Annealing method of large-area perovskite film layer, annealing equipment and application thereof

Abstract

The application discloses an annealing method of a large-area perovskite film layer, an annealing device and application thereof. The annealing method of the perovskite film layer comprises the following steps: irradiating the perovskite film layer with light of a selected wavelength at a set irradiation intensity and for a set irradiation time to realize primary annealing; and after the primary annealing is completed, uniformly heating the perovskite film layer by using a heating device to realize secondary annealing. The annealing method of the perovskite film layer provided by the application firstly pre-anneals the perovskite layer of an intermediate phase by using light of a selected wavelength for a short time, so as to remove the solvent quickly and improve the interface contact, then secondarily anneals the pre-annealed perovskite layer by using the heating device, that is, adopts a relatively stable annealing mode with good uniformity, so that the crystal growth is continued, and better crystallization quality is realized.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of solar cells, and particularly relates to an annealing method for a large-area perovskite film layer, an annealing device and application thereof. BACKGROUND

[0002] With global climate deterioration and non-renewable energy consumption, people are increasing the use of clean and renewable energy such as solar energy. As a new type of solar cell, perovskite solar cells have the advantages of simple preparation, low cost, high conversion efficiency and flexible components, and are expected to gradually replace the current commercial silicon solar cells. At present, the efficiency of small-area perovskite cell devices in the laboratory has reached more than 25%. The preparation of large-size perovskite cell components still faces some difficulties. The annealing process of small-area perovskite cells is relatively simple, and generally uses hot plate annealing. For large-area cells, the hot plate is unevenly heated, and the temperature difference will cause the glass to bend and deform, thereby further affecting the uniformity of annealing.

[0003] Although the non-hot plate contact type ultraviolet annealing and infrared annealing and dry oven annealing have good uniformity, they still have certain annealing defects. For example, although the infrared annealing process has a fast heating speed, the infrared light acts on the glass substrate, and then the perovskite layer is annealed through heat conduction. This annealing method has a low heat utilization rate, and still has the problem of glass bending caused by temperature difference. Since infrared light is used for rapid annealing, the precise temperature control of the glass substrate is not very ideal. Ultraviolet annealing can accurately heat the perovskite layer, and has an advantage that cannot be compared with infrared light. However, since the perovskite layer is sensitive to ultraviolet light, excessive irradiation will cause the perovskite to decompose; low-power ultraviolet light annealing cannot achieve the purpose of rapid annealing, and high-power ultraviolet light has strict requirements on irradiation time, and a few more seconds will have a destructive effect on the perovskite film layer, and a few less seconds will result in insufficient crystallization.

[0004] The non-hot plate contact type liquid medium annealing is to immerse the perovskite substrate in hot liquid, and after annealing, the substrate is taken out and dried. This method has good annealing uniformity for the perovskite layer, but the process is relatively complex, and there are still many difficulties in industrial production. The tunnel furnace or the hierarchical furnace needs to use a fan to transfer the heat generated by the infrared lamp to the substrate. This annealing method can achieve uniform annealing, but the substrate has a slow heating speed, and the heat transferred through the hot air causes the surface of the perovskite to dry and crystallize before the inside, which may cause the residual solvent in the inside to be unable to be effectively removed, which has an influence on the crystallization quality and the interface between the perovskite layer and the transport layer. Microwave annealing faces the edge effect and tip effect, and cannot achieve uniform annealing on a large size. SUMMARY

[0005] The main purpose of the present application is to provide an annealing method, an annealing device and an application thereof for large-area perovskite film layers to overcome the deficiencies in the prior art.

[0006] To achieve the above-mentioned purposes, the technical solutions adopted by the embodiments of the present application include:

[0007] The embodiments of the present application provide an annealing method for large-area perovskite film layers, which comprises:

[0008] Irradiating the perovskite film layer with light of a selected wavelength at a set irradiation intensity and a set irradiation time to realize primary annealing;

[0009] After completing the primary annealing, uniformly heating the perovskite film layer by using a heating device to realize secondary annealing.

[0010] Further, the annealing method for large-area perovskite film layers specifically comprises:

[0011] Making the perovskite film layer pass through the irradiation area of the light source at a set speed to complete the primary annealing, wherein the light source can emit light of the selected wavelength; and

[0012] Making the perovskite film layer that has undergone the primary annealing enter the heating area of the heating device and perform secondary annealing.

