CN112563419B - Non-lead double perovskite solar cell and preparation method thereof - Google Patents

Non-lead double perovskite solar cell and preparation method thereof Download PDF

Info

Publication number
CN112563419B
CN112563419B CN202011443632.7A CN202011443632A CN112563419B CN 112563419 B CN112563419 B CN 112563419B CN 202011443632 A CN202011443632 A CN 202011443632A CN 112563419 B CN112563419 B CN 112563419B
Authority
CN
China
Prior art keywords
solution
annealing
solar cell
transport layer
spin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011443632.7A
Other languages
Chinese (zh)
Other versions
CN112563419A (en
Inventor
王晓峰
王保宁
于大明
尤霆
袁林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Truetank New Energy Technology Changchun Co ltd
Original Assignee
Truetank New Energy Technology Changchun Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Truetank New Energy Technology Changchun Co ltd filed Critical Truetank New Energy Technology Changchun Co ltd
Priority to CN202011443632.7A priority Critical patent/CN112563419B/en
Publication of CN112563419A publication Critical patent/CN112563419A/en
Application granted granted Critical
Publication of CN112563419B publication Critical patent/CN112563419B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention relates to a lead-free double perovskite solar cell and a preparation method thereof, belonging to the technical field of perovskite solar cells. Solves the existing problem of Cs-based2AgBiBr6Due to Cs, the lead-free double perovskite solar cell2AgBiBr6The wider optical band gap leads to poorer optical absorption capability and lower photocurrent, thereby leading to the technical problem of lower efficiency of the device. The non-lead double perovskite solar cell provided by the invention is based on Cs and takes carboxyl-containing chlorophyll derivative C-Chl sensitized titanium dioxide as an electron transport layer2AgBiBr6The solar cell of (1). The C-Chll sensitized titania contributes both to the optical absorption and photocurrent of the device. Compared with devices prepared based on other electron transport materials, the device prepared by the preparation method provided by the invention has the advantages that the photocurrent is obviously improved, the highest photoelectric conversion efficiency reaches 3.11%, and the device is a non-lead double perovskite solar cell with the highest efficiency.

