Universal treatment solution, treatment method and application of perovskite layer

Abstract

The present invention discloses a universal treatment liquid, treatment method and application of a perovskite layer. The universal treatment liquid includes a polar solvent and a non-polar solvent, and the polar solvent contains an amine group and / or a sulfonate group. The treatment method includes: providing a perovskite layer; contacting the perovskite layer with the universal treatment liquid for modification treatment; and removing the universal treatment liquid. The universal treatment liquid and treatment method provided by the present invention can significantly improve the performance of the perovskite material, and because its working principle does not change with the type and composition of the perovskite material, it has a significant effect on perovskite materials of almost all current compositions; at the same time, because the universal treatment liquid of the present invention has extremely strong reactivity, the treatment method has an extremely short treatment time, and has low requirements on the treatment temperature and treatment equipment, which significantly improves the treatment efficiency of the perovskite layer and reduces the treatment cost, which is very conducive to popularization and application in the industry.

Description

Technical Field

[0001] The present invention relates to the technical field of optoelectronic materials, and in particular to a universal treatment liquid, a treatment method and an application of a perovskite layer. Background Art

[0002] Perovskite materials are widely used in various optoelectronic devices due to their superior potential optoelectronic properties: solar cells (PV), light-emitting diodes (LED), photodetectors, etc. However, the stability of perovskite materials, especially to adverse environmental factors such as humidity, temperature, light, etc., is still far from meeting the requirements of commercial applications.

[0003] At the same time, there is still room for improvement in the efficiency of various perovskite devices. Therefore, it is necessary to comprehensively improve the performance of perovskite materials. At present, the stability improvement of perovskite optoelectronic devices mainly relies on physical encapsulation with lower water and oxygen permeability and the addition of additives to the perovskite precursor (for example, existing literature: Chu, Z. et al. Adv. Mater. 33, e2007169, (2021). Guo, Z. et al. Adv. Mater. 33, e2102246, (2021)), and the improvement of the efficiency of perovskite devices is also highly dependent on the addition of additives.

[0004] However, in the traditional methods currently used to improve the performance of perovskites, the improvement of physical packaging effects requires expensive and complex high-vacuum equipment, the device structure is complex and the manufacturing cost is greatly increased. At the same time, the stability problem of perovskites is not fundamentally solved. Once the packaging fails, the device will be quickly damaged.

[0005] The solution of adding additives to the precursor is quite specific. Specific additives are often only effective for specific material systems and are difficult to extend to perovskite systems with other components, which also increases the difficulty and cost of research and development. Therefore, it is particularly necessary to develop a universal and simple treatment method that can effectively improve the performance of perovskites of various components.

[0006] In order to fundamentally improve the performance of perovskites, a processing method is needed that can optimize the perovskite structure at the microscopic level and is universal and can be effectively applied to perovskite systems of different components.

[0007] However, in the prior art, some treatment solutions that are commonly used in different perovskite systems require a long treatment time, a high treatment temperature, and specific reaction equipment, which reduces the treatment efficiency on the one hand and increases the treatment cost on the other hand, which is not conducive to the promotion and application of perovskite optoelectronic devices. Summary of the invention

[0008] In view of the deficiencies in the prior art, the object of the present invention is to provide a universal treatment solution, treatment method and application of perovskite layer.

[0009] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0010] In a first aspect, the present invention provides a universal treatment solution for a perovskite layer, comprising a polar solvent and a non-polar solvent, wherein the polar solvent contains an amine group and / or a sulfonate group.

[0011] In a second aspect, the present invention also provides a general method for processing a perovskite layer, comprising:

[0012] 1) providing a perovskite layer;

[0013] 2) contacting the perovskite layer with the above-mentioned universal treatment solution to perform a modification treatment, wherein the modification treatment time is 2-10 seconds;

[0014] 3) removing the common treatment solution from the modified perovskite layer.

[0015] In a third aspect, the present invention further provides a perovskite photoelectric device, comprising a first transmission layer, a perovskite layer and a second transmission layer, wherein the perovskite layer is arranged between the first transmission layer and the second transmission layer, and the perovskite layer is modified by the above-mentioned general processing method.

[0016] In a fourth aspect, the present invention further provides a method for manufacturing a perovskite photoelectric device, comprising:

[0017] The step of forming a first transmission layer;

[0018] A step of forming a perovskite layer on the surface of the first transmission layer;

[0019] The perovskite layer is modified by the general treatment method mentioned above;

[0020] The step of forming a second transmission layer on the surface of the modified perovskite layer.

[0021] Based on the above technical solution, compared with the prior art, the beneficial effects of the present invention at least include:

[0022] The universal treatment liquid and treatment method provided by the present invention utilize the selective solubility of perovskite materials in polar solvents and non-polar solvents to react with various defects or non-ideal phases formed in the perovskite preparation process, remove the defects and harmful non-ideal phases that cause perovskite degradation, and significantly improve the performance of the perovskite material. Moreover, since its working principle does not change with the type and composition of the perovskite material, it has a significant effect on perovskite materials of almost all compositions currently available.

[0023] At the same time, since the specific groups in the universal treatment liquid provided by the present invention have extremely strong reactivity, the treatment method provided by the present invention has an extremely short treatment time and low requirements for treatment temperature and treatment equipment, which significantly improves the treatment efficiency of the perovskite layer and reduces the treatment cost, and is very conducive to promotion and application in the industry.

[0024] The above description is only an overview of the technical solution of the present invention. In order to enable those skilled in the art to more clearly understand the technical means of the present application and implement them according to the contents of the specification, the following is a description of the preferred embodiments of the present invention in conjunction with detailed drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic flow chart of a general method for treating a perovskite layer provided in a typical embodiment of the present invention;

[0026] Figure 2a It is a current efficiency test diagram of a perovskite device provided by a typical implementation case of the present invention and a comparative case;

[0027] Figure 2b It is a test diagram of the operating life of the perovskite device provided by a typical implementation case of the present invention and a comparative case;

[0028] Figure 3 It is a schematic diagram of the principle of a general processing method provided by a typical implementation case of the present invention and a comparative case. DETAILED DESCRIPTION

[0029] In the prior art, a general processing method for perovskite layer is provided, but this method requires a long reaction time and can only be performed by immersion reaction, a high reaction temperature and requires specific reaction equipment, and is therefore not conducive to large-scale industrial applications.

[0030] In view of the deficiencies in the prior art, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. The technical solution, its implementation process and principle will be further explained as follows.

[0031] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Therefore, the protection scope of the present invention is not limited to the specific embodiments disclosed below.

[0032] Moreover, relational terms such as “first” and “second” are merely used to distinguish one component or method step from another with the same name, but do not necessarily require or imply any such actual relationship or order between these components or method steps.

[0033] The inventors have found that in a universal treatment solution, the reaction activity of amine groups and sulfonate groups is much greater than that of polar solvents in the prior art. Therefore, based on the above findings, an embodiment of the present invention provides a universal treatment solution for a perovskite layer, comprising a polar solvent and a non-polar solvent, wherein the polar solvent contains amine groups and / or sulfonate groups.

[0034] In some embodiments, the polar solvent may include any one or a combination of two or more of n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, pentanesulfonic acid, hexanesulfonic acid, and heptanesulfonic acid, but is not limited thereto.

[0035] In some embodiments, the volume fraction of the polar solvent in the universal treatment solution may be 0.01-5%.

[0036] In some embodiments, when the polar solvent contains only sulfonate groups, the volume fraction of the polar solvent may be 0.01-2%, and when it contains only amine groups, the volume fraction may be 0.01-5%.

[0037] In some embodiments, the non-polar solvent includes benzene and / or benzene derivatives.

[0038] See also Figure 1 The embodiment of the present invention also provides a general processing method for a perovskite layer, comprising the following steps:

[0039] 1) Providing a perovskite layer.

[0040] 2) contacting the perovskite layer with the universal treatment solution described in any of the above embodiments to perform a modification treatment, wherein the modification treatment time is 2-10 seconds.

[0041] 3) removing the common treatment solution from the modified perovskite layer.

[0042] In some embodiments, the temperature of the modification treatment is 0-50°C.

[0043] In some embodiments, step 3) may specifically include the following steps:

[0044] The modified perovskite layer is dried.

[0045] Or, the modified perovskite layer is annealed.

[0046] In some embodiments, the annealing treatment is performed at a temperature of 60-150° C. and for a time of 10-600 s.

[0047] Figure 3The principle of the above treatment method is shown. This universal treatment solution for improving the performance of perovskite can utilize the selective solubility of perovskite materials in polar solvents and non-polar solvents to react with various defects or non-ideal phases formed during the preparation of perovskite, remove defects and harmful non-ideal phases that cause perovskite degradation, and significantly improve the performance of perovskite materials. Since its working principle does not change with the type and composition of perovskite materials, it has a significant effect on perovskite materials of almost all current compositions.

[0048] As some typical application examples of the above technical solutions, the embodiments of the present invention provide a general liquid treatment method for improving the stability of perovskite, wherein the main components of the treatment liquid used include polar solvent and non-polar solvent. The polar solvent is mainly organic small molecules or ions containing amine or sulfonate groups, and the non-polar solvent is mainly composed of benzene and its derivatives. The relative proportion of the polar and non-polar parts in the treatment liquid should be controlled within a specific range to ensure the treatment effect.

[0049] When using the universal treatment solution, the pre-prepared perovskite layer can be completely immersed in the treatment solution, and after the reaction is fully reacted for a few seconds, it can be taken out and the wet perovskite surface can be dried. Annealing treatment can be used as an optional subsequent treatment method to accelerate the volatilization of the treatment solution and shorten the treatment time. The universal treatment solution can be used for perovskite materials with various components.

[0050] The treatment method of the treatment liquid is not limited to immersion. Since the treatment time is extremely short, it is not necessary to completely immerse the perovskite layer in the reaction liquid for a long time (10-120 minutes) as in the prior art, but the treatment liquid can pass through the surface of the perovskite layer. In addition, it does not need to be heated (80-200°C) and kept warm as in the prior art. It can fully react at room temperature or even below room temperature, and there is no need to match a special reaction container. Therefore, the same technical effect can be achieved by using simple treatment methods such as spraying and dripping. The technical method provided by the prior art cannot achieve the efficiency and convenience of the treatment method provided by the embodiment of the present invention, and its cost is naturally much higher than that of the present invention.

[0051] As a more specific example, Figure 1 As shown in the figure, in a typical process of treating perovskite materials with a general treatment solution, the pre-prepared perovskite layer is completely dripped and immersed in 300 microliters of mixed treatment solution, and after the reaction is sufficient, it is taken out and the wet perovskite surface is dried. Annealing is an optional subsequent treatment method that can accelerate the volatilization of the treatment solution and shorten the treatment time. The annealing temperature can be selected in the same or similar range as the perovskite annealing temperature, usually between 60 and 150°C.

[0052] In a typical case, Figure 2a and Figure 2b As shown, by treating the perovskite material with a general treatment solution at a concentration of 1%, the current efficiency of the prepared perovskite light-emitting diode can be increased to more than twice that of the untreated device, and the operating life is increased by more than two orders of magnitude.

[0053] An embodiment of the present invention also provides a perovskite photoelectric device, comprising a first transmission layer, a perovskite layer and a second transmission layer, wherein the perovskite layer is arranged between the first transmission layer and the second transmission layer, and the perovskite layer is modified by the general processing method provided in any of the above embodiments.

[0054] The present invention also provides a method for manufacturing a perovskite photoelectric device, comprising the following steps:

[0055] The step of forming a first transmission layer.

[0056] The step of forming a perovskite layer on the surface of the first transmission layer.

[0057] The perovskite layer is modified by using the general treatment method provided in any of the above embodiments.

[0058] The step of forming a second transmission layer on the surface of the modified perovskite layer.

[0059] The technical solution of the present invention is further described in detail below through several embodiments and in conjunction with the accompanying drawings. However, the selected embodiments are only used to illustrate the present invention, and do not limit the scope of the present invention.

[0060] Example 1

[0061] This embodiment illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, as shown below:

[0062] A glass substrate with an indium tin oxide electrode prepared in advance is provided, wherein the electrode thickness is 100 nm and the glass thickness is 0.7 cm.

[0063] A hole transport layer of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) material with a thickness of 50 nm was formed on the substrate by spin coating and drying.

[0064] The perovskite layer of the formamidinium lead bromide perovskite material with a thickness of 50 nm is formed by spin coating and drying.