[0013] Further, the light of the selected wavelength is ultraviolet light, but is not limited to ultraviolet light, the set irradiation intensity is 0.1-3 W / cm 2 , and the set irradiation time is 1-10 s.

[0014] Further, the temperature for the secondary annealing is 100-150℃, and the time is 10-30 minutes.

[0015] The embodiments of the present application also provide an annealing device for large-area perovskite film layers, which comprises a light source, a heating device and a conveying device.

[0016] The light source can emit light of the selected wavelength, and the irradiation area of the light source is set as a primary annealing area for performing primary annealing on the perovskite film layer.

[0017] The heating area of the heating device is set as a secondary annealing area for performing secondary annealing on the perovskite film layer.

[0018] The conveying device is used to drive the perovskite film layer to pass through the primary annealing area and the secondary annealing area in sequence.

[0019] Further, the light source comprises an ultraviolet light source, and the irradiation intensity of the ultraviolet light in the primary annealing area is 0.1-3 W / cm 2And, the time for the conveying device to drive the perovskite film layer through the first annealing area is 1-10 seconds.

[0020] Further, the temperature in the second annealing area is 100-150 DEG C, and the time for the conveying device to drive the perovskite film layer through the second annealing area is 10-30 minutes.

[0021] Further, the conveying device comprises a conveying belt, which continuously passes through the first annealing area and the second annealing area.

[0022] The embodiment of the present application also provides a preparation method of the perovskite battery assembly, which comprises the steps of manufacturing a first electrode, a first modification layer, a perovskite layer, a second modification layer and a second electrode respectively; wherein the step of manufacturing the perovskite layer comprises:

[0023] manufacturing a perovskite film layer; and

[0024] The perovskite film layer is annealed by the method.

[0025] Further, the preparation method of the perovskite battery assembly specifically comprises: coating a perovskite precursor solution on the first modification layer to form a coating layer, and then drying the coating layer, so as to form the perovskite film layer.

[0026] The embodiment of the present application also provides a perovskite battery assembly, which is prepared by the method.

[0027] Compared with the prior art, the present application has the following beneficial effects:

[0028] The annealing method of the large-area perovskite film layer of the present application firstly pre-anneals the perovskite layer in the intermediate phase by light with a selected wavelength for a short time, so as to remove the solvent quickly and improve the interface contact, then secondarily anneals the pre-annealed perovskite layer by a heating device, that is, adopts a more stable and uniform annealing method, so as to continue the crystal growth and realize better crystallization quality; the annealing of the large-area perovskite film layer is better controlled, a more uniform perovskite layer is obtained, and the interface between the perovskite layer and the transport layer is improved. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without any creative effort.

[0030] Figure 1is a structural schematic diagram of an annealing device for a large-area perovskite film layer in an embodiment of the present application.

[0031] Figure 2 is a structural schematic diagram of a large-area perovskite battery assembly in an embodiment of the present application.

[0032] Legend: 1, first electrode; 2, hole transport layer; 3, perovskite layer; 4, electron transport layer; 5, second electrode; 6, light source; 7, heating device; 71, secondary annealing area; 72, feeding port; 73, discharging port. DETAILED DESCRIPTION

[0033] One aspect of an embodiment of the present application provides an annealing method for a large-area perovskite film layer, comprising:

[0034] irradiating the perovskite film layer with light of a selected wavelength at a set irradiation intensity and for a set irradiation time to achieve primary annealing;

[0035] after the primary annealing is completed, uniformly heating the perovskite film layer using a heating device to achieve secondary annealing.

[0036] In some preferred embodiments, the annealing method for the perovskite film layer specifically comprises:

[0037] passing the perovskite film layer through an irradiation area of a light source at a set speed, so as to complete primary annealing, the light source being capable of emitting light of the selected wavelength; and

[0038] passing the perovskite film layer that has undergone primary annealing into a heating area of a heating device to perform secondary annealing.

[0039] In some preferred embodiments, the light of the selected wavelength includes ultraviolet light, but is not limited thereto; the set irradiation intensity is 0.1-3 W / cm 2 , and the set irradiation time is 1-10 s.

[0040] In some preferred embodiments, the secondary annealing is performed at a temperature of 100-150℃ for 10-30 minutes.

[0041] In some preferred embodiments, the heating device can include a tunnel furnace, a hierarchical furnace, or an oven, but is not limited thereto.

