CN111883665B - Organic solar cell for constructing internal electric field by doping nano particles in charge transport layer and preparation method thereof - Google Patents
Organic solar cell for constructing internal electric field by doping nano particles in charge transport layer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic solar cell for constructing an internal electric field by doping nano particles in a charge transport layer and a preparation method thereof, which belong to the field of photoelectric devices and sequentially comprise a substrate, an electrode layer, an electron transport layer, an organic functional layer, a hole transport layer and a metal electrode layer from bottom to top, wherein the electron transport layer is doped with P-type semiconductor nano particles with the mass fraction of 0.5-3.5%, and the hole transport layer is doped with N-type semiconductor nano particles with the mass fraction of 0.5-3.5%. According to the invention, the internal electric field is constructed by doping the nano particles in the charge transport layer, so that the transport and collection efficiency of carriers is improved, the photoelectric conversion efficiency is improved, and the preparation method is simple and efficient, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of photoelectric devices, and particularly relates to an organic solar cell for constructing an internal electric field by doping nano particles in a charge transport layer and a preparation method thereof.
Background
The organic solar cell has the characteristics of low cost, flexibility and the like, and has wide application in the aspects of saving a plurality of resources, protecting the environment, utilizing energy, daily use in home and the like. In order to meet the requirements of practical applications, organic solar cells should have high photoelectric conversion efficiency and long service life to achieve high efficiency of energy use. However, since the organic solar cell has a complicated mechanism and the generated excitons are difficult to separate, the organic solar cell is often difficult to separate into free electrons and holes after the photogenerated excitons are generated, and the photoelectric conversion efficiency is low. Therefore, how to improve the separation of the photogenerated excitons into free electrons and holes and reduce the energy loss caused by exciton recombination while ensuring the generation of more photogenerated excitons becomes a major and difficult point of organic solar cell research.
Disclosure of Invention
The invention aims to: aiming at the problems that photo-generated excitons generated by the liquid organic solar cell are not easy to generate energy loss caused by easy recombination of free electrons and holes, and the carrier transmission efficiency is low to cause lower device performance, the invention provides the organic solar cell for constructing the internal electric field by doping nano particles in a charge transmission layer and the preparation method thereof.
The technical scheme adopted by the invention is as follows:
an organic solar cell for constructing an internal electric field by doping nano particles in a charge transport layer sequentially comprises a substrate, an electrode layer, an electron transport layer, an organic functional layer, a hole transport layer and a metal electrode layer from bottom to top, wherein the electron transport layer is doped with P-type semiconductor nano particles with the mass fraction of 0.5-3.5%, and the hole transport layer is doped with N-type semiconductor nano particles with the mass fraction of 0.5-3.5%.
According to the invention, the internal electric field is constructed by doping nano particles in the charge transport layer, so that the transport and collection efficiency of carriers is improved, the photoelectric conversion efficiency is improved, and the preparation method is simple and efficient, and is suitable for large-scale production.
Preferably, the raw material of the electron transport layer is any one or more of PC61BM, ZnO, MoOx, NiOx, TiO2, SnOx, PFN, PEIE, and PANIO, wherein x is 2 or 3, and the material of the P-type semiconductor nanoparticles doped in the electron transport layer is any one or more of Cu1.8s, Cu2O, TiO2, indium, aluminum, boron, and manganese.
Preferably, the hole transport layer is made of MnO3, PEDOT, PSS, CuSCN, CuI, NiOm, TiO2 and SnOx, wherein x is 2 or 3, and m is 2 or 4; the N-type semiconductor nano-particles doped in the hole transport layer are made of any one or more of arsenic, phosphorus, antimony, Ta2O5 and silver.
Preferably, the electrode layer is made of Indium Tin Oxide (ITO), gold, silver, aluminum, copper, silver nanowires, calcium, any one of electrodes in the conductive polymer film, silver nanowires and the conductive polymer film, and the thickness of the electrode layer is 2-30 nm.
Preferably, the organic functional layer is any one of organic donor-acceptor material bulk heterojunction PBDB-T, ITIC, PM6, Y6, PBDB-T, IT4F, PBTTT, PCBM, P3HT, PCBM and C60, and the thickness is 100nm-200 nm.
Preferably, the metal electrode layer is made of any one of Indium Tin Oxide (ITO), gold, silver, copper, aluminum and calcium electrodes, silver nanowires and conductive polymer films, and the thickness of the metal electrode layer is 50-150 nm.
