CN114094019A - Method for improving adsorption density of self-assembled monomolecular carrier transport layer - Google Patents

Method for improving adsorption density of self-assembled monomolecular carrier transport layer Download PDF

Info

Publication number
CN114094019A
CN114094019A CN202111279464.7A CN202111279464A CN114094019A CN 114094019 A CN114094019 A CN 114094019A CN 202111279464 A CN202111279464 A CN 202111279464A CN 114094019 A CN114094019 A CN 114094019A
Authority
CN
China
Prior art keywords
substrate
transport layer
self
hole transport
nio
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.)
Pending
Application number
CN202111279464.7A
Other languages
Chinese (zh)
Inventor
寿春晖
孙娟娟
杨熹
应智琴
贺海晏
黄绵吉
丁莞尔
盛江
孙靖淞
闫宝杰
叶继春
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.)
Ningbo Institute of Material Technology and Engineering of CAS
Zhejiang Energy Group Research Institute Co Ltd
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
Zhejiang Energy Group Research Institute 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 Ningbo Institute of Material Technology and Engineering of CAS, Zhejiang Energy Group Research Institute Co Ltd filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN202111279464.7A priority Critical patent/CN114094019A/en
Publication of CN114094019A publication Critical patent/CN114094019A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605Carbon
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0694Halides
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • C23C14/083Oxides of refractory metals or yttrium
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • C23C14/085Oxides of iron group metals
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/18Metallic material, boron or silicon on other inorganic substrates
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • C23C14/26Vacuum evaporation by resistance or inductive heating of the source
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/35Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80Constructional details
    • H10K30/88Passivation; Containers; Encapsulations
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/15Hole transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/84Passivation; Containers; Encapsulations
    • H10K50/844Encapsulations
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention relates to a method for improving the adsorption density of a self-assembled monomolecular carrier transport layer, which comprises the following steps: preparing NiO on clean substrate by utilizing magnetron sputtering coating equipment at normal temperaturexA hole transport layer; regulating and controlling the binding sites on the substrate, selecting the organic matter containing anchoring groups and NiO on the surface of the substrate due to the hydroxyl contained on the surface of the substratexThe substrate of the hole transport layer reacts. The invention has the beneficial effects that: selecting organic matter containing anchoring group and NiO as surfacexReacting the substrate of the hole transport layer, selecting proper (molecular weight, symmetry, polarity and the like) organic matters containing anchoring groups by regulating and controlling the binding sites of the substrate, and preparing the required performances of high adsorption density, strong polarity and the like by regulating the content, deposition mode, growth direction and the like of the anchoring groups; the addition of a layer containing-OR functional groups prevents direct contact of the transparent conductive oxide substrate with the active layer; is favorable for improving the adsorption density of the organic matters containing the anchoring groups.

