from an n-type silicon wafer or a p-type silicon wafer.
In some embodiments of the present invention, the device further comprises a front transparent conductive layer 211 disposed on the hole transport layer 210 and a back transparent conductive layer 202 disposed under the amorphous silicon n-layer 203. The positive electrode (amorphous silicon p layer 207) of the silicon-based heterojunction cell is in contact with the tunneling junction, and the negative electrode (amorphous silicon n layer 203) is in contact with the back transparent conductive layer 202; the cathode (electron transport layer) of the perovskite cell is the same layer as or in contact with the tunneling junction, and the anode (hole transport layer 210) of the perovskite cell is in contact with the front transparent conductive layer 211.
Further, the thickness of the front transparent conductive layer 211 is 50nm to 150 nm; the thickness of the back transparent conductive layer 202 is 50nm to 500 nm;
further, the material of the front transparent conductive layer 211 or the back transparent conductive layer 202 is selected from Indium Tin Oxide (ITO), indium tungsten oxide (IWO), indium titanium oxide (ITiO), aluminum-doped zinc oxide (AZO), or boron-doped zinc oxide (BZO).
In some embodiments of the present invention, the positive electrode is disposed on the front transparent conductive layer 211, and the negative electrode is disposed under the back transparent conductive layer 202. Further, the positive electrode of the tandem solar cell is the front conductive grid line 212, and the negative electrode of the tandem solar cell is the back conductive grid line 201.
Further, the material of the front conductive grid line 212 or the back conductive grid line 201 is selected from a metal compound containing copper or silver; the copper-containing metal complex is Ti/Cu or Sn/Cu.
The invention further provides a preparation method of the laminated solar cell, which comprises the steps of respectively depositing a first intrinsic amorphous silicon layer 206 and a second intrinsic amorphous silicon layer 204 on two sides of a silicon wafer 205, sequentially depositing an amorphous silicon p layer 207, a metal oxide layer (which is also a tunneling junction), an absorption layer 209, a hole transmission layer 210 and a front transparent conductive layer 211 on the first intrinsic amorphous silicon layer 206, sequentially depositing an amorphous silicon n layer 203 and a back transparent conductive layer 202 on the second intrinsic amorphous silicon layer 204, and respectively preparing a front conductive grid line 212 and a back conductive grid line 201 on the front transparent conductive layer 211 and the back transparent conductive layer 202.
In some embodiments of the invention, the metal oxide layer is fabricated by magnetron sputtering, Reactive Plasma Deposition (RPD), or chemical vapor deposition.
Further, the chemical vapor deposition method is selected from Plasma Enhanced Chemical Vapor Deposition (PECVD), Atomic Layer Deposition (ALD), Low Pressure Chemical Vapor Deposition (LPCVD), or Metal Organic Chemical Vapor Deposition (MOCVD).
In some embodiments of the present invention, the first intrinsic amorphous silicon layer 206, the second intrinsic amorphous silicon layer 204, the amorphous silicon p-layer 207 and the amorphous silicon n-layer 203 are fabricated using Plasma Enhanced Chemical Vapor Deposition (PECVD).
In some embodiments of the present invention, when the hole transport layer 210 is nickel oxide (NiO), it can be fabricated by magnetron sputtering, Reactive Plasma Deposition (RPD), or chemical vapor deposition, and has a thickness of 5nm to 100 nm. Further, the chemical vapor deposition herein is selected from Atomic Layer Deposition (ALD), Low Pressure Chemical Vapor Deposition (LPCVD), or Metal Organic Chemical Vapor Deposition (MOCVD).
In some embodiments of the present invention, the hole transport layer 210 is made of cuprous thiocyanate (CuSCN) by vacuum evaporation to a thickness of 5nm to 100 nm.
In some embodiments of the present invention, the positive transparent conductive layer 211 or the negative transparent conductive layer 202 is prepared using magnetron sputtering deposition or Reactive Plasma Deposition (RPD).