[0042] Another aspect of an embodiment of the present application provides an annealing device for a large-area perovskite film layer, comprising a light source, a heating device, and a conveying device;

[0043] The light source is capable of emitting light of the selected wavelength, and an irradiation area of the light source is set as a primary annealing area for performing primary annealing on the perovskite film layer.

[0044] The heating area of the heating device is set as a secondary annealing area for secondary annealing of the perovskite film layer.

[0045] The conveying device is used to drive the perovskite film layer to pass through the primary annealing area and the secondary annealing area in sequence.

[0046] In some preferred embodiments, the light source includes an ultraviolet light source, but is not limited to an ultraviolet light source, and the irradiation intensity of ultraviolet light in the primary annealing area is 0.1-3 W / cm 2 , and the time for the conveying device to drive the perovskite film layer to pass through the primary annealing area is 1-10 seconds.

[0047] In the implementation process, the ultraviolet light source adopts an ultraviolet lamp provided with a matrix type LED lamp group.

[0048] In some more preferred embodiments, the wavelength of the ultraviolet lamp is selected from 365 nm, 395 nm or 405 nm.

[0049] In some preferred embodiments, the temperature in the secondary annealing area is 100-150℃, and the time for the conveying device to drive the perovskite film layer to pass through the secondary annealing area is 10-30 minutes.

[0050] In some preferred embodiments, the conveying device includes a conveying belt, and the conveying belt continuously passes through the primary annealing area and the secondary annealing area.

[0051] Another aspect of the embodiments of the present application also provides a preparation method of a perovskite battery assembly, which includes the steps of respectively manufacturing a first electrode, a first modification layer, a perovskite layer, a second modification layer and a second electrode.

[0052] The step of manufacturing the perovskite layer includes:

[0053] manufacturing a perovskite film layer; and

[0054] annealing the perovskite film layer by the method.

[0055] In some preferred embodiments, the preparation method of the perovskite battery assembly specifically includes: coating a perovskite precursor solution on the first modification layer to form a coating layer, and then drying the coating layer to form the perovskite film layer.

[0056] Another aspect of the embodiments of the present application also provides a perovskite battery assembly, which is prepared by the method.

[0057] In the implementation process, the first modification layer and the second modification layer are one of an electron transport layer and a hole transport layer.

[0058] In some preferred embodiments, the first electrode can be selected from FTO conductive glass or ITO conductive glass, but not limited thereto.

[0059] In some preferred embodiments, the material of the electron transport layer can be selected from one or more of PCBM, TiO2, SnO2, ZnO, Nb2O5, etc., but not limited thereto.

[0060] In some preferred embodiments, the material of the hole transport layer can be selected from one or more of NiO, Spiro-OMeTAD, CuGaO2, CuSCN, P3HT, PEDOT:PSS, etc., but not limited thereto.

[0061] In some preferred embodiments, the structure of the perovskite layer can be any one of MAPbI3, FAPbI3, FAMAPbI3, FACsPbI3, or FAMACsPbI3 (wherein MA is methylamine and FA is formamidinium), but not limited thereto.

[0062] In some preferred embodiments, the second electrode is a metal electrode or a transparent electrode.

[0063] In some more preferred embodiments, the metal electrode can be any one of Ag, Al, Au, etc., but not limited thereto.

[0064] In some more preferred embodiments, the transparent electrode can be one or more of metal oxides, silver nanowires, transparent conductive polymer materials, etc., but not limited thereto; wherein the metal oxide can be ITO or IWO, but not limited thereto.

[0065] In the specific implementation process, the preparation method of the large-area perovskite battery assembly is as follows:

[0066] Preparation of the modification layer one: using one of the deposition methods including but not limited to magnetron sputtering, thermal evaporation, reactive plasma deposition, vapor deposition, atomic layer deposition, or slot coating, spraying, screen printing, etc. to prepare on the transparent conductive glass.

[0067] Preparation of the perovskite layer: using slot coating, spraying, blade coating, screen printing, etc. to uniformly coat the perovskite precursor solution on the modification layer one, and using one or more desolvation methods such as vacuum flash evaporation, air knife method, anti-solvent method, etc. to preliminarily dry the perovskite layer to form an intermediate phase active layer.

[0068] Two-step annealing process: first, the intermediate phase perovskite layer is pre-annealed with light of a selected wavelength for a short time to remove the solvent quickly and improve the interface contact; then, the pre-annealed perovskite layer is subjected to secondary annealing, and the secondary annealing is performed by using a tunnel furnace, a layered furnace or an oven, etc. with good stability and uniformity, so as to continue to grow crystals and achieve better crystalline quality.

