A method for controlling photoelectric parameters of a transparent conductive electrode and its application in stacked solar cells

Abstract

The present invention provides a method for regulating photoelectric parameters of a transparent conductive electrode and its application in a stacked solar cell, belonging to the technical field of stacked photovoltaic cells, and is specifically achieved by subjecting the deposited transparent conductive electrode to humidity and oxygen immersion aging treatment; wherein the humidity of the treatment is 3-10%, the oxygen concentration of the treatment is 20-25%, and the aging time of the treatment is 8-12 h. Through the above treatment, the crystal structure of the transparent conductive electrode can be optimized, the resistivity of the transparent conductive electrode can be reduced, the conductivity, carrier migration performance and light transmittance can be improved, and the photoelectric conversion efficiency of the stacked solar cell can be improved. The photoelectric parameter regulation method of the present invention is simple, easy to control, has the advantage of low cost, and is suitable for wide application.

Description

Technical Field

[0001] The present invention belongs to the technical field of laminated photovoltaic cells, and in particular relates to a method for regulating photoelectric parameters of a transparent conductive electrode and an application thereof in laminated solar cells. Background Art

[0002] Perovskite / silicon tandem solar cells integrate the advantages of both crystalline silicon and perovskite materials, and have the characteristics of high photoelectric conversion efficiency, low production cost, and strong material adjustability. In tandem devices, transparent conductive electrodes play a key role. Their high light transmittance and excellent conductivity can effectively improve light transmittance and charge transfer efficiency, and optimize the photoelectric performance of the device. In addition, transparent conductive electrodes can reduce light absorption losses, enhance the spectral response of tandem devices, and improve overall conversion efficiency.

[0003] At present, perovskite / silicon tandem solar cells often use magnetron sputtered indium zinc oxide (IZO) films as transparent conductive electrodes, with a thickness of 40-70 nm. This thickness range usually has low transmittance for short-wavelength light, resulting in optical losses in the tandem device. In addition, when the thickness of the transparent conductive electrode is small (about 40 nm), its resistivity will be high, affecting the carrier collection efficiency, thereby reducing the photoelectric conversion efficiency of the tandem device. Summary of the invention

[0004] In response to the problems existing in transparent conductive electrodes in stacked devices, the present invention provides a method for regulating the photoelectric parameters of a transparent conductive electrode and its application in stacked solar cells. By subjecting the deposited transparent conductive electrode to humidity and oxygen immersion aging treatment, the resistivity of the transparent conductive electrode is significantly reduced, and the conductivity, carrier migration performance and light transmittance are improved, thereby improving the photoelectric conversion efficiency of the stacked solar cell.

[0005] In order to achieve the above purpose, the technical method adopted by the present invention is as follows:

[0006] A method for regulating photoelectric parameters of a transparent conductive electrode is achieved by subjecting the deposited transparent conductive electrode to humidity and oxygen immersion aging treatment; wherein the humidity of the treatment is 3-10%, the oxygen concentration of the treatment is 20-25%, and the aging time of the treatment is 8-12 h.

[0007] Furthermore, the material of the transparent conductive electrode is metal oxide.

[0008] Furthermore, the metal oxide is indium tin oxide (ITO), indium zinc oxide or indium tungsten oxide (IWO).

[0009] Furthermore, the thickness of the transparent conductive electrode is 40-70 nm.

[0010] Furthermore, the transparent conductive electrode is obtained by magnetron sputtering, plasma enhanced chemical vapor deposition (PECVD) or pulsed laser deposition (PLD).

[0011] Furthermore, the magnetron sputtering adopts a direct current mode or a radio frequency mode.

[0012] Preferably, when the magnetron sputtering adopts the DC mode, the sputtering rate is 0.23-0.26 Å / s and the vacuum degree is 8.5-9.5×10 -4 Pa, the argon flow rate is 6~10 sccm, and the oxygen flow rate is 0.3~0.5 sccm.

[0013] The present invention also provides the application of the transparent conductive electrode obtained by the photoelectric parameter regulation method in a stacked solar cell.

[0014] Furthermore, the tandem solar cell is a perovskite / silicon tandem solar cell.

