WO2025175671A1 - 一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体 - Google Patents

一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体

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Publication number
WO2025175671A1
WO2025175671A1 PCT/CN2024/100643 CN2024100643W WO2025175671A1 WO 2025175671 A1 WO2025175671 A1 WO 2025175671A1 CN 2024100643 W CN2024100643 W CN 2024100643W WO 2025175671 A1 WO2025175671 A1 WO 2025175671A1
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perovskite
semiconductor
perovskite semiconductor
ion
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French (fr)
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狄大卫
熊文涛
赵保丹
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Zhejiang University
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Zhejiang University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • 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
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • 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
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/135—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising mobile ions
    • 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

Definitions

  • the present invention relates to the technical field of semiconductor materials and devices, and in particular to a perovskite semiconductor capable of achieving p-type, n-type and i-type conductivity through doping.
  • silicon a traditional semiconductor material, as an example, silicon can be doped into either n-type (electrons as the primary charge carrier) or p-type (holes as the primary charge carrier) by introducing electron acceptors (such as boron) or electron donors (such as phosphorus) into its crystal lattice.
  • electron acceptors such as boron
  • electron donors such as phosphorus
  • Perovskite materials are a new type of ionic crystal semiconductor with a crystal structure, including but not limited to cubic structures, in which different ions are held together by interionic forces. These materials offer advantages such as continuously tunable band gaps, easy carrier diffusion, solution-processable processing, strong light absorption, high luminescence quantum efficiency, and spectrally pure luminescence.
  • controllable electrical doping of perovskites is difficult to achieve, hindering their further development and application in the semiconductor industry. Since their first report in 2009, perovskite solar cells have seen rapid growth in efficiency, now exceeding 26%. However, they still lag behind traditional inorganic silicon cells in terms of stability and energy conversion efficiency.
  • perovskite is a highly luminescent material that can be prepared using a solution process.
  • LEDs light-emitting diodes
  • Their efficiency has now exceeded 30%, comparable to inorganic and organic light-emitting diodes.
  • controllable electrical doping of perovskite semiconductors has yet to be achieved, making precise control of their conductivity type and electrical properties difficult, hindering further development in the field of perovskite semiconductors and optoelectronic devices. Controllable doping of perovskite semiconductor materials has many benefits: 1.
  • perovskite semiconductor materials It can precisely control the conductivity type (polarity), resistivity, conductivity, carrier concentration, carrier mobility, Fermi level, band position and photoelectric properties of perovskite semiconductor materials; 2. It can realize the design and development of a series of p-type, n-type and i-type perovskite semiconductor materials, and design and prepare homojunctions or heterojunctions with different functions based on one or more perovskite semiconductor materials, which further expands the building blocks of perovskite devices and helps realize a variety of new perovskite semiconductor devices, including but not limited to diodes, transistors, solar cells, detectors, scintillators, light-emitting diodes, semiconductor lasers, etc.; 3.
  • Controllably doped perovskite semiconductor materials can free perovskite devices from dependence on transport layer materials, and can realize perovskite optoelectronic devices without hole or electron transport layers, greatly simplifying the preparation process of perovskite devices. 4.
  • Controllable doping strategies for perovskite semiconductor materials can significantly enrich the types of perovskite semiconductor materials, enabling them to achieve performance comparable to or exceeding that of traditional semiconductors (such as silicon and III-V semiconductors). Therefore, the controllable doping of perovskite semiconductors achieved by this invention is crucial to the development of the emerging field of perovskite semiconductors and optoelectronic devices, promising unprecedented device performance and accelerating the creation of new semiconductor devices.
  • the present invention proposes a perovskite semiconductor that can achieve p-type, n-type and i-type conductivity through doping.
  • perovskite semiconductors As an emerging semiconductor material, perovskite semiconductors have a relatively complex structure and composition. Controllable electrical doping of perovskite semiconductors has not yet been achieved, making it difficult to precisely regulate their conductivity type and electrical properties, hindering further development in the field of perovskite semiconductors and optoelectronic devices. To address this important technical issue, the present invention achieves controllably doped perovskite semiconductor materials and optoelectronic devices. Doped perovskite semiconductor materials can be further divided into p-type perovskites, which primarily conduct holes, n-type perovskites, which primarily conduct electrons, and i-type perovskites, which exhibit bipolar transport.
  • P-type dopants can inhibit the formation of electron-donating levels in perovskite materials or exhibit electron-withdrawing effects, resulting in perovskite semiconductor materials with enhanced p-type semiconductor properties or weakened n-type semiconductor properties.
  • N-type dopants can inhibit the formation of electron-accepting levels in perovskite materials or exhibit electron-donating effects, resulting in perovskite semiconductor materials with enhanced n-type semiconductor properties or weakened p-type semiconductor properties.
  • the structural characteristics of dopants are that they contain functional groups with lone pairs of electrons, or their functional groups can provide empty electron orbitals or ionize to produce ions that partially replace certain ions in the perovskite crystal.
  • Dopants can be classified by type, including but not limited to organic polymer materials, organic small molecule materials, organic salts, inorganic salts, Lewis acids, and Lewis bases.
  • the preparation method and doping method of controllable doped perovskite semiconductor material include but are not limited to: 1.
  • A'X (one or more), AX (one or more), BX (one or more) and dopant are dissolved in a solvent to obtain a perovskite precursor solution, and the doped perovskite material can be prepared by a solution method; 2.
  • A'X (one or more), AX (one or more), BX (one or more) are dissolved in a solvent to obtain a perovskite precursor solution and prepare a perovskite material, and the dopant is introduced into the perovskite by a doping process such as anti-solvent treatment, surface modification, solution fumigation, solid-state diffusion, plasma implantation, etc. to obtain a doped perovskite semiconductor material; 3.
  • A'X (one or more), AX (one or more), BX (one or more) are mixed by magnetic field.
  • the perovskite semiconductor material is prepared by non-solution methods such as controlled sputtering, solid-state reaction, vapor deposition, and evaporation, and the dopant is introduced into the perovskite through doping processes such as anti-solvent treatment, surface modification, solution fumigation, solid-state diffusion, and plasma injection to obtain a doped perovskite semiconductor material; 2.
  • the doped perovskite semiconductor material is prepared by a combination of two or more of the above processes.
  • One or more of the different doped perovskite semiconductor materials prepared by the above dopants and methods can form homojunctions or heterojunctions with different functions, enriching the building blocks of perovskite electronic or optoelectronic devices, and can be used to prepare perovskite electronic or optoelectronic devices including but not limited to diodes, transistors, solar cells, detectors, scintillators, light-emitting diodes, semiconductor lasers, etc.
