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CN106159094A - A kind of perovskite solar cell based on silica-based micro-nano structure and preparation method thereof - Google Patents

A kind of perovskite solar cell based on silica-based micro-nano structure and preparation method thereof Download PDF

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Publication number
CN106159094A
CN106159094A CN201610519030.2A CN201610519030A CN106159094A CN 106159094 A CN106159094 A CN 106159094A CN 201610519030 A CN201610519030 A CN 201610519030A CN 106159094 A CN106159094 A CN 106159094A
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perovskite
solar cell
silica
layer
silicon
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朱小宁
黄林泉
常远程
吴强
田占元
邓增社
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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Shaanxi Coal and Chemical Technology Institute 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
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/87—Light-trapping means
    • 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
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • 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

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Abstract

The invention provides a kind of perovskite solar cell based on silica-based micro-nano structure and preparation method thereof, it is formed with light trapping structure at monocrystalline silicon surface, on the one hand the optical loss of the heterojunction boundary that perovskite is formed can be reduced with monocrystal silicon, on the other hand, light trapping structure can be effectively increased the area of hetero-junctions, form more carrier transport passage, the exciton (electron hole pair) promoting calcium titanium ore bed to absorb photon and to produce efficiently separates at heterojunction boundary and transports, and improves battery performance further.Specifically, the design of light trapping structure, so that incident illumination is in the repeatedly interface reflection-absorption of perovskite/silica-based micro-nano structure, increase the optical absorption of calcium titanium ore bed.

Description

A kind of perovskite solar cell based on silica-based micro-nano structure and preparation method thereof
Technical field
The invention belongs to technical field of solar cells, a kind of perovskite solar cell based on silica-based micro-nano structure And preparation method thereof.
Background technology
Perovskite battery is one of the most rapid novel solar cell of current development.In the end of the year 2013, Science periodical will A kind of organic metal halogenide perovskite structure is utilized to be classified as generation then as all solid state perovskite solar cell of light absorbent One of big Progress & New Products in boundary ten, and it is called an important breakthrough of heliotechnics.Afterwards, perovskite solar cell becomes state The focus of inside and outside solar cell research field, conversion efficiency from 15.9% raising of 2013 to 2015 20.2%, in effect Rate aspect has exceeded the solar cell years of researches achievement such as dye sensitization, organic, quantum dot so that be combined with organic/inorganic Perovskite battery is that the photovoltaic technology of representative has brighter development prospect.With existing photovoltaic material compared with technology, calcium Titanium ore material and battery have following several respects advantage: (1) material high comprehensive performance, efficient absorption sunlight also completes photoproduction The exciting of carrier, transport, multiple processes such as separation；(2) energy gap is 1.5eV, absorbs cutoff wavelength and reaches 800nm, covers Lid visible light wave range；(3) carrier diffusion length is big, efficiently completes the bipolarity carrier transport of electrons；(4) battery Simple in construction, typically by transparency electrode, electron transfer layer, hole transmission layer, perovskite light absorbing zone, hole transmission layer and metal The part such as electrode is constituted, and both can make p-i-n structure, and can form hetero-junctions with other types photovoltaic material or tie knot more again Structure；(5) perovskite material wide material sources, preparation technology is not related to vacuum process, and temperature is low.