[0015] A perovskite / silicon stacked solar cell comprises a silicon heterojunction bottom cell, a hole transport layer, a perovskite absorption layer, an electron transport layer, a buffer layer, a transparent conductive electrode, a positive electrode and an anti-reflection layer stacked in sequence; wherein the transparent conductive electrode is obtained by processing the photoelectric parameter regulation method.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] 1. The present invention proposes a method for controlling photoelectric parameters of a transparent conductive electrode and its application in a stacked solar cell. By subjecting the deposited transparent conductive electrode to an immersion aging treatment at a specific humidity and a specific oxygen concentration, the crystal structure of the transparent conductive electrode is optimized, the resistivity of the transparent conductive electrode is reduced, and the conductive performance, carrier migration performance and light transmittance are improved, thereby improving the photoelectric conversion efficiency of the stacked solar cell.

[0018] 2. Specifically, on the one hand, under a specific oxygen concentration, the number of oxygen vacancies in the transparent conductive electrode is significantly reduced, which effectively reduces the resistivity of the transparent conductive electrode and improves the conductivity. Specific humidity conditions will also promote the penetration of oxygen into the transparent conductive electrode to further improve the carrier migration characteristics. On the other hand, the introduction of oxygen can fill the film defects of the transparent conductive electrode and reduce light absorption and scattering losses. The auxiliary effect of humidity can further optimize the surface flatness and transparency of the transparent conductive electrode. Then, under the synergistic effect of oxygen and humidity, the light transmittance of the transparent conductive electrode in the visible light and near-infrared bands is significantly improved, so that more light passes through the transparent conductive electrode to enter the light absorption layer, greatly improving the photoelectric conversion efficiency of the stacked solar cell.

[0019] 3. The photoelectric parameter control method of the present invention is simple, easy to control, has the advantage of low cost, and is suitable for wide application. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0021] Figure 1 A schematic diagram of the structure of a perovskite / silicon tandem solar cell provided by the present invention;

[0022] Figure 2 : This is a contact resistivity comparison curve of the transparent conductive electrode after immersion aging treatment at a humidity of 5% and an oxygen concentration of 20% in Example 1 and the transparent conductive electrode without immersion aging treatment in Comparative Example 4;

[0023] Figure 3 JV curves of the perovskite / silicon tandem solar cells obtained in Example 1 and Comparative Example 4;

[0024] Figure 4 The light transmittance curves of the transparent conductive electrodes after immersion aging treatment at different humidity and oxygen concentration of 20% in Example 1, Example 4, Example 5, Comparative Example 1 and Comparative Example 3;

[0025] The descriptions of the symbols in the accompanying drawings are as follows:

[0026] 1-Silicon heterojunction bottom cell; 2-Hole transport layer; 3-Perovskite absorption layer; 4-Electron transport layer; 5-Buffer layer; 6-Transparent conductive electrode; 7-Positive electrode; 8-Anti-reflection layer. DETAILED DESCRIPTION

[0027] In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with the examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the invention. All raw materials of the present invention are not particularly limited in their sources, and can be purchased on the market or prepared according to conventional methods well known to those skilled in the art.

[0028] The first aspect of the present invention provides a method for regulating the photoelectric parameters of a transparent conductive electrode, which is achieved by subjecting the deposited transparent conductive electrode to humidity and oxygen immersion aging treatment; wherein the treatment humidity is 3-10%, the treatment oxygen concentration is 20-25%, and the treatment aging time is 8-12 h.

[0029] Furthermore, the material of the transparent conductive electrode is metal oxide, and the metal oxide is indium tin oxide, indium zinc oxide or indium tungsten oxide.

[0030] Furthermore, the thickness of the transparent conductive electrode is 40-70 nm.

[0031] Furthermore, the transparent conductive electrode is obtained by magnetron sputtering (DC mode) deposition; wherein the sputtering rate of the magnetron sputtering is 0.23-0.26 Å / s, and the vacuum degree is 8.5-9.5×10 -4 Pa, argon flow rate is 6~10 sccm, oxygen flow rate is 0.3~0.5 sccm, substrate temperature is 23~25℃, sputtering intensity is 190~200 W, and sputtering time is 180~270 s.