A preparation method of an organic solar cell for constructing an internal electric field by doping nanoparticles in a charge transport layer comprises the following steps:
(1) cleaning a glass substrate with an ITO electrode, drying and then carrying out ultraviolet oxidation treatment;
(2) spin-coating an electron transport layer doped with P-type semiconductor nano particles on a glass substrate, and annealing for later use;
(3) spin-coating an organic donor-acceptor solution on the electron transport layer to form an organic functional layer, and annealing for later use;
(4) spin-coating a hole transport layer doped with an N-type semiconductor on the organic functional layer, and annealing for later use;
(5) and evaporating a silver electrode on the hole transport layer.
Preferably, the specific steps of the step (2) are that the glass substrate is placed on a spin coater under the atmospheric condition, 40-60ul of solution of electron transport layer raw material doped with P-type semiconductor nano-particles with the mass fraction of 0.5-3.5% is added dropwise, the rotating speed is 4500-5500rpm, the time is 50-70s, then annealing treatment is carried out, the annealing temperature is controlled at 140-160 ℃, and the time is 10-20 min.
Preferably, the specific step of the step (3) is to transfer the experimental device into a glove box, spin-coat an organic functional layer on the electron transport layer doped with the P-type semiconductor nanoparticles in an inert atmosphere, control the rotation speed to 3500-.
Preferably, the step (4) is specifically carried out by transferring the organic functional layer which is spin-coated to a vacuum evaporation device, evaporating a layer of raw material solution doped with the N-type semiconductor nanoparticle hole transport layer with the mass fraction of 0.5-3.5% in an environment with the vacuum degree of less than (2-5) multiplied by 10-3Pa, and then cooling for 20-30min in a vacuum environment.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the electron transport layer is doped with the P-type semiconductor nanoparticles, the hole transport layer is doped with the N-type semiconductor nanoparticles, an internal electric field can be constructed after a passage is formed, the capability of separating excitons into free electron holes is increased, the carrier mobility of electrons and holes is improved, and the performance of the device can be improved;
(2) according to the invention, the Fermi level of the transmission layer is changed by doping the electron transmission layer and the hole transmission layer, and the energy level matching between the transmission layer and the organic functional layer can be realized by controlling the doping concentration, so that the collection of current carriers is facilitated;
(3) according to the invention, by utilizing a traditional organic solar cell structure and combining a simple and efficient spin coating process, higher photoelectric conversion capability can be obtained only by doping a small amount of charge transmission layer, and the cost performance is extremely high; the method has guiding significance for large-scale industrial preparation of detectors in organic solar cells and other fields.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a graph of carrier transport and energy level change before and after doping of semiconductor nanoparticles in a charge transport layer;
FIG. 3 is a schematic structural diagram of an electron donor material PBDB-T and an electron acceptor material ITIC adopted by the invention;
FIG. 4 is a JV curve comparison of example one and example two.
Labeled as: 1-substrate, 2-electrode layer, 3-electron transport layer, 4-organic functional layer, 5-hole transport layer and 6-metal electrode layer.
Detailed Description
The present invention will be described in further detail in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The invention aims to solve the problems that photogenerated excitons generated by an organic solar cell are not easy to generate free electrons and holes and are easy to recombine to generate energy loss, and the device performance is low due to low carrier transmission efficiency. The low-concentration P-type semiconductor nanoparticles are doped in the electron transport layer, so that positive charge of electrons is easily lost, and negative charge of electrons is easily obtained by doping the low-concentration N-type semiconductor nanoparticles in the hole transport layer, so that an electric field is formed in the active layer, free electrons and holes generated by the active layer are acted by the electric field force, transmission and collection of the free electrons and the holes are facilitated, the carrier concentration of the active layer to an acceptor interface is reduced, and exciton separation is promoted. And the energy levels of the electron transport layer and the hole transport layer are changed, so that the energy level structures between the charge transport layer and the active layer are more matched. (as shown in fig. 2).
Example 1
An organic solar cell for constructing an internal electric field by doping nanoparticles in a charge transport layer, as shown in fig. 1, comprises a substrate, wherein the substrate is provided with an electrode layer, an electron transport layer doped with P-type semiconductor nanoparticles is plated on the electrode layer, the electron transport layer doped with P-type semiconductor nanoparticles is sequentially coated with an organic functional layer and a hole transport layer doped with N-type semiconductor nanoparticles from bottom to top, and a metal electrode layer is plated on the hole transport layer doped with N-type semiconductor nanoparticles.