Description

Non-lead double perovskite solar cell and preparation method thereof
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a Cs-based organic electroluminescent (CPS) solar cell using carboxyl-containing Chlorophyll derivative Carboxy-chlorophyllil (C-Chl) sensitized titanium dioxide thin film as an electron transmission layer2AgBiBr6A lead-free double perovskite solar cell used as a perovskite light absorption layer and a preparation method thereof.
Background
The perovskite solar cell has since its first emergence caused a wide rangeOf general interest, to date, the highest energy conversion efficiency of perovskite solar cells has exceeded 25%. However, the traditional MAPbI3The problems that the perovskite contains lead element and the long-term stability of the device is poor always restrict the large-scale commercial use of the perovskite solar cell. To solve this problem, many groups of subjects have been focusing on developing new non-lead perovskite materials having low toxicity and high stability. The substitution of tin, a positive divalent element of the same main group, for lead is one choice among many groups of subjects, but Sn2+Is easily oxidized into Sn in the air4+The regular octahedral structure of the perovskite is decomposed, resulting in poor stability of the tin-based perovskite in air. Another possible alternative to the lead element is A2M+M3+X6Wherein the element A may be cesium, rubidium, a methylamine group or a methyl ether group, M+And M3+Are monovalent and trivalent metal cations, respectively, and the element X is a halogen atom. I.e. simultaneous replacement of two adjacent MAPbI's by one monovalent cation and one trivalent cation3Divalent lead ions in the unit cell. As the most widely studied non-lead double perovskite material at present, however, Cs2AgBiBr6The optical band gap of (2.1eV) is wider, so that the optical absorption capacity is poor, the photocurrent is low, and the device efficiency is low.
Current improvements are based on Cs2AgBiBr6Is mainly through the absorption of Cs2AgBiBr6And (5) regulating and controlling energy bands. Since the common hole transport material is not a photosensitive material, there is no report in the literature on increasing Cs by optimizing the electron transport layer2AgBiBr6Photovoltaic absorption properties of solar cells.
Disclosure of Invention
The invention aims to solve the problem of Cs-based technology in the prior art2AgBiBr6Due to Cs of the lead-free double perovskite solar cell2AgBiBr6The wider optical band gap leads to the technical problems of poorer optical absorption capability and lower photocurrent, thereby leading to lower device efficiency, and provides a dioxide sensitized by carboxyl-containing Chlorophyll derivative Carboxy-chlorophyl (C-Chl)Cs-based titanium as electron transport layer2AgBiBr6A lead-free double perovskite solar cell used as a perovskite light absorption layer and a preparation method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a non-lead double perovskite solar cell which sequentially comprises a transparent conductive glass cathode, an electron transport layer, a perovskite layer, a hole transport layer and a metal anode from bottom to top;
it is characterized in that the preparation method is characterized in that,
the electron transmission layer is carboxyl-containing Chlorophyll derivative Carboxy-chlorophyllil (C-Chl) sensitized titanium dioxide;
the perovskite layer is Cs2AgBiBr6。
In the above technical solution, preferably, the electron transport layer is c-TiO2/m-TiO2/C-Chl。
In the above technical solution, preferably, the cathode of the transparent conductive glass is fluorine-doped indium tin oxide FTO.
In the above embodiment, the hole transport layer is preferably 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-omatad), and the metal anode is preferably Ag.
In the above technical solution, preferably, the thickness of the electron transport layer and the thickness of the perovskite layer are both 430nm, the thickness of the hole transport layer is 80nm, and the thickness of the metal anode is 45 nm.
The invention also provides a preparation method of the non-lead double perovskite solar cell, which comprises the following steps:
1) carrying out ultraviolet ozone pretreatment on a transparent conductive glass cathode;
2) spin coating an electron transport layer on transparent conductive glass;
3) spin coating a perovskite layer on the electron transport layer;
4) spin coating a hole transport layer on the perovskite layer;
5) evaporating a metal anode on the hole transport layer;
characterized in that the step 2) comprises the following steps:
placing the transparent conductive glass pretreated by ultraviolet ozone in the step 1) in a spin coater, spin-coating isopropyl titanate solution, then placing in a muffle furnace for annealing treatment, placing in the spin coater again after annealing, spin-coating titanium dioxide nano particle colloidal solution, then placing in the muffle furnace for annealing treatment, and placing in TiCl after annealing treatment4In solution, it was finally immersed in a solution of C-Chl in ethanol.