In some embodiments of the present invention, there are two methods for preparing the front conductive grid line 212 and the back conductive grid line 201, which are screen printing and electroplating respectively.
Further, a layer of metal silver grid lines is prepared on the back transparent conductive layer 202 or the front transparent conductive layer 211 through screen printing to correspondingly form a back conductive grid line 201 or a front conductive grid line 212, wherein the thickness of the silver grid is 5 micrometers to 200 micrometers, and the width of the silver grid is 1 micrometer to 200 micrometers.
Further, a thin layer of titanium (Ti) or tin (Sn) is evaporated or sputtered on the back transparent conductive layer 202 or the front transparent conductive layer 211 through a mask to serve as a front body, the thickness of the front body is 5nm to 100nm, the width of the front body is 1 micron to 200 microns, then a layer of Cu grid lines is electroplated on the Ti or Sn front body in a Cu salt solution, the thickness of the Cu grid lines is 100nm to 20 microns, the width of the Cu grid lines is 1 micron to 200 microns, a back conductive grid line 201 or a front conductive grid line 212 is correspondingly formed, and the corresponding thickness is 100nm to 20 microns.
The structure and the preparation method of the perovskite/silicon-based heterojunction tandem solar cell of the invention are further illustrated by the specific examples below.
Example 1
In this embodiment, the electron transport of the tunnel junction and the perovskite cell is the same layer, and the material is SnO2The silver grid line on the perovskite solar cell layer is the anode of the cell, the silver grid line under the SHJ cell layer is the cathode of the cell, and the preparation method comprises the following steps:
step 1: plating an intrinsic amorphous silicon layer on each of two surfaces of a cleaned and textured n-type silicon wafer through plasma enhanced chemical vapor deposition, wherein the thicknesses of the intrinsic amorphous silicon layers are 10nm and 8nm respectively;
step 2: then depositing a layer of n-type amorphous silicon with the thickness of 10nm on the second intrinsic amorphous silicon layer 204 with the thickness of 8nm, and depositing a layer of p-type amorphous silicon with the thickness of 15nm on the first intrinsic amorphous silicon layer 206 with the thickness of 10 nm;
and step 3: preparing a back transparent conductive layer 202 on the n-type amorphous silicon layer by magnetron sputtering, wherein the material is Indium Tin Oxide (ITO) and the thickness is 120 nm;
and 4, step 4: the tunneling junction is prepared on the p-type amorphous silicon layer through magnetron sputtering, and the tunneling junction is also an electron transport layer of the perovskite solar cell and is made of SnO2The thickness is 50 nm;
and 5: SnO in electron transport layer2Depositing perovskite absorption layer 209 on the surface, the absorption layer is made of FA0.9MA0.1PbI3(ii) a The deposition method comprises vacuum co-evaporation, wherein the evaporation raw materials are respectively formamidine iodide (FAI), methylamine iodide (MAI) and PbI2The FAI evaporation temperature is 200 ℃, the MAI evaporation temperature is 120 ℃,PbI2the evaporation temperature is 400 ℃, the temperature of the substrate material is 30 ℃, and the thickness of the perovskite absorption layer is 400 nm;
step 6: depositing a hole transport layer 210 on the deposited perovskite absorption layer 209, wherein the material is PTAA, the deposition method is vacuum evaporation, the evaporation temperature of the raw material is 150 ℃, the substrate temperature is 30 ℃, and the film thickness is 80 nm;
and 7: depositing a front transparent conductive layer 211 on the deposited hole transport layer 210, wherein the material is Indium Tin Oxide (ITO), the deposition method is Reactive Plasma Deposition (RPD), and the thickness of the deposited film is 80 nm;
and 8: preparing silver grid lines on the deposited front transparent conductive layer 211 through screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 2 millimeters;
and step 9: preparing silver grid lines on the deposited back transparent conductive layer 202 through screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 1.5 millimeters;
to this end, the fabrication of the tandem solar cell is completed.
