Manufacturing method of perovskite cell
In the production of perovskite batteries, the dense first sub-layer is first formed by using the atomic layer deposition process, and then filling the trench with the physical vapor deposition process, the problems of poor functional layer cladding and substrate damage are solved, and the battery performance is improved and reliability.
Patent Information
- Application Number
- CN202411244334.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-05
- Publication Date
- 2024-12-13
AI Technical Summary
During the production of perovskite batteries, it is difficult for the physical vapor deposition process to effectively fill the trench on the substrate, resulting in poor cladding of the inner wall of the trench, affecting the battery performance, and bombardment of high-energy particles may damage the substrate.
The first sublayer is deposited on the substrate by atomic layer deposition process, followed by the second sublayer being deposited on the first sublayer using a physical vapor deposition process or a rapid plasma deposition process, forming a dense functional layer to fill the trench to ensure the substrate No damage.
The functional layer is able to fill the trench and protect the substrate, improve battery performance and reliability, reduce the density and flatness of the functional layer, and avoid metal penetration and battery aging.
Smart Images
Figure CN119136628A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the field of photovoltaic technology, and more specifically, to a method for manufacturing a perovskite cell. Background Art
[0002] In the process of making perovskite cells, some of the functional layers are formed through deposition processes, such as hole transport layers, transparent conductive layers, etc. Physical vapor deposition is a common deposition process, which is widely used in the production of functional layer structures such as transparent conductive layers. Some functional layers of perovskite cells need to be deposited on a substrate with grooves, and the functional layers prepared by physical vapor deposition have poor filling effects on the grooves, that is, it is difficult to coat the inner wall of the groove well, which will have a negative impact on the performance of perovskite cells. In addition, taking the magnetron sputtering process in the physical vapor deposition process as an example, it uses high-energy particles to bombard the target material. The atoms on the surface of the target material gain energy and escape from the surface and then deposit on the surface of the substrate to form an oxide film. However, high-energy particles can easily damage the substrate and affect the performance of the battery. Summary of the invention
[0003] The purpose of the present application is to provide a method for manufacturing a perovskite battery, which can fill the grooves on the substrate well without easily damaging the substrate, thereby ensuring the battery performance.
[0004] In order to achieve the above object, the present invention provides a method for manufacturing a perovskite battery, comprising:
[0005] Scratching grooves on the substrate;
[0006] Depositing a first sublayer on the substrate by an atomic layer deposition process, wherein the first sublayer covers the wall surface of the groove;
[0007] The second sub-layer is deposited on the first sub-layer by adopting a physical vapor deposition process or a rapid plasma deposition process. The first sub-layer and the second sub-layer together form a functional layer, and the functional layer fills the groove.
[0008] In an optional embodiment, the first sub-layer and the second sub-layer are made of the same material.
[0009] In an optional embodiment, the substrate is a photoelectric conversion layer, and the functional layer is a transparent conductive layer; along the direction gradually away from or gradually approaching the transparent conductive layer, the photoelectric conversion layer includes an electron transport layer, a perovskite layer and a hole transport layer stacked in sequence, and the groove runs through the electron transport layer, the perovskite layer and the hole transport layer.
[0010] In an optional embodiment, the thickness of the first sublayer is 10-15 nm, and the thickness of the second sublayer is 5-10 nm.
[0011] In an optional embodiment, the material of the functional layer is indium tin oxide, and the step of depositing the first sublayer on the substrate by an atomic layer deposition process includes:
[0012] A vapor phase indium precursor and a vapor phase tin precursor are alternately used with an oxidant for reaction deposition to obtain an alternately stacked indium oxide film and a tin oxide film.
[0013] In an optional embodiment, the step of depositing the indium oxide thin film by reacting the vapor phase indium precursor with an oxidant comprises:
[0014] The vapor phase indium precursor is reacted with a first oxidant and a second oxidant in sequence to deposit the indium oxide film;
[0015] Wherein, neither the first oxidant nor the second oxidant contains ozone.
[0016] In an optional embodiment, the first oxidant is selected from one of water, hydrogen peroxide, oxygen and oxygen plasma, and the second oxidant is selected from another of water, hydrogen peroxide, oxygen and oxygen plasma.
[0017] In an optional embodiment, the step of depositing the tin oxide thin film by reacting the vapor phase tin precursor with an oxidant comprises:
[0018] Depositing the tin oxide thin film by reacting a vapor phase tin precursor with a third oxidant;
[0019] Wherein, the third oxidant is selected from one of water, hydrogen peroxide, oxygen, ozone and oxygen plasma.
[0020] In an optional embodiment, the gas-phase indium precursor is cyclopentadienyl indium, and the gas-phase tin precursor is tetrakis(dimethylamino)tin.
[0021] In an optional embodiment, the method for manufacturing the perovskite cell further includes:
[0022] A metal electrode is deposited on the functional layer.
[0023] In an optional embodiment, the substrate is conductive glass, and the functional layer is a hole transport layer.
[0024] In an optional embodiment, the step of depositing a first sublayer on the substrate by an atomic layer deposition process, and depositing a second sublayer on the first sublayer by a physical vapor deposition process or a fast plasma deposition process comprises:
[0025] Using a nickel-containing precursor and an oxidant to perform reaction deposition to obtain a first nickel oxide film;
[0026] A second nickel oxide film is deposited on the first nickel oxide film by using a physical vapor deposition process or a rapid plasma deposition process.
[0027] In an optional embodiment, the oxidant is selected from at least one of water, ozone and oxygen plasma;
[0028] And / or, the nickel-containing precursor is selected from at least one of bis(cyclopentadienyl)nickel, bis(methylcyclopentadienyl)nickel and bis(ethylcyclopentadienyl)nickel.
[0029] In an optional embodiment, the reaction temperature for depositing the first sub-layer is 80-200° C. and the pressure is 0.2-10 mbar.
[0030] In an optional embodiment, the physical vapor deposition process includes a magnetron sputtering process or an evaporation process.