HIT (hetero junction with intrinsic thin-layer) solar cell is by monocrystal silicon and non- Crystal silicon carries out the novel solar cell that lamination obtains, and within 1997, realizes practical.In HIT solar battery structure, at N-shaped monocrystal silicon The two sides of cell piece is respectively completed the deposition of i type and p-type and i type and N-shaped amorphous silicon membrane.Advantage includes: (1) monocrystal silicon forbidden band Width is 1.1eV, and absorption cutoff wavelength is 1100nm, and p-type amorphous silicon membrane band gap is 1.7eV and adjustable, absorbs cutoff wavelength For 730nm, p-type non-crystalline silicon and N-shaped monocrystal silicon constitute hetero-junctions, on the premise of not affecting the absorption of monocrystal silicon light, greatly Add the open-circuit voltage of battery, thus improve battery efficiency；(2) on the one hand monocrystalline silicon surface is formed by i type amorphous silicon layer Well passivated, the p-i-n type electric field structure on the other hand formed, can improve separation and the transfer rate of photo-generated carrier, carry High battery photoproduction electric current density；(3) compared with common pn-junction single crystal silicon solar cell, HIT can use thinner monocrystal silicon, fall The low cost of raw material；(4) HIT solar cell has the feature of symmetrical configuration, it is possible to achieve generating electricity on two sides.
In addition to the heterojunction solar battery that non-crystalline silicon and monocrystal silicon are formed, it is also possible to use energy gap more than monocrystal silicon Thin-film material and monocrystal silicon form heterojunction solar battery, such as CIGS, cadmium telluride, perovskite etc..Have at present The hetero-junctions that perovskite and monocrystal silicon are formed is used for the research of solar cell, chemical solution method or gas phase mainly will be used auxiliary Help calcium titanium ore bed preparation prepared by sedimentation with without the N-shaped monocrystalline substrate of sunken optical processing on, energy gap is 1.5eV's Calcium titanium ore bed absorbs the incident light spectrum medium wavelength wave band less than 800nm, and energy gap is that the monocrystal silicon of 1.1eV absorbs not by calcium titanium The wavelength that ore bed the absorbs wave band less than 1100nm.
In such an embodiment, TCO electrode and TiO are sequentially passed through due to incident illumination2Reflection can be produced during electron transfer layer damage Lose, cause perovskite light absorbing zone can not fully absorb whole incident illuminations.Additionally, due to the monocrystal silicon without sunken optical processing Burnishing surface is up to more than 30% to the reflectance of incident illumination, also result in a large amount of losses of incident illumination, directly influences photoproduction electricity The size of stream.
Summary of the invention
It is an object of the invention to provide a kind of perovskite solar battery structure based on silica-based micro-nano structure and preparation side thereof Method, mainly solves in prior art owing to monocrystalline silicon buffing affects the size of photogenerated current in the face of a large amount of losses of incident illumination.
The present invention is achieved through the following technical solutions:
A kind of perovskite solar cell based on silica-based micro-nano structure, including having the monocrystal silicon of light trapping structure, this monocrystalline Silicon forms heterojunction structure with perovskite light absorbing zone, and described perovskite absorbed layer is as side to light.
Further, described light trapping structure is crystalline cone structure or the loose structure using chemical attack to remove surface damage.
Further, described crystalline cone structure is that quasi-sequence is distributed at monocrystalline silicon surface, and described crystalline cone structure is by laser pulse The conical structure of irradiation formation or class conical structure.
Further, described loose structure is randomly distributed in monocrystalline silicon surface, and described loose structure is by the change of metal catalytic Learn the cavernous structure that corrosion is formed.
Further, the chemical corrosion liquid used by described metal catalytic is the Fluohydric acid. of tetra chlorauric acid catalysis and going of hydrogen peroxide Deionized water solution, tetra chlorauric acid: hydrogen peroxide: the volume ratio of water is: 1:5:2.
Further, the concrete structure of this perovskite solar cell is: monocrystalline substrate surface is followed successively by: hole transmission layer, Perovskite light absorbing zone, electron transfer layer and transparency conductive electrode, the monocrystalline substrate back side is metal electrode.
Further, described hole transmission layer is that inorganic, metal oxide nickel oxide, molybdenum oxide, chromium oxide or ruthenium-oxide are thin Film；Described perovskite light absorbing zone is methylamino lead iodine compound；Described electron transfer layer is fine and close titanium deoxid film Or aluminium sesquioxide thin film or zirconia film or zinc-oxide film.