[0032] The present invention proposes a method for controlling the photoelectric parameters of a transparent conductive electrode and its application in a stacked solar cell. By subjecting the deposited transparent conductive electrode to an immersion aging treatment at a specific humidity and a specific oxygen concentration, the crystal structure of the transparent conductive electrode is optimized, the resistivity of the transparent conductive electrode is reduced, and the conductivity, carrier migration performance and light transmittance are improved, thereby improving the photoelectric conversion efficiency of the stacked solar cell.

[0033] On the one hand, under a specific oxygen concentration, the number of oxygen vacancies in the transparent conductive electrode is significantly reduced, effectively reducing the resistivity of the transparent conductive electrode and improving the conductivity, while specific humidity conditions will also promote the penetration of oxygen into the transparent conductive electrode to further improve the carrier migration characteristics; on the other hand, the introduction of oxygen can fill the film defects of the transparent conductive electrode and reduce light absorption and scattering losses, while the auxiliary effect of humidity can further optimize the surface flatness and transparency of the transparent conductive electrode, and then under the synergistic effect of oxygen and humidity, the light transmittance of the transparent conductive electrode in the visible light and near-infrared bands is significantly improved, allowing more light to pass through the transparent conductive electrode to enter the light absorption layer, greatly improving the photoelectric conversion efficiency of the stacked solar cell.

[0034] In a second aspect of the present invention, a perovskite / silicon tandem solar cell is provided, the structure of which is as follows: Figure 1 As shown, it includes a silicon heterojunction bottom cell 1, a hole transport layer 2, a perovskite absorption layer 3, an electron transport layer 4, a buffer layer 5, a transparent conductive electrode 6, a positive electrode 7 and an anti-reflection layer 8 stacked in sequence; wherein the material of the hole transport layer 2 is 2PACz (2-phenylamino pyridinium salt), Me-4PACz (methyl-4-phenylamino pyridinium salt) or MeO-2PACz (methoxy-2-phenylamino pyridinium salt); the material of the perovskite absorption layer 3 is Cs x FA 1-x Pb(I / Br) 3 or Cs xFA y MA 1-x-y Pb(I / Br) 3 The material of the electron transport layer 4 is a lithium fluoride layer (LiF layer) / fullerene thin layer (C 60 Layer), PC 60 BM ([6,6]-phenyl-C61-butyric acid methyl ester) or ICBA (m-isopropylphenyl-C60 diadduct); the material of the buffer layer 5 is zinc oxide, tin oxide or aluminum oxide; the material of the transparent conductive electrode 6 is indium tin oxide, indium zinc oxide or indium tungsten oxide; the material of the positive electrode 7 is Au or Ag; the material of the anti-reflection layer 8 is magnesium fluoride, lithium fluoride or yttrium fluoride.

[0035] As an example, the materials of each structure are as follows: the material of the hole transport layer 2 is nickel oxide layer / 2PACz layer; the material of the perovskite absorption layer 3 is Cs x FA y MA 1-x-y Pb(I / Br) 3 ; The material of the electron transport layer 4 is LiF layer / C 60 buffer layer 5 is made of zinc oxide; the material of the transparent conductive electrode 6 is indium zinc oxide; the material of the positive electrode 7 is silver; the material of the anti-reflection layer 8 is LiF.

[0036] The preparation process of the above-mentioned perovskite / silicon tandem solar cell is as follows:

[0037] Step 1, providing a silicon heterojunction bottom cell 1;

[0038] Step 2: preparing a hole transport layer 2 on the silicon heterojunction bottom cell 1, specifically:

[0039] The silicon heterojunction bottom cell 1 is placed in the mask of the hole transport layer 2, and the nickel oxide layer is sputtered by magnetron sputtering (RF mode); wherein the vacuum degree is 8.5~9.5×10 -4 Pa, sputtering power is 85-90 W, argon flow rate is 18-25 sccm, and sputtering time is 8-15 min;

[0040] A 2PACz layer is spin-coated on the surface of the nickel oxide layer; wherein the amount of 2PACz is 60-100 µL, the spin-coating speed is 2800-3000 rpm, and the spin-coating time is 25-30 s;

[0041] The silicon heterojunction bottom cell 1 with the spin-coated 2PACz layer is placed on a hot stage and annealed at 95-100°C for 8-10 min to form a hole transport layer 2;

[0042] Step 3: preparing a perovskite absorption layer 3 on the hole transport layer 2, specifically:

