Perovskite solar cell
By setting a metal nitride interface modification layer on the NiOx hole transport layer, the photoelectric conversion efficiency and stability problems of perovskite solar cells were solved, resulting in higher cell efficiency and longer lifespan.
Patent Information
- Application Number
- CN202423021569.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-06
- Publication Date
- 2025-12-02
- Estimated Expiration
- 2034-12-06
AI Technical Summary
Existing perovskite solar cells have low photoelectric conversion efficiency and stability, especially since traditional organic hole transport layers are prone to degradation in humid and high-temperature environments, which limits their commercial application.
A NiOx hole transport layer is used, and a metal nitride interface modification layer is set on it, including zinc nitride, copper nitride, cobalt nitride, iron nitride, titanium nitride or nickel nitride, to improve NiOx surface defects, suppress redox reactions, improve energy level matching and conductivity, and enhance device stability.
This improves the photoelectric conversion efficiency and stability of perovskite solar cells, enhances the interface matching between the NiOx hole transport layer and the perovskite layer, reduces the resistivity of nickel oxide, promotes hole generation, and extends the lifespan of the device.
Smart Images
Figure CN223626281U_ABST
Abstract
Description
Technical Field
[0001] This utility model belongs to the field of perovskite solar cell technology, and specifically relates to a perovskite solar cell. Background Technology
[0002] Since its development in 2009, perovskite solar cells (PSCs) have seen significant improvements in their photoelectric conversion efficiency (PCE), demonstrating enormous commercial potential. However, due to the degradation of perovskite, stability remains a major constraint on the commercialization of PSCs. Inverting (pin) devices are one of the most promising structures for achieving both high efficiency and stability in PSCs.
[0003] Hole transport layers (HTLs) have a significant impact on the performance and long-term stability of p-type semiconductor cells (PSCs). Many organic hole transport materials (HTMs) have been used, including poly(3,4-ethylenedioxythiophene), poly(styrene sulfonate) (PEDOT:PSS), and poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine) (PTAA). Traditional organic HTMs suffer from high fabrication costs, difficulty in deposition on large-area substrates, and potential degradation in humid and high-temperature environments, limiting the application and commercialization of PSCs. Inorganic p-type semiconductors can replace these organic HTLs in inverse-structure PSCs. Various inorganic HTMs, including CuSCN, NiOx, CuI, VOx, and WO3, have been used in PSCs to replace organic HTMs. Among them, NiOx has attracted widespread attention due to its high transmittance, good alignment work function, intrinsic stability, and significant cost advantages in battery cells.
[0004] The photoelectric conversion efficiency and stability of inverted perovskite solar cells based on NiOx hole transport layers still need further improvement. Summary of the Invention
[0005] Therefore, the technical problem to be solved by this invention is to overcome the shortcomings of low photoelectric conversion efficiency and stability of perovskite solar cells in the prior art, thereby providing a perovskite solar cell.
[0006] Therefore, the present invention provides the following technical solution:
[0007] A perovskite solar cell includes a first electrode layer, a hole transport layer, an interface modification layer, a perovskite layer, an electron transport layer, and a second electrode layer, which are stacked sequentially.
[0008] The hole transport layer is NiOx, and the interface modification layer is made of metal nitrides.
[0009] In one possible implementation, the metal nitride includes one or more of zinc nitride, copper nitride, cobalt nitride, iron nitride, titanium nitride, and nickel nitride.
[0010] In one possible implementation, the thickness of the interface modification layer is 1–5 nm. For example, the thickness of the interface modification layer can be 1 nm, 2 nm, 3 nm, 4 nm, or 5 nm.
[0011] In one possible implementation, the hole transport layer has a thickness of 10–30 nm. For example, the hole transport layer thickness can be 10 nm, 15 nm, 20 nm, 25 nm, or 30 nm.
[0012] In one possible implementation, the material of the perovskite layer is FA. 0.9 Cs 0.1 PbI3, wherein the thickness of the perovskite layer is 300–700 nm. For example, the thickness of the perovskite layer can be 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, or 700 nm.
[0013] In one possible implementation, the material of the electron transport layer is C. 60 SnO2, ZnO or TiO2;
[0014] and / or
[0015] The thickness of the electron transport layer is 10-30 nm; for example, the thickness of the electron transport layer can be 10 nm, 15 nm, 20 nm, 25 nm or 30 nm.