[0069] Preparation of the second modification layer: one of deposition methods including but not limited to magnetron sputtering, thermal evaporation, reactive plasma deposition, vapor deposition, atomic layer deposition or slit coating, spraying, screen printing, etc. is used to prepare the second modification layer on the perovskite layer.

[0070] Preparation of the second electrode: one or a combination of deposition methods including magnetron sputtering, thermal evaporation, reactive plasma deposition, vapor deposition, atomic layer deposition or slit coating, spraying, screen printing, etc. is used to prepare the second electrode.

[0071] The technical solutions in the embodiments of the present application will be described in detail below with reference to the drawings of the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0072] Embodiment 1

[0073] The embodiments of the present application provide an annealing equipment for large-area perovskite film, as shown in Figure 1 The annealing equipment includes a light source 6, a heating device 7 and a conveying device.

[0074] The light source 6 can emit light of a selected wavelength, and the irradiation area of the light source 6 is set as a primary annealing area for primary annealing of the perovskite film layer.

[0075] The heating area of the heating device 7 is set as a secondary annealing area 71 for secondary annealing of the perovskite film layer, and the heating device 7 further includes an upper feeding port 72 and a lower feeding port 73 arranged in sequence along the feeding direction.

[0076] The conveying device is used to drive the perovskite film layer to pass through the primary annealing area and the secondary annealing area in sequence.

[0077] In the embodiment, the light source 6 is an ultraviolet light source, and specifically, the ultraviolet light source is an ultraviolet lamp provided with a matrix LED lamp group. In addition, the conveying device includes a conveying belt, and the conveying belt continuously passes through the primary annealing area and the secondary annealing area.

[0078] Embodiment 2

[0079] This invention provides an annealing method based on the annealing apparatus of Example 1 for a large-area perovskite film, comprising:

[0080] First, the mesophase perovskite film is conveyed via conveyor belt to a UV lamp equipped with a matrix LED light group, and then cooled at a wavelength of 365nm at a rate of 0.1–3W / cm. 2 The perovskite film was irradiated with irradiation intensity and irradiation time of 1 to 10 seconds to achieve a single annealing process.

[0081] After the first annealing, the perovskite film is uniformly heated in a layered furnace to achieve a second annealing; the temperature for the second annealing is 100-150℃ and the time is 10-30 minutes.

[0082] Example 3

[0083] This invention provides a large-area perovskite solar cell module, such as... Figure 2 As shown, it includes a first electrode 1, a hole transport layer 2, a perovskite layer 3, an electron transport layer 4, and a second electrode 5 arranged sequentially.

[0084] The large-area perovskite solar cell module of this invention is prepared through the following steps:

[0085] Provide ITO conductive glass; etch P1 using a 1064nm laser;

[0086] NiO, a hole transport layer material, was deposited on the surface of ITO conductive glass by measurement and control sputtering to form a hole transport layer 2 with a thickness of about 40 nm.

[0087] CsI, FAI, MAI, and PbI₂ were dissolved in a DMF:NMP mixed solvent according to a certain stoichiometric ratio, and stirred at 70°C for 12 hours to form a precursor perovskite solution. The perovskite composition is CsI. 0.05 FA 0.85 MA 0.1 The volume ratio of PbI3, DMF, and NMP was 9:1, and the solution concentration was 1 mol / L. The precursor solution was coated onto the hole transport layer 2 using a slit coating process, and the perovskite liquid film was initially dried using a vacuum flash evaporation method to form the active layer of the intermediate phase.

[0088] like Figure 2 As shown, the mesophase perovskite layer is first conveyed via conveyor belt 7 to a UV lamp 6 equipped with a matrix LED light group, and then pre-annealed with UV light at a wavelength of 365nm. The UV irradiance is 0.1-3W / cm². 2, irradiation time is 1-10s; then the pre-annealed perovskite layer 3 is subjected to secondary annealing by a hierarchical furnace; the desired high-quality perovskite layer 3 is obtained; then P2 is etched by a 532nm laser;

[0089] The electron transport layer material PCBM is dissolved in anhydrous chlorobenzene to prepare a solution with a concentration of 10mg / ml, and the PCBM solution is coated on the perovskite layer 3 by a slot coating process. The liquid film is blown dry with an air knife during coating, and heated at 100℃ for 5min to obtain the electron transport layer 4;

[0090] An ITO layer with a thickness of 200nm is sputtered on the surface of the electron transport layer 4 by a sputtering device as the second electrode 5. P3 is etched by a 532nm laser to obtain a large-area perovskite battery assembly.