In the above technical solution, preferably, in the step 2): the conditions of spin-coating isopropyl titanate solution are that the rotation speed is 4000rpm for 30s, and the annealing temperature and the annealing time are 500 ℃ for 30 minutes.
In the above technical solution, preferably, in the step 2): the conditions of spin-coating the titanium dioxide nanoparticle colloidal solution were that the rotation speed was 2000rpm for 30s, and the annealing temperature and time were 500 ℃ for 30 minutes.
In the above technical solution, preferably, in the step 2): annealing and placing it on TiCl4Keeping the temperature and the time in the solution at 70 ℃ for 1 h; after the annealing is finished, the glass is immersed in a C-Chl ethanol solution, the concentration of the solution is 0.1mg/mL, and the immersion time is 12 h.
In the above technical solution, it is preferable that a specific embodiment of the method for manufacturing the non-lead double perovskite solar cell is as follows:
1) and (3) treating a transparent conductive glass cathode:
carrying out ultraviolet ozone pretreatment on the cleaned transparent conductive glass for 20 minutes;
2) preparing and processing an electron transport layer:
placing the transparent conductive glass pretreated by ultraviolet ozone in the step 1) in a spin coater, spin-coating isopropyl titanate solution, rotating at 4000rpm for 30s, and then placing in a muffle furnace for annealing at 500 ℃ for 30 min; cooling the substrate, spin-coating titanium dioxide nanoparticle colloidal solution on the substrate, rotating at 2000rpm for 30s, and annealing in a muffle furnace at 500 deg.C for 30 minA clock; annealing and placing the silicon carbide substrate on TiCl4In the solution, keeping the temperature and the time at 70 ℃ for 1 h; after the annealing is finished, soaking the glass fiber in a C-Chl ethanol solution for 12 hours, wherein the concentration of the solution is 0.1 mg/mL;
3) preparation of perovskite layer:
subjecting perovskite precursor Cs2AgBiBr6The solution is placed on a hot bench at 100 ℃ and stirred for 2 hours by magnetic force, and after the solution is cooled to room temperature, the perovskite precursor Cs is added2AgBiBr6Filtering the solution through a 20-micron filter membrane; putting the device in the step 2) into a glove box filled with nitrogen, and spin-coating a perovskite precursor Cs on the electron transport layer2AgBiBr6The spin coating speed of the solution is 2000rpm, the time is 60 seconds, the solution is placed on a hot bench for annealing treatment after the spin coating is finished, and the annealing temperature and the annealing time are 280 ℃ for annealing for 10 minutes;
4) preparation of hole transport layer:
Spiro-OMeTAD was dissolved in chloroform solution at a concentration of 80mg/mL, 10.5. mu.L of 4-tert-butylpyridine (TBP) and 46.5. mu.L of an acetonitrile solution of Li-TFSI at 170mg/mL were added, and after sufficient magnetic stirring, the Spiro-OMeTAD solution was spin-coated on the perovskite layer at 4000rpm for 30 seconds;
5) preparing a metal anode:
using a vacuum evaporation coating machine to carry out vacuum evaporation coating under the condition that the pressure is less than 6 x 10-4Evaporating metal anode on the hole transport layer at Pa with the evaporation rate of
Figure BDA0002830817800000041
The invention has the beneficial effects that:
the invention provides a non-lead double perovskite solar cell which takes carboxyl-containing chlorophyll derivative C-Chl sensitized titanium dioxide as an electron transport layer and is based on Cs2AgBiBr6The solar cell of (1). The C-Chll sensitized titania contributes both to the optical absorption and photocurrent of the device.
Compared with devices prepared based on other electron transport materials, the device prepared by the preparation method provided by the invention has the advantages that the photocurrent is obviously improved, the highest photoelectric conversion efficiency reaches 3.11%, and the device is a non-lead double perovskite solar cell with the highest efficiency.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a Cs-based electron transport layer of the present invention with C-Chl sensitized titanium dioxide2AgBiBr6The structural diagram of the high-efficiency non-lead double perovskite solar cell device serving as the perovskite light absorption layer.
Fig. 2 is a diagram of the energy level structure and electron transport path of the photovoltaic device of the present invention.
FIG. 3 shows Cs-based samples prepared according to the present invention using C-Chl sensitized titania and ordinary titania as electron transport layers2AgBiBr6The J-V curve diagram of the high-efficiency non-lead double perovskite solar cell device as the perovskite light absorption layer.
Detailed Description
The invention provides a non-lead double perovskite solar cell which sequentially comprises a transparent conductive glass cathode, an electron transport layer, a perovskite layer, a hole transport layer and a metal anode from bottom to top;