[0016] In one possible implementation, an electrode blocking layer is provided on the surface of the electron transport layer away from the perovskite layer; the electrode blocking layer is made of IWO, IWTO, ICO, or ITIO.
[0017] and / or
[0018] The thickness of the electrode barrier layer is 50–100 nm. For example, the thickness of the electrode barrier layer can be 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm.
[0019] In one possible implementation, an inorganic buffer layer is provided on the surface of the electrode blocking layer away from the electron transport layer. The material of the inorganic buffer layer is ITO, IZO, MoO3 or YbOx.
[0020] and / or
[0021] The thickness of the inorganic buffer layer is 30–60 nm. For example, the thickness of the inorganic buffer layer can be 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, or 60 nm.
[0022] In one possible implementation, the material of the second electrode layer is Cu, Ag, Au, or Al; and / or
[0023] The thickness of the second electrode layer is 40–80 nm. For example, the thickness of the second electrode layer can be 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, or 80 nm.
[0024] In one possible implementation, the first electrode layer is an FTO transparent conductive layer, the hole transport layer is made of NiOx, the interface modification layer is a 1-3 nm thick zinc nitride layer, and the perovskite layer is made of FA. 0.9 Cs 0.1 PbI3.
[0025] The technical solution of this utility model has the following advantages:
[0026] The perovskite solar cell of this invention comprises a first electrode layer, a hole transport layer, an interface modification layer, a perovskite layer, an electron transport layer, and a second electrode layer stacked sequentially; the hole transport layer is NiOx, and the interface modification layer is made of a metal nitride.
[0027] Setting metal nitrides as a modification layer on the NiOx hole transport layer can reduce hydroxyl defects on the NiOx surface and suppress redox reactions and non-radiative recombination at the perovskite layer-NiOx interface. This improves the Ni... 3+ / Ni 2+ The ratio of nickel oxide to perovskite can reduce its resistivity and increase its conductivity, promoting the generation of more holes and improving the energy level matching between the NiOx hole transport layer and the perovskite layer, thereby improving the overall cell efficiency. Furthermore, the interface modification layer protects the perovskite from the influence of the active Ni material in the nickel oxide layer and prevents perovskite degradation, resulting in higher device stability. Attached Figure Description
[0028] To more clearly illustrate the specific embodiments of this utility model or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this utility model. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0029] Figure 1This is a schematic diagram of the structure of the inverted perovskite solar cell of this utility model.
[0030] Figure label:
[0031] 1-Transparent conductive layer; 2-Hole transport layer; 3-Interface modification layer; 4-Perovskite layer; 5-Electron transport layer; 6-Electrode blocking layer; 7-Inorganic buffer layer; 8-Electrode layer. Detailed Implementation
[0032] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described herein. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.
[0033] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.
[0034] This invention provides a perovskite solar cell, such as... Figure 1 As shown, it includes a transparent conductive layer 1, a hole transport layer 2, an interface modification layer 3, a perovskite layer 4, an electron transport layer 5, an electrode blocking layer 6, an inorganic buffer layer 7, and an electrode layer 8, which are stacked in sequence.
[0035] Methods for fabricating inverted perovskite solar cells include:
[0036] (1) Transparent conductive layer: After cleaning, the FTO transparent conductive layer 1 is dried in an oven at 50-80°C, and then subjected to plasma treatment for 10-20 minutes. After the treatment, it is placed in a magnetron sputtering equipment to be coated.
[0037] (2) Hole transport layer: A hole transport layer NiOx was deposited on one side of the transparent conductive layer using magnetron sputtering: a nickel oxide target was used for magnetron sputtering, argon and oxygen were introduced, the sputtering power was 630-1260W, the pressure was 0.2-0.6Pa, and the oxygen content was 0.2-1.2 vol%. A hole transport layer 2 with a thickness of 10-30 nm was obtained.
[0038] (3) Interface decoration layer:
[0039] ① Using zinc nitride (ZnN), copper nitride (CuN), cobalt nitride (CoN), iron nitride (FeN), titanium nitride (TiN), or nickel nitride (NiN) as the target material, Ar gas is introduced, and magnetron sputtering is performed on the NiOx surface. The sputtering power is 50-150W and the pressure is 0.2-0.6Pa.
[0040] or
[0041] ② Using zinc (Zn), copper (Cu), cobalt (N), iron (Fe), titanium (Ti), or nickel (Ni) targets, nitrogen and Ar gases are introduced, and magnetron sputtering is performed on the NiOx surface. The sputtering power is 50-150W and the pressure is 0.2-0.6Pa.