[0043] Weigh 22.1 mg CsI, 28.6 mg MABr (methylammonium bromide), 233.9 mg FAI (formamidine hydroiodide), and PbI 2 560.4 mg, PbBr 2 177.8 mg was dissolved in 1 mL of a mixed solution of DMF (N,N-dimethylformamide) and DMSO (dimethyl sulfoxide) (volume ratio 4:1) and stirred at room temperature overnight to obtain a perovskite precursor solution;

[0044] The obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 was transferred to a glove box, and the perovskite precursor solution was spin-coated on its surface; wherein, the amount of the perovskite precursor solution was 80-100 µL, and the spin-coating procedure was first spin-coated at 2000 rpm for 40 s, then spin-coated at 6000 rpm for 8 s, and at the high-speed start stage, 200 µL of anti-solvent was added dropwise;

[0045] The substrate with the spin-coated perovskite precursor solution was placed on a hot stage and annealed at 95-100°C for 18-22 min to form a perovskite absorption layer 3;

[0046] Step 4: preparing an electron transport layer 4 on the perovskite absorption layer 3, specifically:

[0047] The obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 is placed in the mask of electron transport layer 4, and LiF layer and C layer are deposited on the surface of perovskite absorption layer 3 in sequence. 60 layer to obtain the electron transport layer 4; wherein the deposition rate of the LiF layer is 0.09~0.12 Å / s, the thickness is 0.8~1.2 nm, and the vacuum degree is 8.5~9.5×10 -4 Pa; C 60 The deposition rate of the layer is 0.2~0.5 Å / s, the thickness is 8~12 nm, and the vacuum degree is 8.5~9.5×10 -4 Pa;

[0048] Step 5: preparing a buffer layer 5 on the electron transport layer 4, specifically:

[0049] Zinc oxide is deposited on the surface of the electron transport layer 4 using an atomic layer deposition system (ALD) to obtain a buffer layer 5; wherein the deposition temperature is 90-100°C, the vacuum degree is 18-25 Pa, the number of cycles is 80-120 times, and the deposition thickness is 12-15 nm;

[0050] Step 6: preparing a transparent conductive electrode 6 on the buffer layer 5, specifically:

[0051] The obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 / buffer layer 5 was placed in the mask of transparent conductive electrode 6, and an IZO layer was prepared on the surface of buffer layer 5 by magnetron sputtering (DC mode) to obtain transparent conductive electrode 6; wherein the substrate temperature of magnetron sputtering was 23-25°C, and the vacuum degree was 8.5-9.5×10 -4 Pa, argon flow rate is 6~10 sccm, oxygen flow rate is 0.3~0.5 sccm, sputtering intensity is 190~200 W, and sputtering time is 180~270 s;

[0052] Step 7: preparing a positive electrode 7 on the transparent conductive electrode 6, specifically:

[0053] A silver grid was deposited on the surface of the transparent conductive electrode 6 by thermal evaporation to further enhance current collection; the thickness of the silver grid was 600 nm and the vacuum degree was 9.5~10.5×10 -4 Pa; gradient rate deposition was adopted, the first gradient rate was 0.8~1.2 Å / s, the deposition thickness was 30 nm; the second gradient rate was 1.8~2.2 Å / s, the deposition thickness was 120 nm; the third gradient rate was 3.8~4.2 Å / s, the deposition thickness was 450 nm;

[0054] Step 8: preparing an anti-reflection layer 8 on the positive electrode 7, and finally obtaining a perovskite / silicon stacked solar cell, specifically:

[0055] LiF was evaporated on the surface of the transparent conductive electrode 6 prepared with the positive electrode 7 as an anti-reflection layer, and the pattern of the insulating LiF was completely within the framework of the silver grid without destroying the contact; wherein, the deposition rate was 1.2~1.5 Å / s, the thickness was 100 nm, and the vacuum degree was 9.5~10.5×10 -4 Pa.