Example 2
In this embodiment, the electron transport of the tunnel junction and the perovskite cell is the same layer, and the material is TiO2The silver grid line on the perovskite solar cell layer is the anode of the cell, the silver grid line under the SHJ cell layer is the cathode of the cell, and the preparation method comprises the following steps:
step 1: plating an intrinsic amorphous silicon layer on each of two surfaces of a cleaned and textured n-type silicon wafer through plasma enhanced chemical vapor deposition, wherein the thickness of each intrinsic amorphous silicon layer is 10 nm;
step 2: then depositing a layer of p-type amorphous silicon and a layer of n-type amorphous silicon on the intrinsic amorphous silicon layers on the two sides respectively, wherein the thickness of the p-type amorphous silicon is 20nm, and the thickness of the n-type amorphous silicon is 15 nm;
and step 3: preparing a back transparent conductive layer 202 on the n-type amorphous silicon layer through magnetron sputtering, wherein the material is aluminum-doped zinc oxide (AZO) and the thickness is 200 nm;
and 4, step 4: in thatpreparing a tunneling junction on the p-type amorphous silicon layer by Atomic Layer Deposition (ALD), and simultaneously forming an electron transport layer of the perovskite solar cell, wherein the material is TiO2The thickness is 40 nm;
and 5: then TiO is arranged on the electron transport layer2Depositing perovskite absorption layer 209 on the surface, the absorption layer is made of FA0.7MA0.3PbI3The deposition method comprises vacuum co-evaporation of FAI, MAI and PbI as raw materials2(ii) a FAI evaporation temperature is 200 ℃, MAI evaporation temperature is 140 ℃, PbI evaporation temperature is2The evaporation temperature is 400 ℃; the temperature of the substrate material is 30 ℃, and the thickness of the perovskite absorption layer is 400 nm;
step 6: depositing a hole transport layer 210 on the deposited perovskite absorption layer, wherein the material is cuprous thiocyanate (CuSCN), the deposition method is vacuum evaporation, the evaporation temperature of the raw material is 120 ℃, the substrate temperature is 30 ℃, and the film thickness is 20 nm;
and 7: depositing a front transparent conductive layer 211 on the deposited hole transport layer 210, wherein the material is indium tungsten oxide (IWO), the deposition method is Reactive Plasma Deposition (RPD), and the deposition film thickness is 80 nm;
and 8: preparing silver grid lines on the deposited front transparent conductive layer 211 through screen printing, wherein the height of the silver grid lines is 15 micrometers, the width of the silver grid lines is 60 micrometers, and the distance between the silver grid lines is 2 millimeters;
and step 9: preparing silver grid lines on the deposited back transparent conductive layer 202 through screen printing, wherein the height of the silver grid lines is 15 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 1.5 millimeters;
to this end, the fabrication of the tandem solar cell is completed.
Example 3
The embodiment provides a perovskite/silicon-based heterojunction tandem solar cell, wherein the electron transmission of a tunneling junction and the electron transmission of the perovskite cell are the same layer, the material is ZnO, the silver grid line on the perovskite solar cell layer is the positive electrode of the cell, the silver grid line on the SHJ cell layer is the negative electrode of the cell, and the perovskite/silicon-based heterojunction tandem solar cell is prepared by the following preparation method, including:
step 1: plating an intrinsic amorphous silicon layer on each of two surfaces of a cleaned and textured n-type silicon wafer through plasma enhanced chemical vapor deposition, wherein the thicknesses of the intrinsic amorphous silicon layers are 10nm and 8nm respectively;
step 2: then plating a layer of p-type nano-silicon on the first intrinsic amorphous silicon layer 206 with the thickness of 8nm through plasma enhanced chemical vapor deposition, wherein the thickness of the p-type nano-silicon is 30nm, and plating a layer of n-type nano-silicon on the second intrinsic amorphous silicon layer 204 with the thickness of 10nm through plasma enhanced chemical vapor deposition, wherein the thickness of the n-type nano-silicon is 20 nm;