Description

Method for improving adsorption density of self-assembled monomolecular carrier transport layer
Technical Field
The invention belongs to the field of photovoltaics, and particularly relates to a method for improving the adsorption density of a self-assembled monomolecular carrier transport layer.
Background
In recent decades, photovoltaic technologies such as organic light emitting diodes, photodetectors, dye-sensitized solar cells, quantum dot solar cells, organic solar cells, and perovskite solar cells have been rapidly developed. Among them, organic-inorganic hybrid perovskite solar cells are receiving wide attention due to the advantages of high light absorption coefficient, long diffusion length, high carrier mobility, low exciton binding energy, adjustable band gap and the like, and the photoelectric conversion efficiency of a single perovskite solar cell is improved from 3.8% to 25.5% in nearly ten years. However, with the further improvement of the quality of perovskite crystals, efficient, stable and cheap carrier transport materials are of great importance for the further development of perovskite solar cells. The photoelectric conversion efficiency of the organic solar cell is close to the predicted limit value of 20%, and in order to further improve the efficiency and stability of the organic solar cell, the carrier transport material is also important to research.
Currently, several commonly used carrier transport materials are described below:
(1) perovskite solar cell: common hole transport materials include PEDOT PSS, PTAA, NiOX,CuOXCuSCN, poly-TPD and SAMs, etc.; common electron transport materials include PCBM, C60/BCP,TiO2,SnO2And SAMs, and the like.
(2) Organic solar cell: the material is usually PEDOT, PSS, which is used as a hole transport material; commonly used electron transport materials include PNDIT-F3N, PFN-Br, PDINO, ZnO, SAMs and the like.
Wherein SAMs refers to self-assembled monolayer materials consisting essentially of a head anchoring group (including-Si (OR))3,-P(OH)3-COOH, etc.), a central linking group and a tail functional group. SAMs has the advantages of simple preparation (spin coating, soaking, spraying, etc.), small parasitic absorption, low material consumption, conformal substrate, adjustable substrate energy level, and passivation of functional groupsThe advantages of the layer are widely noted. Since Albrecht et al 2018, SAM V1036 is applied to perovskite solar cells as a hole transport material for the first time, and various SAMs such as MeO-2PACz, 2PACz, Me-4PACz, Br-2PACz, TPA, EADR04 and the like are widely applied to perovskite solar cells and organic solar cells. SAMs are mostly used as SnO, although in other photovoltaic fields2And interface modification of ITO and the like (for example, 5-MePIFA, 5-DPIFA, FPA and the like are commonly used as modifiers in organic light emitting diodes), but can simultaneously function as a transport layer and an interface modifier as long as appropriate SAMs materials are selected.
For photovoltaic cells, the photoactive layer, the transport layer, and the electrodes are not critical to the performance of the device. With the rapid development of photovoltaic technology, the existing transport layer materials generally have the following problems, which greatly limit the further development of photovoltaic technology:
(1) conventional organic transport layer materials are expensive, have poor stability, and require complex doping processes.
(2) Conventional inorganic transport materials have interface defects and poor electrical conductivity.
(3) SAMs transport materials are adsorbed in a single layer and easily tunneled or formed into pores.
Therefore, developing a new transport layer material is a direct method to solve the above problems, but is not the fastest method to solve the above problems because the development of a new material takes a long time.
Aiming at the problem of poor conductivity of the traditional inorganic material, the problem is usually solved by adopting a doping mode at present. With NiOXTransport Material for example, Defect from Nickel oxide equation 2NiNi x+1/2O2(g)→2NiNi ·+Oo x+VNiThe conduction mechanism is known as follows: two in-situ Ni under oxygen atmosphere2+Will generate two Ni3+And a nickel vacancy, Ni2+And Ni3+There is charge transfer between them to make them conductive. Therefore, NiO is improvedXBesides doping, the conductivity of the material can be improved to a certain extent by changing the growth conditions.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for improving the adsorption density of a self-assembled monomolecular carrier transport layer.
The method for improving the adsorption density of the self-assembled monomolecular carrier transport layer comprises the following steps:
step 1, preparing NiO on a clean (TCO) substrate by utilizing magnetron sputtering coating equipment at normal temperaturexHole transport layer: when the working pressure of the magnetron sputtering coating equipment is smaller than a set value (the smaller the working pressure is, the higher the vacuum degree is, the less the residual impurity gas is, and the influence on the coating is smaller), the NiO is changedxThe flow rates of oxygen and argon are controlled to control the growth conditions of the hole transport layer2/(Ar+O2) Controlling to adjust the oxygen content O in the mixed gas of argon and oxygen2/(Ar+O2) To within 0-50%; electrons collide with argon atoms (due to equipment problem, after the power exceeds 80W, the surface temperature of a sample is high, and the sample is easy to crack) in the process of flying to the substrate under the action of an electric field with the power of 30-80W, and the argon atoms are ionized to generate Ar+And a new electron, Ar+Bombarding the surface of the cathode target under the action of an electric field; the thickness/time is estimated, the generated neutral target atoms or molecules are deposited on the substrate at a speed of 0.01-0.05 nm/s within 200-1000 s under a set pressure, and NiO is preparedxThe hole transport layer improves the conductivity to a certain extent; the higher the argon content is, the faster the growth rate of the film is; while an increase in oxygen content accelerates defect equation 2NiNi x+1/2O2(g)→2NiNi ·+Oo x+VNiProceeding to the right, Ni3+ and nickel vacancies increase, i.e. carrier concentration increases, mobility increases, and Ni3+The black color is gray, which can reduce the transmittance;
step 2, regulating and controlling the binding sites on the substrate treated in the step 1, wherein the surface of the substrate contains hydroxyl, and organic matters containing anchoring groups and NiO on the surface are selectedxThe substrate of the hole transport layer reacts.
Preferably, the step ofThe substrate 1 includes metal oxide substrate, metal substrate, non-metal oxide substrate, and substrate containing-Si (OR)3、-P(OR)3、-COOR、-SO3A substrate for an R, -COR, -SH, OR-OR group and a substrate without a linking group.
Preferably, in step 2:
when the substrate is a metal oxide substrate, the anchoring group comprises-Si (OR)3、-P(OR)3、-COOR、-SO3R and-COR;
when the substrate is a metal substrate, the anchoring group comprises-Si (OR)3、-P(OR)3、-COOR、-SO3R, -COR, -SH and-NH3
When the substrate is a non-metal oxide, the anchoring group comprises-Si (OR)3、-P(OR)3、-COOR、-SO3R and-COR;
the substrate is a film containing-Si (OR)3,-P(OR)3、-COOR、-SO3When the substrate for the R, -COR, -SH OR-OR group is present, the anchor group comprises-Si (OR)3、-P(OR)3、-COOR、-SO3R and-COR;
when the substrate is a substrate without connecting groups, firstly, ultraviolet ozone treatment is carried out to introduce dangling bonds, and then, groups are introduced on the dangling bonds, wherein the introduced groups comprise-Si (OR)3,-P(OR)3、-COOR、-SO3R and-COR.
Preferably, the NiO prepared in step 1xThe thickness of the hole transport layer is 1-10 nm; the electric field power during sputtering in step 1 was 80W, and the pressure during deposition was 0.4 Pa.
Preferably, the working pressure set value of the magnetron sputtering coating equipment in the step 1 is 4 multiplied by 10-4Pa。
Preferably, when the working pressure of the magnetron sputtering coating equipment in the step 1 is less than 4 multiplied by 10-4At Pa, adjusting O2/(Ar+O2) The ratio of (A) to (B) is 5 to 25 percent.
The method for improving the adsorption density of the self-assembled monomolecular carrier transport layer is applied to the preparation of the solar cell and comprises the following steps:
step 1, dissolving a self-assembly monomolecular layer material in an absolute ethyl alcohol solution to prepare a hole transport layer precursor solution;
step 2, after stirring the precursor solution of the hole transport layer at room temperature for a set time, dripping the precursor solution of the hole transport layer in NiOxThe surface of the substrate of the hole transport layer rotates at a set rotating speed for a set time length to form NiOxA substrate for a hole transport layer;
step 3, the surface is fully distributed with the NiO of the hole transport layer precursor solutionxAfter stopping the substrate of the hole transport layer, putting the substrate on a heating table for annealing; after cooling, washing the material by using a solution of the self-assembled monomolecular layer material at a set rotating speed to obtain a self-assembled monomolecular carrier transmission layer, and removing the unadsorbed material self-assembled monomolecular layer material;
step 4, preparing a perovskite thin film on the surface of the self-assembly monomolecular carrier transmission layer;
step 5, preparing a hole transport layer C on the surface of the perovskite thin film in the step 4 by adopting a thermal evaporation method60a/BCP and Ag electrode.
Preferably, the degree of vacuum in the vapor deposition in step 5 is less than 8 × 10-6Pa, evaporation rate of
Figure BDA0003325500190000041
The method for improving the adsorption density of the self-assembled monomolecular carrier transport layer is applied to the preparation of the organic light-emitting diode, and specifically comprises the following steps:
step 1, selecting F5BnPA as the self-assembled monomolecular layer material with NiOxPreparing a self-assembled monomolecular carrier transport layer on the substrate surface of the hole transport layer: the interface is different from the bulk phase, because the surface has a dangling bond with strong activity, the-OH and the adsorbed water molecules generally exist on the interface of the metal oxide, and NiO is formed at the set temperaturexSubstrate for hole transport layer in F5Soaking in a BnPA toluene solution; then NiOxRotating the substrate of the hole transport layer at a set rotation speed, washing with anhydrous ethanol, and removing unadsorbed self-assembled sheetsA molecular layer material;
step 2, preparing Ir (mppy) by spin coating method3TCTA film, preparing LiF and MoO in turn by thermal evaporation method3And an Al electrode to obtain the organic light emitting diode.
The invention has the beneficial effects that:
mainly researches magnetron sputtering NiOXAt different O2/(Ar+O2) In the atmosphere, Ni2+And Ni3+The NiO with better performance is prepared by the content change and the regulation and control of the power, the temperature and the deposition pressure during the magnetron sputteringXThe material provides a modification layer to improve the adsorption density of the monomolecular layer. In addition, the invention combines the defect problem of the traditional inorganic material and the adsorption density problem of the self-assembled monolayer, and experiments show that the adsorption mode and the adsorption density of the SAM can be changed by selecting different oxide substrates, and the SAM can adjust the substrate energy level and passivate the active layer.
The invention selects organic matter containing anchoring group and NiO on the surfacexReacting the substrate of the hole transport layer, selecting proper (molecular weight, symmetry, polarity and the like) organic matters containing anchoring groups by regulating and controlling the binding sites of the substrate, and preparing the required performances of high adsorption density, strong polarity and the like by regulating the content, deposition mode, growth direction and the like of the anchoring groups;
the addition of the layer containing the-OR functional group in the invention can prevent the Transparent Conductive Oxide (TCO) substrate from directly contacting with the active layer; the adsorption density of the organic matter containing the anchoring group is improved; the increase of the adsorption density of the organic matter containing the anchoring group can improve the passivation capability of the interface; and the organic matter with proper functional groups is selected, so that the energy level alignment of the carrier transport layer and the active layer can be adjusted.
Drawings
FIG. 1 shows ITO/HTL/C60A semi-logarithmic current density-voltage plot for the/BCP/Ag hole-electron structure;
FIG. 2 is a graph of half-log current density versus voltage for ITO/HTL/PVK/spiro-OMeTAD/Ag with hole-only structures;
FIG. 3 is MeO-2PACz and NiOXUltraviolet electron spectrum curve diagram of the secondary cut-off edge of the/MeO-2 PAC after differential processing.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for a person skilled in the art, several modifications can be made to the invention without departing from the principle of the invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.
Example one
The embodiment of the application provides an application of a method for improving the adsorption density of a self-assembled monomolecular carrier transport layer in the preparation of a perovskite solar cell, which comprises the following steps:
preparation of NiO on clean Transparent Conductive Oxide (TCO) substrate using magnetron sputtering coating equipmentXA hole transport layer. When the working pressure is less than 4 x 10-4At Pa, adjusting O2/(Ar+O2) The ratio of (A) to (B) is 0-50%. The mechanism of magnetron sputtering is that electrons collide with argon atoms in the process of flying to a substrate under the action of an electric field so as to ionize the argon atoms to generate Ar+And new electrons. Ar (Ar)+Bombarding the surface of the cathode target under the action of an electric field, and depositing the generated neutral target atoms or molecules on a substrate to form a film. The higher the argon content, the faster the growth rate of the film. The increase of the oxygen content accelerates the rightward progress of the defect equation to generate high-valence nickel and nickel vacancies, and causes the change of the properties such as carrier concentration, mobility, transmittance and the like. When the film is deposited, the sputtering power is set to be 80W, the deposition pressure is 0.4Pa, and NiO with better performance is prepared at normal temperatureXA film material.
In NiOXAnd preparing a self-assembly monomolecular layer material MeO-2PACz on the surface. The interface is different from the bulk phase, and because the surface has a dangling bond with strong activity, the-OH and adsorbed water molecules generally exist on the interface of the metal oxide. MeO-2PACz was dissolved in an anhydrous ethanol solution to prepare a hole transport layer precursor solution having a concentration of 2 mmol/l. After stirring at room temperature for 15min, the above liquid was dropped on NiOXSurface ofThe upper rotation is 30s, and the rotation speed is 4000 rpm. After the run was stopped, it was annealed for 10min on a heating stage at a temperature of 100 ℃. After cooling, the non-adsorbed material was removed by dynamic rinsing twice with anhydrous ethanol at 4000 rpm. ITO glass substrate and ITO glass substrate/NiO before and after spin coating of MeO-2PACzXThe atomic contents of the main elements in the film are shown in table 1 below:
TABLE 1 ITO glass substrate and ITO glass substrate/NiO before and after spin coating with MeO-2PACzXAtomic content table of main element in thin film
Figure BDA0003325500190000061
In the above table, N/A indicates that the element is not present in the sample, and the unit of each parameter is% indicates the atomic concentration percentage. From the above table, it can be seen that the addition of the layer containing an-OR functional group is advantageous for increasing the adsorption density of the organic substance containing an anchor group.
Perovskite thin films were prepared by spin coating: dissolving perovskite powder in a solvent with a DMF/DMSO ratio of 4:1, and stirring for 2h for use; dropwise adding the filtered perovskite precursor solution into ITO/NiO covered by MeO-2PACzXThe surface of the film is rotated for 35s at 3500 rmp; dripping 330 μ l chlorobenzene continuously 25s before the program is finished, and annealing for 20min on a heating table at 100 deg.C; and finishing the preparation of the perovskite solar cell.
Preparing the hole transport layer C by thermal evaporation60BCP, and Ag electrode: 24nm C60 and 6nm BCP were prepared in sequence by thermal evaporation at a rate of 0.1A/s to 3A/s. 100nm Ag electrode is prepared by thermal evaporation method, and the evaporation rate is 0.1-5A DEG/s. Vacuum degree during vapor deposition is lower than 8 x 10-6Pa, evaporation rate of
Figure BDA0003325500190000062
Example two
The second embodiment of the present application provides an application of the method for improving the adsorption density of the self-assembled monomolecular carrier transport layer in the preparation of an organic solar cell:
preparation of NiO on clean Transparent Conductive Oxide (TCO) substrate using magnetron sputtering coating equipmentXA hole transport layer. When the working pressure is less than 4 x 10-4At Pa, adjusting O2/(Ar+O2) The ratio of (A) to (B) is 0-50%. The mechanism of magnetron sputtering is that electrons collide with argon atoms in the process of flying to a substrate under the action of an electric field so as to ionize the argon atoms to generate Ar+And new electrons. Ar (Ar)+Bombarding the surface of the cathode target under the action of an electric field, and depositing the generated neutral target atoms or molecules on a substrate to form a film. The higher the argon content, the faster the growth rate of the film. The increase of the oxygen content accelerates the rightward progress of the defect equation to generate high-valence nickel and nickel vacancies, and causes the change of the properties such as carrier concentration, mobility, transmittance and the like. When the film is deposited, the sputtering power is set to be 80W, the deposition pressure is 0.4Pa, and NiO with better performance is prepared at normal temperatureXA film material.
In NiOXPreparing self-assembly monomolecular layer material Br-2PACz on the surface. The interface is different from the bulk phase, and because the surface has a dangling bond with strong activity, the-OH and adsorbed water molecules generally exist on the interface of the metal oxide. Br-2PACz was dissolved in an anhydrous ethanol solution to prepare a hole transport layer precursor solution having a concentration of 0.3 mg/mL. After stirring at room temperature for 1h, the above liquid was dropped on NiOXThe surface was spun for 30s at 3000 rpm. After the run was stopped, it was annealed for 5min on a heating stage at a temperature of 50 ℃. After cooling, the unadsorbed material was removed by dynamic washing twice with 0.3mg/mL Br-2PACz solution at 4000 rpm.
And finishing the preparation of the organic solar cell. PEDOT PSS film, PM6 BTP-eC9 PC was prepared in this order by spin-coating71BM film and PFN-Br film, and Ag electrode is prepared through thermal evaporation process. Vacuum degree during vapor deposition is lower than 8 x 10-6Pa, evaporation rate of
Figure BDA0003325500190000071
EXAMPLE III
The third embodiment of the present application provides an application of the method for improving the adsorption density of the self-assembled monomolecular carrier transport layer in the preparation of an organic light emitting diode:
preparation of NiO on clean Transparent Conductive Oxide (TCO) substrate using magnetron sputtering coating equipmentXA hole transport layer. When the working pressure is less than 4 x 10-4At Pa, adjusting O2/(Ar+O2) The ratio of (A) to (B) is 0-50%. The mechanism of magnetron sputtering is that electrons collide with argon atoms in the process of flying to a substrate under the action of an electric field so as to ionize the argon atoms to generate Ar+And new electrons. Ar (Ar)+Bombarding the surface of the cathode target under the action of an electric field, and depositing the generated neutral target atoms or molecules on a substrate to form a film. The higher the argon content, the faster the growth rate of the film. The increase of the oxygen content accelerates the rightward progress of the defect equation to generate high-valence nickel and nickel vacancies, and causes the change of the properties such as carrier concentration, mobility, transmittance and the like. When the film is deposited, the sputtering power is set to be 80W, the deposition pressure is 0.4Pa, and NiO with better performance is prepared at normal temperatureXA film material.
In NiOXSurface preparation of self-assembled monolayer Material F5BnPA. The interface is different from the bulk phase, and because the surface has a dangling bond with strong activity, the-OH and adsorbed water molecules generally exist on the interface of the metal oxide. The substrate was immersed in F at a concentration of 1mmol/l5BnPA in toluene. Soaking at 50 deg.C for 8 hr. The non-adsorbed material was then removed by dynamic washing twice with absolute ethanol at 4000 rpm.
And finishing the preparation of the organic light emitting diode. Preparation of Ir (mppy) by spin coating3TCTA film, sequentially preparing LiF and MoO by thermal evaporation3And an Al electrode. Vacuum degree during vapor deposition is lower than 8 x 10-6Pa, evaporation rate of
Figure BDA0003325500190000072
Experiments prove that:
as shown in FIG. 1, the addition of a layer containing-OR functionality may prevent direct contact of the TCO with the active layer;
as shown in fig. 2, the increase in adsorption density of the organic substance containing an anchor group can improve the interfacial passivation ability.
As shown in fig. 3, the selection of organic materials with appropriate functional groups is beneficial to adjusting the energy level alignment of the carrier transport layer and the active layer.
By the gain of the effect, the performance of the finally prepared device is obviously improved.

Claims (9)

1. A method for improving the adsorption density of a self-assembled monomolecular carrier transport layer is characterized by comprising the following steps:
step 1, preparing NiO on a clean substrate by utilizing magnetron sputtering coating equipmentxHole transport layer: when the working pressure of the magnetron sputtering coating equipment is less than a set value, the flow rate of oxygen and argon is controlled to carry out O reaction2/(Ar+O2) Controlling to adjust the oxygen content O in the mixed gas of argon and oxygen2/(Ar+O2) To within 0-50%; preparation of NiOxA hole transport layer;
step 2, regulating and controlling the binding sites on the substrate treated in the step 1, selecting an organic matter containing an anchoring group and NiO on the surfacexThe substrate of the hole transport layer reacts.
2. The method for increasing the adsorption density of a self-assembled monomolecular carrier transport layer according to claim 1, wherein: the substrate in step 1 comprises a metal oxide substrate, a metal substrate, a non-metal oxide substrate, a substrate containing-Si (OR)3、-P(OR)3、-COOR、-SO3A substrate for an R, -COR, -SH, OR-OR group and a substrate without a linking group.
3. The method for increasing the adsorption density of a self-assembled monomolecular carrier transport layer according to claim 2, wherein in the step 2:
when the substrate is a metal oxide substrate, the anchoring group comprises-Si (OR)3、-P(OR)3、-COOR、-SO3R and-COR;
when the substrate is a metal substrate, the anchoring group comprises-Si (OR)3、-P(OR)3、-COOR、-SO3R, -COR, -SH and-NH3
When the substrate is a non-metal oxide, the anchoring group comprises-Si (OR)3、-P(OR)3、-COOR、-SO3R and-COR;
the substrate is a film containing-Si (OR)3,-P(OR)3、-COOR、-SO3When the substrate for the R, -COR, -SH OR-OR group is present, the anchor group comprises-Si (OR)3、-P(OR)3、-COOR、-SO3R and-COR;
when the substrate is a substrate without connecting groups, firstly, ultraviolet ozone treatment is carried out to introduce dangling bonds, and then, groups are introduced on the dangling bonds, wherein the introduced groups comprise-Si (OR)3,-P(OR)3、-COOR、-SO3R and-COR.
4. The method for increasing the adsorption density of a self-assembled monomolecular carrier transport layer according to claim 1, wherein: NiO prepared in step 1xThe thickness of the hole transport layer is 1-10 nm; the electric field power during sputtering in step 1 was 80W, and the pressure during deposition was 0.4 Pa.
5. The method for increasing the adsorption density of a self-assembled monomolecular carrier transport layer according to claim 1, wherein: the working pressure setting value of the magnetron sputtering coating equipment in the step 1 is 4 multiplied by 10-4Pa。
6. The method for increasing the adsorption density of a self-assembled monomolecular carrier transport layer according to claim 1, wherein: when the working pressure of the magnetron sputtering coating equipment is less than 4 multiplied by 10 in the step 1-4At Pa, adjusting O2/(Ar+O2) The ratio of (A) to (B) is 5 to 25 percent.
7. The application of the method for improving the adsorption density of the self-assembled monomolecular carrier transport layer according to claim 1 in the preparation of solar cells is characterized by comprising the following steps:
step 1, dissolving a self-assembly monomolecular layer material in an absolute ethyl alcohol solution to prepare a hole transport layer precursor solution;
step 2, after stirring the precursor solution of the hole transport layer at room temperature for a set time, dripping the precursor solution of the hole transport layer in NiOxThe surface of the substrate of the hole transport layer rotates at a set rotating speed for a set time length to form NiOxA substrate for a hole transport layer;
step 3, the surface is fully distributed with the NiO of the hole transport layer precursor solutionxAfter stopping the substrate of the hole transport layer, putting the substrate on a heating table for annealing; after cooling, washing the solution of the self-assembly monomolecular layer material at a set rotating speed to obtain a self-assembly monomolecular carrier transmission layer;
step 4, preparing a perovskite thin film on the surface of the self-assembly monomolecular carrier transmission layer;
step 5, preparing a hole transport layer C on the surface of the perovskite thin film in the step 4 by adopting a thermal evaporation method60a/BCP and Ag electrode.
8. The application of the method for improving the adsorption density of the self-assembled monomolecular carrier transport layer according to claim 7 in the preparation of solar cells is characterized in that: the vacuum degree during vapor deposition in the step 5 is lower than 8 multiplied by 10-6Pa, evaporation rate of
Figure FDA0003325500180000021
9. The application of the method for improving the adsorption density of the self-assembled monomolecular carrier transport layer according to claim 1 in the preparation of the organic light-emitting diode is characterized by comprising the following steps:
step 1, selecting F5BnPA as the self-assembled monomolecular layer material with NiOxPreparing a self-assembled monomolecular carrier transport layer on the substrate surface of the hole transport layer: at a set temperature, NiO is addedxSubstrate for hole transport layer in F5Soaking in a BnPA toluene solution; then NiOxRotating the substrate of the hole transport layer at a set rotation speed, washing with anhydrous ethanol, and removingUnadsorbed self-assembled monolayer material;
step 2, preparing Ir (mppy) by spin coating method3TCTA film, preparing LiF and MoO in turn by thermal evaporation method3And an Al electrode to obtain the organic light emitting diode.
CN202111279464.7A 2021-10-28 2021-10-28 Method for improving adsorption density of self-assembled monomolecular carrier transport layer Pending CN114094019A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111279464.7A CN114094019A (en) 2021-10-28 2021-10-28 Method for improving adsorption density of self-assembled monomolecular carrier transport layer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111279464.7A CN114094019A (en) 2021-10-28 2021-10-28 Method for improving adsorption density of self-assembled monomolecular carrier transport layer

Publications (1)

Publication Number Publication Date
CN114094019A true CN114094019A (en) 2022-02-25

Family

ID=80298490

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111279464.7A Pending CN114094019A (en) 2021-10-28 2021-10-28 Method for improving adsorption density of self-assembled monomolecular carrier transport layer

Country Status (1)

Country Link
CN (1) CN114094019A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230345745A1 (en) * 2022-04-21 2023-10-26 Alliance For Sustainable Energy, Llc Formulations for the manufacture of perovskite devices

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230345745A1 (en) * 2022-04-21 2023-10-26 Alliance For Sustainable Energy, Llc Formulations for the manufacture of perovskite devices

Similar Documents

Publication Publication Date Title
Zhang et al. Highly efficient and stable planar heterojunction perovskite solar cells via a low temperature solution process
CN109728166B (en) Methylamine lead iodine perovskite solar cell containing organic luminescent micromolecular interface modification layer
CN104183697B (en) Solar cell of perovskite structure and preparing method of solar cell
Huang et al. Modification of SnO2 electron transport Layer: Brilliant strategies to make perovskite solar cells stronger
WO2019153906A1 (en) Additive-doped perovskite film, preparation method therefor and application thereof
WO2019128864A1 (en) Ion stabilizer-doped perovskite film, preparation method therefor and application thereof
Li et al. A simple synthesis method to prepare a molybdenum oxide hole-transporting layer for efficient polymer solar cells
CN107369766B (en) Perovskite solar cell with high-quality metal oxide electron transport layer and preparation method thereof
CN112216799A (en) Method for passivating perovskite and preparation process of perovskite solar cell
CN108807694B (en) Flat perovskite solar cell with ultralow temperature stability and preparation method thereof
Qiu et al. Rapid hybrid chemical vapor deposition for efficient and hysteresis-free perovskite solar modules with an operation lifetime exceeding 800 hours
CN110176539B (en) Preparation method of efficient perovskite solar cell with stable full-spectrum light
CN108767117B (en) Perovskite solar cell based on carbon quantum dot doped anti-solvent passivated grain boundary defects and preparation method thereof
CN111710780B (en) Preparation method of cathode in-situ modified perovskite solar cell without electron transport layer
Zhao et al. Effect of Li-doped TiO2 layer on the photoelectric performance of carbon-based CsPbIBr2 perovskite solar cell
Thambidurai et al. Highly stable and efficient planar perovskite solar cells using ternary metal oxide electron transport layers
Makenali et al. Efficiency improvement of perovskite solar cells by charge transport balancing using length tunable ZnO nanorods and optimized perovskite morphology
CN115568237A (en) Perovskite solar cell and preparation method thereof
Chan et al. High-performance perovskite solar cells based on low-temperature processed electron extraction layer
CN108832001B (en) Lead-free perovskite solar cell device and preparation method thereof
CN114094019A (en) Method for improving adsorption density of self-assembled monomolecular carrier transport layer
Xie et al. Highly air-stable and efficient CH3NH3PbI3 solar cells enhanced by ZnO-embedded PCBM electron transport layers
CN111192964B (en) Perovskite quantum dot solar cell and preparation method thereof
CN116847670A (en) Perovskite solar cell of passivation composite hole transport layer
Sun et al. Improved performance of hole-transporting layer-free perovskite solar cells by using graphene oxide sheets as the nucleation centers

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