[0031] The beneficial effects of the method for manufacturing a perovskite battery provided in the embodiment of the present application are as follows:
[0032] The method for making a perovskite cell provided in an embodiment of the present application includes scratching a groove on a substrate; depositing a first sublayer on the substrate using an atomic layer deposition process, and depositing a second sublayer on the first sublayer using a physical vapor deposition process or a rapid plasma deposition process, wherein the first sublayer and the second sublayer jointly form a functional layer, and the functional layer fills the groove. Compared with the existing physical vapor deposition process, the film layer formed by the atomic layer deposition process has a higher density, so the first high-density sublayer deposited first is more complete and uniform for the coating of the inner corner and the outer corner of the groove, so that the functional layer finally deposited can also fill the groove well, ensuring the close combination of the functional layer and the substrate. Moreover, the atomic layer deposition process has a lower reaction temperature and less energy than the physical vapor deposition process (such as a magnetron sputtering process), and is not easy to damage the substrate. Since the dense first sublayer covers the surface of the substrate, it is not easy to damage the substrate when the second sublayer is subsequently deposited using a physical vapor deposition process or a rapid plasma deposition process.
[0033] Other features and advantages of the present application will be described in detail in the subsequent specific implementation section. BRIEF DESCRIPTION OF THE DRAWINGS
[0034] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.
[0035] Figure 1A schematic diagram of forming a functional layer on a substrate using a magnetron sputtering process in the related art;
[0036] Figure 2 This is a schematic diagram of a process for manufacturing a perovskite battery in one embodiment of the present application;
[0037] Figure 3 This is a schematic diagram of depositing a functional layer on a substrate in one embodiment of the present application;
[0038] Figure 4 This is a schematic diagram of depositing a functional layer on a substrate in another embodiment of the present application;
[0039] Figure 5 This is a schematic diagram of the structure of a perovskite battery (transform) in one embodiment of the present application;
[0040] Figure 6 This is a schematic diagram of the structure of a perovskite battery (formal) in one embodiment of the present application.
[0041] Icon: 10-substrate; 10'-substrate; 11-groove; 11'-groove; 20-functional layer; 20'-functional layer; 21-first sublayer; 22-second sublayer; 30-substrate; 100-conductive glass; 101-transparent carrier; 110-first groove; 200-photoelectric conversion layer; 210a-hole transport layer; 210b-hole transport layer; 220-perovskite layer; 230a-electron transport layer; 230b-electron transport layer; 300-transparent conductive layer; 400-metal electrode; 240-second groove; 410-third groove. DETAILED DESCRIPTION
[0042] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. The components of the embodiments of the present application described and shown in the drawings here can be arranged and designed in various different configurations.
[0043] In the description of this application, it should be noted that the terms "inside", "outside", etc. indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship in which the product of the application is usually placed when in use, which is only for the convenience of describing this application and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on this application. In addition, the terms "first", "second", etc. are only used to distinguish the description, and cannot be understood as indicating or implying relative importance.
[0044] In the description of this application, it should also be noted that, unless otherwise clearly specified and limited, the terms "disposed" and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a direct connection, or an indirect connection through an intermediate medium, or it can be the internal communication of two elements. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.
[0045] Figure 1 Schematic diagram of forming a functional layer on a substrate using a magnetron sputtering process in the related art. The functional layer 20' (such as a transparent conductive layer) in the perovskite cell in the related art is made using a physical vapor deposition (PVD) process, such as a magnetron sputtering process under this process category. The basic principle of this process is that under the action of an electromagnetic field, the accelerated gas high-energy particles (Ar + ) bombards the coating target, and the atoms on the surface of the target gain energy and escape from the surface and then deposit on the surface of the substrate 10' to form an oxide film. In the process of growing the transparent conductive layer by magnetron sputtering, high-load particles will cause certain damage to the substrate, which will have a negative impact on the battery performance. On the other hand, when the functional layer 20' is deposited on the substrate 10' with the groove 11', the existing process cannot make the functional layer fill the groove 11' well, that is, there may be a gap between the functional layer 20' and the inner wall of the groove 11', which will also affect the battery performance. Figure 1 As shown, the functional layer produced by the magnetron sputtering process cannot well cover the inner and outer corners of the groove 11' on the substrate, and gaps are likely to appear at the inner and outer corners. In addition, the thickness of the functional layer 20' formed by the magnetron sputtering process is uneven, and the sidewalls of the groove 11' are likely to be incompletely covered. In addition, when the functional layer 20' is a transparent conductive layer and the substrate 10' is a photoelectric conversion layer, a metal electrode (such as a copper electrode) is often provided on the transparent conductive layer. The material of the metal electrode may penetrate downward, and the transparent conductive layer should play a role in preventing the metal from penetrating downward into the photoelectric conversion layer. The transparent conductive layer in the related art is manufactured by a magnetron sputtering process, and has low density, poor flatness, and poor coating effect on the wall of the groove 11'. Therefore, the transparent conductive layer manufactured in the related art has poor protection effect on the diffused metal, and the metal easily enters the perovskite layer in the photoelectric conversion layer downward or from the side wall of the groove 11'. After the metal (such as copper) penetrates into the perovskite layer, it will cause direct penetration, aging and reduce the long-term photothermal stability of the battery, thereby affecting the reliability of the battery.
[0046] To this end, an embodiment of the present application provides a method for manufacturing a perovskite battery, by sequentially using two different processes to deposit the functional layer, so that the functional layer has a better filling effect on the groove and less damage to the substrate during the functional layer manufacturing process.
[0047] Figure 2 This is a schematic diagram of a process for manufacturing a perovskite battery in one embodiment of the present application; Figure 3 This is a schematic diagram of depositing a functional layer 20 on a substrate 10 in one embodiment of the present application; Figure 4 FIG. 2 is a schematic diagram of depositing a functional layer 20 on a substrate 10 in another embodiment of the present application. Figures 2 to 4 As shown, the method for manufacturing a perovskite battery provided in an embodiment of the present application comprises the following steps:
[0048] Step S100, carving a groove 11 on the substrate 10;
[0049] Step S200, depositing a first sub-layer 21 on the substrate 10 by using an atomic layer deposition process, wherein the first sub-layer 21 covers the wall surface of the groove 11;
[0050] Step S300 , depositing the second sub-layer 22 on the first sub-layer 21 by physical vapor deposition or rapid plasma deposition, the first sub-layer 21 and the second sub-layer 22 together form a functional layer 20 , and the functional layer 20 fills the groove 11 .
[0051] like Figure 3 and Figure 4 As shown, the groove 11 penetrates the substrate 10 along the thickness direction of the substrate 10. When the functional layer 20 is deposited, the substrate 10 is stacked on the substrate 30 so that the bottom end of the groove 11 is closed. It should be understood that the perovskite cell has multiple layer structures. In the process of making the perovskite cell, the above-mentioned substrate 10 and functional layer 20 are two adjacent layer structures in the perovskite cell, wherein the substrate 10 is a layer structure with the groove 11. Since there is more than one layer structure with the groove 11 in the perovskite cell, there is more than one corresponding functional layer 20. Therefore, the above-mentioned steps S100 to S300 can be applied to the preparation of the functional layer 20 on different substrates 10. For example, some perovskite cells usually include depositing conductive glass on a transparent substrate, and then scratching a first groove on the conductive glass; then depositing a hole transport layer, a perovskite layer, and an electron transport layer in sequence, the three forming a photoelectric conversion layer, and then scratching a second groove on the photoelectric conversion layer; then depositing a transparent conductive layer on the photoelectric conversion layer, making a metal electrode on the transparent conductive layer, and then scratching a third groove, the third groove runs through the metal electrode, the transparent conductive layer, and the photoelectric conversion layer. In the above steps S100 to S300, the substrate 10 can be a conductive glass, the functional layer 20 is a hole transport layer, and the groove 11 is a first groove; or, the substrate 10 is a photoelectric conversion layer, the functional layer 20 is a transparent conductive layer, and the groove 11 is a second groove.
[0052] Since the atomic layer deposition process can deposit dense films, the first sublayer 21 can better fit and cover the surface of the substrate 10, including completely covering the sidewalls and bottom wall of the groove 11. Depending on the width of the groove 11, the groove 11 can be filled with the first sublayer 21, or with the first sublayer 21 and the second sublayer 22. Figure 3 In the embodiment, the groove 11 is narrow, and the first sub-layer 21 fills the groove 11 on the substrate 10 to ensure close contact with the inner wall of the groove 11; Figure 4 In the embodiment, the groove 11 is relatively wide, and the first sub-layer 21 can tightly cover the sidewalls and bottom wall of the groove 11, but does not completely fill the groove. The groove 11 is filled by the first sub-layer 21 and the second sub-layer 22. Figure 3 and Figure 4 As shown, the first sublayer 21 in the functional layer 20 produced in the embodiment of the present application has good flatness and adhesion, and can better cover the groove 11, which is conducive to improving the electrical performance of the battery. On the other hand, the reaction temperature of the atomic layer deposition process is low, and no high-energy particles impact the substrate 10, so the substrate 10 can be prevented from being damaged during the deposition of the functional layer 20, which is conducive to ensuring that the battery performance is not lost.
[0053] In the embodiment of the present application, the physical vapor deposition process may be a magnetron sputtering process or an evaporation process.
[0054] Figure 5 This is a schematic diagram of the structure of a perovskite battery (transform) in one embodiment of the present application; Figure 6 Schematic diagram of the structure of a perovskite battery (formal) in one embodiment of the present application. Figure 5 and Figure 6 As shown, the perovskite cell includes a transparent carrier 101, a conductive glass 100, a photoelectric conversion layer 200, a transparent conductive layer 300 and a metal electrode 400 which are stacked in sequence. The conductive glass 100 is provided with a first groove 110, which penetrates the conductive glass 100 and is filled with the photoelectric conversion layer 200; the photoelectric conversion layer 200 has a second groove 240, which penetrates the photoelectric conversion layer 200 and is filled with the transparent conductive layer 300. The perovskite cell also has a third groove 410, which penetrates the metal electrode 400, the transparent conductive layer 300 and the photoelectric conversion layer 200 along the thickness direction of the cell, and the conductive glass 100 forms the bottom wall of the third groove 410.
[0055] The photoelectric conversion layer 200 includes a hole transport layer, a perovskite layer 220 and an electron transport layer which are stacked in sequence. Figure 5 In the inverse perovskite cell of the embodiment, the hole transport layer 210a contacts the conductive glass 100 and fills the first groove 110 on the conductive glass 100, and the electron transport layer 230a contacts the transparent conductive layer 300. Figure 6 In the formal perovskite cell in the embodiment, the electron transport layer 230 b contacts the conductive glass 100 and fills the first groove 110 on the conductive glass 100 , and the hole transport layer 210 b contacts the transparent conductive layer 300 .
[0056] When the above-mentioned perovskite cell is manufactured using the manufacturing method of the perovskite cell provided in the embodiment of the present application, the photoelectric conversion layer 200 can be used as the substrate 10, the transparent conductive layer 300 can be used as the functional layer 20, and the second groove 240 can be used as the groove 11, so as to achieve the deposition of the transparent conductive layer 300. At this time, the conductive glass 100 is used as the substrate 30. Further, in the manufacturing Figure 5 When the inverse perovskite cell of the embodiment is used, the conductive glass 100 can also be used as the substrate 10, the hole transport layer 210a can be used as the functional layer 20, the first groove 110 can be used as the groove 11, and the transparent carrier 101 can be used as the substrate 30 to manufacture the hole transport layer 210a. Figure 5 In the perovskite cell of the embodiment, one of the hole transport layer 210a and the transparent conductive layer 300 can be used as the functional layer 20 and manufactured by the method of the above steps S100 to S300; or, both the hole transport layer 210a and the transparent conductive layer 300 can be manufactured by the above steps S100 to S300.
