CN105957965A - Efficient and stable perovskite solar cell without hole transporting layer and preparation method thereof - Google Patents

Efficient and stable perovskite solar cell without hole transporting layer and preparation method thereof Download PDF

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CN105957965A
CN105957965A CN201610318902.9A CN201610318902A CN105957965A CN 105957965 A CN105957965 A CN 105957965A CN 201610318902 A CN201610318902 A CN 201610318902A CN 105957965 A CN105957965 A CN 105957965A
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perovskite
solar cell
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王文庆
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Dongguan Lianzhou Intellectual Property Operation and Management Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses an efficient and stable perovskite solar cell without a hole transporting layer, which comprises a conductive substrate, a titanium dioxide layer, a titanium dioxide nanotube layer, an interface modification layer, a perovskite light absorption layer and a metal electrode, and is characterized in that the titanium dioxide layer is on the conductive substrate, the titanium dioxide nanotube layer vertically grows on the titanium dioxide layer, the interface modification layer is spun on the titanium dioxide nanotube layer, the perovskite light absorption layer is spun on the interface modification layer, the metal electrode is evaporated on the perovskite light absorption layer, the interface modification material is C60, and the perovskite light abruption layer is prepared by adopting a gas phase assistance solution method. The invention further discloses a preparation method of the efficient and stable perovskite solar cell. The perovskite solar cell is simple in structure, mild in preparation process condition, low in production cost, good in stability and high in photoelectric conversion efficiency.

Description

A kind of perovskite solar cell of efficient stable without hole transmission layer and preparation method thereof
Technical field:
The present invention relates to technical field of solar cells, be specifically related to the calcium titanium of a kind of efficient stable without hole transmission layer Ore deposit solar cell.
Background technology:
In the face of the day by day exhausted of fossil energy and its in use pollution to environment, new exploitation of energy resources is mankind's literary compositions Bright sustainable development provides important leverage, and photovoltaic is the most promising scheme.How to improve solar energy The electricity conversion of battery reduces photovoltaic generation cost, is the core research topic of current photovoltaic art.Organic nothing The halogen perovskite material of machine hydridization was used in solaode first in 2009, and its electricity conversion was only at that time Have 3.8%.After 2011, people obtain a series of breakthroughs to the research of this battery, and its electricity conversion was in 2013 More than 15%, have been carried out 19.3% in May, 2014.Short in two years, the efficiency of perovskite solaode is first After surmount organic solar batteries (11%) and dye-sensitized cell (13%), be expected to can reach monocrystaline silicon solar cell (25.6%), the level of PANASONIC.Along with the record of perovskite solar battery efficiency is constantly refreshed, people start more Pay attention in the stability of this battery, service life, the replacement of heavy metal element lead and the preparation etc. of large area flexible device The research of aspect.
All containing Hole transporting layers in the perovskite solar cell of prior art, hole-conducting materials price comparison is expensive, Considerably increase the production cost of solar cell.The battery of perovskite without hole mobile material can simplify battery knot further Structure, reduces cost, is conducive to improving stability test, is perovskite battery important development direction.
Summary of the invention:
It is an object of the invention to provide the perovskite solar cell of a kind of efficient stable without hole transmission layer, this battery is tied Structure is simplified further, reduces the production cost of battery, is conducive to improving the stability of battery, and its photoelectricity Transformation efficiency is high.
It is a further object to provide the preparation method of this perovskite solar cell.
For achieving the above object, the present invention is by the following technical solutions:
The perovskite solar cell of a kind of efficient stable without hole transmission layer, including on conducting base, conducting base Titanium dioxide layer, vertical-growth titania nanotube layer on titanium dioxide layer, it is spun on titania nanotube Interface-modifying layer on layer, the perovskite light absorbing zone being spun on interface-modifying layer and be deposited with in perovskite light absorb Metal electrode on layer, described modifying interface material is C60, described perovskite light absorbing zone uses gas phase assisted solution method Preparation.