The preparation method of a kind of perovskite solar cell based on silica-based micro-nano structure, prepares on monocrystalline substrate surface Light trapping structure, then forms heterojunction structure, using calcium titanium ore bed as side to light with perovskite light absorbing zone.
Further, following steps are specifically included:
(1) laser pulse irradiation is used to prepare crystalline cone structure at monocrystalline silicon surface or use metal catalytic to corrode at monocrystalline Silicon face prepares loose structure；
(2) using chemical attack to remove the surface damage of monocrystal silicon, corrosive liquid is that Fluohydric acid. is water-soluble with the deionization of nitric acid Liquid, wherein, Fluohydric acid. excess, etching time 30-300s；
(3) magnetron sputtering or ald is used to prepare the hole transport that thickness is 10-300nm at monocrystalline silicon surface Layer, hole transmission layer is NiO2、MoO3、Cr2O3Or RuO2Thin film；
(4) using double source coevaporation method to prepare perovskite light absorbing zone, evaporation source is PbI2Or PbCl2Or PbBr2Or HC (NH2)2I or HC (NH2)2Br and CH3NH3I, mass ratio is 1:1-1:3, forms CH after reaction3NH3PbI3Light absorbing zone or CH3NH3PbI3-xClxAbsorbed layer or CH3NH3PbI3-xBrxAbsorbed layer or CH3NH3SnxPb1-xI3Absorbed layer or HC (NH2)2PbI3Inhale Receive layer or HC (NH2)2PbBr3Absorbed layer, thickness is 100-600nm；
(5) being sequentially prepared electron transfer layer and transparency conductive electrode with magnetron sputtering, wherein, the target of electron transfer layer is TiO2Or Al2O3Or ZrO or ZnO, thickness is 10-300nm；The thickness of transparency conductive electrode is 50-200nm；
(6) using magnetron sputtering or thermal evaporation to prepare argent or aluminum electrode layer at the monocrystalline substrate back side, thickness is 30- 500nm。
Further, in step (1), the crystalline cone height of described crystalline cone structure is 0.05-100 μm, and halfwidth is 0.05-50 μ M, prepares the surface reflectivity fall not higher than 6% in 380nm-1100nm wave band of the monocrystal silicon after crystalline cone；Described loose structure The porous silicon degree of depth be 20-1000nm, aperture is 50-800nm, prepares the monocrystal silicon after loose structure at 380nm-1100nm ripple Surface reflectivity fall not higher than 5% in Duan.
Compared with prior art, the present invention at least has the advantages that
The present invention is formed with light trapping structure at monocrystalline silicon surface, on the one hand can reduce perovskite different with what monocrystal silicon was formed The optical loss of matter junction interface, on the other hand, light trapping structure can be effectively increased the area of hetero-junctions, forms more carrier Transmission channel, the exciton (electron hole pair) that promotion calcium titanium ore bed absorbs photon and produces occurs effectively at heterojunction boundary Separate and transport, improve battery performance further.Specifically, the design of light trapping structure so that incident illumination perovskite/ The repeatedly interface reflection-absorption of silica-based micro-nano structure, increases the optical absorption of calcium titanium ore bed.
Accompanying drawing explanation
The structural representation of a kind of based on silica-based micro-nano structure the perovskite silica-based solar cell that Fig. 1 provides for the present invention Figure.
Wherein, 1, monocrystalline substrate；2, hole transmission layer；3, perovskite light absorbing zone；4, electron transfer layer；5, conduction electricity Pole；6, metal electrode.
Detailed description of the invention
If the monocrystalline silicon surface contacted with perovskite is performed etching process, form effective light trapping structure, on the one hand Can reduce the optical loss of the heterojunction boundary that perovskite is formed with monocrystal silicon, on the other hand, light trapping structure can effectively increase Add the area of hetero-junctions, form more carrier transport passage, the exciton (electronics that promotion calcium titanium ore bed absorbs photon and produces Hole to) efficiently separate at heterojunction boundary and transport.