and step 3: preparing a back transparent conductive layer 202 on the n-type nano silicon by Low Pressure Chemical Vapor Deposition (LPCVD), wherein the material is boron-doped zinc oxide (BZO) and the thickness is 300 nm;
and 4, step 4: preparing a tunneling junction 208 on the p-type nano silicon by Low Pressure Chemical Vapor Deposition (LPCVD), and meanwhile, the tunneling junction is also an electron transport layer of the perovskite solar cell, the material is ZnO, and the thickness is 50 nm;
and 5: a perovskite absorber layer 209 is then deposited on the electron transport layer ZnO, the absorber layer being made of FA0.9Cs0.1PbI3The deposition method comprises vacuum co-evaporation of FAI, CsI and PbI as evaporation raw materials2The FAI evaporation temperature is 200 ℃, the CsI evaporation temperature is 300 ℃, the PbI2 evaporation temperature is 400 ℃, the temperature of the substrate material is 30 ℃, the thickness of the perovskite absorption layer is 450nm,
step 6: depositing a hole transport layer 210 on the deposited perovskite absorption layer 209, wherein the material is NiO, the deposition method is Atomic Layer Deposition (ALD), the film thickness is 10nm,
and 7: depositing a front transparent conductive layer 211 on the deposited hole transport layer 210, wherein the material is indium titanium oxide (ITiO), the deposition method is Reactive Plasma Deposition (RPD), the thickness of the deposited film is 80nm,
and 8: silver grid lines are prepared on the deposited front transparent conductive layer 211 through screen printing, the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, the distance between the silver grid lines is 2 millimeters,
and step 9: preparing silver grid lines on the deposited back transparent conductive layer 202 through screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 1.5 millimeters;
to this end, the fabrication of the tandem solar cell is completed.
Comparative example 1
The difference between the comparative example and the example 1 is that the tunneling junction is a composite layer and consists of a nano-silicon n layer and a nano-silicon p layer, and the preparation method is as follows:
and 4, step 4: sequentially preparing a nano silicon p layer and a nano silicon n layer on the p-type amorphous silicon layer by Plasma Enhanced Chemical Vapor Deposition (PECVD), wherein the thicknesses of the nano silicon p layer and the nano silicon n layer are both 20 nm; preparing an electron transmission layer of the perovskite solar cell on the nano silicon n layer by magnetron sputtering, wherein the material is SnO2And the thickness is 50 nm.
Comparative example 2
The tandem solar cell in the present comparative example is the prior art, that is, the negative electrode of the tandem solar cell is disposed on the perovskite cell layer, and the positive electrode is disposed under the SHJ cell layer, and the preparation method thereof is as follows:
step 1: plating an intrinsic amorphous silicon layer on each of two surfaces of a cleaned and textured n-type silicon wafer through plasma enhanced chemical vapor deposition, wherein the thicknesses of the intrinsic amorphous silicon layers are 10nm and 8nm respectively;
step 2: then depositing a layer of p-type amorphous silicon on the second intrinsic amorphous silicon layer 104 with the thickness of 8nm, wherein the thickness is 15nm, and depositing a layer of n-type amorphous silicon on the first intrinsic amorphous silicon layer 106 with the thickness of 10nm, wherein the thickness is 10 nm;
and step 3: preparing a back transparent conductive layer 102 on the p-type amorphous silicon layer 103 by magnetron sputtering, wherein the material is Indium Tin Oxide (ITO) and the thickness is 120 nm;
and 4, step 4: sequentially preparing a nano-silicon n layer 108 and a nano-silicon p layer 109 on the n-type amorphous silicon layer 107 by Plasma Enhanced Chemical Vapor Deposition (PECVD), wherein the thicknesses of the nano-silicon n layer and the nano-silicon p layer are both 20nm, and a tunneling junction composite layer is formed;
and 5: depositing a hole transport layer 110 on the deposited nano silicon p layer 109, wherein the material is PTAA, the deposition method is vacuum evaporation, the evaporation temperature of the raw material is 150 ℃, the substrate temperature is 30 ℃, and the film thickness is 80 nm;
step 6: depositing a perovskite absorber layer 111 on the hole transport layer 110, the absorber layer being made of FA0.9MA0.1PbI3(ii) a Deposition method vacuum co-evaporationThe evaporation raw materials are respectively formamidine iodide (FAI), methylamine iodide (MAI) and PbI2FAI evaporation temperature of 200 ℃, MAI evaporation temperature of 120 ℃, PbI2The evaporation temperature is 400 ℃, the temperature of the substrate material is 30 ℃, and the thickness of the perovskite absorption layer is 400 nm;
and 7: preparing an electron transport layer 112 of the perovskite solar cell on the absorption layer 111 through magnetron sputtering, wherein the material is SnO2The thickness is 50 nm;
and 8: depositing a front transparent conductive layer 113 on the deposited electron transport layer 112, wherein the material is Indium Tin Oxide (ITO), the deposition method is Reactive Plasma Deposition (RPD), and the thickness of the deposited film is 80 nm;
and 8: preparing silver grid lines on the deposited front transparent conductive layer 113 through screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 2 millimeters;
and step 9: preparing silver grid lines on the deposited back transparent conductive layer 102 through screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 1.5 millimeters;
to this end, the fabrication of the tandem solar cell is completed.
Comparative example 3
The difference between the comparative example and the comparative example 2 is that the tunnel junction is a metal oxide layer, specifically:
and 4, step 4: preparing a tunneling junction on the n-type amorphous silicon layer 107 by magnetron sputtering, wherein the material is SnO2And the thickness is 50 nm.
Performance testing
The perovskite/silicon-based heterojunction tandem solar cells provided in comparative example and example were respectively tested for performance, and the results are shown in table 1.
TABLE 1 comparison of cell parameters for the examples and comparative examples
The tunneling junctions of the tandem solar cells in the comparative examples 1 and 2 are formed by a composite layer composed of a nano-silicon n layer and a nano-silicon p layer, and the difference is only that the anode of the tandem solar cell in the comparative example 1 is arranged on a perovskite cell layer, the cathode of the tandem solar cell in the comparative example 1 is arranged under a silicon-based heterojunction cell layer, the anode of the tandem solar cell in the comparative example 2 is arranged under the silicon-based heterojunction cell layer, and the cathode of the tandem solar cell in the prior art is arranged on the perovskite cell layer. As can be seen from the data in table 1, the cell efficiency of the tandem solar cell in comparative example 1 is better than that of the tandem solar cell in comparative example 2, which indicates that the technical scheme of the present invention in which the positive electrode is disposed on the perovskite cell layer and the negative electrode is disposed under the silicon-based heterojunction cell layer is beneficial to improving the cell efficiency of the perovskite/silicon-based heterojunction solar cell. Further, in comparative example 3, compared with examples 1 to 3, all the tunnel junctions are metal oxide layers, and the difference is that in the technical scheme in the examples, the positive electrode is disposed on the perovskite cell layer, the negative electrode is disposed under the silicon-based heterojunction cell layer, the stacked solar cell in comparative example 3 adopts the technical scheme in the prior art, the positive electrode is disposed under the silicon-based heterojunction cell layer, and the negative electrode is disposed on the perovskite cell layer, the cell efficiencies of the examples are respectively 24.16, 23.67 and 24.02 which are significantly higher than the cell efficiency of 20.74 in comparative example 3, and it is again explained that the positive electrode is disposed on the perovskite cell layer, and the technical scheme in which the negative electrode is disposed under the silicon-based heterojunction cell layer is beneficial to improving the cell efficiency of the perovskite/silicon-based heterojunction solar cell.