the preparation method is characterized in that the electron transport layer is carboxyl-containing Chlorophyll derivative Carboxy-chlorophyllil (C-Chl) sensitized titanium dioxide (TiO)2) (ii) a The perovskite layer is Cs2AgBiBr6。
The carboxyl-containing Chlorophyll derivative is Carboxy-Chlorophyl (C-Chl), specifically trans 32Carboxy-pyropheophorbide-a (C-Chl), the structure of which is shown below, and the preparation method is described in chem.
Figure BDA0002830817800000051
Preferably, the electron transport layer is c-TiO2/m-TiO2C-Chl (wherein C-TiO)2Is a dense layer of titanium dioxide, m-TiO2Is mesoporous layer titanium dioxide).
Preferably, the transparent conductive glass cathode is fluorine-containing indium tin oxide (FTO); the hole transport layer is Spiro-OMeTAD; the metal anode is Ag.
The invention has no special requirement on the thickness of each layer of the non-lead double perovskite solar cell, and the required thickness can be prepared according to the actual requirement. Preferably, the electron transport layer and the perovskite layer are both 430nm thick, the hole transport layer is 80nm thick and the metal anode is 45nm thick.
The invention also provides a preparation method of the non-lead double perovskite solar cell, which comprises the following steps:
1) and (3) treating a transparent conductive glass cathode:
carrying out ultraviolet ozone pretreatment on the cleaned transparent conductive glass for 20 minutes;
2) preparing and processing an electron transport layer:
placing the transparent conductive glass pretreated by ultraviolet ozone in the step 1) in a spin coater, spin-coating isopropyl titanate solution, rotating at 4000rpm for 30s, and then placing in a muffle furnace for annealing at 500 ℃ for 30 min; after the substrate is cooled, spin-coating titanium dioxide nano particle colloidal solution on the substrate, rotating at 2000rpm for 30s, and then placing the substrate in a muffle furnace for annealing treatment, wherein the annealing temperature and the annealing time are 500 ℃ for annealing for 30 minutes; annealing and placing the silicon carbide substrate on TiCl4In the solution, keeping the temperature and the time at 70 ℃ for 1 h; after the annealing is finished, soaking the glass fiber in a C-Chl ethanol solution for 12 hours, wherein the concentration of the solution is 0.1 mg/mL;
3) preparation of perovskite layer:
subjecting perovskite precursor Cs2AgBiBr6The solution is placed on a hot table at 100 ℃ and stirred magnetically for 2 hours, and after the solution is cooled to room temperature, the perovskite precursor Cs is2AgBiBr6Filtering the solution through a 20-micron filter membrane; putting the device in the step 2) into a glove box filled with nitrogen, and spin-coating a perovskite precursor Cs on the electron transport layer2AgBiBr6The spin coating speed of the solution is 2000rpm, the time is 60 seconds, the solution is placed on a hot bench for annealing treatment after the spin coating is finished, and the annealing temperature and the annealing time are 280 ℃ for annealing for 10 minutes;
4) preparation of hole transport layer:
dissolving Spiro-OMeTAD in chloroform solution at a concentration of 80mg/mL, adding 10.5. mu.L of 4-tert-butylpyridine (TBP) and 46.5. mu.L of Li-TFSI solution (170mg/mL in acetonitrile), and after sufficient magnetic stirring, spin-coating Spiro-OMeTAD solution on the perovskite layer at 4000rpm for 30 seconds;
5) preparing a metal anode:
using a vacuum evaporation coating machine to carry out vacuum evaporation coating under the condition that the pressure is less than 6 x 10-4Evaporating metal anode on the hole transport layer at Pa with the evaporation rate of
Figure BDA0002830817800000071
The perovskite precursor Cs of the invention2AgBiBr6The preparation process of the solution is as follows:
in a nitrogen glove box, 0.5mMol of BiBr3224.3mg and 0.5mMol of AgBr 93.9mg and 1mMol of CsBr 212.8mg were dissolved in 1mL of DMSO solution and stirred at 280 ℃ for 2 hours.
In order to further understand the present invention, the following technical solutions are clearly and completely described with reference to the following embodiments, but the embodiments of the present invention are only for explaining the present invention and do not limit the present invention, and all other embodiments obtained by those skilled in the art without creative efforts belong to the protection scope of the present invention.
The starting materials used in the following examples are all commercially available products.
Example 1