[0057] The following takes the preparation of an inverse perovskite cell as an example to introduce the method for preparing a perovskite cell provided in the embodiment of the present application, wherein the hole transport layer 210a and the transparent conductive layer 300 are both obtained through the above steps S200 and S300.
[0058] The following describes the specific implementation of the above steps S100 to S300 by taking the conductive glass 100 as the base 10 , the hole transport layer 210 a as the functional layer 20 , the first groove 110 as the groove 11 , and the transparent carrier 101 as the substrate 30 .
[0059] Step S100 specifically includes: carving a first groove 110 on the conductive glass 100. The first groove 110 penetrates the conductive glass 100 and extends to the transparent carrier 101. The conductive glass 100 is cut into a plurality of independent strip electrodes through the first groove 110.
[0060] Before step S100, the method for manufacturing a perovskite cell further includes depositing a conductive glass 100 on a transparent substrate 101. The first groove 110 can be formed by laser scribing. The conductive glass 100 can be made of fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO) or indium tin oxide (ITO).
[0061] The step of depositing the first sub-layer 21 on the substrate 10 by using an atomic layer deposition process in step S200 specifically includes:
[0062] A nickel-containing precursor and an oxidant are used for reaction deposition to obtain a first nickel oxide film.
[0063] The step of depositing the second sub-layer 22 on the first sub-layer 21 by using a physical vapor deposition process or a rapid plasma deposition process in step S300 specifically includes:
[0064] The second nickel oxide film is deposited on the first nickel oxide film by using a physical vapor deposition process or a rapid plasma deposition process.
[0065] The first nickel oxide film can cover the wall surface of the first trench 110. Since it is deposited by an atomic layer deposition process, it has compactness and can well cover the sidewalls and bottom wall of the first trench 110. In addition, the atomic layer deposition process has a low temperature and no high-energy particles are generated, which can protect the substrate 10 (here, the conductive glass 100) from damage.
[0066] Specifically, the deposition method of the first nickel oxide film is as follows:
[0067] The substrate 10 is placed in an atomic layer deposition device, and the reaction temperature is controlled at 80-200°C and the reaction pressure is 0.2-10 mbar. First, a nickel-containing precursor is introduced, and then an inert gas (such as nitrogen or argon) is introduced to purge the residual chemical source, and then an oxidant is introduced, and then an inert gas is introduced to purge, to complete a sub-cycle of deposition of the first nickel oxide film. Different sub-cycles of deposition can be performed according to actual conditions to obtain a first nickel oxide film of the desired thickness.
[0068] The nickel-containing precursor is selected from at least one of bis(cyclopentadienyl)nickel, di(methylcyclopentadienyl)nickel and di(ethylcyclopentadienyl)nickel. The above-mentioned oxidant is selected from at least one of water, ozone and oxygen plasma.
[0069] The first sublayer 21 (ie, the first nickel oxide layer) of the hole transport layer 210a of the above embodiment was subjected to X-ray photoelectron spectroscopy detection, and the results are shown in the following table.
[0070]
[0071]
[0072] It can be seen that the first sublayer 21 manufactured by the atomic layer deposition process is nickel oxide.
[0073] After the first nickel oxide film is deposited, a second nickel oxide film (i.e., the second sublayer 22 of the hole transport layer 210a) is deposited on the first nickel oxide film by a physical vapor deposition process (such as a magnetron sputtering process, the sputtering target is a NiO target, the sputtering power is 1 to 3 KW, and the temperature is 25 to 200°C) or a rapid plasma deposition process (RPD). The first nickel oxide layer and the second nickel oxide layer together form the hole transport layer 210a. The thickness of the hole transport layer 210a is 10 to 30 nm. Optionally, the thickness of the first nickel oxide film is 5 to 25 nm, and the thickness of the second nickel oxide film is 5 to 25 nm.
[0074] After the hole transport layer 210a is fabricated, a perovskite layer 220 is fabricated on the surface of the hole transport layer 210a. In a specific embodiment, the material of the perovskite layer 220 (such as MA0.7FA0.3PbI3, optionally with a concentration of 1.6M and a thickness of 500nm) is scraped on the surface of the hole transport layer 210a, and thermal annealing is performed at 110°C for 20 minutes to obtain the perovskite layer 220. The total thickness of the perovskite layer 220 can be selected to be 450 to 600nm.
[0075] After the perovskite layer 220 is formed, an electron transport layer 230a is formed on the surface of the perovskite layer 220. In a specific embodiment, a vacuum evaporation method is used to form an electron transport layer 230a on the surface of the perovskite layer 220. -4 Under the conditions of 200 Å / s Pa, fullerene C60 and bathocuproine (BCP) are deposited by thermal evaporation to obtain an electron transport layer 230a. Optionally, the thickness of the electron transport layer 230a is 20 to 40 nm. Optionally, the thickness of fullerene C60 is 20 nm, and the thickness of bathocuproine is 8 nm.
[0076] After the electron transport layer 230a is manufactured, the photoelectric conversion layer 200 composed of the hole transport layer 210a, the perovskite layer 220 and the electron transport layer 230a is obtained. Thereafter, a transparent conductive layer 300 needs to be manufactured on the photoelectric conversion layer 200. In this embodiment, the above-mentioned steps S100 to S300 can also be applied to the manufacture of the transparent conductive layer 300. The following takes the photoelectric conversion layer 200 as the substrate 10, the transparent conductive layer 300 as the functional layer 20, and the conductive glass 100 as the substrate 30 as an example to introduce the specific contents of steps S100 to S300. The material of the transparent conductive layer 300 can be fluorine-doped tin oxide (FTO), or aluminum-doped zinc oxide (AZO) or indium tin oxide (ITO).
[0077] Step S100 specifically includes: scribing a second groove 240 on the photoelectric conversion layer 200. The second groove 240 penetrates the photoelectric conversion layer 200 and extends onto the conductive glass 100. The second groove 240 can be obtained by laser scribing.
[0078] The step of depositing the first sublayer 21 on the substrate 10 by using an atomic layer deposition process in step S200 specifically includes: alternately using a vapor phase indium precursor and a vapor phase tin precursor to react with an oxidant for deposition to obtain alternately stacked indium oxide films and tin oxide films.