  • the perovskite electronic or optoelectronic device is composed of a doped perovskite material and one or more of the device functional materials such as a substrate, an anode, an electron transport material, a hole transport material, and a cathode.
  • Doped perovskite semiconductors can get rid of the dependence on complex electron transport layers or hole transport layers, and thus even perovskite optoelectronic devices without transport layers can be realized.
  • Such devices have simpler preparation processes, which can reduce the complexity and cost of device preparation and improve the repeatability and yield of device preparation.
  • the present invention discloses controllably doped perovskite materials, doping methods, and optoelectronic devices thereof.
  • the preparation method and doping method of the controllably doped perovskite semiconductor material can be one or a combination of the following preparation methods.
  • A'X (one or more), AX (one or more), BX (one or more) and a dopant are dissolved in a solvent to obtain a perovskite precursor solution, and a doped perovskite material can be prepared by a solution method;
  • A'X (one or more), AX (one or more), and BX (one or more) are dissolved in a solvent to obtain a perovskite precursor solution and prepared into a perovskite material, and the dopant is introduced into the perovskite through a doping process such as anti-solvent treatment, surface modification, solution fumigation, solid-state diffusion, and plasma injection to obtain a doped perovskite semiconductor material;
  • A'X (one or more), AX (one or more), and BX (one or more) are prepared into a perovskite semiconductor material through
  • Common functional groups containing lone pairs of electrons in the organic dopant molecules and common functional groups in Lewis bases include, but are not limited to, phosphoric acid group (-PO(OH) 2 ), phosphoryl chloride group (-P(O)Cl 2 ), phosphoryl group (-P(O)R 2 ), organophosphate group (-OP(O)(OR) 2 ), sulfonic acid group (-SO 3 H), thiol group (-S( ⁇ O)—R), amino group (-NH 2 ), hydroxyl group (-OH), cyano group (-CN), aldehyde group (-CHO), carboxyl group (-COOH), ketone group (-C ⁇ OR), and nitrogen nitrile group (-N ⁇ C).
  • Common functional groups containing empty electron orbitals in the organic dopant molecules and common functional groups in Lewis acids include, but are not limited to, carbon-carbon double bond group (-C ⁇ C), carbon-carbon triple bond group (-C ⁇ C), and boric acid (BF 3 ).
  • Common ions in the inorganic dopant molecules include, but are not limited to, sodium ions (Na + ), potassium ions (K + ), rubidium ions (Rb + ), europium ions (Eu 2+ ), strontium ions (Sr 2+ ), silver ions (Ag + ), indium ions (In 2+ ), and bismuth ions (Bi 2+ ).
  • FIG9 is a schematic diagram of the surface contact potential difference of the perovskite film with different doping concentrations in Example 1 of the present invention.
  • FIG10 is a Hall coefficient test result of perovskite materials with different doping concentrations in Example 1 of the present invention.
  • FIG11 shows the main carrier types and density test results of perovskite materials with different doping concentrations in Example 1 of the present invention
  • FIG12 is a theoretical calculation model of the undoped perovskite material in Example 2 of the present invention.
  • FIG13 is a theoretical calculation model of the doped perovskite material in Example 2 of the present invention.
  • FIG14 shows the calculation results of the formation energy of different defects in the undoped perovskite in Example 2 of the present invention.
  • FIG15 is a diagram showing the electron cloud density distribution of undoped perovskite in Example 2 of the present invention.
  • FIG16 is a diagram showing the electron cloud density distribution of the doped perovskite in Example 2 of the present invention.
  • FIG. 17 is a graph showing the state density/(EE V ) of the perovskite before and after doping in Example 2 of the present invention.
  • FIG19 is a nuclear magnetic resonance spectrum of 4PACz with or without the addition of PbBr2 in Example 2 of the present invention.
  • FIG21 is an X-ray photoelectron spectrum of the undoped and doped perovskite materials in Example 2 of the present invention.
  • FIG24 is a performance comparison diagram of light-emitting diode devices without a hole transport layer based on perovskites with different doping concentrations in Example 3 of the present invention.
  • FIG28 is an external quantum efficiency-brightness curve of a perovskite light-emitting diode without a hole transport layer based on an undoped and 5% doped structure in Example 3 of the present invention.
  • FIG29 is a graph showing the energy conversion efficiency-brightness curve of the perovskite light-emitting diode without a hole transport layer based on undoped and 5% doped examples in Example 3 of the present invention.
  • FIG31 is a transient photoluminescence spectrum of the undoped and 5% doped perovskite films in Example 3 of the present invention.
  • Figure 1 shows the crystal structure of an undoped perovskite material
  • Figure 2 shows the crystal structure of a doped perovskite material.
  • the unsaturated B sites in the perovskite can interact with the acidic groups in the dopant.
  • the dopant provides electron-donating or electron-withdrawing groups to the perovskite material, suppressing the amount of unsaturated lead in the perovskite and thus the formation of electron-donating or electron-accepting energy levels caused by related defects. This regulates the type (electrons or holes) and amount of the primary carriers in the perovskite material, and thus the conductivity of the perovskite material.
  • the perovskite material can achieve the appropriate carrier mobility and carrier density, enabling the successful fabrication of high-efficiency, high-brightness light-emitting diodes without a hole or electron transport layer.
  • the perovskite precursor solution is prepared by dissolving A'X, AX, BX2 , and a dopant P in a solvent (which can be any one or a mixture of DMF, DMSO, GBL, NMP, acetonitrile, G-butyrolactone, etc.).
  • a solvent which can be any one or a mixture of DMF, DMSO, GBL, NMP, acetonitrile, G-butyrolactone, etc.
  • A' is an organic amine cation
  • A is a monovalent cation such as cesium (Cs + ), methylamine (MA + ), methylamine (FA + ), ethylamine (EA + ), hydrazine (HA + ), guanidine (GA + ), isopropylamine (IPA + ), or imidazolium (IA + );
  • the B-position is a divalent metal cation such as lead (Pb2 + ), tin (Sn2 + ), or germanium (Ge2 + ); and the X-position anions include chloride ( Cl- ), bromide ( Br- ), or iodide ( I- ).
  • the concentration of the perovskite precursor solution is 0.01-2 mol/L.
  • the substrate is sequentially soaked in water, deionized water, acetone, and isopropyl alcohol. It is then cleaned in an ultrasonic machine for more than 15 minutes.
  • the ITO glass substrate is treated with a plasma machine for 15 minutes.
  • the perovskite film is then prepared directly on the ITO using a solution method and annealed for a certain period of time.
  • an anti-solvent such as chlorobenzene, toluene, ethyl acetate, anhydrous ether, chloroform, or any one or more mixed solvents is introduced.
  • the electron or hole transport layer is then prepared by spin coating, evaporation, magnetron sputtering, atomic layer deposition, etc.
  • the electrode layer is prepared by evaporation, magnetron sputtering, atomic layer deposition, etc.
  • a two-step spin coating method was used to deposit perovskite films on substrates including, but not limited to, ITO substrates, quartz glass substrates, sapphire substrates, and silicon wafers. The first spin coating step involved hanging coating at 500 rpm for 10 seconds, and the second spin coating step involved hanging coating at 5000 rpm for 90 seconds.
  • Figure 3 shows the UV photoelectron spectroscopy results for perovskite materials with different doping concentrations.
  • IP represents the ionization potential
  • WF represents the work function.
  • Figure 4 shows the energy level configurations for perovskite materials with different doping concentrations.
  • EV represents the valence band bottom, and EC represents the conduction band top.
  • Figure 5 shows a Darwin's probe microscopy image of the surface of an undoped perovskite film; the scale bar is 400 nm.
  • Figure 6 shows a Darwin's probe microscopy image of the surface of a perovskite film with a 1% doping concentration (dopant relative to Pb 2+ ); the scale bar is 400 nm.
  • Figure 7 shows a Darwin's probe microscopy image of the surface of a perovskite film with a 3% doping concentration (dopant relative to Pb 2+ ); the scale bar is 400 nm.
  • Figure 8 shows a Darwin's probe microscopy image of the surface of a perovskite film with a 5% doping concentration (dopant relative to Pb 2+ ); the scale bar is 400 nm.
  • Figure 9 shows a schematic diagram of the contact potential difference on the surface of perovskite films with different doping concentrations.
  • Figure 10 shows the Hall coefficient test results for perovskite materials with different doping concentrations.
  • Figure 11 shows the main carrier type and density test results for perovskite materials with different doping concentrations.
  • Figure 12 is the theoretical calculation model of the undoped perovskite material.
  • Figure 13 is the theoretical calculation model of the doped perovskite material;
  • Figure 14 is the calculation results of the formation energy of different defects in the undoped perovskite;
  • Figure 15 is the electron cloud density distribution diagram of the undoped perovskite;
  • Figure 16 is the electron cloud density distribution diagram of the doped perovskite;
  • Figure 17 is the perovskite neutral state density/(EE V ) diagram before and after doping;
  • Figure 18 is based on the density functional calculation results.
  • FIG. 19 Schematic diagram of the perovskite doping mechanism
  • Figure 19 is the nuclear magnetic resonance spectrum of 4PACz with or without the addition of PbBr2
  • Figure 20 is the Fourier transform infrared absorption spectrum of 4PACz and doped perovskite materials
  • Figure 21 is the X-ray photoelectron spectrum of undoped and doped perovskite materials.
  • the substrate was sequentially soaked in water, deionized water, acetone, and isopropyl alcohol and cleaned in an ultrasonic machine for at least 15 minutes. Before spin coating, the substrate was treated with a plasma machine for 15 minutes.
  • a two-step spin coating method was used to deposit perovskite thin films on substrates including but not limited to ITO, quartz glass, sapphire, and silicon wafers.
  • the first spin coating step was performed at 500 rpm for 10 seconds, and the second spin coating step was performed at 5000 rpm for 90 seconds. Approximately 40 seconds after the start of the second spin coating step, 100 ⁇ L of an antisolvent (2 mg/mL TPBI in chloroform) was added dropwise to the sample. After spin coating, the perovskite film was annealed at 90°C for 10 minutes.
  • the electron transport layer was PO-T2T, and the electrode material was Yb/Ag.
  • Figure 22 a device structure diagram of a perovskite light-emitting diode without a hole transport layer is shown;
  • Figure 23 is a transmission electron micrograph of a cross-section of a perovskite light-emitting diode without a hole transport layer;
  • Figure 24 is a performance comparison diagram of light-emitting diode devices without a hole transport layer based on perovskites with different doping concentrations;
  • Figure 25 is a luminescence spectrum diagram of a perovskite light-emitting diode without a hole transport layer based on an undoped and 5% doped perovskite;
  • Figure 26 is a current density-voltage curve of a perovskite light-emitting diode without a hole transport layer based on an undoped and 5% doped perovskite;
  • Figure 27 is a brightness-voltage curve of a perovskite light-emitting diode without a hole transport layer based on

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Abstract

一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体材料；其中，掺杂的钙钛矿半导体材料根据导电类型又可分为p型、n型以及i型(本征)。这些钙钛矿半导体材料特性可调，经掺杂后的钙钛矿半导体材料组分为A' 2A n-1B nX 3n+1:D或ABX 3:D，其中A'为有机阳离子，A为一价阳离子，B为金属阳离子，X为一价阴离子，D为掺杂剂。基于经掺杂的钙钛矿半导体材料的光电子器件可以摆脱对电子传输层或空穴传输层的依赖，从而简化器件工艺，降低器件制备复杂性和成本。基于可控掺杂的钙钛矿半导体材料的发光二极管、太阳能电池和晶体管展现出优异的性能。

Description

一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体 技术领域
本发明涉及半导体材料与器件技术领域，尤其涉及的是一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体。
技术背景
对半导体导电极性和电导率的可靠调控，是现代电子工业的核心技术，引致了二极管、晶体管、太阳能电池、光电探测器、发光二极管、半导体激光器等多项革命性的发明。以传统半导体材料—硅为例，可以通过引入电子受主(如硼)或者电子施主(如磷)到其晶格中，以实现硅的n型(电子为主要载流子)或者p型(空穴为主要载流子)掺杂，实现了对电学传输性能的调控，并利用p-n结的整流特性等实现了多种电子与光电子器件。钙钛矿材料是一种新型的离子晶体半导体，具有包括但不限于立方体等晶体结构，其中不同离子靠离子间相互作用力组合在一起，具有带隙连续可调、载流子易扩散、可溶液法加工、吸光性强、发光量子效率高、发光光谱纯等优势，但是由于其晶体结构的复杂性和特殊性，钙钛矿的可控电学掺杂难以实现，这制约了钙钛矿材料的进一步发展，制约了其在半导体产业中的进一步应用。钙钛矿太阳能电池自2009年被首次报道以后，效率得到了突飞猛进的发展，现在已超过了26％，但是在稳定性和能量转换效率上与传统无机硅电池还有一定的差距。同时，钙钛矿也是一种可用溶液法加工制备的性能优异的发光材料，并于2014年被首次报道可以用来做钙钛矿发光二极管，拉开了钙钛矿发光二极管研究的序幕，并获得了广泛的关注。如今其效率已经突破30％，可与无机和有机发光二极管相媲美。钙钛矿半导体的可控电学掺杂尚未实现，难以对其导电类型与电学性质进行精准调控，制约了钙钛矿半导体及光电子器件领域的进一步发展。钙钛矿半导体材料的可控掺杂具有诸多好处：1、可以精确调控钙钛矿半导体材料的包括但不限于导电类型(极性)、电阻率、电导率、载流子浓度、载流子迁移率、费米能级、能带位置以及光电特性等；2、可以实现一系列p型、n型和i型钙钛矿半导体材料的设计与开发，并基于其中一种或者多种钙钛矿半导体材料设计并制备功能各异的同质结或者异质结，这进一步扩展了钙钛矿器件的构筑单元，帮助多种新型钙钛矿半导体器件的实现，包括但不限于二极管、晶体管、太阳能电池、探测器、闪烁体、发光二极管、半导体激光器等；3、可控掺杂的钙钛矿半导体材料可以使钙钛矿器件摆脱对传输层材料的依赖，可实现无空穴或者无电子传输层的钙钛矿光电子器件，大幅简化了钙钛矿器件的制备条 件，降低了成本，提高了产品的重复性和良率；4、钙钛矿半导体材料的可控掺杂策略可以大大地丰富钙钛矿半导体材料的类型，使其具备可以媲美或超越传统半导体(如硅、III-V族半导体等)的性能。因此，本发明所实现的可控掺杂的钙钛矿半导体，对钙钛矿半导体及光电子器件这一新兴领域的发展至关重要，有望实现前所未有的器件性能，并加速新型半导体器件的创生。
发明内容
本发明针对现有技术的不足，提出了一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体。
作为一种新兴半导体材料，钙钛矿半导体的结构与成分较为复杂。钙钛矿半导体的可控电学掺杂尚未实现，难以对其导电类型与电学性质进行精准调控，制约了钙钛矿半导体及光电子器件领域的进一步发展。针对这一重要技术问题，本发明实现了可控掺杂的钙钛矿半导体材料及其光电子器件。掺杂的钙钛矿半导体材料又可分为以空穴为主要导电介质的p型钙钛矿、以电子为主要导电介质的n型钙钛矿、以及双极性传输的i型钙钛矿。经掺杂后的钙钛矿材料组分为A’2An-1BnX3n+1:D(n＝1,2,3,…)或ABX3:D，其中A’为有机阳离子，A为一价阳离子，B为金属阳离子，X为一价阴离子，D为掺杂剂(以金属阳离子B为基准，D与B的摩尔比例在0％-80％范围)。掺杂剂按照掺杂效果划分p型掺杂剂和n型掺杂剂，p型掺杂剂可以抑制钙钛矿材料中给电子能级形成或者表现出吸电子作用，可实现p型半导体特性增强或n型半导体特性减弱的钙钛矿半导体材料；n型掺杂剂可以抑制钙钛矿材料中受电子能级形成或者表现出给电子作用，可实现n型半导体特性增强或p型半导体特性减弱的钙钛矿半导体材料。掺杂剂的结构特征在于，含有带有孤对电子的官能团或者其官能团能提供空的电子轨道或者可以电离产生离子部分替代钙钛矿晶体中某种离子的位置，这使掺杂剂可以与钙钛矿晶体结构中的离子发生包括但不限于配位作用、共价键作用、离子间相互作用以及氢键作用等，从而达到上述掺杂效果。掺杂剂按类型可以分为包括但不限于有机聚合物材料、有机小分子材料、有机盐、无机盐、路易斯酸、路易斯碱等。可控掺杂钙钛矿半导体材料的制备方法和掺杂方法，包括但不限于：1、将A’X(一种或者多种)、AX(一种或者多种)、BX(一种或者多种)和掺杂剂溶于溶剂中得到钙钛矿前驱体溶液，可通过溶液法制备掺杂的钙钛矿材料；2、将A’X(一种或者多种)、AX(一种或者多种)、BX(一种或者多种)溶于溶剂中得到钙钛矿前驱体溶液并制备成钙钛矿材料，并将掺杂剂通过反溶剂处理、表面修饰、溶液熏蒸、固态扩散、等离子注入等掺杂工艺引入到钙钛矿中，以获得掺杂的钙钛矿半导体材料；3、将A’X(一种或者多种)、AX(一种或者多种)、BX(一种或者多种)通过磁 控溅射、固态反应、气相沉积、蒸镀等非溶液法制备形成钙钛矿半导体材料，并将掺杂剂通过反溶剂处理、表面修饰、溶液熏蒸、固态扩散、等离子注入等掺杂工艺引入到钙钛矿中，以获得掺杂的钙钛矿半导体材料；4、采用以上两种或多种工艺的组合来制备掺杂的钙钛矿半导体材料。利用上述掺杂剂和方法所制备的不同的掺杂的钙钛矿半导体材料中的一种或者多种可形成功能各异的同质结或者异质结，丰富了钙钛矿电子或者光电子器件的构筑单元，可用于制备包括但不限于二极管、晶体管、太阳能电池、探测器、闪烁体、发光二极管、半导体激光器等钙钛矿电子或者光电子器件。所述钙钛矿电子或光电子器件由经掺杂的钙钛矿材料与衬底、阳极、电子传输材料、空穴传输材料、阴极等器件功能材料中的一种或多种组成。经掺杂的钙钛矿半导体可以摆脱对复杂电子传输层或者空穴传输层的依赖，因此甚至可以实现无传输层的钙钛矿光电子器件，这类器件具有更简单的制备工艺，可降低器件制备复杂性和成本，提高器件制备可重复性和良率。
本发明的技术方案如下：
本发明公开了可控掺杂的钙钛矿材料、掺杂方法及其光电子器件。钙钛矿半导体材料的结构通式为D:A’2An-1BnX3n+1(n＝1,2,3,…)或D:ABX3，其中A’为有机阳离子；A为一价阳离子，如铯离子(Cs+)、甲胺离子(MA+)、甲眯离子(FA+)、乙胺离子(EA+)、肼离子(HA+)、胍离子(GA+)、异丙基胺离子(IPA+)、咪唑离子(IA+)等。B为金属阳离子，如铅离子(Pb2+)、锡离子(Sn2+)、锗离子(Ge2+)等；X为阴离子包括：氯离子(Cl-)、溴离子(Br-)、碘离子(I-)等，D为掺杂剂。
p型钙钛矿半导体指的是其中负责导电的多数载流子为空穴的钙钛矿材料，展现p型传输特性；n型钙钛矿半导体指的是其中负责导电的多数载流子为电子的钙钛矿材料，展现n型传输特性；i型钙钛矿半导体指的是其中负责导电的电子与空穴浓度相当，展现绝缘特性或者双极性传输特性；其半导体禁带宽度可调，其带隙一般在0.5eV–4eV范围；在室温条件下，其载流子浓度在1010cm-3 -1020cm-3范围；在室温条件下，其载流子迁移率在10-4cm2V-1s-1–1000cm2V-1s-1范围；其荧光量子产率在0.1％-95％范围；可通过在钙钛矿半导体中引入掺杂剂，实现上述电学特性或光电特性的可靠调控。
所述掺杂剂包括但不限于有机聚合物材料，有机小分子材料，有机盐、无机盐、路易斯碱以及路易斯酸等。抑制给电子能级的形成或者具有吸电子作用的掺杂剂可使钙钛矿材料表现出p型掺杂增强或者n型掺杂减弱特性；抑制受电子能级的形成或者具有给电子作用的掺杂剂可使钙钛矿材料表现出n型掺杂增强或者p型掺杂减弱特性；同时使用一种或者多种掺杂剂，平衡了钙钛矿材料中给电子能级和受电子能级的形成，以及平衡了掺杂剂的吸电子作用和给电子作用，可用来制备i型(本征)钙钛矿半导体，表现出 绝缘特性或者双极性传输特性。可控掺杂钙钛矿半导体材料的制备方法和掺杂方法可以是以下制备方法的一种或者多种的组合。将A’X(一种或者多种)、AX(一种或者多种)、BX(一种或者多种)和掺杂剂溶于溶剂中得到钙钛矿前驱体溶液，可通过溶液法制备掺杂的钙钛矿材料；将A’X(一种或者多种)、AX(一种或者多种)、BX(一种或者多种)溶于溶剂中得到钙钛矿前驱体溶液并制备成钙钛矿材料，并将掺杂剂通过反溶剂处理、表面修饰、溶液熏蒸、固态扩散、等离子注入等掺杂工艺引入到钙钛矿中，以获得掺杂的钙钛矿半导体材料；将A’X(一种或者多种)、AX(一种或者多种)、BX(一种或者多种)通过磁控溅射、固态反应、气相沉积、蒸镀等非溶液法制备形成钙钛矿半导体材料，并将掺杂剂通过反溶剂处理、表面修饰、溶液熏蒸、固态扩散、等离子注入等掺杂工艺引入到钙钛矿中，以获得掺杂的钙钛矿半导体材料。由该制备与掺杂方法获得的钙钛矿半导体的物理形态，可包括但不限于多晶薄膜、单晶、纳米晶体、量子点、纳米线、纳米片，以及上述钙钛矿材料与有机小分子、聚合物、金属氧化物、三五(III-V)族半导体、二六(II-VI)族半导体，金属、无机电介质、纳米材料等的一种与多种的混合材料。所述的制备和掺杂方法中，掺杂剂包括但不仅限于以下所列化合物，可以是以下任何一种或者任意比例混合物：(2-(9H-咔唑-9-基)乙基)膦酸(2PACz)，2-(3,6-二甲氧基-9H-咔唑-9-基)乙基]膦酸(MeO-2PACz),[2-(3,6-二甲基-9H-咔唑-9-基)乙基]磷酸(ME-2PACz)，[2-(3,6-二溴-9H-咔唑-9-基)乙基]膦酸(Br-2PACz)，[4-(9H-咔唑-9-基)丁基]膦酸(4PACz)，[4-(3,6-二溴-9H-咔唑-9-基)丁基]膦酸(Br-4PACz)，[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]膦酸(MeO-4PACz),[4-(3,6-二甲基-9H-咔唑-9-基)丁基]磷酸(ME-4PACz)，3-(咔唑-9-基)丙酸，溴化钾，溴化钠，溴化铷，溴化铕等。所述有机掺杂剂分子中常见的含有孤对电子的和路易斯碱中常见的官能团包括但不限于：磷酸基团(-PO(OH)2)、磷酰氯基团(-P(O)Cl2)、磷酰基团(-P(O)R2)、有机磷酸酯基团(-OP(O)(OR)2)、磺酸基团(-SO3H)、硫酮基团(-S(＝O)-R)、氨基基团(-NH2)、羟基基团(-OH)、氰基基团(-CN)、醛基基团(-CHO)、羧基基团(-COOH)、酮基基团(-C＝O-R)、以及氮腈基团(-N≡C)等。所述有机掺杂剂分子中常见的含有空的电子轨道和路易斯酸常见的官能团包括但不限于：碳碳双键基团(-C＝C)、碳碳三键基团(-C≡C)、以及硼酸(BF3)等。所述无机掺杂剂分子中常见的离子包括但不限于：钠离子(Na+)、钾离子(K+)、铷离子(Rb+)、铕离子(Eu2+)、锶离子(Sr2+)、银离子(Ag+)铟离子(In2+)、以及铋离子(Bi2+)等。
基于可控掺杂的钙钛矿半导体材料的电子与光电子器件通常由经掺杂的钙钛矿材料与衬底、阳极、电子传输材料、空穴传输材料、阴极等器件功能材料中的一种或多种组 成，包括但不限于二极管、晶体管、太阳能电池、探测器、闪烁体、发光二极管、半导体激光器等。由一种或者多种掺杂的钙钛矿半导体材料组成的功能各异同质结或者异质结也是上述电子或者光电子器件的重要构筑单元。可控掺杂钙钛矿半导体材料的实现大大丰富了此类构筑单元的类型。经掺杂的钙钛矿半导体可以摆脱对电子传输层或空穴传输层的依赖，因此甚至可以实现无传输层的钙钛矿光电子器件，这类器件具有更简单的制备工艺，可降低器件制备复杂性和成本，提高器件制备可重复性和良率。基于掺杂的钙钛矿半导体材料的发光二极管器件，最大外量子效率(EQE)在10％-30％范围，优化后的最大外量子效率可达到30％以上；电致发光峰波长在300nm-2000nm范围；最高辐亮度(radiance)大于20W sr-1m-2(若为可见光发光二极管，最高亮度(luminance)大于10000cd m-2)，优化后的最高辐亮度大于2000W sr-1m-2(若为可见光发光二极管，优化后的最高亮度大于1000000cd m-2)。基于掺杂的钙钛矿半导体材料的太阳能电池器件，在单结电池构型、1-sun标准光照条件下，功率转换效率(PCE)在10％-30％范围，优化后的功率转换效率可达到30％以上；填充因子(FF)在60％-85％范围，优化后的填充因子可达到85％以上。采用多结叠层电池等构型，其功率转换效率可达到35％以上。基于掺杂的钙钛矿半导体材料的晶体管器件，在室温条件下，载流子迁移率大于10-4cm2V-1s-1，优化后的迁移率可达到100cm2V-1s-1或以上。
当p型钙钛矿半导体中的空穴浓度达到1018cm-3以上时，也可称为“重掺杂p型钙钛矿半导体”或“p+型钙钛矿半导体”；当n型钙钛矿半导体中的电子浓度达到1018cm-3以上时，也可称为“重掺杂n型钙钛矿半导体”或“n+型钙钛矿半导体”。
本发明具有以下有益效果：
(1)本发明实现了掺杂可控的p型、n型和i型钙钛矿半导体，实现了对钙钛矿半导体的导电类型(极性)、电阻率、电导率、载流子浓度、载流子迁移率、费米能级、能带位置以及光电特性等的精确调控。
(2)本发明可用于构筑钙钛矿电子或光电子器件，包括但不限于二极管、晶体管、太阳能电池、探测器、闪烁体、发光二极管、半导体激光器等。
(3)本发明利用p型、n型或者i型钙钛矿半导体材料中的一种或多种形成同质结或者异质结，拓展了钙钛矿器件的基本构筑单元，可由此实现多种新型半导体器件。
(4)本发明所实现的可控掺杂的钙钛矿半导体材料，可以摆脱对电子传输层或空穴传输层的依赖，可实现无传输层的钙钛矿电子与光电子器件，这类器件具有更简单的制备工艺，可降低器件制备复杂性和成本，提高器件制备的重复性和良率。
(5)本发明涉及的可控掺杂的钙钛矿半导体材料和技术，可实现对钙钛矿半导体的 电学与光电性能的精准调控，可获得性能接近或超越传统半导体(如硅、III-V族半导体等)器件的钙钛矿电子与光电子器件。
附图说明
图1为本发明的实施例1中未掺杂的钙钛矿材料晶体结构图；
图2为本发明的实施例1中掺杂后钙钛矿材料的晶体结构图；
图3为本发明的实施例1中钙钛矿发光二极管电流密度-电压特性关系图；
图4为本发明的实施例1中钙钛矿发光二极管辐亮度-电压特性关系图；
图4为本发明的实施例1中不同掺杂浓度的钙钛矿材料的能级排布图；
图5为本发明的实施例1中未掺杂的钙钛矿薄膜表面的达尔文探针里显微镜图；
图6为本发明的实施例1中1％掺杂浓度(掺杂剂相对于Pb2+)的钙钛矿薄膜表面的达尔文探针里显微镜图；
图7为本发明的实施例1中3％掺杂浓度(掺杂剂相对于Pb2+)的钙钛矿薄膜表面的达尔文探针里显微镜图；
图8为本发明的实施例1中5％掺杂浓度(掺杂剂相对于Pb2+)的钙钛矿薄膜表面的达尔文探针里显微镜图；
图9为本发明的实施例1中不同掺杂浓度的钙钛矿薄膜表面接触电势差示意图；
图10为本发明的实施例1中不同掺杂浓度的钙钛矿材料的霍尔系数测试结果；
图11为本发明的实施例1中不同掺杂浓度的钙钛矿材料的主要载流子类型以及密度测试结果；
图12为本发明的实施例2中未掺杂的钙钛矿材料的理论计算模型。
图13为本发明的实施例2中掺杂后的钙钛矿材料的理论计算模型。
图14为本发明的实施例2中未掺杂钙钛矿中不同缺陷的形成能计算结果。
图15为本发明的实施例2中未掺杂钙钛矿电子云密度分布图。
图16为本发明的实施例2中掺杂后钙钛矿电子云密度分布图。
图17为本发明的实施例2中掺杂前后钙钛矿中态密度/(E-EV)图。
图18为本发明的实施例2中基于密度泛函计算结果的钙钛矿掺杂机理示意图。
图19为本发明的实施例2中4PACz加入或者不加入PbBr2后的核磁共振谱图。
图20为本发明的实施例2中4PACz和掺杂的钙钛矿材料的傅里叶变换红外吸收谱图。
图21为本发明的实施例2中未掺杂和掺杂后的钙钛矿材料的X射线光电子能谱。
图22为本发明的实施例3中无空穴传输层钙钛矿发光二极管器件结构图。
图23为本发明的实施例3中无空穴传输层钙钛矿发光二极管横截面透射电镜图。
图24为本发明的实施例3中基于不同掺杂浓度钙钛矿的无空穴传输层发光二极管器件性能对比图。
图25为本发明的实施例3中基于未掺杂和5％掺杂后无空穴传输层钙钛矿发光二极管发光光谱图。
图26为本发明的实施例3中基于未掺杂和5％掺杂后无空穴传输层钙钛矿发光二极管电流密度-电压曲线。
图27为本发明的实施例3中基于未掺杂和5％掺杂后无空穴传输层钙钛矿发光二极管亮度-电压曲线。
图28为本发明的实施例3中基于未掺杂和5％掺杂后无空穴传输层钙钛矿发光二极管外量子效率-亮度曲线。
图29为本发明的实施例3中基于未掺杂和5％掺杂后无空穴传输层钙钛矿发光二极管能量转换效率-亮度曲线。
图30为本发明的实施例3中不同掺杂浓度的钙钛矿薄膜光致发光效率统计图。
图31为本发明的实施例3中基于未掺杂和5％掺杂后的钙钛矿薄膜瞬态光致发光谱图。
具体实施方式
图1为未掺杂的钙钛矿材料晶体结构图；图2为掺杂后钙钛矿材料的晶体结构图。钙钛矿中非饱和B位可以和掺杂剂中的酸性基团发生作用。掺杂剂为钙钛矿材料提供给电子基团或者吸电子基团，抑制钙钛矿中非饱和铅的数量从而抑制相关缺陷所造成的给电子或者受电子能级的形成，调控相关钙钛矿材料中主要载流子的类型(电子或者空穴)以及其数量，调控相关钙钛矿材料的导电类型。经过精细掺杂调控后的钙钛矿材料可以得到合适的载流子迁移率和载流子密度，从而实现无空穴传输层或电子传输层并且高效、高亮的发光二极管的成功制备。
(1)准备钙钛矿前驱体溶液
钙钛矿前驱体溶液准备是通过溶解A’X、AX、BX2、掺杂剂P溶于溶剂(可以是DMF、DMSO、GBL、NMP、乙腈、G-丁内酯等任意一种或者混合溶剂)中得到，其中A’为有机胺阳离子，A为一价阳离子，如铯离子(Cs+)、甲胺离子(MA+)、甲眯离子(FA+)、乙胺离子(EA+)、肼离子(HA+)、胍离子(GA+)、异丙基胺离子(IPA+)、咪唑离子(IA+)等；B位二价金属阳离子，如铅离子(Pb2+)、锡离子(Sn2+)、锗离子(Ge2+)等；X位阴离子包括：氯离子(Cl-)、溴离子(Br-)、碘离子(I-)等。钙钛矿前驱体溶液的浓度为0.01-2mol/L。
(2)钙钛矿发光二极管的制备
基底依次用水、去离子水、丙酮、异丙醇浸泡ITO基底，并且在超声机中清洗15分钟以上。在旋涂前，用等离子体机处理ITO玻璃基底15分钟。然后直接在ITO上使用溶液法制备钙钛矿薄膜，并退火一定时间，在旋涂过程中引入反溶剂如氯苯、甲苯、乙酸乙酯、无水乙醚、氯仿等任意一种或者几种混合溶剂。然后采用旋涂、蒸镀、磁控溅射、原子层沉积等方式制备电子或者空穴传输层。最后采用蒸镀、磁控溅射、原子层沉积等方式制备电极层。
1.实施例1钙钛矿材料的可控掺杂
钙钛矿前驱体溶液通过将FABr,MABr,GABr,CsBr,PbBr2,以及掺杂剂4PACz按照0.8:0.1:0.1:0.15:1:x(x＝0-0.8)的摩尔比溶于1ml DMSO中制备成0.95mol L-1浓度的溶液。两步旋涂法被用来在基底上制备钙钛矿薄膜，基底包括但不限于ITO基底、石英玻璃基底、蓝宝石基底以及硅片等，其中第一步悬涂条件为500r转速下悬涂10s，第二步悬涂法条件为5000r转速下悬涂90s，并在第二步旋涂过程开始后约40s时，将100μL的反溶剂滴加到样品上，反溶剂为溶有2mg/ml TPBI的氯仿溶剂，旋涂结束后90℃退火10min得到钙钛矿薄膜。
如图3所示，为不同掺杂浓度的钙钛矿材料的紫外光电子能谱测试结果。其中IP代表电离势，WF代表功函；如图4所示，为不同掺杂浓度的钙钛矿材料的能级排布图。其中EV代表价带底，EC代表导带顶；如图5所示，为未掺杂的钙钛矿薄膜表面的达尔文探针里显微镜图；其中标尺为400nm。如图6所示，为1％掺杂浓度(掺杂剂相对于Pb2+)的钙钛矿薄膜表面的达尔文探针里显微镜图；其中标尺为400nm。如图7所示，为3％掺杂浓度(掺杂剂相对于Pb2+)的钙钛矿薄膜表面的达尔文探针里显微镜图；其中标尺为400nm。如图8所示，为5％掺杂浓度(掺杂剂相对于Pb2+)的钙钛矿薄膜表面的达尔文探针里显微镜图；其中标尺为400nm。如图9所示，为不同掺杂浓度的钙钛矿薄膜表面接触电势差示意图。如图10所示，为不同掺杂浓度的钙钛矿材料的霍尔系数测试结果。如图11所示，为不同掺杂浓度的钙钛矿材料的主要载流子类型以及密度测试结果。
2.实施例2钙钛矿材料掺杂模型建立及其机理研究
基于密度泛函理论的第一性原理计算被用来研究钙钛矿掺杂机理。相关模型被成功建立，并且在此基础上进行了一系列计算。其中图12为未掺杂的钙钛矿材料的理论计算模型。图13为掺杂后的钙钛矿材料的理论计算模型；图14为未掺杂钙钛矿中不同缺陷的形成能计算结果；图15为未掺杂钙钛矿电子云密度分布图；图16为掺杂后钙钛矿电子云密度分布图；图17为掺杂前后钙钛矿中态密度/(E-EV)图；图18基于密度泛函计算结果的 钙钛矿掺杂机理示意图；图19为4PACz加入或者不加入PbBr2后的核磁共振谱图；图20为4PACz和掺杂的钙钛矿材料的傅里叶变换红外吸收谱图；图21为未掺杂和掺杂后的钙钛矿材料的X射线光电子能谱。
3.实施例3制备无空穴传输层钙钛矿发光二极管
依次用水、去离子水、丙酮、异丙醇浸泡基底，并且在超声机中清洗15分钟以上。在旋涂前，用等离子体机处理基底15分钟。钙钛矿前驱体溶液通过将FABr,MABr,GABr,CsBr,PbBr2,以及掺杂剂4PACz按照0.8:0.1:0.1:0.15:1:x(x＝0-0.8)的摩尔比溶于1ml DMSO中制备成0.95mol L-1浓度的溶液。两步旋涂法被用来在基底上制备钙钛矿薄膜，基底包括但不限于ITO基底、石英玻璃基底、蓝宝石基底以及硅片等，其中第一步悬涂条件为500r转速下悬涂10s，第二步悬涂法条件为5000r转速下悬涂90s，并在第二步旋涂过程开始后约40s时，将100μL的反溶剂滴加到样品上，反溶剂为溶有2mg/ml TPBI的氯仿溶剂，旋涂结束后90℃退火10min得到钙钛矿薄膜。电子传输层材料为PO-T2T，电极材料为Yb/Ag。如图22所示，为无空穴传输层钙钛矿发光二极管器件结构图；图23为无空穴传输层钙钛矿发光二极管横截面透射电镜图；图24为基于不同掺杂浓度钙钛矿的无空穴传输层发光二极管器件性能对比图；图25为基于未掺杂和5％掺杂后无空穴传输层钙钛矿发光二极管发光光谱图；图26为基于未掺杂和5％掺杂后无空穴传输层钙钛矿发光二极管电流密度-电压曲线；图27为基于未掺杂和5％掺杂后无空穴传输层钙钛矿发光二极管亮度-电压曲线；图28为基于未掺杂和5％掺杂后无空穴传输层钙钛矿发光二极管外量子效率-亮度曲线；图29为基于未掺杂和5％掺杂后无空穴传输层钙钛矿发光二极管能量转换效率-亮度曲线；图30为不同掺杂浓度的钙钛矿薄膜光致发光效率统计图；图31为基于未掺杂和5％掺杂后的钙钛矿薄膜瞬态光致发光谱图。

Claims (10)

  1. 一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体，其特征在于：经掺杂后的钙钛矿材料组分为A’2An-1BnX3n+1:D或ABX3:D，其中n＝1,2,3,…，A’为有机阳离子，A为一价阳离子，B为金属阳离子，X为一价阴离子，D为掺杂剂，以金属阳离子B为基准，D与B的摩尔比例在0％-80％范围；p型钙钛矿半导体指的是其中负责导电的多数载流子为空穴的钙钛矿材料，展现p型传输特性；n型钙钛矿半导体指的是其中负责导电的多数载流子为电子的钙钛矿材料，展现n型传输特性；i型钙钛矿半导体指的是其中负责导电的电子与空穴浓度相当，展现绝缘特性或者双极性传输特性；其半导体禁带宽度可调，其带隙一般在0.5eV–4eV范围；在室温条件下，其载流子浓度在1010cm-3-1020cm-3范围；在室温条件下，其载流子迁移率在10-4cm2V-1s-1–1000cm2V-1s-1范围；其荧光量子产率在0.1％-95％范围；可通过在钙钛矿半导体中引入掺杂剂，实现上述电学特性或光电特性的可靠调控。
  2. 根据权利要求1所述的一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体，其特征在于：掺杂后能够让钙钛矿半导体展现p型特性、增强p型特性或减弱n型特性的掺杂剂，为p型钙钛矿掺杂剂；掺杂后能够让钙钛矿半导体展现n型特性、增强n型特性或减弱p型特性的掺杂剂，为n型钙钛矿掺杂剂；其中，p型钙钛矿掺杂剂在钙钛矿材料中展现得电子能力，属于电子受体即受主，为钙钛矿半导体提供更多的空穴，使其费米能级向价带移动；n型钙钛矿掺杂剂在钙钛矿材料中展现失电子能力，属于电子给体即施主，为钙钛矿半导体提供更多的电子，使其费米能级向导带移动；在p型钙钛矿中引入n型钙钛矿掺杂剂，可以实现i型或n型钙钛矿半导体；在n型钙钛矿中引入p型钙钛矿掺杂剂，可以实现i型或p型钙钛矿半导体；对钙钛矿半导体进行掺杂时，使用一种或多种掺杂类型相同或相反的掺杂剂，并精确调控其用量，以实现对钙钛矿半导体导电类型、电阻率、电导率、载流子浓度、载流子迁移率、费米能级、能带位置以及光电特性的精确调控。
  3. 根据权利要求1所述的一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体，其特征在于：所述的A’为有机阳离子；A为一价阳离子，如铯离子、甲胺离子、甲眯离子、乙胺离子、肼离子、胍离子、异丙基胺离子、咪唑离子；B为金属阳离子，包括铅离子、锡离子、锗离子；X为阴离子包括：氯离子、溴离子、碘离子；D包括但不限于有机聚合物材料，有机小分子材料，有机盐、无机盐、路 易斯碱以及路易斯酸。
  4. 根据权利要求1所述的一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体，其特征在于：所述的钙钛矿半导体掺杂方式为：将A’X一种或者多种、AX一种或者多种、BX一种或者多种和掺杂剂溶于溶剂中得到钙钛矿前驱体溶液，通过溶液法制备掺杂的钙钛矿材料；将A’X一种或者多种、AX一种或者多种、BX一种或者多种溶于溶剂中得到钙钛矿前驱体溶液并制备成钙钛矿材料，并将掺杂剂通过反溶剂处理、表面修饰、溶液熏蒸、固态扩散、等离子注入的工艺引入到钙钛矿中，以获得掺杂的钙钛矿半导体材料；将A’X一种或者多种、AX一种或者多种、BX一种或者多种通过非溶液法制备形成钙钛矿半导体材料，并将掺杂剂通过反溶剂处理、表面修饰、溶液熏蒸、固态扩散、等离子注入工艺引入到钙钛矿中，以获得掺杂的钙钛矿半导体材料。
  5. 根据权利要求1所述的一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体，其特征在于：所述的钙钛矿半导体的物理形态，包括多晶薄膜、单晶、纳米晶体、量子点、纳米线、纳米片，以及上述钙钛矿材料与有机小分子、聚合物、金属氧化物、三五(III-V)族半导体、二六(II-VI)族半导体，金属、无机电介质、纳米材料中的一种与多种的混合材料。
  6. 根据权利要求1所述的一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体，其特征在于：所述的掺杂剂包括(2-(9H-咔唑-9-基)乙基)膦酸，2-(3,6-二甲氧基-9H-咔唑-9-基)乙基]膦酸,[2-(3,6-二甲基-9H-咔唑-9-基)乙基]磷酸，[2-(3,6-二溴-9H-咔唑-9-基)乙基]膦酸，[4-(9H-咔唑-9-基)丁基]膦酸，[4-(3,6-二溴-9H-咔唑-9-基)丁基]膦酸，[4-(3,6-二甲氧基-9H-咔唑-9-基)丁基]膦酸,[4-(3,6-二甲基-9H-咔唑-9-基)丁基]磷酸，3-(咔唑-9-基)丙酸，溴化钾，溴化钠，溴化铷，溴化铕；所述有机掺杂剂分子中常见的含有孤对电子的和路易斯碱中常见的官能团包括但不限于：磷酸基团、磷酰氯基团、磷酰基团、有机磷酸酯基团、磺酸基团、硫酮基团、氨基基团、羟基基团、氰基基团、醛基基团、羧基基团、酮基基团、以及氮腈基团；所述有机掺杂剂分子中常见的含有空的电子轨道和路易斯酸常见的官能团包括但不限于：碳碳双键基团、碳碳三键基团、以及硼酸；所述无机掺杂剂分子中常见的离子包括但不限于：钠离子、钾离子、铷离子、铕离子、锶离子、银离子铟离子、以及铋离子中一种或者任意比例混合物。
  7. 根据权利要求1所述的一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体，其特征在于：所述的一种或多种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体形成的同质或者异质结；形成上述同质结的一种或多种钙钛矿半导体材料总体成分相似，具有相同的带隙；形成上述异质结的一种或多种钙钛矿半导体材料总体成分有显著区别，一般具有不同的带隙，在特殊情况下也可能具有相同的带隙；上述同质结和异质结用于构筑电子或光电子器件，包括但不限于二极管、晶体管、太阳能电池、探测器、闪烁体、发光二极管、半导体激光器。
  8. 根据权利要求1所述的一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体，其特征在于：其载流子浓度达到1020cm-3以上；其载流子迁移率达到1000cm2V-1s-1以上；其荧光量子产率达到95％以上。
  9. 根据权利要求1所述的一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体，其特征在于：当p型钙钛矿半导体中的空穴浓度达到1018cm-3以上时，也可称为“重掺杂p型钙钛矿半导体”或“p+型钙钛矿半导体”；当n型钙钛矿半导体中的电子浓度达到1018cm-3以上时，也可称为“重掺杂n型钙钛矿半导体”或“n+型钙钛矿半导体”。
  10. 根据权利要求7所述的一种经掺杂可实现p型、n型以及i型导电性的钙钛矿半导体，其特征在于：所述的同质结或者异质结制备的光电子器件由经掺杂的钙钛矿材料与衬底、阳极、电子传输材料、空穴传输材料、阴极中的一种或多种组成；经掺杂的钙钛矿半导体可以摆脱对电子传输层或空穴传输层的依赖，实现无传输层的钙钛矿光电子器件。
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