And (2) carrying out ultrasonic treatment on the etched ITO by using an ITO cleaning agent, deionized water, acetone, alcohol and isopropanol in sequence for 30 minutes, then preparing an isopropyl titanate solution, and mixing the deionized water, the isopropyl titanate and hydrochloric acid in a volume ratio of 100:10:1 to obtain the isopropyl titanate solution. Pretreating ITO ultraviolet ozone for 30 minutes, then placing the ITO ultraviolet ozone on a spin coater, spin-coating isopropyl titanate solution for 30 seconds at the rotating speed of 4000rpm, and then immediately placing the ITO ultraviolet ozone in a muffle furnace for annealing treatment, wherein the annealing temperature and the annealing time are 500 ℃ for annealing for 30 minutes; then configureMixing titanium dioxide colloidal particles and ethanol in a mass ratio of 1:2 to obtain titanium dioxide colloidal solution, spin-coating the titanium dioxide colloidal solution at a rotating speed of 2000rpm for 30s, immediately placing the titanium dioxide colloidal solution in a muffle furnace for annealing treatment at the annealing temperature and the annealing time of 500 ℃ for 30 minutes; then preparing an aqueous titanium tetrachloride solution, adding 67.5. mu.L of titanium tetrachloride to 10mL of ultrapure water to obtain an aqueous titanium tetrachloride solution, placing the substrate in the aqueous titanium tetrachloride solution and placing the substrate in an oven at 70 ℃ for 1 hour, and finally immersing the substrate in a 0.1mg/mL C-Chl ethanol solution for 12 hours. Preparation of Cs in Nitrogen glove Box2AgBiBr6Precursor solution, 0.5mMol of BiBr3(224.3mg) and 0.5mMol of AgBr (93.9mg) and 1mMol of CsBr (212.8mg) were dissolved in 1mL of DMSO solution and stirred at 280 ℃ for 2 hours. And (2) conveying the substrate into a glove box, spin-coating the perovskite precursor solution on the electron transport layer at the rotating speed of 2000rpm for 60 seconds, and after the spin-coating is finished, putting the substrate on a hot bench for annealing at the annealing temperature and the annealing time of 280 ℃ for 10 minutes. A solution of Spiro-OMeTAD was then prepared in a nitrogen glove box, dissolved in 80mg/mL chloroform, added with 10.5. mu.L of 4-tert-butylpyridine (TBP) and 46.5. mu.L of Li-TFSI solution (170mg/mL in acetonitrile), and after sufficient magnetic stirring, the Spiro-OMeTAD solution was spin-coated on the perovskite layer at 4000rpm for 30 seconds to form a Spiro-OMeTAD film. Finally, the substrate is sent into an organic evaporation coating machine, and when the pressure in the cavity is lower than 6 x 10-4Pa time silver electrode and evaporation rate thereof
Figure BDA0002830817800000081
The silver film thickness was 45 nm. Thus, the above-mentioned C-Chl-sensitized titanium dioxide is obtained as an electron transport layer, Cs2AgBiBr6A high efficiency non-lead double perovskite solar cell as a light absorbing layer. The device structure is shown in fig. 1. The electron transport layer/perovskite layer in this example were all 430nm thick, the hole transport layer 80nm thick and the metal anode 45nm thick.
The thickness of the electron transport layer, the thickness of the perovskite layer, the thickness of the hole transport layer and the thickness of the metal anode in the above embodiments may be any value within the above-defined thickness range, and are not listed here.
Comparative example 1
The difference from example 1 is that in comparative example 1, ordinary titanium dioxide which is not sensitized by C-Chl is used as an electron transport material, and the rest of the preparation method is the same as that of example 1.
TABLE 1 titanium dioxide sensitized with C-Chl (C-Chl-TiO)2) And ordinary titanium dioxide (TiO)2) Cs-based materials prepared separately as electron transport layers2AgBiBr6And various photovoltaic parameters of the high-efficiency non-lead double perovskite solar cell device used as the perovskite light absorption layer. Compared with a solar cell prepared based on common titanium dioxide, the solar cell prepared by taking the C-Chl sensitized titanium dioxide as the electron transport layer has the advantage that the short-circuit current density is improved by 27%. The photoelectric conversion efficiency of the C-Chl device is as high as 3.11%.
TABLE 1
Figure BDA0002830817800000091
Fig. 2 is a diagram of the energy level structure and electron transport path of the photovoltaic device of the present invention. Due to the addition of the C-Chl, photoelectrons excited in the interior of the perovskite layer can be directly transmitted into the titanium dioxide and can also be indirectly transmitted into the titanium dioxide through the C-Chl, and an extra photocurrent is provided by the extra photoelectron transmission path, so that the photocurrent density of the device is higher than that of a photovoltaic device prepared based on a common titanium dioxide electron transmission material. Illustrating the C-Chl pair increasing Cs2AgBiBr6The energy conversion efficiency of solar cells has a positive contribution.
FIG. 3 shows Cs-based materials prepared by the present invention using C-Chl sensitized titanium dioxide and general titanium dioxide as electron transport layers2AgBiBr6J-V plots of high efficiency non-lead double perovskite solar cell devices and correspond to the data of table 1. The C-Chl sensitized dioxygen prepared by the inventionCs-based prepared by taking titanium oxide as electron transport layer2AgBiBr6Compared with a device prepared by taking common titanium dioxide as an electron transport layer, the perovskite solar cell serving as a perovskite light absorption layer has the advantages that the short-circuit current density is improved by 27%, and the highest energy conversion efficiency reaches 3.11%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (9)