The preparation method of the perovskite solar cell of a kind of efficient stable without hole transmission layer, comprises the following steps:
(1) conducting base acetone, deionized water are washed 2-3 time respectively, after drying, process 10-15min with UVO；
(2) being deposited with by pure titanium on the conducting base after step (1) processes, evaporation a layer thickness is 100-200nm Pure titanium, then the conducting base being coated with pure titanium is prepared titanium dioxide layer by organic electrolyte anodizing one step With titania nanotube layer, after cleaning, put into 500-550 DEG C of annealing 30min, then furnace cooling in Muffle furnace；
(3) spin coating C on titania nanotube layer60Organic solution, the speed of spin coating is 2000-4000rpm, Then at 50-70 DEG C, heat 15-30min, obtain interface-modifying layer；
(4) by PbX2Precursor solution is spin-coated on interface-modifying layer, then heats 10-25min at 70-100 DEG C, Being placed in vacuum drying oven together with iodide powder after natural cooling, be 10-20KPa at pressure, temperature is At 150-170 DEG C, heat iodide powder, with PbX after evaporation2Thin film reaction 50-120min, generates perovskite, from So it is carried out with isopropanol after cooling, at 150-170 DEG C, is finally dried 15-30min, obtains perovskite light and absorb Layer；
(5) on perovskite light absorbing zone, evaporation metal material, as electrode, obtains the perovskite sun electricity of efficient stable Pond.
Preferred as technique scheme, described conducting base is electro-conductive glass FTO.
Preferred as technique scheme, in step (2), the condition of described evaporation is 150-250A for evaporation power, Evaporation rate is 5-10nm/min.
Preferred as technique scheme, in step (2), the condition of described organic electrolyte anodizing is sun Pole oxidation voltage is 50-60V, and anodizing time is 30-60min.
Preferred as technique scheme, in step (3), described C60Organic solution be C60O-dichlorohenzene molten Liquid, C60Concentration be 5-15mg/mL.
Preferred as technique scheme, in step (4), described iodide powder is CH3NH3I powder or HC (NH2)2I Powder.
Preferred as technique scheme, in step (4), described PbX2In, X is the one in I, Br, Cl Or multiple mixing.
Preferred as technique scheme, in step (4), described PbX2The solvent of precursor solution is N, N-diformazan One in base Methanamide, dimethyl sulfoxide, gamma-butyrolacton, N,N-dimethylacetamide, described PbX2Presoma is molten PbX in liquid2Concentration be 350-550mg/mL.
Preferred as technique scheme, in step (4), the thickness of described perovskite light absorbing zone is 50-100nm.
The method have the advantages that
The present invention uses gas phase assisted solution method to prepare perovskite thin film as light absorbing zone, system light absorbing zone quality Height, electronics and hole transport speed are big；And use titanium dioxide layer and titania nanotube layer as electron transfer layer, Utilize C simultaneously60Organic solution modify electron transfer layer and light absorbing zone, improve between electron transfer layer light absorbing zone Interracial contact, reduce the hesitation of perovskite solar cell；
Perovskite solar cell good stability prepared by the method, photoelectric transformation efficiency is high, and preparation method is simple, raw Produce low cost.
Detailed description of the invention:
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving Release the present invention, the present invention will not be constituted any restriction.
Embodiment 1
The preparation method of the perovskite solar cell of a kind of efficient stable without hole transmission layer, comprises the following steps:
(1) FTO glass acetone, deionized water are washed 2-3 time respectively, after drying, process 10min with UVO；
(2) pure titanium is deposited with on the FTO glass after step (1) processes, is 150A at evaporation power, evaporation speed Rate is to be deposited with the pure titanium that a layer thickness is 100nm under conditions of 5nm/min, is then led to by the FTO glass being coated with pure titanium Crossing organic electrolyte anodizing at anodic oxidation voltage is 50V, and anodizing time is a step under conditions of 30min Prepare titanium dioxide layer and titania nanotube layer, put into 500 DEG C of annealing 30min in Muffle furnace after cleaning, so Rear furnace cooling；
(3) on titania nanotube layer, spin coating concentration is the C of 5mg/mL60O-dichlorobenzene solution, the speed of spin coating Degree is 2000rpm, then heats 15min at 50 DEG C, obtains interface-modifying layer；
(4) it is the PbI of 350mg/mL by concentration2DMF solution be spin-coated on interface-modifying layer, Then at 70 DEG C, 10min is heated, with CH after natural cooling3NH3I powder is placed in vacuum drying oven together, at pressure For 10KPa, temperature is at 150 DEG C, heats CH3NH3I powder, with PbI after evaporation2Thin film reaction 50min, generates calcium Titanium ore, is carried out with isopropanol after natural cooling, is finally dried 15min at 150 DEG C, and obtaining thickness is 50nm Perovskite light absorbing zone；
(5) on perovskite light absorbing zone, evaporation Au, as electrode, obtains the perovskite solar cell of efficient stable.