[0042] An interface modification layer 3 with a thickness of 1–5 nm was prepared.
[0043] (4) Perovskite layer: A perovskite layer 4 with a thickness of 300-700 nm is coated on the surface of the interface modification layer 3 away from the hole transport layer 2. The composition of the perovskite layer 4 is FA. 0.9 Cs 0.1 PbI3.
[0044] (5) Electron transport layer: On the surface of the perovskite layer 4 away from the interface modification layer 3, an electron transport layer 5 with a thickness of 10-30 nm is deposited by physical vapor deposition. The material of the electron transport layer 5 is C. 60 SnO2, ZnO or TiO2.
[0045] (6) Electrode barrier layer: On the side of the electron transport layer 5 away from the perovskite layer 4, an electrode barrier layer 6 with a thickness of 50-100 nm is deposited by plasma deposition. The electrode barrier layer 6 is IWO (tungsten-doped indium oxide), IWTO (tungsten and tin-doped indium oxide), ICO (indium cerium oxide) or ITIO (titanium-doped indium oxide).
[0046] (7) Inorganic buffer layer: On the side of the electrode blocking layer 6 away from the electron transport layer, an inorganic buffer layer 7 with a thickness of 30-60 nm is deposited by magnetron sputtering. The material of the inorganic buffer layer 7 is ITO (tin-doped indium oxide), IZO (zinc-doped indium oxide), MoO3 or YbOx.
[0047] (8) Electrode layer: On the side of the inorganic buffer layer 7 away from the electrode blocking layer 6, an electrode layer 8 with a thickness of 40-80 nm is deposited by magnetron sputtering. The material of the electrode layer 8 is Cu, Ag, Au or Al.
[0048] Example 1
[0049] This embodiment provides an inverted perovskite solar cell, comprising a transparent conductive layer 1, a hole transport layer 2, an interface modification layer 3, a perovskite layer 4, an electron transport layer 5, an electrode blocking layer 6, an inorganic buffer layer 7, and an electrode layer 8, which are sequentially stacked. The hole transport layer 2 is nickel oxide, and the interface modification layer 3 is zinc nitride.
[0050] The fabrication method of the inverted perovskite solar cell in this embodiment includes the following steps:
[0051] (1) Transparent conductive layer: After cleaning, the FTO transparent conductive layer is dried in an oven at 80°C, then subjected to plasma treatment for 15 minutes, and then enters the magnetron sputtering equipment to be coated.
[0052] (2) Hole transport layer: A hole transport layer NiOx was deposited on one side of the transparent conductive layer by magnetron sputtering: a nickel target was used for magnetron sputtering, argon and oxygen were introduced, the sputtering power was 630W, the pressure was 0.4Pa, and the oxygen content was 0.2vol%. A hole transport layer with a thickness of 15nm was obtained.
[0053] (3) Interface modification layer: Zinc nitride (ZnN) target material was used, Ar gas was introduced, and magnetron sputtering was performed on the NiOx surface. The sputtering power was 50W and the pressure was 0.4Pa. The thickness of the obtained interface modification layer was 2nm.
[0054] (4) Perovskite layer: A perovskite layer with a thickness of 500 nm is coated on the surface of the interface modification layer away from the hole transport layer. The composition of the perovskite layer is FA. 0.9 Cs 0.1 PbI3.
[0055] (5) Electron transport layer: On the surface of the perovskite layer away from the interface modification layer, a 20 nm thick electron transport layer is deposited by physical vapor deposition. The material of the electron transport layer is C. 60 .
[0056] (6) Electrode barrier layer: On the side of the electron transport layer away from the perovskite layer, an electrode barrier layer with a thickness of 60 nm is deposited by plasma deposition. The electrode barrier layer is made of IWO.
[0057] (7) Inorganic buffer layer: On the side of the electrode blocking layer away from the electron transport layer, an inorganic buffer layer with a thickness of 45 nm is deposited by magnetron sputtering. The material of the inorganic buffer layer is ITO.
[0058] (8) Electrode layer: On the side of the inorganic buffer layer away from the electrode barrier layer, an electrode layer with a thickness of 70 nm is deposited by magnetron sputtering. The electrode layer is made of Cu.
[0059] Example 2
[0060] This embodiment provides an inverted perovskite solar cell, which is basically the same as that in Embodiment 1, except that the interface modification layer 3 is copper nitride.