[0079] It should be understood that in this embodiment, the material of the transparent conductive layer 300 is indium tin oxide (ITO), and the alternately stacked indium oxide films and tin oxide films constitute the first sublayer 21 of the transparent conductive layer 300 (as the functional layer 20 ).
[0080] Furthermore, the step of using a vapor phase indium precursor to react with an oxidant to deposit an indium oxide film may include: reacting the vapor phase indium precursor with a first oxidant and a second oxidant in sequence to deposit the indium oxide film. Specifically, the deposition method of the indium oxide film is as follows:
[0081] The reaction temperature of the reaction chamber is controlled at 80-200°C, and the pressure is controlled at 0.2-10 mbar. A gaseous indium precursor is introduced, and then an inert gas (such as nitrogen or argon) is introduced to purge the residual chemical source; secondly, a first oxidant is introduced, and then an inert gas is introduced to purge; finally, a second oxidant is introduced. Then an inert gas is introduced to purge, and a sub-cycle of deposition of an indium oxide film is completed. Different sub-cycles of deposition can be performed according to actual conditions to obtain an indium oxide film of a certain thickness.
[0082] Specifically, the first oxidant is selected from one of water, hydrogen peroxide, oxygen and oxygen plasma, and the second oxidant is selected from another of water, hydrogen peroxide, oxygen and oxygen plasma. For example, the first oxidant is selected as deionized water, and the second oxidant is selected as oxygen; in other embodiments, the first oxidant and the second oxidant can be interchanged, or other oxidant types can be selected. The gas phase indium precursor can be selected as cyclopentadiene indium.
[0083] In this embodiment, considering that ozone will reduce the oxygen vacancies of the indium oxide film, in this embodiment, both the first oxidant and the second oxidant do not contain ozone. Specifically, the use of ozone has the following disadvantages: 1) the reaction temperature needs to be above 250°C, which is significantly higher than that of the first oxidant and the second oxidant; 2) the resistivity of the indium oxide film produced is high; 3) the uniformity of the indium oxide film produced using ozone as an oxidant is worse.
[0084] The step of using a vapor phase tin precursor to react with an oxidant to deposit a tin oxide film comprises: reacting a third oxidant with the vapor phase tin precursor to deposit a tin oxide film. Specifically, the deposition method of the tin oxide film is as follows:
[0085] The reaction temperature of the reaction chamber is controlled at 80-200°C, and the pressure is controlled at 0.2-10 mbar. A vapor phase tin precursor is introduced, and then an inert gas (such as nitrogen or argon) is introduced to purge the residual chemical source; then a third oxidant is introduced; and finally an inert gas is introduced for purging to complete a sub-cycle of deposition of the tin oxide film. Different sub-cycles of deposition can be performed according to actual conditions to obtain a tin oxide film of a certain thickness.
[0086] Optionally, the third oxidant is selected from one of water, hydrogen peroxide, oxygen, ozone and oxygen plasma. The vapor phase tin precursor may be tetrakis(dimethylamino)tin.
[0087] In the embodiment of the present application, the ratio of indium and tin elements in the first sub-layer 21 in the transparent conductive layer 300 can be controlled by the number of sub-cycles in the indium oxide thin film deposition step and the number of sub-cycles in the tin oxide thin film deposition step.
[0088] In the embodiment of the present application, the step of depositing the indium oxide film and the step of depositing the tin oxide film can be performed alternately for multiple times, so that an indium oxide film and a tin oxide film that are alternately stacked can be formed, that is, the first sublayer 21 of the indium tin oxide material. The thickness of the first sublayer 21 in the transparent conductive layer 300 can be controlled to be 10 to 15 nm.
[0089] After the first sublayer 21 of the transparent conductive layer 300 is manufactured, the second sublayer 22 is deposited on the first sublayer 21 by using a physical vapor deposition method or a rapid plasma deposition process.
[0090] In an optional embodiment, the second sublayer 22 of the transparent conductive layer 300 is prepared by magnetron sputtering, and the sputtering target is an ITO target. Optionally, the mass ratio of In2O3 and SnO2 in the ITO target is 85:15 to 99:1, for example, the mass ratio of In2O3 and SnO2 is 97:3 or 90:10. The sputtering power can be selected to be 1 to 3KW, for example, 3KW; the substrate temperature is 25 to 200°C, the vacuum chamber pressure is 0.2 to 0.6Pa; and the oxygen partial pressure accounts for 0.25 to 1.5%.
[0091] Optionally, the thickness of the first sublayer 21 of the transparent conductive layer 300 is 10-15 nm, and the thickness of the second sublayer 22 is 5-10 nm. A portion of the transparent conductive layer 300 (i.e., the first sublayer 21) is made by an atomic layer deposition process, which has a relatively low process cost and a faster growth rate than the entire transparent conductive layer 300 made by an atomic layer deposition process.
[0092] In other optional embodiments, the material of the transparent conductive layer 300 may also be indium tungsten oxide (IWO) or tungsten-doped indium tin oxide (IWTO).
[0093] After the transparent conductive layer 300 is manufactured, a metal electrode 400 is manufactured on the transparent conductive layer 300. In this embodiment, the metal electrode 400 may be a copper electrode, which may be manufactured by a magnetron sputtering process, and the thickness may be 30-50 nm.
[0094] After the transparent conductive layer 300 and the metal electrode 400 are deposited, a laser can be used to scribe the third groove 410, which penetrates the metal electrode 400, the transparent conductive layer 300, and the photoelectric conversion layer 200 and extends to the conductive glass 100, that is, the conductive glass 100 forms the bottom wall of the third groove 410. It should be noted that the transparent conductive layer 300 and the metal electrode 400 should not be too thick, otherwise it is easy to cause problems such as edge collapse, burrs, and sub-battery short circuit when the third groove 410 is scribed by laser.
[0095] In the embodiment of the present application, the first sublayer 21 of the transparent conductive layer 300 can fill the second groove 240 well, and the dense first sublayer 21 can fit closely with the inner wall of the second groove 240. Since the first sublayer 21 of the transparent conductive layer 300 has high density and uniformity, it has a good protective effect on the sidewall of the second groove 240, preventing the copper electrode material from penetrating into the perovskite layer 220, causing metal diffusion, and affecting the reliability of the perovskite battery. Since the first sublayer 21 of the transparent conductive layer 300 is formed by an atomic layer deposition process, the reaction temperature is low and there is no high-energy particle participation, so it can reduce the damage to the substrate 10 (that is, the photoelectric conversion layer 200). Moreover, the first sublayer 21 of the transparent conductive layer 300 is closely attached to and protects the photoelectric conversion layer 200, so that the subsequent preparation process of the second sublayer 22 will not damage the photoelectric conversion layer 200, thereby ensuring the performance of the battery.
[0096] It can be seen from the above embodiments that the hole transport layer 210a and the transparent conductive layer 300 of the inverse perovskite cell can be made by steps S100 to S300, that is, the first sublayer 21 is deposited first, and then the second sublayer 22 is deposited, and the first sublayer 21 is deposited by an atomic layer deposition process, and the second sublayer 22 is deposited by a physical vapor deposition process or a rapid plasma deposition process. In other optional embodiments, one of the hole transport layer 210a and the transparent conductive layer 300 can adopt the process steps of steps S100 to S300 of the present application, and the other can be made by a conventional process.
[0097] In the embodiment of the present application, the manufacturing method of the formal perovskite cell is similar to the manufacturing method of the inverse perovskite cell, the difference is that the manufacturing order of the electron transport layer and the hole transport layer is reversed, the first groove 110 is filled with the electron transport layer, and the process method of each layer structure can refer to the above introduction to the manufacturing method of the inverse perovskite cell.
[0098] The following is a detailed introduction to the method for making a perovskite battery in conjunction with Examples 1 and 2.
[0099] Example 1
[0100] This embodiment manufactures an inverse perovskite battery, and the specific steps are as follows:
[0101] Fluorine-doped tin oxide (FTO) is deposited on a transparent substrate 101 to obtain a conductive glass 100 , and a first groove 110 is scribed by laser. The first groove 110 penetrates the conductive glass 100 and extends to the transparent substrate 101 .
[0102] The transparent carrier 101 and the conductive glass 100 are placed in an atomic layer deposition device, and the reaction temperature is controlled at 80°C and the reaction pressure is 0.6 mbar. First, bis(cyclopentadienyl) nickel is introduced as a nickel-containing precursor, and then argon gas is introduced to purge the residual chemical source, and then water is introduced as an oxidant, and then argon gas is introduced to purge, completing a sub-cycle of deposition of the first nickel oxide film. Repeat the above steps to complete 100 sub-cycles of deposition to obtain a first nickel oxide film of about 10 nm.
[0103] A second nickel oxide film is deposited on the first nickel oxide film by magnetron sputtering, wherein the sputtering target is a NiO target, the sputtering power is 3KW, and the temperature is 200° C. A 15 nm second nickel oxide film is deposited. The first nickel oxide film and the second nickel oxide film together form a hole transport layer 210a.
[0104] MA0.7FA0.3PbI3 was scraped onto the surface of the hole transport layer 210a with a concentration of 1.6M and a thickness of 500nm. The layer was thermally annealed at 110°C for 20min to obtain a perovskite layer 220. The total thickness of the perovskite layer 220 was 500nm.
[0105] Using vacuum evaporation method, the vacuum degree is less than 10 -4 Under the condition of Pa, fullerene C60 and bathocuproine (BCP) are deposited by thermal evaporation to obtain the electron transport layer 230a. The thickness of the electron transport layer 230a is 28nm, wherein the thickness of fullerene C60 is 20nm and the thickness of bathocuproine is 8nm.
[0106] The electron transport layer 230 a , the perovskite layer 220 , and the hole transport layer 210 a are scribed by laser to obtain a second groove 240 . The second groove 240 extends to the surface of the conductive glass 100 .
[0107] The semi-finished product of the battery is placed in the reaction chamber of the atomic layer deposition device. The reaction temperature of the reaction chamber is controlled at 80°C and the pressure is controlled at 0.6mbar. Cyclopentadiene indium is introduced as a gas phase indium precursor (temperature 40°C, injection time 2s, flow rate 500sccm), and then argon gas is introduced for purging (purge time 15s, flow rate 500sccm); secondly, water is introduced as the first oxidant (normal temperature, injection time 2s, flow rate 500sccm), and then argon gas is introduced for purging (purge time 15s, flow rate 500sccm); finally, oxygen is introduced as the second oxidant (normal temperature, injection time 2s, flow rate 500sccm). Then argon gas is introduced for purging (purge time 15s, flow rate 500sccm) to complete the deposition of a sub-cycle of indium oxide film, and this cycle is repeated 19 times to obtain an indium oxide film of a certain thickness.
[0108] Tetrakis(dimethylamino)tin was introduced as a vapor phase tin precursor (temperature 70°C, injection time 1s, flow rate 500sccm), and then argon gas was introduced to purge the residual chemical source (purge time 15s, flow rate 500sccm); then water was introduced as the third oxidant (room temperature, injection time 1s, flow rate 500sccm); finally, argon gas was introduced to purge (purge time 15s, flow rate 500sccm) to complete the deposition of a sub-cycle of tin oxide film. In this embodiment, a single tin oxide film is obtained by 1 sub-cycle deposition.
[0109] According to the above method, indium oxide thin films and tin oxide thin films are deposited alternately, and five indium oxide thin films and tin oxide thin films are deposited in total, thereby forming the first sublayer 21 of the transparent conductive layer 300 with a thickness of about 10 nm.
[0110] The second sublayer 22 of the transparent conductive layer 300 is prepared by magnetron sputtering, and the sputtering target is an ITO target. Optionally, the mass ratio of In2O3 and SnO2 in the ITO target is 90:10. The sputtering power is 3KW; the substrate temperature is 200°C, the vacuum chamber pressure is 0.6Pa; the oxygen partial pressure is 1%. The thickness of the second sublayer 22 is 10nm.
[0111] The metal electrode 400 is deposited on the transparent conductive layer 300 by magnetron sputtering. The sputtering target is a copper target and the sputtering power is 3KW. The temperature of the transparent conductive layer 300 is 200° C. and the vacuum chamber pressure is 0.6Pa.
[0112] After the metal electrode 400 is manufactured, a third groove 410 is scribed by laser. The third groove 410 penetrates the metal electrode 400 , the transparent conductive layer 300 , and the photoelectric conversion layer 200 , and extends to the conductive glass 100 . That is, the conductive glass 100 forms the bottom wall of the third groove 410 .
[0113] Example 2
[0114] This embodiment produces a formal perovskite battery, and the specific steps are as follows:
[0115] Fluorine-doped tin oxide (FTO) is deposited on a transparent substrate 101 to obtain a conductive glass 100 , and a first groove 110 is scribed by laser. The first groove 110 penetrates the conductive glass 100 and extends to the transparent substrate 101 .
[0116] Tin oxide is deposited on the conductive glass 100 by atomic layer deposition or chemical bath deposition to obtain an electron transport layer with a thickness of 20 nm.
[0117] MA0.7FA0.3PbI3 was scraped on the surface of the electron transport layer 230b with a concentration of 1.6M and a thickness of 500nm. The perovskite layer 220 was thermally annealed at 110°C for 20min to obtain the perovskite layer 220. The total thickness of the perovskite layer 220 was 500nm.
[0118] The semi-finished battery is placed in an atomic layer deposition device, and the reaction temperature is controlled at 120°C and the reaction pressure is 0.6 mbar. First, bis(cyclopentadienyl) nickel is introduced as a nickel-containing precursor, and then argon is introduced to purge the residual chemical source. Next, water is introduced as an oxidant, and then argon is introduced to purge, completing a sub-cycle of deposition of the first nickel oxide film. Repeat the above steps to complete 100 sub-cycles of deposition to obtain a first nickel oxide film covering the perovskite layer 220, with a thickness of about 10 nm.
[0119] A second nickel oxide film is deposited on the first nickel oxide film by a magnetron sputtering process, wherein the sputtering target is a NiO target, the sputtering power is 3KW, and the temperature is 200°C. A 15nm second nickel oxide film is deposited. The first nickel oxide film and the second nickel oxide film together form a hole transport layer 210b. The first nickel oxide is deposited by atomic layer deposition, which can reduce the deposition temperature and the strength of the particle bombardment-based perovskite layer, reduce the reaction energy, and improve the protection of the perovskite layer. Then, the second nickel oxide is deposited by magnetron sputtering. Since the magnetron sputtering deposition speed is fast and the cost is lower than that of atomic layer deposition, the second nickel oxide can be deposited by magnetron sputtering to increase the deposition speed and reduce the deposition cost.
[0120] The hole transport layer 210 b , the perovskite layer 220 , and the electron transport layer 230 b are scribed by laser to obtain a second groove 240 . The second groove 240 extends to the surface of the conductive glass 100 .
[0121] The semi-finished battery is placed in the reaction chamber of the atomic layer deposition device. The reaction temperature of the reaction chamber is controlled at 120°C and the pressure is controlled at 0.6mbar. Cyclopentadiene indium is introduced as a gas phase indium precursor (temperature 40°C, injection time 2s, flow rate 500sccm), and then argon is introduced for purging (purge time 15s, flow rate 500sccm); secondly, water is introduced as the first oxidant (normal temperature, injection time 2s, flow rate 500sccm), and then argon is introduced for purging (purge time 15s, flow rate 500sccm); finally, oxygen is introduced as the second oxidant (normal temperature, injection time 2s, flow rate 500sccm). Then argon is introduced for purging (purge time 15s, flow rate 500sccm) to complete the deposition of a sub-cycle of indium oxide film, and this cycle is repeated 19 times to obtain an indium oxide film of a certain thickness.
[0122] Tetrakis(dimethylamino)tin was introduced as a vapor phase tin precursor (temperature 70°C, injection time 1s, flow rate 500sccm), and then argon gas was introduced to purge the residual chemical source (purge time 15s, flow rate 500sccm); then water was introduced as the third oxidant (room temperature, injection time 1s, flow rate 500sccm); finally, argon gas was introduced to purge (purge time 15s, flow rate 500sccm) to complete the deposition of a sub-cycle of tin oxide film. In this embodiment, a single tin oxide film is obtained by 1 sub-cycle deposition.
[0123] According to the above method, indium oxide thin films and tin oxide thin films are deposited alternately, and five indium oxide thin films and tin oxide thin films are deposited in total, thereby forming the first sublayer 21 of the transparent conductive layer 300 with a thickness of about 10 nm.
[0124] The second sublayer 22 of the transparent conductive layer 300 is prepared by magnetron sputtering, and the sputtering target is an ITO target. Optionally, the mass ratio of In2O3 and SnO2 in the ITO target is 90:10. The sputtering power is 3KW; the substrate temperature is 200°C, the vacuum chamber pressure is 0.6Pa; the oxygen partial pressure is 1%. The thickness of the second sublayer 22 is 10nm.
[0125] The metal electrode 400 is deposited on the transparent conductive layer 300 by magnetron sputtering. The sputtering target is a copper target and the sputtering power is 3KW. The temperature of the transparent conductive layer 300 is 200° C. and the vacuum chamber pressure is 0.6Pa.
[0126] After the metal electrode 400 is manufactured, a third groove 410 is scribed by laser. The third groove 410 penetrates the metal electrode 400 , the transparent conductive layer 300 , and the photoelectric conversion layer 200 , and extends to the conductive glass 100 . That is, the conductive glass 100 forms the bottom wall of the third groove 410 .
[0127] The first sublayer 21 of the transparent conductive layer 300 in the above-mentioned embodiment 1 was subjected to X-ray photoelectron spectroscopy detection, and the results are shown in the following table.
[0128]
[0129]
[0130] It can be seen that the first sublayer 21 of the transparent conductive layer 300 deposited by the above process is an indium tin oxide thin film.
[0131] In summary, the present application provides a method for manufacturing a perovskite cell. The manufacturing method includes scratching a groove 11 on a substrate 10; depositing a first sublayer 21 on the substrate 10 using an atomic layer deposition process, and depositing a second sublayer 22 on the first sublayer 21 using a physical vapor deposition process or a rapid plasma deposition process, wherein the first sublayer 21 and the second sublayer 22 together form a functional layer 20, and the functional layer 20 fills the groove 11. Compared with the existing physical vapor deposition process, the atomic layer deposition process is used to first deposit a first sublayer 21. The density of the first sublayer 21 enables it to cover the inner wall of the groove 11 well, and the functional layer 20 finally deposited can also fill the groove 11 well, ensuring the close combination of the functional layer 20 and the substrate 10; when used to make a transparent conductive layer 300, since the dense first sublayer 21 can closely fit and cover the wall surface of the groove 11, including the side wall and the bottom wall, it can also effectively prevent the material of the metal electrode 400 on the subsequent transparent conductive layer 300 from penetrating into the perovskite layer 220 through the side wall of the groove 11, causing metal diffusion, thereby ensuring the reliability of the battery. Moreover, compared with the physical vapor deposition process, the atomic layer deposition process has a lower reaction temperature, less energy, and is not easy to damage the substrate 10. In addition, the second sublayer 22 is deposited by a physical vapor deposition process or a rapid plasma deposition process, which can also alleviate the cost problem caused by excessive use of the atomic layer deposition process and ensure growth efficiency.
[0132] The above are only preferred embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. A method for manufacturing a perovskite battery, characterized in that: include: Scratching grooves on the substrate; Depositing a first sublayer on the substrate by an atomic layer deposition process, wherein the first sublayer covers the wall surface of the groove; The second sublayer is deposited on the first sublayer by using a physical vapor deposition process or a rapid plasma deposition process. The first sublayer and the second sublayer together form a functional layer. The functional layer fills the groove.
2. The method for manufacturing a perovskite battery according to claim 1, characterized in that: The first sub-layer and the second sub-layer are made of the same material.
3. The method for manufacturing a perovskite battery according to claim 2, characterized in that: The substrate is a photoelectric conversion layer, and the functional layer is a transparent conductive layer; along the direction gradually away from or gradually approaching the transparent conductive layer, the photoelectric conversion layer includes an electron transport layer, a perovskite layer and a hole transport layer stacked in sequence, and the groove runs through the electron transport layer, the perovskite layer and the hole transport layer.
4. The method for manufacturing a perovskite battery according to claim 3, characterized in that: The thickness of the first sublayer is 10-15 nm, and the thickness of the second sublayer is 5-10 nm.
5. The method for manufacturing a perovskite battery according to claim 3, characterized in that: The material of the functional layer is indium tin oxide, and the step of depositing a first sublayer on the substrate by an atomic layer deposition process includes: A vapor phase indium precursor and a vapor phase tin precursor are alternately used with an oxidant for reaction deposition to obtain an alternately stacked indium oxide film and a tin oxide film.
6. The method for manufacturing a perovskite battery according to claim 5, characterized in that: The step of using the vapor phase indium precursor to react with an oxidant to deposit the indium oxide film comprises: The vapor phase indium precursor is reacted with a first oxidant and a second oxidant in sequence to deposit the indium oxide film; Wherein, neither the first oxidant nor the second oxidant contains ozone.
7. The method for manufacturing a perovskite battery according to claim 6, characterized in that: The first oxidant is selected from one of water, hydrogen peroxide, oxygen and oxygen plasma, and the second oxidant is selected from another of water, hydrogen peroxide, oxygen and oxygen plasma.
8. The method for manufacturing a perovskite battery according to claim 5, characterized in that: The step of using the vapor phase tin precursor to react with an oxidant to deposit the tin oxide film comprises: Depositing the tin oxide thin film by reacting a vapor phase tin precursor with a third oxidant; Wherein, the third oxidant is selected from one of water, hydrogen peroxide, oxygen, ozone and oxygen plasma.
9. The method for manufacturing a perovskite battery according to claim 5, characterized in that: The gas phase indium precursor is cyclopentadienyl indium, and the gas phase tin precursor is tetrakis(dimethylamino)tin.
10. The method for manufacturing a perovskite battery according to claim 3, characterized in that: The method for manufacturing the perovskite battery also includes: A metal electrode is deposited on the functional layer.
11. The method for manufacturing a perovskite battery according to claim 2 or 3, characterized in that: The substrate is conductive glass, and the functional layer is a hole transport layer.
12. The method for manufacturing a perovskite battery according to claim 11, characterized in that: The steps of depositing a first sublayer on the substrate by an atomic layer deposition process, and depositing a second sublayer on the first sublayer by a physical vapor deposition process or a rapid plasma deposition process include: Using a nickel-containing precursor and an oxidant to perform reaction deposition to obtain a first nickel oxide film; A second nickel oxide film is deposited on the first nickel oxide film by using a physical vapor deposition process or a rapid plasma deposition process.
13. The method for manufacturing a perovskite battery according to claim 12, characterized in that: The oxidant is selected from at least one of water, ozone and oxygen plasma; And / or, the nickel-containing precursor is selected from at least one of bis(cyclopentadienyl)nickel, bis(methylcyclopentadienyl)nickel and bis(ethylcyclopentadienyl)nickel.
14. The method for manufacturing a perovskite cell according to any one of claims 1 to 10, 12 to 13, characterized in that: The reaction temperature for depositing the first sub-layer is 80-200° C. and the pressure is 0.2-10 mbar.
15. The method for manufacturing a perovskite cell according to any one of claims 1 to 10, 12 to 13, characterized in that: The physical vapor deposition process includes a magnetron sputtering process or an evaporation process.