[0056] Example 1

[0057] This embodiment prepares a perovskite / silicon tandem solar cell, which specifically includes the following steps:

[0058] Step 1: Cut the silicon wafer into 2×2 cm 2 The silicon heterojunction bottom cell 1 has a 1.2×1.2cm 2 The substrate composite layer is cut with a cutting accuracy error within 1 mm, and the cut silicon wafer is annealed at 200°C for 15 min for later use; wherein the thickness of the silicon heterojunction bottom cell 1 is 150 µm, and the thickness of the substrate composite layer is 10 nm;

[0059] Step 2: Place the silicon heterojunction bottom cell 1 obtained in step 1 in a mask plate for sputtering nickel oxide, place the mask plate with the silicon heterojunction bottom cell 1 in a magnetron sputtering device, and evacuate to 9.9×10 -4 When Pa, the RF magnetron sputtering mode was selected, the power was adjusted to 90 W, the argon gas flow rate was set to 20 sccm, and the sputtering time was 10 min to obtain a nickel oxide layer;

[0060] Step 3: After the sputtering is completed, the silicon heterojunction bottom cell 1 sputtered with the nickel oxide layer is transferred to a spin coater in a nitrogen glove box, and a 2PACz layer is spin-coated; wherein the amount of 2PACz is 100 µL, the rotation speed is 3000 rpm, the time is 30 s, and the acceleration is 3000 rpm / s;

[0061] Then, the silicon heterojunction bottom cell 1 with the 2PACz layer spin-coated thereon is moved to a hot stage and annealed at 100°C for 10 min to form a hole transport layer 2, thereby obtaining a stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2;

[0062] Step 4: Weigh 22.1 mg CsI, 28.6 mg MABr, 233.9 mg FAI, and PbI 2 560.4 mg, PbBr 2 177.8 mg was dissolved in 1 mL of a mixed solution of DMF and DMSO (volume ratio 4:1) and stirred at room temperature overnight to obtain a perovskite precursor solution;

[0063] Step 5: The obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 was transferred to a glove box, and 100 µL of perovskite precursor solution was added for spin coating, first at 2000 rpm for 40 s, then at 6000 rpm for 8 s, and at the high speed start stage, 200 µL of anti-solvent was dynamically added;

[0064] Step 6: Place the substrate after spin coating the perovskite precursor solution on a hot stage and anneal at 100°C for 20 min to form a perovskite absorption layer 3, thereby obtaining a stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3;

[0065] Step 7: Place the obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 in the mask of electron transport layer 4, and place the mask in a vacuum deposition device with a vacuum degree of 9.9×10 -4 Pa, LiF and C were evaporated 60 , the deposition rates were 0.1 Å / s and 0.3 Å / s, the thicknesses were 1 nm and 10 nm, respectively, and a stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 was obtained;

[0066] Step 8: placing the obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 in the chamber of an atomic layer deposition system for zinc oxide deposition to prepare a buffer layer 5, the vacuum degree is 20 Pa, the chamber temperature is 100°C, the deposition cycle number is set to 200 times, the deposition thickness is 15 nm, and a stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 / buffer layer 5 is obtained;

[0067] Step 9: Place the obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 / buffer layer 5 in the mask of transparent conductive electrode 6, and then place the mask in magnetron sputtering with a vacuum degree of 9.9×10 -4 When the temperature is 0.0447 W / m2, IZO is prepared to obtain a transparent conductive electrode 6; wherein the sputtering mode is DC sputtering, the substrate temperature is 25°C, the argon flow rate is 20 sccm, the oxygen flow rate is 0.3 sccm, the sputtering intensity is 200 W, the sputtering time is 210 s, the sputtering thickness is 55 nm, and a stacked structure of a silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 / buffer layer 5 / transparent conductive electrode 6 is obtained;

[0068] Step 10: placing the obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 / buffer layer 5 / transparent conductive electrode 6 in a vacuum desiccator, and placing a saturated salt solution (such as lithium chloride, magnesium sulfate, sodium chloride, etc.) and a desiccant (such as silica gel, molecular sieve, etc.) therein to control the humidity in the desiccator, so as to construct an atmosphere with different humidity;

[0069] Then use a mechanical pump to evacuate the vacuum dryer and fill it with nitrogen and oxygen in different proportions to create an atmosphere with different oxygen concentrations.