[0061] In step (3) of the method for preparing an inverted perovskite solar cell, a copper nitride (CuN) target is used.
[0062] Example 3
[0063] This embodiment provides an inverted perovskite solar cell, which is basically the same as that in Embodiment 1, except that the interface modification layer 3 is cobalt nitride.
[0064] In step (3) of the method for preparing an inverted perovskite solar cell, a cobalt nitride (CoN) target is used.
[0065] Example 4
[0066] This embodiment provides an inverted perovskite solar cell, which is basically the same as that in Embodiment 1, except that the interface modification layer 3 is iron nitride.
[0067] In step (3) of the method for preparing an inverted perovskite solar cell, an iron nitride (FeN) target is used.
[0068] Example 5
[0069] This embodiment provides an inverted perovskite solar cell, which is basically the same as that in Embodiment 1, except that the interface modification layer 3 is titanium nitride.
[0070] In step (3) of the method for preparing an inverted perovskite solar cell, a titanium nitride (TiN) target is used.
[0071] Example 6
[0072] This embodiment provides an inverted perovskite solar cell, which is basically the same as that in Embodiment 1, except that the interface modification layer 3 is nickel nitride.
[0073] In step (3) of the method for preparing an inverted perovskite solar cell, a nickel nitride (NiN) target is used.
[0074] Example 7
[0075] This embodiment provides an inverted perovskite solar cell, comprising a transparent conductive layer 1, a hole transport layer 2, an interface modification layer 3, a perovskite layer 4, an electron transport layer 5, an electrode blocking layer 6, an inorganic buffer layer 7, and an electrode layer 8, which are sequentially stacked. The hole transport layer 2 is nickel oxide, and the interface modification layer 3 is zinc nitride.
[0076] The fabrication method of the inverted perovskite solar cell in this embodiment includes the following steps:
[0077] (1) Transparent conductive layer: After cleaning, the FTO transparent conductive layer is dried in an oven at 80°C, then subjected to plasma treatment for 15 minutes, and then enters the magnetron sputtering equipment to be coated.
[0078] (2) Hole transport layer: A hole transport layer NiOx was deposited on one side of the transparent conductive layer by magnetron sputtering: a nickel target was used for magnetron sputtering, argon and oxygen were introduced, the sputtering power was 630W, the pressure was 0.4Pa, and the oxygen content was 0.2vol%. A hole transport layer with a thickness of 15nm was obtained.
[0079] (3) Interface modification layer: A zinc target was used, and N2 and Ar gases were introduced. The nitrogen to argon flow rate ratio was 3:1. The NiOx surface was sputtered by magnetron sputtering at a sputtering power of 80W and a pressure of 0.4Pa. The thickness of the obtained interface modification layer was 2nm.
[0080] (4) Perovskite layer: A perovskite layer with a thickness of 500 nm is coated on the surface of the interface modification layer away from the hole transport layer. The composition of the perovskite layer is FA. 0.9 Cs 0.1 PbI3.
[0081] (5) Electron transport layer: On the surface of the perovskite layer away from the interface modification layer, a 20 nm thick electron transport layer is deposited by physical vapor deposition. The material of the electron transport layer is C. 60 .
[0082] (6) Electrode barrier layer: On the side of the electron transport layer away from the perovskite layer, an electrode barrier layer with a thickness of 60 nm is deposited by plasma deposition. The electrode barrier layer is made of IWO.
[0083] (7) Inorganic buffer layer: On the side of the electrode blocking layer away from the electron transport layer, an inorganic buffer layer with a thickness of 45 nm is deposited by magnetron sputtering. The material of the inorganic buffer layer is ITO.
[0084] (8) Electrode layer: On the side of the inorganic buffer layer away from the electrode barrier layer, an electrode layer with a thickness of 70 nm is deposited by magnetron sputtering. The electrode layer is made of Cu.
[0085] Example 8
[0086] This embodiment provides an inverted perovskite solar cell, which is basically the same as that in Embodiment 7, except that the interface modification layer 3 is copper nitride.
[0087] In step (3) of the method for preparing an inverted perovskite solar cell, a copper target is used.
[0088] Example 9
[0089] This embodiment provides an inverted perovskite solar cell, which is basically the same as that in Embodiment 7, except that the interface modification layer 3 is cobalt nitride.
[0090] In step (3) of the method for preparing inverted perovskite solar cells, a pure cobalt target is used.