Wherein, the substrate is a glass substrate.
The electrode layer adopts an ITO transparent conductive electrode arranged on the glass substrate.
The electron transport layer doped with the P-type semiconductor nano particles adopts a ZnO film with the thickness of 10nm and doped with 2 wt% Cu2O nano particles.
The organic functional layer 5 adopts PBDB-T bulk heterojunction with the thickness of 150nm, namely ITIC (structural formula shown in figure 3).
The hole transport layer 6 used a 10nm thick MnO3 film doped with 2 wt% arsenic nanoparticles.
The metal electrode layer 7 is a silver electrode having a thickness of 100 nm.
A preparation method of an organic solar cell for constructing an internal electric field by doping nanoparticles in a charge transport layer comprises the following preparation steps:
1. cleaning a substrate: and (3) sequentially putting the glass substrate with the conductive electrode 2 into a detergent, acetone, deionized water and isopropanol, ultrasonically cleaning for 15min each time, then blowing the glass substrate to dry by inert gas, and oxidizing by ultraviolet rays for 15 min.
2. Spin-coating an electron transport layer doped with P-type semiconductor nanoparticles: under the atmospheric condition, a glass substrate is placed on a spin coater, 50ul of ZnO solution added with 2 wt% of Cu2O nano particles is dripped, the rotating speed is controlled to be 5000rpm, the time is 60s, then annealing treatment is carried out, the annealing temperature is controlled to be 150 ℃, and the time is 15 min.
3. Spin coating an organic functional layer: at the moment, the experimental device is transferred into a glove box, an organic functional layer is spin-coated on the electron transport layer doped with the P-type semiconductor nano particles in the nitrogen atmosphere, the rotating speed is controlled to be 4000rpm, the time is 20s, then annealing treatment is carried out, the annealing temperature is controlled to be 130 ℃, and the time is 15 min.
4. Evaporating and doping an N-type semiconductor nanoparticle hole transport layer: and transferring the organic functional layer which is spin-coated to vacuum evaporation equipment, evaporating a layer of MnO3 doped with N-type semiconductor nano particles in an environment with the vacuum degree of less than 3 x 10 < -3 > Pa, and cooling for 30min in a vacuum environment.
5. And (3) evaporating a metal electrode 6: and then evaporating a layer of Ag electrode in an environment with the vacuum degree of less than 3.0 multiplied by 10 < -3 > Pa.
Under standard test conditions (AM 1.5, 100mW/cm2), the open circuit Voltage (VOC) of the device was 0.884577V, the short circuit current (JSC) was 14.5886mA/cm2, the Fill Factor (FF) was 0.619375, and the energy conversion efficiency (PCE) was 7.99286%.
Example 2: comparative example
On the basis of embodiment 1, the difference between this embodiment and embodiment 1 is that the organic solar cell is fabricated by using a conventional process without any doping of the electron transport layer and the hole transport layer, which is not enough to establish the internal electric field of the device, and constitutes a control group with example 1.
The glass substrate used for the substrate, the ITO electrode used for the electrode layer, the ZnO used for the electron transport layer, the PBDB-T used for the organic functional layer, the ITIC bulk heterojunction, the MnO3 used for the hole transport layer and the silver electrode used for the electrode layer 6.
The preparation method comprises the following steps:
1. cleaning a substrate: and (3) sequentially putting the glass substrate with the conductive electrode 2 into a detergent, acetone, deionized water and isopropanol, ultrasonically cleaning for 15min each time, then blowing the glass substrate to dry by inert gas, and oxidizing by ultraviolet rays for 15 min.
2. Spin coating an electron transport layer: under the atmospheric condition, a glass substrate is placed on a spin coater, 50ul of ZnO solution is dripped, the rotating speed is controlled to be 5000rpm, the time is 60s, then annealing treatment is carried out, the annealing temperature is controlled to be 150 ℃, and the time is 15 min.
3. Spin coating an organic functional layer: at the moment, the experimental device is transferred into a glove box, an organic functional layer is spin-coated on the electron transport layer in the nitrogen atmosphere, the rotating speed is controlled to be 4000rpm, the time is 20s, then annealing treatment is carried out, the annealing temperature is controlled to be 130 ℃, and the time is 15 min.
4. Evaporating a hole transport layer: and transferring the organic functional layer which is spin-coated to a vacuum evaporation device, evaporating a layer of MnO3 in an environment with the vacuum degree of less than 3 x 10 < -3 > Pa, and then cooling for 30min in a vacuum environment.