[0065] A universal treatment solution is prepared by mixing an amine-based polar solvent n-hexylamine and benzene, in which the volume fraction of the amine-based polar solvent is 0.01%. Then 300 μL of the treatment solution is dropwise applied to the perovskite layer, kept at room temperature (about 25°C) for 5 seconds, and then annealed at 80°C for 60 seconds to form a treated perovskite layer.

[0066] An electron transport layer of 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene material with a thickness of 40 nm was formed by vapor deposition on the perovskite layer.

[0067] Electrodes are formed to electrically connect the hole transport layer and the electron transport layer, respectively, and finally a perovskite light-emitting diode is formed.

[0068] Example 2

[0069] This embodiment illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of embodiment 1, except that:

[0070] The volume fraction of the amine-based polar solvent in the universal treatment solution is 1%.

[0071] Example 3

[0072] This embodiment illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of embodiment 1, except that:

[0073] The volume fraction of the amine-based polar solvent in the universal treatment solution is 5%.

[0074] Comparative Example 1-1

[0075] This comparative example illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of Example 1, except that:

[0076] No amine-based polar solvents are added to the general treatment fluid.

[0077] Comparative Example 1-2

[0078] This comparative example illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of Example 1, except that:

[0079] The volume fraction of the amine-based polar solvent in the universal treatment solution is 10%.

[0080] The light-emitting diodes provided in the above-mentioned embodiments 1-3 and comparative examples 1-1 and 1-2 were subjected to luminous efficiency tests and operating life tests, wherein the luminous efficiency test is to scan the maximum luminous efficiency of the light-emitting diode in the voltage range of 0 to 10 volts under the environmental conditions of room temperature (about 25°C) and medium humidity (30 to 80%), and the operating life test is to adjust the voltage so that the brightness reaches the initial brightness under the environmental conditions of room temperature (about 25°C) and medium humidity (30 to 80%), and ensure the life of the light-emitting diode when it operates under the corresponding constant current.

[0081] Table 1 below shows the relationship between the maximum efficiency of the treated perovskite light-emitting diodes and the concentration of the treatment solution used in the above-mentioned embodiments and comparative examples.

[0082] Table 1 Relationship between the maximum efficiency of the treated perovskite light-emitting diode and the concentration of the treatment solution

[0083]

[0084]

[0085] It can be seen that in the range of volume concentration of 1 part per ten thousand to 5%, the maximum efficiency of the treated perovskite light-emitting diode is improved compared with that of the untreated one. Therefore, in actual use, the relative proportion of the polar and non-polar parts of the amine group should be controlled within a specific range to ensure the best treatment effect.

[0086] Regarding the luminous efficiency and operating life, the test results of the light emitting diodes of Example 2 and Comparative Example 1 are as follows: Figure 2a and Figure 2b As shown, it can be seen that by treating the perovskite material with the universal treatment solution of 1% concentration in Example 2, the current efficiency of the prepared perovskite light-emitting diode can be increased to more than twice that of the untreated device, and the operating life is increased by more than two orders of magnitude.

[0087] Example 4

[0088] This embodiment illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of embodiment 1, except that:

[0089] The amine-based polar solvent in the general treatment solution is replaced by a sulfonate-based polar solvent, and its compound name is heptanesulfonic acid.

[0090] Example 5

[0091] This embodiment illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of embodiment 4, except that:

[0092] The volume fraction of the sulfonate polar solvent in the universal treatment liquid is 1%.

[0093] Example 6

[0094] This embodiment illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of embodiment 4, except that:

[0095] The volume fraction of the sulfonate polar solvent in the universal treatment liquid is 2%.

[0096] Comparative Example 2-1

[0097] This comparative example illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of Example 4, except that:

[0098] No sulfonate polar solvent is added to the general treatment solution.

[0099] Comparative Example 2-2

[0100] This comparative example illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of Example 4, except that:

[0101] The volume fraction of the sulfonate polar solvent in the universal treatment liquid is 5%.

[0102] Comparative Examples 2-3

[0103] This comparative example illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of Example 4, except that:

[0104] The volume fraction of the sulfonate polar solvent in the universal treatment liquid is 10%.

[0105] The light-emitting diodes provided in the above-mentioned embodiments 4-6 and comparative examples 2-1, 2-2, and 2-3 were subjected to luminous efficiency tests and operating life tests. The following Table 2 shows the relationship between the maximum efficiency of the treated perovskite light-emitting diodes in the above-mentioned embodiments and comparative examples and the concentration of the treatment solution used.

[0106] Table 1 Relationship between the maximum efficiency of the treated perovskite light-emitting diode and the concentration of the treatment solution

[0107] Sulfonate molecular content (%vol) Maximum efficiency of light emitting diode (%) 0 12.1 0.01 14.1 1 23.9 2 15.8 5 2.3 10 0.1

[0108] It can be seen that in the range of volume concentration of 1 / 10,000 to 2 / 10,000, the maximum efficiency of the treated perovskite light-emitting diode is improved compared with that of the untreated one. Therefore, in actual use, the relative proportion of the polar and non-polar parts of the sulfonate group should be controlled within a specific range to ensure the best treatment effect.

[0109] Comparative Example 3

[0110] Suggestions:

[0111] A common mixed treatment liquid in the prior art was used: a mixed solvent of chlorobenzene and dimethylformamide, in which the volume content of dimethylformamide was 1%. The same treatment time and treatment temperature as in Example 1 were used, and the same drop coating method (300 μl) was used. Since its reaction activity was significantly lower than that of the present invention, its maximum efficiency was only 13.4%, far lower than 27.8% of Example 2; at the same time, its operating life was 1 / 20 of that of Example 2.

[0112] Example 7

[0113] This comparative example illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of Example 1, except that:

[0114] The material of the perovskite layer is replaced with methylamine lead bromide perovskite.

[0115] After the treatment, the luminous efficiency and operating life of the perovskite device provided in this embodiment are still greatly improved similar to those in Example 1.

[0116] Example 8

[0117] This comparative example illustrates a preparation process of a perovskite device, which includes a treatment process for a perovskite layer, which is substantially the same as that of Example 1, except that:

[0118] The material of the perovskite layer is replaced with cesium lead iodine perovskite.

[0119] After the treatment, the luminous efficiency and operating life of the perovskite device provided in this embodiment are still greatly improved similar to those in Example 1.

[0120] Based on the above embodiments and comparative examples, it is clear that the universal treatment solution and treatment method provided in the embodiments of the present invention utilize the selective solubility of perovskite materials in polar solvents and non-polar solvents to react with various defects or non-ideal phases formed during the preparation of perovskite, remove defects and harmful non-ideal phases that cause perovskite degradation, and significantly improve the performance of perovskite materials. Since its working principle does not change with the type and composition of perovskite materials, it has a significant effect on perovskite materials of almost all current compositions.

[0121] At the same time, since the specific groups in the general treatment liquid and treatment method provided in the embodiments of the present invention have extremely strong reactivity, the treatment method provided by the present invention has an extremely short treatment time and low requirements for treatment temperature and treatment equipment, which significantly improves the treatment efficiency of the perovskite layer and reduces the treatment cost, and is very conducive to promotion and application in the industry.

[0122] It should be understood that the above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A general method for treating a perovskite layer, characterized in that: include: 1) Providing a perovskite layer; 2) contacting the perovskite layer with a universal treatment solution to perform a modification treatment, wherein the temperature of the modification treatment is 0-50° C. and the time is 2-10 s; 3) removing the common treatment solution from the modified perovskite layer; The universal treatment liquid includes a polar solvent and a non-polar solvent, and the volume fraction of the polar solvent is 0.01-2%; the polar solvent includes any one or a combination of two or more of pentanesulfonic acid, hexanesulfonic acid and heptanesulfonic acid, and only contains one polar group, namely, sulfonate; the non-polar solvent includes benzene and / or benzene derivatives.

2. The general processing method according to claim 1, characterized in that: Step 3) specifically includes: Drying the modified perovskite layer; Or, the modified perovskite layer is annealed.

3. The general processing method according to claim 2, characterized in that: The annealing treatment is performed at a temperature of 60-150° C. and for a time of 10-600 s.

4. A method for manufacturing a perovskite photoelectric device, characterized in that: include: The step of forming a first transmission layer; A step of forming a perovskite layer on the surface of the first transmission layer; The perovskite layer is modified by the general treatment method described in any one of claims 1 to 3; The step of forming a second transmission layer on the surface of the modified perovskite layer.

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