Therefore, in order to improve the efficiency of light absorption of silica-based perovskite heterojunction solar battery, improve the product of photo-generated carrier Raw rate, promotes carrier separation and the transport efficiency of calcium titanium ore bed, and the present invention proposes the silica-based micro-nano structure of a kind of employing as silicon Solar battery structure of based perovskite heterojunction boundary and preparation method thereof.Melting with corrasion at list by laser pulse Crystal silicon surface forms micron-sized crystalline cone structure, and crystalline cone structure is that quasi-sequence is distributed at monocrystalline silicon surface, commonly referred to black silicon, Crystalline cone has bigger depth-width ratio, so that incident illumination forms reflection repeatedly and absorption on surface, can be effectively improved crystalline silicon Absorptivity.
As the alternative of crystalline cone structure, prepare nano level many by metal catalytic caustic solution in the monocrystal silicon table second Pore structure, the loose structure of formation is randomly distributed in monocrystalline silicon surface, makes silicon face form the hole of a large amount of depth-to-width ratio, makes incidence Light, in hole wall generation multiple reflections and absorption, is equally effectively improved the absorptivity of monocrystal silicon.
Carry out the monocrystalline substrate surface in perovskite silicon substrate heterojunction solar cell falling into optical processing, prepare above-mentioned two Plant micro-nano structure, the optical loss of monocrystalline substrate, and the increase of hetero-junctions area can be reduced, photo-generated carrier can be improved Separation and transport efficiency, improve battery performance further.
The structure of a kind of perovskite solar cell based on silica-based micro-nano structure disclosed by the invention is: have light trapping structure Monocrystalline substrate 1 surface be followed successively by hole transmission layer 2, perovskite light absorbing zone 3, electron transfer layer 4 and transparency conductive electrode 5, monocrystalline substrate 1 back side is metal electrode 6.
Wherein, monocrystalline substrate 1 is the monocrystalline silicon piece of p-type electric-conducting, and described hole transmission layer 2 is inorganic, metal oxide oxygen Changing nickel (NiO2), molybdenum oxide (MoO3), chromium oxide (Cr2O3) or ruthenium-oxide (RuO2) thin film, described perovskite light absorbing zone 3 is Methylamino lead iodine compound (CH3NH3PbI3), described electron transfer layer 4 is compact titanium dioxide (TiO2) thin film.
Described light trapping structure is crystalline cone structure or the loose structure using chemical attack to remove surface damage.Described crystalline cone is tied Structure is the circular cone formed by laser pulse irradiation or class conical structure.Described laser pulse is nanosecond, psec or femtosecond magnitude.Institute Stating loose structure is the cavernous structure formed by the chemical attack of metal catalytic.The chemical corrosion liquid of described metal catalytic is tetrachloro Auric acid (HAuCl4) Fluohydric acid. (HF) that is catalyzed and hydrogen peroxide (H2O2) deionized water solution.
This solar cell preparation method is:
Step 1:a: using laser pulse irradiation to prepare crystalline cone structure on p-type monocrystalline substrate 1 surface, laser can be to receive Second (ns) laser, psec (ps) laser, or femtosecond (fs) laser, corresponding pulse width is respectively 1-100ns, 10- 400ps, or 20-800fs.Optical maser wavelength is 532-1064nm, and laser power is 5-500mW.The crystalline cone height of preparation is 0.05-100 μm, halfwidth is 0.05-50 μm, makes monocrystal silicon surface reflectivity fall in 380nm-1100nm wave band not higher than 6%.
B: using metal catalytic corrosion to prepare loose structure on p-type monocrystalline substrate 1 surface, catalyst is 0.01-1mM's Tetra chlorauric acid (HAuCl4) solution, corrosive liquid is Fluohydric acid. (HF) and hydrogen peroxide (H2O2) deionized water solution, HF:H2O2: The volume ratio of H2O is 1:5:2.The porous silicon degree of depth of preparation is 20-1000nm, and aperture is 50-800nm, makes monocrystal silicon exist Surface reflectivity fall not higher than 5% in 380nm-1100nm wave band.