1. A non-lead double perovskite solar cell is characterized by sequentially comprising a transparent conductive glass cathode, an electron transport layer, a perovskite layer, a hole transport layer and a metal anode from bottom to top;
it is characterized in that the preparation method is characterized in that,
the electron transmission layer is carboxyl-containing Chlorophyll derivative Carboxy-chlorophyllil (C-Chl) sensitized titanium dioxide; wherein the carboxyl-containing Chlorophyll derivative (C-Chl) is trans 32-carboxy-pyropheophorbide-a (C-Chl);
the perovskite layer is Cs2AgBiBr6。
2. The non-lead double perovskite solar cell of claim 1, wherein the transparent conductive glass cathode is fluorine doped indium tin oxide (FTO).
3. The non-lead double perovskite solar cell of claim 1, wherein the hole transport layer is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-ome tad), 4-tert-butylpyridine (TBP) and Li-TFSI and the metal anode is Ag.
4. The non-lead double perovskite solar cell according to claim 1, wherein the electron transport layer and the perovskite layer are each 430nm thick, the hole transport layer is 80nm thick, and the metal anode is 45nm thick.
5. A method of manufacturing a non-lead double perovskite solar cell according to any one of claims 1 to 4, comprising the steps of:
1) carrying out ultraviolet ozone pretreatment on a transparent conductive glass cathode;
2) spin coating an electron transport layer on transparent conductive glass;
3) spin coating a perovskite layer on the electron transport layer;
4) spin coating a hole transport layer on the perovskite layer;
5) evaporating a metal anode on the hole transport layer;
characterized in that the step 2) comprises the following steps:
placing the transparent conductive glass pretreated by ultraviolet ozone in the step 1) in a spin coater, spin-coating an isopropyl titanate solution, then placing in a muffle furnace for annealing, placing in the spin coater again after annealing, spin-coating a titanium dioxide nano particle colloidal solution, then placing in the muffle furnace for annealing, and placing in TiCl after annealing4In solution, it was finally immersed in a solution of C-Chl in ethanol.
6. The method for producing a non-lead double perovskite solar cell according to claim 5, wherein in the step 2): the conditions of spin-coating isopropyl titanate solution are that the rotation speed is 4000rpm and is rotated for 30s, and the annealing temperature and the annealing time are 500 ℃ and are annealed for 30 minutes.
7. The method for producing a non-lead double perovskite solar cell according to claim 5, wherein in the step 2): the conditions of spin-coating the titanium dioxide nanoparticle colloidal solution were that the rotation speed was 2000rpm for 30s, and the annealing temperature and time were 500 ℃ for 30 minutes.
8. According to the claimsThe method for manufacturing a non-lead double perovskite solar cell according to claim 5, wherein in the step 2): annealing and placing the silicon carbide substrate on TiCl4Keeping the temperature and time in the solution at 70 ℃ for 1 h; after the annealing is finished, the glass is immersed in a C-Chl ethanol solution, the concentration of the solution is 0.1mg/mL, and the immersion time is 12 h.
9. The method of manufacturing a non-lead double perovskite solar cell according to claim 5, wherein one embodiment thereof is as follows:
1) and (3) treating a transparent conductive glass cathode:
carrying out ultraviolet ozone pretreatment on the cleaned transparent conductive glass for 20 minutes;
2) preparing and processing an electron transport layer:
placing the transparent conductive glass pretreated by ultraviolet ozone in the step 1) in a spin coater, spin-coating isopropyl titanate solution, rotating at 4000rpm for 30s, and then placing in a muffle furnace for annealing at 500 ℃ for 30 min; after the substrate is cooled, spin-coating titanium dioxide nano particle colloidal solution on the substrate, rotating at 2000rpm for 30s, and then placing the substrate in a muffle furnace for annealing treatment at the annealing temperature and time of 500 ℃ for 30 minutes; annealing and placing the silicon carbide substrate on TiCl4In the solution, keeping the temperature and the time at 70 ℃ for 1 h; after the annealing is finished, soaking the glass fiber in a C-Chl ethanol solution for 12 hours, wherein the concentration of the solution is 0.1 mg/mL;
3) preparation of perovskite layer:
subjecting perovskite precursor Cs2AgBiBr6The solution is placed on a hot bench at 100 ℃ and stirred for 2 hours by magnetic force, and after the solution is cooled to room temperature, the perovskite precursor Cs is added2AgBiBr6Filtering the solution through a 20-micron filter membrane; putting the device in the step 2) into a glove box filled with nitrogen, and spin-coating a perovskite precursor Cs on the electron transport layer2AgBiBr6The spin coating speed of the solution is 2000rpm, the time is 60 seconds, the solution is placed on a hot bench for annealing treatment after the spin coating is finished, and the annealing temperature and the annealing time are 280 ℃ for annealing for 10 minutes;
4) preparation of hole transport layer:
Spiro-OMeTAD was dissolved in chloroform solution at a concentration of 80mg/mL, 10.5. mu.L of 4-tert-butylpyridine (TBP) and 46.5. mu.L of an acetonitrile solution of Li-TFSI at 170mg/mL were added, and after sufficient magnetic stirring, the Spiro-OMeTAD solution was spin-coated on the perovskite layer at 4000rpm for 30 seconds;
5) preparing a metal anode:
using vacuum evaporation coating machine to make pressure less than 6 x 10-4Evaporating metal anode on the hole transport layer at Pa with the evaporation rate of
Figure FDA0003668651440000031
CN202011443632.7A 2020-12-11 2020-12-11 Non-lead double perovskite solar cell and preparation method thereof Active CN112563419B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011443632.7A CN112563419B (en) 2020-12-11 2020-12-11 Non-lead double perovskite solar cell and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011443632.7A CN112563419B (en) 2020-12-11 2020-12-11 Non-lead double perovskite solar cell and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112563419A CN112563419A (en) 2021-03-26
CN112563419B true CN112563419B (en) 2022-07-19