5. And (3) evaporating a metal electrode 6: and then evaporating a layer of Ag electrode in an environment with the vacuum degree of less than 3.0 multiplied by 10 < -3 > Pa.
Under standard test conditions (AM 1.5, 100mW/cm2), the open circuit Voltage (VOC) of the device was 0.868293V, the short circuit current (JSC) was 13.9225mA/cm2, the Fill Factor (FF) was 0.582131, and the energy conversion efficiency (PCE) was 7.03727%.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (8)
1. An organic solar cell for constructing an internal electric field by doping nanoparticles in a charge transport layer sequentially comprises a substrate, an electrode layer, an electron transport layer, an organic functional layer, a hole transport layer and a metal electrode layer from bottom to top, and is characterized in that the electron transport layer is doped with P-type semiconductor nanoparticles with the mass fraction of 0.5-3.5%, and the hole transport layer is doped with N-type semiconductor nanoparticles with the mass fraction of 0.5-3.5%;
the raw material of the electron transport layer is PC 61 BM、ZnO、MoO x 、NiO x 、TiO 2 、SnO x And any one or more of PFN, PEIE and PANIO, wherein the value of x is 2 or 3, and the material of the P-type semiconductor nano-particles doped in the electron transport layer is Cu 1.8 S、Cu 2 O、TiO 2 Any one or more of indium, aluminum, boron and manganese;
the hole transport layer is made of MnO 3 PEDOT PSS, CuSCN, CuI and NiO m 、TiO 2 、SnO x Wherein x is 2 or 3, and m is 2 or 4; the N-type semiconductor nano-particles doped with the hole transport layer are made of arsenic, phosphorus, antimony and Ta 2 O 5 And silver.
2. The organic solar cell of claim 1, wherein the charge transport layer is doped with nanoparticles to construct the internal electric field, and the electrode layer is made of indium tin oxide, gold, silver, aluminum, copper, silver nanowires, calcium, any one of electrodes in a conductive polymer film, silver nanowires and a conductive polymer film, and has a thickness of 2-30 nm.
3. The organic solar cell of claim 1, wherein the organic functional layer is any one of PBDB-T ITIC, PM6: Y6, PBDB-T: IT4F, PBTTT: PCBM, P3HT: PCBM, and C60: CuPc, and has a thickness of 100nm to 200 nm.
4. The organic solar cell according to claim 1, wherein the charge transport layer is doped with nanoparticles to construct the internal electric field, and the metal electrode layer is made of any one of gold, silver, copper, aluminum, calcium electrode and silver nanowire and has a thickness of 50-150 nm.
5. The method for preparing the organic solar cell for constructing the internal electric field by doping nanoparticles on the charge transport layer according to any one of claims 1 to 4, comprising the following steps:
(1) cleaning a glass substrate with an ITO electrode, drying and then carrying out ultraviolet oxidation treatment;
(2) spin-coating an electron transport layer doped with P-type semiconductor nano particles on a glass substrate, and annealing for later use;
(3) spin-coating an organic donor-acceptor solution on the electron transport layer to form an organic functional layer, and annealing for later use;
(4) spin-coating a hole transport layer doped with an N-type semiconductor on the organic functional layer, and annealing for later use;
(5) and evaporating a silver electrode on the hole transport layer.
6. The method as claimed in claim 5, wherein the step (2) comprises the steps of placing the glass substrate on a spin coater under atmospheric conditions, dropping 40-60ul of a solution of electron transport layer raw material doped with P-type semiconductor nanoparticles with a mass fraction of 0.5-3.5%, controlling the rotation speed at 4500-.
7. The method as claimed in claim 6, wherein the step (3) comprises transferring the device into a glove box, spin-coating an organic functional layer on the electron transport layer doped with P-type semiconductor nanoparticles under inert atmosphere, controlling the rotation speed at 3500-4500rpm for 15-25s, and annealing at 120-140 deg.C for 10-20 min.
8. The method for preparing an organic solar cell for establishing an internal electric field by doping nanoparticles into a charge transport layer according to claim 7, wherein the step (4) comprises transferring the spin-coated organic functional layer to a vacuum evaporation apparatus under a vacuum degree of less than (2-5) x 10 -3 Evaporating a layer of raw material solution doped with an N-type semiconductor nanoparticle hole transport layer with the mass fraction of 0.5-3.5% in a Pa environment, and then cooling for 20-30min in a vacuum environment.
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