[0091] Example 4

[0092] This embodiment provides a preparation method of the large-area perovskite battery assembly in Example 3, and the preparation steps are basically the same, and the difference lies in that visible light pre-annealing is used. Specifically, the ultraviolet light source can be replaced by a safer visible light LED lamp set, such as a blue light LED, a green light LED, etc. Considering the absorption efficiency of the intermediate phase perovskite layer, a larger wavelength of visible light requires a larger power, which may not be suitable.

[0093] The performance of the large-area perovskite battery assembly is tested. Due to the ultraviolet light pre-annealing and secondary annealing process, the crystallization quality of the perovskite layer is improved, and the interface is optimized. The efficiency of the assembly is increased by 20% compared with the conventional annealing process.

[0094] In addition, the inventors of the present case have also carried out tests with other raw materials, process operations and process conditions described in the specification with reference to the foregoing examples, and all have obtained relatively ideal results.

[0095] Although the present application has been described with reference to the illustrative embodiments, those with ordinary skill in the art will appreciate that various other alterations, omissions, and / or additions can be made to the embodiments without departing from the spirit and scope of the present application. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the present application without departing from the scope of the present application. Accordingly, the present application is not intended to be limited to the disclosed embodiments for carrying out the present application, but is intended to encompass all embodiments falling within the scope of the appended claims. Furthermore, unless specifically stated otherwise, any use of the terms first, second, etc. does not indicate any order or importance, but is used for the purpose of nomenclature.

Claims

1. An annealing method for a large-area perovskite film, characterized in that, include: Using ultraviolet light with an irradiance of 0.1~3 W / cm 2 The perovskite film is irradiated for 1-10 seconds to achieve a single annealing process. After the first annealing is completed, the perovskite film is uniformly heated using a heating device to achieve a second annealing.

2. The annealing method for large-area perovskite films according to claim 1, characterized in that, Specifically, it includes: An annealing process is completed by passing the perovskite film through the irradiation area of ​​a light source at a set speed, wherein the light source is capable of emitting ultraviolet light; And the perovskite film layer that has undergone one annealing is brought into the heating zone of the heating device and subjected to a second annealing.

3. The annealing method for large-area perovskite films according to claim 1 or 2, characterized in that: The secondary annealing is performed at a temperature of 100-150℃ for 10-30 minutes. And / or, the heating device includes a tunnel furnace, a layered furnace, or an oven.

4. An annealing device for large-area perovskite films, characterized in that, Includes a light source, a heating device, and a conveying device; The light source is capable of emitting ultraviolet light, and the irradiation area of ​​the light source is set as a primary annealing area for primary annealing of the perovskite film. The heating area of ​​the heating device is set as a secondary annealing area for secondary annealing of the perovskite film layer; The conveying device is at least used to drive the perovskite film layer through the primary annealing region and the secondary annealing region in sequence. The ultraviolet irradiance within the primary annealing region is 0.1~3 W / cm². 2 Furthermore, the time for the conveying device to drive the perovskite film through the primary annealing region is 1 to 10 seconds.

5. The annealing equipment for large-area perovskite films according to claim 4, characterized in that: The temperature in the secondary annealing zone is 100-150℃, and the conveying device drives the perovskite film through the secondary annealing zone for 10-30 minutes.

6. The annealing equipment for large-area perovskite films according to claim 4, characterized in that: The conveying device includes a transmission belt that continuously passes through the primary annealing region and the secondary annealing region.

7. A method for fabricating a perovskite solar cell module, comprising the steps of fabricating a first electrode, a first modification layer, a perovskite layer, a second modification layer, and a second electrode respectively; Its features are, The steps involved in creating the perovskite layer include: Fabrication of perovskite films; and The perovskite film is annealed using the method described in any one of claims 1-3.

8. The method for preparing a perovskite solar cell module according to claim 7, characterized in that, Specifically, it includes: A perovskite precursor solution is coated onto a first modification layer to form a coating, which is then dried to form the perovskite film.

9. A perovskite solar cell module, characterized in that, It is prepared by the method described in any one of claims 7-8.

Images