Family

ID=75060961

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011443632.7A Active CN112563419B (en) 2020-12-11 2020-12-11 Non-lead double perovskite solar cell and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112563419B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116004229B (en) * 2023-01-04 2023-12-05 吉林大学 Chlorophyll-modified CsPbCl3: yb3+ perovskite film and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110993797A (en) * 2019-12-20 2020-04-10 储天新能源科技（长春）有限公司 Non-lead double perovskite solar cell and preparation method thereof
CN111987222A (en) * 2020-08-28 2020-11-24 西安电子科技大学 Solar cell based on double perovskite material and preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110993797A (en) * 2019-12-20 2020-04-10 储天新能源科技（长春）有限公司 Non-lead double perovskite solar cell and preparation method thereof
CN111987222A (en) * 2020-08-28 2020-11-24 西安电子科技大学 Solar cell based on double perovskite material and preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Bilayer chlorophyll derivatives as efficient hole-transporting layers for perovskite solar cells;W.Zhao等;《MATERIALS CHEMISTRY》;20191231;全文 *
非铅钙钛矿材料及其光伏性能研究;肖立新 等;《第四届新型太阳能电池学术研讨会》;20170527;全文 *

Also Published As

Publication number Publication date
CN112563419A (en) 2021-03-26

Similar Documents

Publication Publication Date Title
CN110993797B (en) Non-lead double perovskite solar cell and preparation method thereof
JP6616291B2 (en) Solar cell and manufacturing method thereof
CN109461818B (en) Efficient perovskite solar cell and preparation method thereof
CN112216799B (en) Method for passivating perovskite and preparation process of perovskite solar cell
US10720282B2 (en) Producing method of mesoporous thin film solar cell based on perovskite
US20090320894A1 (en) Method for preparing nanocrystalline transparent films of tungsten oxide
CN110176539B (en) Preparation method of efficient perovskite solar cell with stable full-spectrum light
CN108807694B (en) Flat perovskite solar cell with ultralow temperature stability and preparation method thereof
CN112331740B (en) Preparation method of inorganic perovskite solar cell adopting spin coating-evaporation two-step method
CN111987222A (en) Solar cell based on double perovskite material and preparation method
KR20180083823A (en) Perovskite based solar cell and method of manufacturing the same
CN112563419B (en) Non-lead double perovskite solar cell and preparation method thereof
CN111987221A (en) Solar cell based on vacancy perovskite material and preparation method
CN111048422A (en) Preparation method of efficient cesium-lead-iodine-bromine inorganic perovskite film and solar cell based on efficient cesium-lead-iodine-bromine inorganic perovskite film
JPH11219734A (en) Semiconductor for photoelectric conversion material, laminate using the semiconductor, manufacture of those and photocell
CN114188485A (en) Tin-based perovskite solar cell based on indene additive and preparation method thereof
CN110634965B (en) All-inorganic perovskite solar cell and preparation method thereof
CN113629192A (en) Dye-sensitized and double-perovskite hybrid solar cell and preparation method thereof
CN113903862B (en) SnO modified based on phenylboronic acid derivative 2 Perovskite solar cell preparation method
CN113421975A (en) Method for modifying tin dioxide by ammonium hexafluorophosphate and application of tin dioxide in perovskite solar cell
CN114107960B (en) SnO preparation by using stannous oxalate as raw material2Method for forming electron transport layer film
CN110444668A (en) A kind of preparation method of plane perovskite solar battery
CN113192843B (en) Preparation method and application of novel non-lead-based perovskite film
JP2003257508A (en) Photoelectric transducer
CN117042555A (en) Preparation method of double-sided perovskite photovoltaic without metal electrode and solar cell

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant