CN113517405A - High-performance self-powered perovskite type photoelectric detector based on CsI ion doped hole transport layer and preparation method thereof - Google Patents
High-performance self-powered perovskite type photoelectric detector based on CsI ion doped hole transport layer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of photoelectric detectors, in particular to a high-performance self-powered perovskite type photoelectric detector based on a CsI ion doped hole transport layer and a preparation method thereof. A high-performance self-powered perovskite type photoelectric detector based on a CsI ion doped hole transport layer mainly comprises a substrate, a conductive cathode, an electron transport layer, a perovskite photoactive layer, a hole transport layer, a modification layer and a metal anode which are sequentially arranged, wherein the hole transport layer is made of a Spiro-OMeTAD material. According to the invention, a solution treatment mode is adopted, a small amount of CsI is introduced into a Spiro-OMeTAD solution, aggregation and hydrolysis of a Spiro-OMeTAD film are effectively inhibited, pinholes and holes are reduced, the carrier extraction capability and mobility of a hole transport layer are enhanced, and the detection rate and stability of the photoelectric detector are obviously improved. The preparation process is simple, and the device cost is greatly reduced.
Description
Technical Field
The invention relates to the technical field of photoelectric detectors, in particular to a high-performance self-powered perovskite type photoelectric detector based on a CsI ion doped hole transport layer and a preparation method thereof.
Background
Perovskite type photoelectric detectors (PPD) combine the advantages of organic-inorganic perovskite materials, have excellent photoelectric properties and simple solution processing technology, become revolutionary photoelectric devices, and are widely applied in various fields. Since the first perovskite cells came into existence, in recent years, the best perovskite solar cells have reached a power conversion efficiency of 25.5% or more, comparable to that of conventional silicon solar cells. With the development of perovskite solar cells, perovskite materials have great development potential in the aspects of light emitting diodes, photodetectors, lasers and the like. In particular, as more and more research is focused on the development of perovskite solar cells, few research attempts have been made to use perovskite materials for manufacturing photodetectors, and the patent focuses on developing a high-performance self-powered perovskite-type photodetector. The traditional photoelectric detectors made of Si, GaN, organic materials and nano photoelectric materials have complex manufacturing processes, need to work at low temperature, are expensive, have low quantum efficiency and poor charge-carrier mobility, and prevent the detection performance from being further improved. Perovskite thin films can be made from low temperature solutions and therefore have the great commercial advantage of low cost. In the planar structure titanium ore type photoelectric detector, the contact property of the interface of the hole transport layer and the perovskite layer has great influence on the performance of the device. At present, a great deal of research work is still needed on how to reduce the charge accumulation of the interface of the titanium ore type photoelectric detector, improve the charge extraction and transmission capability and reduce the dark current. Therefore, it is necessary to find a hole transport material having high chemical stability and high hole mobility, which is a necessary condition for realizing a highly efficient and long-term stable detector.
Disclosure of Invention
To solve the above problems, it is an object of the present invention to provide a high-performance self-powered perovskite-type photodetector based on a CsI ion-doped hole transport layer, which employs a simple solution process for CsI ion-doped Spiro-OMeTAD as a hole transport layer.
The purpose of the invention is realized by the following technical scheme:
a high-performance self-powered perovskite type photoelectric detector based on a CsI ion doped hole transport layer mainly comprises a substrate, a conductive cathode, an electron transport layer, a perovskite photoactive layer, a hole transport layer, a modification layer and a metal anode which are sequentially arranged, wherein the hole transport layer is made of a Spiro-OMeTAD material, and the England name of the hole transport layer is as follows:
2,2',7,7'-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spiro-bifluorene。
further, the substrate is a glass substrate or a PET plastic substrate; the conductive cathode material is ITO or FTO.
Further, the electron transport layer is made of SnO2The thickness is 20-40 nm;
the perovskite photoactive layer is made of MAPbI3The thickness is 400-550 nm;
the thickness of the hole transport layer material Spiro-OMeTAD is 180-220 nm;
the material of the decorative layer is MoO3The thickness is 8-10 nm;
the metal anode is one or more of Al, Ag or Cu, and the thickness of the metal anode is 80-100 nm.
Another objective of the present invention is to provide a method for preparing a high-performance self-powered perovskite-type photodetector based on a CsI ion-doped hole transport layer, wherein the method comprises the following steps:
1) cleaning, drying and ultraviolet ozone treatment are carried out on a substrate consisting of a substrate and a conductive cathode;
2) and carrying out gradient spin coating on the surface of the substrate to obtain SnO2Carrying out solution and gradient annealing to prepare an electron transport layer;
3) gradient spin coating MAPbI on the electron transport layer3Annealing the precursor solution to obtain a perovskite photoactive layer;
4) spin-coating CsI-doped Spiro-OMeTAD solution on the perovskite photoactive layer, and annealing to obtain a hole transport layer;
5) sequentially evaporating MoO on the hole transport layer3And modifying the layer and the metal anode to obtain the required perovskite photoelectric detector.
Further, the cleaning in the step 1) is to use a detergent, an acetone solution, isopropyl alcohol, alcohol and deionized water to perform ultrasonic cleaning on the substrate in sequence, wherein each ultrasonic cleaning is performed for 10-20 minutes.
Further, step 2) SnO described in step 2)2The solution is aqueous colloidal dispersion with solute concentration of 2-3%, and the gradient spin coating and the gradient annealing are both carried out in an air environment;
the procedure of the gradient spin coating is as follows: spin-coating at a rotating speed of 2500-3000 r/min for 10-20 s, and changing the rotating speed into spin-coating at 6000-7000 r/min for 45-60 s;
the gradient annealing comprises the following steps: annealing at 100-130 ℃ for 10-25 min and at 150-180 ℃ for 25-35 min.
Further, the MAPbI in step 3)3The total concentration of the precursor solution is 610-915 mg/mL, and MAPbI is prepared3The raw material PbI used2The molar ratio to MAI is 1: 1; the solvent is DMF (N, N-dimethylformamide) and DMSO (dimethyl sulfoxide), and the volume ratio of the DMF to the DMSO is 8: 2;
the procedure of the gradient spin coating is as follows: spin-coating at 2000-3500 rpm for 10-15 s, and changing the rotation speed to 4000-6000 rpm for 50-55 s;
the annealing temperature is 80-100 ℃, and the annealing time is 20-30 min.
Further, the CsI doping concentration in the Spiro-OMeTAD solution in the step 4) is A, and A is more than 0 and less than or equal to 0.8 wt%;
wherein the total concentration of the Spiro-OMeTAD solution is 70-100 mg/mL, and the solvent is chlorobenzene;
the Spiro-OMeTAD solution comprises 17.5 mu L of Li-TFSI and 28.8 mu L of TBP;
the spin coating procedure is as follows: spin coating at 3000 rpm for 40s in a nitrogen atmosphere.
Further, the evaporation in the step 5) is vacuum evaporation, and the air pressure in the vacuum evaporation machine is controlled to be less than 5 multiplied by 10- 4Pa。
Compared with the prior art, the invention has the beneficial effects that:
1. the device dark current is low. According to the invention, the carrier transport capability of the hole transport layer is improved by using the CsI ion doped Spiro-OMeTAD as the hole transport layer, and the leakage current in the device operation is reduced, so that the dark current is greatly reduced. The device prepared by the method has low dark current density which can reach 9.91 multiplied by 10 under the bias voltage of 0.0V-9A/cm2。
2. The external quantum efficiency is high. The technology that CsI ions are doped with Spiro-OMeTAD to serve as a hole transport layer effectively inhibits aggregation and crystallization of a Spiro-OMeTAD film, improves film quality of the hole transport layer, enhances extraction and transport of photo-generated charges, is self-powered under the bias of 0V, and has external quantum efficiency as high as 88%.
3. The device has high responsivity and detectivity. The technology that CsI ions are doped with Spiro-OMeTAD to serve as the hole transport layer is beneficial to improving contact and charge accumulation between the hole transport layer and the perovskite layer interface, so that the responsivity of the device is improved, the responsivity and the detectivity of the manufactured device are high, the responsivity can reach 0.48A/W under 0V bias voltage, and the detectivity is as high as 2.7 multiplied by 1013Jones。
4. The stability of the device is high. According to the invention, a solution treatment mode is adopted, a small amount of CsI is introduced into a Spiro-OMeTAD solution, the aggregation and hydrolysis of a Spiro-OMeTAD film are effectively inhibited, pinholes and holes are reduced, the carrier extraction capability and the mobility of the hole transport layer are enhanced, and the detection rate and the stability of the photoelectric detector are obviously improved. The preparation process is simple, and the device cost is greatly reduced. And the doped device improves the carrier extraction capability and mobility of the hole transport layer, reduces the dark current of the device, and improves the external quantum efficiency and the responsivity within the visible light range. After the photovoltaic detector is placed in a nitrogen-filled glove box without special packaging for more than two months, the EQE still keeps the original 98.1 percent.
5. The response speed is high. The detector has broadband response from near ultraviolet to near infrared (300-800 nm), and the rising response time is 54.1 mu s; the falling response time was 10.7. mu.s.
Drawings
FIG. 1 is a graph of dark current density for a high performance self-powered perovskite photodetector based on a CsI ion doped hole transport layer according to example 1;
FIG. 2 is a graph of the external quantum efficiency of the high-performance self-powered perovskite-type photodetector based on the CsI ion-doped hole transport layer under a bias voltage of 0V in example 1;
FIG. 3 is the spectral responsivity of the high performance self-powered perovskite-type photodetector based on the CsI ion-doped hole transport layer under a bias of 0V in example 1;
FIG. 4 shows the detectivity of the high performance self-powered perovskite-type photodetector based on the CsI ion-doped hole transport layer under a bias voltage of 0V in example 1;
FIG. 5 is a graph of dark current density at 0V bias for a self-powered perovskite photodetector without a CsI ion-doped hole transport layer of comparative example 1;
FIG. 6 is a graph of the external quantum efficiency at 0V bias for a self-powered perovskite photodetector without a CsI ion-doped hole transport layer of comparative example 1;
FIG. 7 is a graph of the spectral responsivity at 0V bias for a self-powered perovskite photodetector without a CsI ion-doped hole transport layer of comparative example 1;
fig. 8 is a graph of the detectivity of a self-powered perovskite photodetector without a CsI ion doped hole transport layer at 0V bias for comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited to the scope of the examples. These examples are intended to illustrate the invention only and are not intended to limit the scope of the invention. In addition, various modifications may occur to those skilled in the art upon reading the present disclosure, and such equivalent variations are within the scope of the present invention as defined in the appended claims.
The following embodiments provide a high-performance self-powered perovskite type photoelectric detector based on a CsI ion doped hole transport layer, which comprises a substrate, a conductive cathode, an electron transport layer, a perovskite photoactive layer, a hole transport layer, a modification layer and a metal anode which are sequentially arranged from bottom to top. The thickness of the hole transport layer material Spiro-OMeTAD is 180-220 nm.
Example 1
A preparation method of a high-performance self-powered perovskite type photoelectric detector based on a CsI ion doped hole transport layer comprises the following steps:
(1) selecting glass as a substrate, using ITO as a conductive cathode, and sequentially cleaning and pretreating a substrate consisting of the glass substrate and the ITO conductive cathode, wherein the cleaning and pretreating method comprises the following steps: sequentially putting a substrate into a detergent, an acetone solution, isopropyl alcohol, alcohol and deionized water for ultrasonic treatment for 15min, cleaning, blow-drying by using nitrogen, drying, and treating the surface of the substrate by using ultraviolet ozone for 15min for later use;
(2) and spin-coating an electron transport layer on the surface of the cleaned substrate. SnO2The solution is aqueous colloidal dispersion with solute concentration of 2%, SnO is added2The solution was spin coated and annealed in an air environment. The procedure of the gradient spin coating is as follows: the spin speed was 2500 rpm for 10s and changed to 6000 rpm for 45 s. The gradient annealing comprises the following steps: annealing at 100 ℃ for 10min and at 150 ℃ for 25min to obtain the electron transport layer with the thickness of 20-40 nm.
(3) The substrate on which the electron transport layer was spin-coated was transferred to a glove box, and 1mmol of lead iodide and 1mmol of iodomethylamine (molar ratio 1:1) were weighed and dissolved in a mixed solvent of N, N-dimethylformamide (DMF, 0.8mL) and dimethylsulfoxide (DMSO, 0.2mL) in a volume of 1mL to obtain perovskite MAPbI having a total concentration of 610mg/mL in the solution3And (3) precursor solution. In a nitrogen-filled glove boxMAPbI3The precursor solution is spin-coated on the electron transport layer, and the spin-coating procedure is as follows: the spin speed was changed to 3000 rpm for 10s, and then to 5000 rpm for 50 s. And then annealing the substrate at 100 ℃ for 20min to prepare the perovskite light active layer with the thickness of 400-550 nm.
(4) 85mg of Spiro-OMeTAD and 0.4 wt% CsI were dissolved in 1ml of chlorobenzene solvent, and the additives: 17.5. mu.l of Li-TFSI (520mg/mL acetonitrile) and 28.8. mu.L of TBP were stirred at room temperature for 8 hours to obtain a Spiro-OMeTAD mixed solution having a total concentration of 85 mg/mL. The resulting Spiro-OMeTAD mixed solution was spin coated on the perovskite photoactive layer using the following spin coating procedure: spin coating at 3000 rpm for 40s in a nitrogen atmosphere. And then transferring the film to an air environment with the relative humidity of 25% at 25 ℃ for natural oxidation drying for 8 hours to obtain the CsI ion doped hole transport layer with the thickness of 180-220 nm.
(5) Placing the substrate with cathode, electron transport layer, perovskite photoactive layer and hole transport layer into evaporation chamber of high vacuum evaporation plating machine, and evaporating MoO with thickness of 10nm on the perovskite photoactive layer3(ii) a The pressure in the vacuum evaporator was 4.5X 10-4And controlling the film thickness to be 8-10 nm under a Pa high vacuum environment. And finally, evaporating the copper electrode, and controlling the film thickness to be 80-100 nm.
The final product is glass substrate/ITO/SnO2/CH3NH3PbI3/Spiro-OMeTAD(CsI 0.4wt％)/MoO3Perovskite photoelectric detector of/Cu. As shown in FIGS. 1 to 4, the dark current of the perovskite photodetector obtained in this example was 9X 10 at a bias of 0.0V-10A/cm2The external quantum efficiency is up to 88%, the responsivity of the device at 740nm is 0.48A/W, and the highest detectivity is 2.7 multiplied by 1013Jones。
Example 2
Referring to example 1, only step (4) was changed to dissolve 85mg of Spiro-OMeTAD and 0.2 wt% of CsI in 1ml of chlorobenzene solvent, and the conditions of other process parameters were the same as those of example 1, thereby obtaining a glass substrate/ITO/SnO structure2/CH3NH3PbI3/Spiro-OMeTAD(CsI 0.2wt％)/MoO3Perovskite photoelectric detector of/Cu. The deviceThe external quantum efficiency of the device at 0V bias reached 79% and the responsivity at 740nm was 0.41A/W.
Example 3
Referring to example 1, only step (4) was changed to dissolve 85mg of Spiro-OMeTAD and 0.6 wt% CsI in 1ml of chlorobenzene solvent, and the conditions of other process parameters were the same as those of example 1, thereby obtaining a glass substrate/ITO/SnO structure2/CH3NH3PbI3/Spiro-OMeTAD(CsI 0.6wt％)/MoO3Perovskite photoelectric detector of/Cu. The external quantum efficiency of the device under 0V bias reaches 83%, and the responsivity at 740nm is 0.43A/W.
Example 4
Referring to example 1, only step (4) was changed to dissolve 85mg of Spiro-OMeTAD and 0.8 wt% of CsI in 1ml of chlorobenzene solvent, and the conditions of other process parameters were the same as those of example 1, thereby obtaining a glass substrate/ITO/SnO structure2/CH3NH3PbI3/Spiro-OMeTAD(CsI 0.8wt％)/MoO3Perovskite photoelectric detector of/Cu. The external quantum efficiency of the device under 0V bias reaches 81%, and the responsivity at 740nm is 0.42A/W.
Example 5
A preparation method of a high-performance self-powered perovskite type photoelectric detector based on a CsI ion doped hole transport layer comprises the following steps:
(1) selecting PET plastic as a substrate, using FTO as a conductive cathode, and sequentially cleaning and pretreating a base consisting of the substrate and the conductive cathode, wherein the cleaning and pretreating method comprises the following steps: sequentially putting a substrate into a detergent, an acetone solution, isopropyl alcohol, alcohol and deionized water for ultrasonic treatment for 10min, cleaning, blow-drying by using nitrogen, drying, and treating the surface of the substrate by using ultraviolet ozone for 10min for later use;
(2) and spin-coating an electron transport layer on the surface of the cleaned substrate. SnO2The solution is aqueous colloidal dispersion with solute concentration of 2.5%, SnO is added2The solution was spin coated and annealed in an air environment. The procedure of the gradient spin coating is as follows: the rotation speed was 2600 rpm for 15s, and the rotation speed was changed to 6500 rpm for 50 s. The gradient annealing comprises the following steps: temperature 1Annealing at 20 ℃ for 15min and at 160 ℃ for 30min to obtain the electron transport layer with the thickness of 20-40 nm.
(3) The substrate on which the electron transport layer was spin-coated was transferred to a glove box, and 1.5mmol of lead iodide and 1.5mmol of iodomethylamine (molar ratio 1:1) were weighed and dissolved in a mixed solvent of N, N-dimethylformamide (DMF, 0.8mL) and Dimethyl sulfoxide (DMSO, 0.2mL) in a volume of 1mL to obtain a perovskite MAPbI3 precursor solution having a total solution concentration of 915 mg/mL. MAPbI was placed in a nitrogen-filled glove box3The precursor solution is spin-coated on the electron transport layer, and the spin-coating procedure is as follows: the spin speed was 2000 rpm for 12s, and then changed to 4000 rpm for 52 s. And then annealing the substrate at 100 ℃ for 20min to prepare the perovskite light active layer with the thickness of 400-550 nm.
(4) 70mg of Spiro-OMeTAD and 0.4 wt% CsI were dissolved in 1ml of chlorobenzene solvent, and the additives: 17.5. mu.l of Li-TFSI (520mg/mL acetonitrile) and 28.8. mu.L of TBP were stirred at room temperature for 8 hours to obtain a Spiro-OMeTAD mixed solution having a total concentration of 70 mg/mL. The resulting Spiro-OMeTAD mixed solution was spin coated on the perovskite photoactive layer using the following spin coating procedure: spin coating at 3000 rpm for 40s in a nitrogen atmosphere. And then transferring the film to an air environment with the relative humidity of 25% at 25 ℃ for natural oxidation drying for 8 hours to obtain the CsI ion doped hole transport layer with the thickness of 180-220 nm.
(5) Placing the substrate with cathode, electron transport layer, perovskite photoactive layer and hole transport layer into evaporation chamber of high vacuum evaporation plating machine, and evaporating MoO with thickness of 10nm on the perovskite photoactive layer3(ii) a The pressure in the vacuum evaporator was 4.5X 10-4And controlling the film thickness to be 8-10 nm under a Pa high vacuum environment. And finally, evaporating an Al electrode, and controlling the film thickness to be 80-100 nm.
Finally obtaining the structure of PET plastic substrate/FTO/SnO2/CH3NH3PbI3/Spiro-OMeTAD(CsI 0.4wt％)/MoO3Perovskite photoelectric detector of/Al.
Example 6
A preparation method of a high-performance self-powered perovskite type photoelectric detector based on a CsI ion doped hole transport layer comprises the following steps:
(1) selecting glass as a substrate, using ITO as a conductive cathode, and sequentially cleaning and pretreating a substrate consisting of the substrate and the conductive cathode, wherein the cleaning and pretreating method comprises the following steps: sequentially putting a substrate into a detergent, an acetone solution, isopropyl alcohol, alcohol and deionized water for ultrasonic treatment for 20min, cleaning, blow-drying by using nitrogen, drying, and treating the surface of the substrate by using ultraviolet ozone for 20min for later use;
(2) and spin-coating an electron transport layer on the surface of the cleaned substrate. SnO2The solution is aqueous colloidal dispersion with solute concentration of 3%, SnO is added2The solution was spin coated and annealed in an air environment. The procedure of the gradient spin coating is as follows: the spin speed was 3000 rpm for 20s, and was changed to 7000 rpm for 60 s. The gradient annealing comprises the following steps: annealing at 130 ℃ for 25min and at 180 ℃ for 35min to obtain the electron transport layer with the thickness of 20-40 nm.
(3) The substrate on which the electron transport layer was spin-coated was transferred to a glove box, and 1.5mmol of lead iodide and 1.5mmol of iodomethylamine (molar ratio 1:1) were weighed and dissolved in a mixed solvent of N, N-dimethylformamide (DMF, 0.8mL) and Dimethyl sulfoxide (DMSO, 0.2mL) in a volume of 1mL to obtain a perovskite MAPbI having a total solution concentration of 915mg/mL3And (3) precursor solution. MAPbI was placed in a nitrogen-filled glove box3The precursor solution is spin-coated on the electron transport layer, and the spin-coating procedure is as follows: the rotation speed was 3500 rpm for 15s, and then changed to 6000 rpm for 55 s. And then annealing the substrate at 90 ℃ for 30min to prepare the perovskite light active layer with the thickness of 400-550 nm.
(4) 100mg of Spiro-OMeTAD and 0.4 wt% CsI were dissolved in 1ml of chlorobenzene solvent, and the additives: mu.l of Li-TFSI (520mg/mL acetonitrile) and 28.8. mu.L of TBP were stirred at room temperature for 8 hours to obtain a Spiro-OMeTAD mixed solution having a total concentration of 100 mg/mL. The resulting Spiro-OMeTAD mixed solution was spin coated on the perovskite photoactive layer using the following spin coating procedure: spin coating at 3000 rpm for 40s in a nitrogen atmosphere. And then transferring the film to an air environment with the relative humidity of 25% at 25 ℃ for natural oxidation drying for 8 hours to obtain the CsI ion doped hole transport layer with the thickness of 180-220 nm.
(5) Will be provided withPlacing the substrate with cathode, electron transport layer, perovskite photoactive layer and hole transport layer into evaporation chamber of high vacuum evaporation plating machine, and evaporating MoO with thickness of 10nm on the perovskite photoactive layer3(ii) a The pressure in the vacuum evaporator was 4.5X 10-4And controlling the film thickness to be 8-10 nm under a Pa high vacuum environment. And finally, evaporating an Ag electrode, and controlling the film thickness to be 80-100 nm.
The final product is glass substrate/ITO/SnO2/CH3NH3PbI3/Spiro-OMeTAD(CsI 0.4wt％)/MoO3Perovskite photoelectric detector of/Ag.
Comparative example 1
The hole transport layer of the comparative example is not introduced with the CsI ion material, and the CsI ion material is used for verifying the performance of the high-performance self-powered perovskite type photoelectric detector based on the CsI ion doped hole transport layer. Referring to example 1, only step (4) was changed to dissolve 85mg of Spiro-OMeTAD and 0.0 wt% of CsI in 1ml of chlorobenzene solvent, and the conditions of other process parameters were the same as those of example 1, thereby obtaining a glass substrate/ITO/SnO structure2/CH3NH3PbI3/Spiro-OMeTAD(CsI 0.0wt％)/MoO3Perovskite photoelectric detector of/Cu.
As shown in FIGS. 5 to 8, the external quantum efficiency of the detection device of comparative example 1 at 0V bias was 77%, the responsivity at 740nm was 0.40A/W, and the dark current density was 2.6X 10-8A/cm2The highest detectivity is 4.2X 1012Jones。
And (4) conclusion: according to the test data of the embodiment and the comparative example, the CsI ions are doped in the hole transport layer of the perovskite photoelectric detector, so that the dark current can be reduced, the external quantum efficiency is improved, and the responsivity and the detectivity of the device are improved.
The above are examples and comparative examples of the present invention. The embodiments and specific parameters in the embodiments are only for the purpose of clearly illustrating the verification process of the invention and are not intended to limit the scope of the invention, which is defined by the claims, and all equivalent structural changes made by using the contents of the specification and the drawings of the present invention should be covered by the scope of the present invention.
Claims (9)
1. A high-performance self-powered perovskite type photoelectric detector based on a CsI ion doped hole transport layer is characterized by mainly comprising a substrate, a conductive cathode, an electron transport layer, a perovskite photoactive layer, a hole transport layer, a modification layer and a metal anode which are sequentially arranged, wherein the hole transport layer is made of a Spiro-OMeTAD material.
2. The CsI ion doped hole transport layer based high performance self-powered perovskite photodetector of claim 1, wherein the substrate is a glass substrate or a PET plastic substrate; the conductive cathode material is ITO or FTO.
3. The CsI ion-doped hole transport layer-based high-performance self-powered perovskite-type photodetector of claim 1, wherein the electron transport layer is SnO2The thickness is 20-40 nm;
the perovskite photoactive layer is made of MAPbI3The thickness is 400-550 nm;
the thickness of the hole transport layer material Spiro-OMeTAD is 180-220 nm;
the material of the decorative layer is MoO3The thickness is 8-10 nm;
the metal anode is one or more of Al, Ag or Cu, and the thickness of the metal anode is 80-100 nm.
4. A preparation method of a high-performance self-powered perovskite type photoelectric detector based on a CsI ion doped hole transport layer is characterized by comprising the following steps:
1) cleaning, drying and ultraviolet ozone treatment are carried out on a substrate consisting of a substrate and a conductive cathode;
2) and carrying out gradient spin coating on the surface of the substrate to obtain SnO2Carrying out solution and gradient annealing to prepare an electron transport layer;
3) gradient spin coating MAPbI on the electron transport layer3Annealing the precursor solution to obtain a perovskite photoactive layer;
4) spin-coating CsI-doped Spiro-OMeTAD solution on the perovskite photoactive layer, and annealing to obtain a hole transport layer;
5) sequentially evaporating MoO on the hole transport layer3And modifying the layer and the metal anode to obtain the required perovskite photoelectric detector.
5. The preparation method of the high-performance self-powered perovskite-type photodetector based on the CsI ion-doped hole transport layer according to claim 4, wherein the cleaning in the step 1) is ultrasonic cleaning of the substrate sequentially by using a detergent, an acetone solution, isopropyl acetone, alcohol and deionized water, and each ultrasonic cleaning is carried out for 10-20 minutes.
6. The method for preparing a high-performance self-powered perovskite-type photodetector based on a CsI ion-doped hole transport layer according to claim 4, wherein the SnO in step 2) is SnO2The solution is aqueous colloidal dispersion with solute concentration of 2-3%, and the gradient spin coating and the gradient annealing are both carried out in an air environment; the procedure of the gradient spin coating is as follows: spin-coating at a rotating speed of 2500-3000 r/min for 10-20 s, and changing the rotating speed into spin-coating at 6000-7000 r/min for 45-60 s;
the gradient annealing comprises the following steps: annealing at 100-130 ℃ for 10-25 min and at 150-180 ℃ for 25-35 min.
7. The method for preparing a high-performance self-powered perovskite-type photodetector based on the CsI ion-doped hole transport layer according to claim 4, wherein the MAPbI in the step 3) is3The total concentration of the precursor solution is 610-915 mg/mL, and MAPbI is prepared3The raw material PbI used2The molar ratio to MAI is 1: 1; the solvent is DMF and DMSO, and the volume ratio of the DMF to the DMSO is 8: 2;
the procedure of the gradient spin coating is as follows: spin-coating at 2000-3500 rpm for 10-15 s, and changing the rotation speed to 4000-6000 rpm for 50-55 s;
the annealing temperature is 80-100 ℃, and the annealing time is 20-30 min.
8. The method for preparing a high-performance self-powered perovskite-type photodetector based on a CsI ion-doped hole transport layer according to claim 4, wherein the CsI doping concentration in the Spiro-OMeTAD solution in the step 4) is A, and the A is more than 0 and less than or equal to 0.8 wt%;
wherein the total concentration of the Spiro-OMeTAD solution is 70-100 mg/mL, and the solvent is chlorobenzene;
the Spiro-OMeTAD solution comprises 17.5 mu L of Li-TFSI and 28.8 mu L of TBP;
the spin coating procedure is as follows: spin coating at 3000 rpm for 40s in a nitrogen atmosphere.
9. The method for preparing a high-performance self-powered perovskite-type photodetector based on the CsI ion-doped hole transport layer according to claim 4, wherein the evaporation in the step 5) is vacuum evaporation, and the air pressure in the vacuum evaporation machine is controlled to be less than 5 x 10-4Pa。
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