[0070] In this embodiment, an atmosphere with a humidity of 5% and an oxygen concentration of 20% is specifically constructed, and the obtained stacked structure of silicon heterojunction bottom battery 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 / buffer layer 5 / transparent conductive electrode 6 is immersed in the atmosphere for 12 hours to obtain the stacked structure of transparent conductive electrode 6 after photoelectric parameter regulation;

[0071] Step 11: Place the laminated structure obtained in step 10 in the mask of the positive electrode 7, and then place the mask in a vacuum deposition device to prepare the positive electrode 7, with a vacuum degree of 7×10 -4Pa, the thickness of the positive electrode is 600 nm, and a stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 / buffer layer 5 / transparent conductive electrode 6 / positive electrode 7 is obtained;

[0072] Step 12: Place the obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 / buffer layer 5 / transparent conductive electrode 6 / positive electrode 7 in a 1.1×1.1 cm 2 The mask is then placed in a vacuum deposition device to prepare an anti-reflection layer 8, with a vacuum degree of 9.9×10 -4 Pa, with a thickness of 100 nm, to obtain the final perovskite / silicon tandem solar cell.

[0073] Example 2

[0074] In this embodiment, a perovskite / silicon tandem solar cell is prepared. The preparation process is different from that in embodiment 1, except that the sputtering time in step 9 is adjusted to 150 s and the sputtering thickness is adjusted to 40 nm; the other steps and structures are the same.

[0075] Example 3

[0076] In this embodiment, a perovskite / silicon stacked solar cell is prepared. The preparation process is different from that in Embodiment 1, except that the atmosphere constructed in step 10 is adjusted to 5% humidity and 25% oxygen concentration; the other steps and structures are the same.

[0077] Example 4

[0078] In this embodiment, a perovskite / silicon stacked solar cell is prepared. The preparation process is different from that in Embodiment 1, except that the atmosphere constructed in step 10 is adjusted to 3% humidity and 20% oxygen concentration; the other steps and structures are the same.

[0079] Example 5

[0080] In this embodiment, a perovskite / silicon stacked solar cell is prepared. The preparation process is different from that in Embodiment 1, except that the atmosphere constructed in step 10 is adjusted to a humidity of 10% and an oxygen concentration of 20%. The other steps and structures are the same.

[0081] Comparative Example 1

[0082] In this comparative example, a perovskite / silicon stacked solar cell is prepared. The preparation process is different from that of Example 1, except that the atmosphere constructed in step 10 is adjusted to have an oxygen concentration of only 20%, and the humidity is not set.

[0083] Specifically, the obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 / buffer layer 5 / transparent conductive electrode 6 is placed in a vacuum dryer, evacuated by a mechanical pump, and then filled with nitrogen and oxygen in different proportions to construct an atmosphere with different oxygen concentrations, and an oxygen immersion aging treatment is carried out; wherein, the oxygen concentration is set to 20% and the aging treatment time is 12 h.

[0084] The other steps and structures are the same.

[0085] Comparative Example 2

[0086] In this comparative example, a perovskite / silicon stacked solar cell was prepared. The preparation process was different from that in Example 1, except that the atmosphere constructed in step 10 was adjusted to have a humidity of only 5%, and the oxygen concentration was not set.

[0087] Specifically, the obtained stacked structure of silicon heterojunction bottom cell 1 / hole transport layer 2 / perovskite absorption layer 3 / electron transport layer 4 / buffer layer 5 / transparent conductive electrode 6 is placed in a vacuum dryer, and a saturated salt solution and a desiccant are added therein to control the humidity in the dryer, and then the dryer is evacuated using a mechanical pump to construct an atmosphere of different humidity, and an aging treatment by humidity immersion is performed; wherein the humidity is set to 5% and the aging treatment time is 12 h.

[0088] The other steps and structures are the same.

[0089] Comparative Example 3

[0090] In this comparative example, a perovskite / silicon stacked solar cell was prepared. The preparation process was different from that of Example 1, except that the atmosphere constructed in step 10 was adjusted to have a humidity of 20% and an oxygen concentration of 20%. The other steps and structures were the same.

[0091] Comparative Example 4

[0092] In this comparative example, a perovskite / silicon stacked solar cell is prepared. The preparation process is different from that of Example 1 in that step 10 is not included, and steps 11 and 12 are directly performed after step 9. The other steps and structures are the same.

[0093] Comparative Example 5

[0094] In this comparative example, a perovskite / silicon stacked solar cell is prepared. The preparation process is different from that of Example 2 in that step 10 is not included, and steps 11 and 12 are directly performed after step 9. The other steps and structures are the same.

[0095] Comparative Example 6

[0096] In this comparative example, a perovskite / silicon tandem solar cell is prepared. The preparation process is different from that of Example 1, except that step 10 is not included, and steps 11 and 12 are directly performed after step 9. After the perovskite / silicon tandem solar cell is prepared, it is subjected to an immersion aging treatment at a humidity of 5% and an oxygen concentration of 20%.

[0097] Specifically, the perovskite / silicon tandem solar cell obtained in step 12 is placed in a vacuum dryer, and a saturated salt solution and a desiccant are placed therein to control the humidity in the dryer to create an atmosphere with different humidity;

[0098] Then use a mechanical pump to evacuate the vacuum dryer and fill it with nitrogen and oxygen in different proportions to create an atmosphere with different oxygen concentrations.

[0099] This comparative example specifically constructs an atmosphere with a humidity of 5% and an oxygen concentration of 20%, and the obtained perovskite / silicon tandem solar cell is immersed in the atmosphere for 12 hours to obtain a perovskite / silicon tandem solar cell after overall immersion aging treatment.

[0100] The other steps and structures are the same.

[0101] At AM1.5, 25°C, 1000 W / m 2 Under standard test conditions, the performance data of the perovskite / silicon tandem solar cells obtained in Examples 1 to 5 and Comparative Examples 1 to 6 were tested, including open circuit voltage (Voc), short circuit current density (Jsc), fill factor (FF) and conversion efficiency (PCE). The results are shown in Table 1.

[0102] Table 1

[0103] Open circuit voltage V <![CDATA[Short-circuit current density mA / cm 2 > Fill Factor % Conversion efficiency% Example 1 2.005 20.57 82.58 34.07 Example 2 1.957 19.98 82.69 32.34 Example 3 1.989 20.56 82.49 33.76 Example 4 1.981 20.47 82.69 33.54 Example 5 1.981 20.41 82.44 33.35 Comparative Example 1 1.992 20.41 81.87 33.28 Comparative Example 2 1.966 20.51 81.25 32.77 Comparative Example 3 1.957 20.44 81.09 32.44 Comparative Example 4 1.941 20.40 78.39 31.05 Comparative Example 5 1.906 20.18 78.29 30.13 Comparative Example 6 1.943 20.36 80.02 31.66

[0104] By comparing the data in Table 1, the following conclusions can be drawn:

[0105] According to the performance data of Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 4, it can be known that: compared with the situation where there is only oxygen, only humidity, or no immersion aging treatment of humidity and oxygen concentration in the atmosphere constructed in step 10, the prepared transparent conductive electrode 6 after immersion aging treatment with humidity 5% and oxygen concentration 20%, the open circuit voltage, short circuit current density, fill factor and conversion efficiency of the obtained perovskite / silicon tandem solar cell are greatly improved. It can be seen that the immersion aging treatment with specific humidity and specific oxygen concentration is of great help to improve the overall performance of the obtained perovskite / silicon tandem solar cell.

[0106] According to the performance data of Example 1, Example 3 and Comparative Example 2, it can be seen that after the prepared transparent conductive electrode 6 is subjected to immersion aging treatment at a humidity of 5% and different oxygen concentrations (20%, 25%), various performances of the obtained perovskite / silicon stacked solar cell are greatly improved.

[0107] According to the performance data of Example 1, Example 4, Example 5, Comparative Example 1 and Comparative Example 3, it can be known that after the prepared transparent conductive electrode 6 has been immersed and aged at different humidity (3%, 5%, 10%) and oxygen concentration of 20%, various performances of the obtained perovskite / silicon tandem solar cell are greatly improved, but the humidity should not be set too high. When the humidity reaches 20%, the open circuit voltage, fill factor and conversion efficiency of the obtained perovskite / silicon tandem solar cell will be reduced to a certain extent.

[0108] According to the performance data of Example 2 and Comparative Example 5, it can be seen that: when the thickness of the prepared transparent conductive electrode 6 is relatively thin, with a thickness of only 40 nm, after immersion aging treatment at a humidity of 5% and an oxygen concentration of 20%, the open circuit voltage, fill factor and conversion efficiency of the obtained perovskite / silicon stacked solar cell are also greatly improved, indicating that the immersion aging treatment at a specific humidity and a specific oxygen concentration can solve the problem of high resistivity of the traditional thinner transparent conductive electrode 6, which affects the carrier collection efficiency and thus reduces the photoelectric conversion efficiency of the stacked device.

[0109] According to the performance data of Example 1 and Comparative Example 6, it can be seen that: only performing an immersion aging treatment at a specific humidity and a specific oxygen concentration after the transparent conductive electrode 6 is prepared can help to significantly improve the various performances of the obtained perovskite / silicon tandem solar cell, while performing an immersion aging treatment at a specific humidity and a specific oxygen concentration after the perovskite / silicon tandem solar cell is prepared does not significantly improve the various performances of the obtained perovskite / silicon tandem solar cell.

[0110] Figure 2 : The contact resistivity comparison curve of the transparent conductive electrode 6 after immersion aging treatment at 5% humidity and 20% oxygen concentration in Example 1 and the transparent conductive electrode 6 without immersion aging treatment in Comparative Example 4 shows that after immersion aging treatment at 5% humidity and 20% oxygen concentration, the contact resistivity of the transparent conductive electrode 6 increases from 208.4 mΩ•cm to 208.4 mΩ•cm. 2 Reduced to 153.7mΩ•cm 2 , indicating that the immersion aging treatment at a specific humidity and a specific oxygen concentration can help reduce the resistivity of the transparent conductive electrode 6, thereby improving the conductivity and carrier migration performance.

[0111] Figure 3JV curves of the perovskite / silicon tandem solar cells obtained in Example 1 and Comparative Example 4 show that after immersion aging treatment at a humidity of 5% and an oxygen concentration of 20%, various performances of the obtained perovskite / silicon tandem solar cells are improved.

[0112] Figure 4 The light transmittance curves of the transparent conductive electrode 6 after immersion aging treatment at different humidity (0%, 3%, 5%, 10%, 20%) and oxygen concentration of 20% in Example 1, Example 4, Example 5, Comparative Example 1 and Comparative Example 3 show that under the condition of oxygen concentration of 20%, compared with not setting humidity conditions, the immersion aging treatment at humidity of 3% to 10% has obvious effects, and the transmittance of the transparent conductive electrode 6 in the visible light and near-infrared regions increases; among them, when the humidity is 5%, the immersion aging treatment has the best effect; however, when the humidity is too high, for example 20%, the immersion aging treatment will have an inhibitory effect on the transmittance of the transparent conductive electrode 6.

[0113] The present invention uses specific examples to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enables any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements that are not different from the text of the claims, or if they include equivalent structural elements that are not substantially different from the text of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A method for controlling photoelectric parameters of a transparent conductive electrode, characterized in that: This is achieved by subjecting the deposited transparent conductive electrode to humidity and oxygen immersion aging treatment; wherein the material of the transparent conductive electrode is a metal oxide, specifically indium tin oxide, indium zinc oxide or indium tungsten oxide; the treatment humidity is 3-10%, the treatment oxygen concentration is 20-25%, and the treatment aging time is 8-12 h.

2. The method for controlling photoelectric parameters of a transparent conductive electrode according to claim 1, characterized in that: The thickness of the transparent conductive electrode is 40-70 nm.

3. The method for controlling photoelectric parameters of a transparent conductive electrode according to claim 1, characterized in that: The transparent conductive electrode is obtained by magnetron sputtering, plasma enhanced chemical vapor deposition or pulsed laser deposition.

4. The method for controlling photoelectric parameters of a transparent conductive electrode according to claim 3, characterized in that: The magnetron sputtering adopts a DC mode, with a sputtering rate of 0.23-0.26 Å / s and a vacuum degree of 8.5-9.5×10 -4 Pa, the argon flow rate is 6~10sccm, and the oxygen flow rate is 0.3~0.5sccm.

5. A method for controlling photoelectric parameters of a transparent conductive electrode and application of the obtained transparent conductive electrode in a stacked solar cell, characterized in that: The stacked solar cell comprises a silicon heterojunction bottom cell, a hole transport layer, a perovskite absorption layer, an electron transport layer, a buffer layer, a transparent conductive electrode, a positive electrode and an anti-reflection layer stacked in sequence; wherein the transparent conductive electrode is obtained by being processed by the photoelectric parameter control method of the transparent conductive electrode according to any one of claims 1 to 4.

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