Embodiment 2
The preparation method of the perovskite solar cell of a kind of efficient stable without hole transmission layer, comprises the following steps:
(1) FTO glass acetone, deionized water are washed 2-3 time respectively, after drying, process 15min with UVO；
(2) pure titanium is deposited with on the FTO glass after step (1) processes, is 250A at evaporation power, evaporation speed Rate is to be deposited with the pure titanium that a layer thickness is 200nm under conditions of 10nm/min, is then led to by the FTO glass being coated with pure titanium Crossing organic electrolyte anodizing at anodic oxidation voltage is 60V, and anodizing time is a step under conditions of 60min Prepare titanium dioxide layer and titania nanotube layer, put into 550 DEG C of annealing 30min in Muffle furnace after cleaning, so Rear furnace cooling；
(3) on titania nanotube layer, spin coating concentration is the C of 15mg/mL60O-dichlorobenzene solution, spin coating Speed is 4000rpm, then heats 30min at 70 DEG C, obtains interface-modifying layer；
(4) it is the PbI of 550mg/mL by concentration2Dimethyl sulphoxide solution be spin-coated on interface-modifying layer, then exist 25min is heated, with CH after natural cooling at 100 DEG C3NH3I powder is placed in vacuum drying oven together, at pressure is 20KPa, temperature is at 170 DEG C, heats CH3NH3I powder, with PbI after evaporation2Thin film reaction 120min, generates calcium Titanium ore, is carried out with isopropanol after natural cooling, is finally dried 30min at 170 DEG C, and obtaining thickness is 100nm Perovskite light absorbing zone；
(5) on perovskite light absorbing zone, evaporation Au, as electrode, obtains the perovskite solar cell of efficient stable.
Embodiment 3
The preparation method of the perovskite solar cell of a kind of efficient stable without hole transmission layer, comprises the following steps:
(1) FTO glass acetone, deionized water are washed 2-3 time respectively, after drying, process 11min with UVO；
(2) pure titanium is deposited with on the FTO glass after step (1) processes, is 170A at evaporation power, evaporation speed Rate is to be deposited with the pure titanium that a layer thickness is 120nm under conditions of 6nm/min, is then led to by the FTO glass being coated with pure titanium Crossing organic electrolyte anodizing at anodic oxidation voltage is 52V, and anodizing time is a step under conditions of 40min Prepare titanium dioxide layer and titania nanotube layer, put into 510 DEG C of annealing 30min in Muffle furnace after cleaning, so Rear furnace cooling；
(3) on titania nanotube layer, spin coating concentration is the C of 7mg/mL60O-dichlorobenzene solution, the speed of spin coating Degree is 2500rpm, then heats 20min at 55 DEG C, obtains interface-modifying layer；
(4) it is the PbCl of 380mg/mL by concentration2Dimethyl sulphoxide solution be spin-coated on interface-modifying layer, then exist 15min, HC (NH after natural cooling is heated at 80 DEG C2)2I powder is placed in vacuum drying oven together, is 15KPa at pressure, Temperature is at 155 DEG C, heats HC (NH2)2I powder, with PbCl after evaporation2Thin film reaction 70min, generates perovskite, It is carried out with isopropanol after natural cooling, at 155 DEG C, is finally dried 20min, obtains the calcium titanium that thickness is 60nm Ore deposit light absorbing zone；
(5) on perovskite light absorbing zone, evaporation Ag, as electrode, obtains the perovskite solar cell of efficient stable.