[0091] Example 10
[0092] This embodiment provides an inverted perovskite solar cell, which is basically the same as that in Embodiment 7, except that the interface modification layer 3 is iron nitride.
[0093] In step (3) of the method for preparing an inverted perovskite solar cell, a pure iron target is used.
[0094] Example 11
[0095] This embodiment provides an inverted perovskite solar cell, which is basically the same as that in Embodiment 7, except that the interface modification layer 3 is titanium nitride.
[0096] In step (3) of the method for preparing inverted perovskite solar cells, pure titanium target material is used.
[0097] Example 12
[0098] This embodiment provides an inverted perovskite solar cell, which is basically the same as that in Embodiment 7, except that the interface modification layer 3 is nickel nitride.
[0099] In step (3) of the method for preparing inverted perovskite solar cells, a pure nickel target is used.
[0100] Comparative Example 1
[0101] This comparative example provides a perovskite solar cell that is basically the same as that in Example 1, except that it has no interface modification layer.
[0102] Test case
[0103] The performance of the inverted perovskite solar cells provided in the above embodiments and comparative examples was tested. During the test, a standard sunlight (spectral AM 1.5G, incident power 100mW / cm²) was emitted using a solar simulator. 2 (At 25℃), the open-circuit voltage (Voc, V) and short-circuit current density (Jsc, mA / cm²) were tested. 2 ), photoelectric conversion efficiency (PCE, %) and fill factor (FF).
[0104] The stability test involved placing unencapsulated perovskite solar cells on a hot plate at 85°C under a glove box with N2 atmosphere. The total stability test duration was 1000 hours. Every 200 hours, the cells were removed from the hot plate for photoelectric conversion efficiency testing, and the results were normalized to obtain the photoelectric conversion efficiency retention rate. Photoelectric conversion efficiency retention rate = Photoelectric conversion efficiency at stability test time × h / Photoelectric conversion efficiency at 0 h.
[0105] The test results are shown in Tables 1 and 2.
[0106] Table 1 Stability test results
[0107]
[0108] Table 2 Performance test results of inverse perovskite solar cells
[0109]
[0110]
[0111] As shown in Tables 1 and 2, the photoelectric conversion efficiency and stability of the inverted perovskite solar cell of this invention are significantly improved.
[0112] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A perovskite solar cell, characterized in that, It includes a first electrode layer, a hole transport layer, an interface modification layer, a perovskite layer, an electron transport layer, and a second electrode layer, which are stacked sequentially. The hole transport layer is NiOx, and the interface modification layer is made of metal nitride.
2. The perovskite solar cell according to claim 1, characterized in that, The metal nitride is selected from one of zinc nitride, copper nitride, cobalt nitride, iron nitride, titanium nitride, and nickel nitride.
3. The perovskite solar cell according to claim 1, characterized in that, The thickness of the interface modification layer is 1~5nm.
4. The perovskite solar cell according to claim 1, characterized in that, The thickness of the hole transport layer is 10~30 nm.
5. The perovskite solar cell according to claim 1, characterized in that, The material of the perovskite layer is FA. 0.9 Cs 0.1 PbI3, wherein the thickness of the perovskite layer is 300~700nm.
6. The perovskite solar cell according to any one of claims 1-5, characterized in that, The electron transport layer is made of C. 60 SnO2, ZnO or TiO2; and / or The thickness of the electron transport layer is 10~30 nm.
7. The perovskite solar cell according to any one of claims 1-5, characterized in that, An electrode blocking layer is disposed on the surface of the electron transport layer away from the perovskite layer; the electrode blocking layer is made of IWO, IWTO, ICO, or ITIO. and / or The thickness of the electrode barrier layer is 50~100 nm.
8. The perovskite solar cell according to claim 7, characterized in that, An inorganic buffer layer is provided on the side of the electrode blocking layer away from the electron transport layer. The material of the inorganic buffer layer is ITO, IZO, MoO3 or YbOx. and / or The thickness of the inorganic buffer layer is 30~60nm.
9. The perovskite solar cell according to any one of claims 1-5, characterized in that, The material of the second electrode layer is Cu, Ag, Au, or Al; and / or The thickness of the second electrode layer is 40~80nm.
10. The perovskite solar cell according to claim 1, characterized in that, The first electrode layer is an FTO transparent conductive layer, the hole transport layer is made of NiOx, the interface modification layer is a 1-3 nm thick zinc nitride layer, and the perovskite layer is made of FA. 0.9 Cs 0.1 PbI3.