On the other hand, the stacked solar cells in comparative example 2 and comparative example 3 are different only in the tunneling junction, the tunneling junction in comparative example 3 is a metal oxide layer, and as is apparent from the data in table 1, the cell efficiency in comparative example 2 is higher than that in comparative example 3, which indicates that the metal oxide layer is used as a tunneling junction in the stacked solar cell in which the positive electrode is disposed under the silicon-based heterojunction cell layer and the negative electrode is disposed on the perovskite cell layer in the prior art, which is not beneficial to the efficiency improvement of the solar cell. Comparative example 1 and the embodiment both adopt the technical scheme of the invention that the positive electrode is arranged on the perovskite battery layer, and the negative electrode is arranged under the silicon-based heterojunction battery layer, the difference is only that the tunneling junction of the comparative example 1 is formed by a composite layer consisting of a nano-silicon n layer and a nano-silicon p layer, the tunneling junction of the embodiment is a metal oxide, and the data in table 1 show that the battery efficiency of the embodiment is higher than that of the comparative example 1, which indicates that in the technical scheme of the invention that the positive electrode is arranged on the perovskite battery layer and the negative electrode is arranged under the silicon-based heterojunction battery layer, the metal oxide layer has higher battery efficiency as the tunneling junction, and the metal oxide layer is suitable for the battery structure of the technical scheme of the invention as the tunneling junction.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
While the present invention has been described in conjunction with specific embodiments thereof, many alternatives, modifications, and variations of these embodiments will be apparent to those of ordinary skill in the art in light of the foregoing description.
The embodiments of the invention are intended to embrace all such alternatives, modifications and variances that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (12)
1. The perovskite/silicon-based heterojunction tandem solar cell comprises a perovskite cell, a silicon-based heterojunction cell and a tunneling junction between the perovskite cell and the silicon-based heterojunction cell, and is characterized in that a positive electrode is arranged on a perovskite cell layer, a negative electrode is arranged below the silicon-based heterojunction cell layer, and the perovskite cell is in the light incidence direction.
2. The tandem solar cell of claim 1, wherein said tunnel junction is a metal oxide layer.
3. The tandem solar cell according to claim 2, wherein the material of the metal oxide layer is selected from SnO2ZnO or TiO2。
4. The tandem solar cell of claim 1, wherein the perovskite cell comprises an electron transport layer, an absorption layer, and a hole transport layer disposed in that order on the tunnel junction.
5. The tandem solar cell according to claim 4, wherein the silicon-based heterojunction cell comprises an amorphous silicon p layer, a first intrinsic amorphous silicon layer, a crystalline silicon wafer, a second intrinsic amorphous silicon layer and an amorphous silicon n layer which are sequentially arranged below the tunnel junction.
6. The tandem solar cell of claim 4, wherein the tunneling junction and the electron transport layer are the same layer and are made of a metal oxide.
7. The tandem solar cell of claim 6, wherein the tunnel junction has a thickness of 10nm to 200 nm.
8. The tandem solar cell of claim 5, further comprising a front transparent conductive layer disposed on said hole transport layer and a back transparent conductive layer disposed under said amorphous silicon n-layer.
9. The tandem solar cell of claim 8, wherein said positive electrode is disposed on said front transparent conductive layer and said negative electrode is disposed under said back transparent conductive layer.
10. The method for preparing a tandem solar cell according to any one of claims 1 to 9, comprising depositing a first intrinsic amorphous silicon layer and a second intrinsic amorphous silicon layer on both sides of a silicon wafer, depositing an amorphous silicon p layer, a metal oxide layer, an absorption layer, a hole transport layer and a front transparent conductive layer on the first intrinsic amorphous silicon layer in sequence, depositing an amorphous silicon n layer and a back transparent conductive layer on the second intrinsic amorphous silicon layer in sequence, and preparing a front conductive grid line and a back conductive grid line on the front transparent conductive layer and the back transparent conductive layer respectively.
11. The method of claim 10, wherein the metal oxide layer is formed by magnetron sputtering, reactive plasma deposition or chemical vapor deposition.
12. A method of manufacturing as claimed in claim 11, wherein the chemical vapor deposition process is selected from plasma enhanced chemical vapor deposition, atomic layer deposition, low pressure chemical vapor deposition or metalorganic chemical vapor deposition.
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