Embodiment 4
The preparation method of the perovskite solar cell of a kind of efficient stable without hole transmission layer, comprises the following steps:
(1) FTO glass acetone, deionized water are washed 2-3 time respectively, after drying, process 12min with UVO；
(2) pure titanium is deposited with on the FTO glass after step (1) processes, is 190A at evaporation power, evaporation speed Rate is to be deposited with the pure titanium that a layer thickness is 140nm under conditions of 7nm/min, is then led to by the FTO glass being coated with pure titanium Crossing organic electrolyte anodizing at anodic oxidation voltage is 54V, and anodizing time is a step under conditions of 45min Prepare titanium dioxide layer and titania nanotube layer, put into 520 DEG C of annealing 30min in Muffle furnace after cleaning, so Rear furnace cooling；
(3) on titania nanotube layer, spin coating concentration is the C of 9mg/mL60O-dichlorobenzene solution, the speed of spin coating Degree is 3000rpm, then heats 25min at 60 DEG C, obtains interface-modifying layer；
(4) it is the PbCl of 400mg/mL by concentration2Gamma-butyrolacton solution be spin-coated on interface-modifying layer, then exist 20min is heated, with CH after natural cooling at 85 DEG C3NH3I powder is placed in vacuum drying oven together, is 10KPa at pressure, Temperature is at 160 DEG C, heats CH3NH3I powder, with PbCl after evaporation2Thin film reaction 90min, generates perovskite, from So it is carried out with isopropanol after cooling, at 160 DEG C, is finally dried 25min, obtains the perovskite that thickness is 70nm Light absorbing zone；
(5) on perovskite light absorbing zone, evaporation Au, as electrode, obtains the perovskite solar cell of efficient stable.
Embodiment 5
The preparation method of the perovskite solar cell of a kind of efficient stable without hole transmission layer, comprises the following steps:
(1) FTO glass acetone, deionized water are washed 2-3 time respectively, after drying, process 13min with UVO；
(2) pure titanium is deposited with on the FTO glass after step (1) processes, is 210A at evaporation power, evaporation speed Rate is to be deposited with the pure titanium that a layer thickness is 140nm under conditions of 8nm/min, is then led to by the FTO glass being coated with pure titanium Crossing organic electrolyte anodizing at anodic oxidation voltage is 56V, and anodizing time is a step under conditions of 50min Prepare titanium dioxide layer and titania nanotube layer, put into 530 DEG C of annealing 30min in Muffle furnace after cleaning, so Rear furnace cooling；
(3) on titania nanotube layer, spin coating concentration is the C of 11mg/mL60O-dichlorobenzene solution, spin coating Speed is 3500rpm, then heats 30min at 65 DEG C, obtains interface-modifying layer；
(4) it is the PbBr of 450mg/mL by concentration2N,N-dimethylacetamide solution be spin-coated on interface-modifying layer, Then at 90 DEG C, 25min is heated, with HC (NH after natural cooling2)2I powder is placed in vacuum drying oven together, in pressure Strong is 20KPa, and temperature is at 165 DEG C, heats HC (NH2)2I powder, with PbBr after evaporation2Thin film reaction 100min, Generating perovskite, be carried out with isopropanol after natural cooling, be finally dried 25min at 165 DEG C, obtaining thickness is The perovskite light absorbing zone of 80nm；
(5) on perovskite light absorbing zone, evaporation Ag, as electrode, obtains the perovskite solar cell of efficient stable.
Embodiment 6
The preparation method of the perovskite solar cell of a kind of efficient stable without hole transmission layer, comprises the following steps:
(1) FTO glass acetone, deionized water are washed 2-3 time respectively, after drying, process 14min with UVO；
(2) pure titanium is deposited with on the FTO glass after step (1) processes, is 230A at evaporation power, evaporation speed Rate is to be deposited with the pure titanium that a layer thickness is 180nm under conditions of 9nm/min, is then led to by the FTO glass being coated with pure titanium Crossing organic electrolyte anodizing at anodic oxidation voltage is 58V, and anodizing time is a step under conditions of 55min Prepare titanium dioxide layer and titania nanotube layer, put into 540 DEG C of annealing 30min in Muffle furnace after cleaning, so Rear furnace cooling；
(3) on titania nanotube layer, spin coating concentration is the C of 13mg/mL60O-dichlorobenzene solution, spin coating Speed is 4000pm, then heats 30min at 65 DEG C, obtains interface-modifying layer；
(4) it is the PbBr of 500mg/mL by concentration2N,N-dimethylacetamide solution be spin-coated on interface-modifying layer, Then at 95 DEG C, 20min is heated, with CH after natural cooling3NH3I powder is placed in vacuum drying oven together, at pressure For 15KPa, temperature is at 170 DEG C, heats CH3NH3I powder, with PbBr after evaporation2Thin film reaction 110min, generates Perovskite, is carried out with isopropanol after natural cooling, is finally dried 30min at 170 DEG C, and obtaining thickness is 90nm Perovskite light absorbing zone；
(5) on perovskite light absorbing zone, evaporation Ag, as electrode, obtains the perovskite solar cell of efficient stable.

Claims (10)

1. the perovskite solar cell without the efficient stable of hole transmission layer, it is characterised in that this perovskite sun Battery includes the titanium dioxide layer on conducting base, conducting base, vertical-growth titanium dioxide on titanium dioxide layer Nanotube layer, is spun on the interface-modifying layer on titania nanotube layer, the perovskite being spun on interface-modifying layer Light absorbing zone and be deposited with the metal electrode on perovskite light absorbing zone, described modifying interface material is C60, described calcium Titanium ore light absorbing zone uses gas phase assisted solution method to prepare.
The preparation side of the perovskite solar cell of a kind of efficient stable without hole transmission layer the most as claimed in claim 1 Method, it is characterised in that comprise the following steps:
(1) conducting base acetone, deionized water are washed 2-3 time respectively, after drying, process 10-15min with UVO；
(2) being deposited with by pure titanium on the conducting base after step (1) processes, evaporation a layer thickness is 100-200nm Pure titanium, then the conducting base being coated with pure titanium is prepared titanium dioxide layer by organic electrolyte anodizing one step With titania nanotube layer, after cleaning, put into 500-550 DEG C of annealing 30min, then furnace cooling in Muffle furnace；
(3) spin coating C on titania nanotube layer60Organic solution, the speed of spin coating is 2000-4000rpm, Then at 50-70 DEG C, heat 15-30min, obtain interface-modifying layer；
(4) by PbX2Precursor solution is spin-coated on interface-modifying layer, then heats 10-25min at 70-100 DEG C, Being placed in vacuum drying oven together with iodide powder after natural cooling, be 10-20KPa at pressure, temperature is At 150-170 DEG C, heat iodide powder, with PbX after evaporation2Thin film reaction 50-120min, generates perovskite, from So it is carried out with isopropanol after cooling, at 150-170 DEG C, is finally dried 15-30min, obtains perovskite light and absorb Layer；
(5) on perovskite light absorbing zone, evaporation metal material, as electrode, obtains the perovskite sun electricity of efficient stable Pond.
The preparation side of the perovskite solar cell of a kind of efficient stable without hole transmission layer the most as claimed in claim 2 Method, it is characterised in that described conducting base is electro-conductive glass FTO.
The preparation side of the perovskite solar cell of a kind of efficient stable without hole transmission layer the most as claimed in claim 2 Method, it is characterised in that in step (2), the condition of described evaporation is 150-250A for evaporation power, and evaporation rate is 5-10nm/min。
The preparation side of the perovskite solar cell of a kind of efficient stable without hole transmission layer the most as claimed in claim 2 Method, it is characterised in that in step (2), the condition of described organic electrolyte anodizing is that anodic oxidation voltage is 50-60V, anodizing time is 30-60min.
The preparation side of the perovskite solar cell of a kind of efficient stable without hole transmission layer the most as claimed in claim 2 Method, it is characterised in that in step (3), described C60Organic solution be C60O-dichlorobenzene solution, C60Concentration For 5-15mg/mL.
The preparation side of the perovskite solar cell of a kind of efficient stable without hole transmission layer the most as claimed in claim 2 Method, it is characterised in that in step (4), described iodide powder is CH3NH3I powder or HC (NH2)2I powder.
The preparation side of the perovskite solar cell of a kind of efficient stable without hole transmission layer the most as claimed in claim 2 Method, it is characterised in that in step (4), described PbX2In, X is one or more mixing in I, Br, Cl.
The preparation side of the perovskite solar cell of a kind of efficient stable without hole transmission layer the most as claimed in claim 2 Method, it is characterised in that in step (4), described PbX2The solvent of precursor solution be N,N-dimethylformamide, two One in methyl sulfoxide, gamma-butyrolacton, N,N-dimethylacetamide, described PbX2PbX in precursor solution2Dense Degree is 350-550mg/mL.
The preparation of the perovskite solar cell of a kind of efficient stable without hole transmission layer the most as claimed in claim 2 Method, it is characterised in that in step (4), the thickness of described perovskite light absorbing zone is 50-100nm.
CN201610318902.9A 2016-05-12 2016-05-12 Efficient and stable perovskite solar cell without hole transporting layer and preparation method thereof Pending CN105957965A (en)

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Application publication date: 20160921