Step 2: using chemical attack to remove the surface damage of micro-nano structure, corrosive liquid is the deionization of Fluohydric acid. and nitric acid Aqueous solution, HF:HNO3: H2The volume ratio of O is 2:2:3-4:2:3, etching time 30-300s.
Step 3: use magnetron sputtering or ald to prepare NiO at micro-nano structure surface2、MoO3、Cr2O3Or RuO2Thin Film is as hole transmission layer 2, and thickness is 10-300nm.
Step 4: using double source coevaporation method to prepare perovskite light absorbing zone 3, evaporation source is PbI2With CH3NH3I, mass ratio For 1:1-1:3, after reaction, form CH3NH3PbI3Light absorbing zone, thickness is 100-600nm.Wherein, CH3NH3PbI3Light absorbing zone Can also be by CH3NH3PbI3-xClxAbsorbed layer, CH3NH3PbI3-xBrxAbsorbed layer, CH3NH3SnxPb1-xI3Absorbed layer, HC (NH2)2PbI3Absorbed layer or HC (NH2)2PbBr3Absorbed layer substitutes.
Step 5: prepare electron transfer layer 4 with magnetron sputtering, target is TiO2, thickness is 10-300nm.Certainly, target is also Can be Al2O3, ZrO, ZnO etc..
Step: 6 prepare transparency conductive electrode 5 with magnetron sputtering, target is tin indium oxide (ITO) or fluorine doped tin oxide (FTO), thickness is 50-200nm.
Step 7: use magnetron sputtering or thermal evaporation to prepare metal gold, silver or aluminum electrode layer at p-type monocrystalline substrate 1 back side 6, thickness degree is 30-500nm.
Embodiment 1:
Step 1: using laser pulse irradiation p-type monocrystalline silicon surface to prepare crystalline cone structure, pulsewidth is 100-100ps, wavelength For 1064nm, power is 5mW, and hot spot is 30 μm, and radiation mode is mark continuously line by line, and the crystalline cone height of preparation is 60 μm, half High a width of 10 μm.
Step 2: use corrosive liquid (HF:HNO3: H2O=2:2:3) monocrystal silicon and surface crystalline cone structure, scavenging period are cleaned For 180s.
Step 3: use magnetron sputtering to prepare NiO on crystalline cone surface2Thin film is as hole transmission layer, and thickness is 50nm.
Step 4: using double source coevaporation to prepare perovskite light absorbing zone on hole transmission layer, evaporation source is PbI2With CH3NH3I, amount ratio is 1:3.The two reaction forms CH3NH3PbI3Film thickness is 400nm.
Step 5: use magnetron sputtering to prepare TiO on perovskite light absorbing zone2Electron transfer layer, thickness is 150nm.
Step 6: using magnetron sputtering to prepare transparent conductive electrode on the electron transport layer, thickness is 100nm.
Step 7: use magnetron sputtering method to prepare Al electrode at the monocrystal silicon back side, thickness is 200nm.
Embodiment 2:
Step 1: using metal catalytic chemical attack to prepare loose structure at p-type monocrystalline silicon surface, catalyst is 0.05mM HAuCl4Solution, corrosive liquid is HF and H2O2Deionized water solution (HF:H2O2: H2O=1:5:2), corrosion is in ultrasonic water bath In carry out, etching time 180s, the porous silicon degree of depth of preparation is 20nm, and aperture is 50nm.
Step 2: use corrosive liquid (HF:HNO3: H2O=2:2:3) monocrystal silicon and surface crystalline cone structure, scavenging period are cleaned For 150s.
Step 3: use magnetron sputtering to prepare NiO on crystalline cone surface2Thin film is as hole transmission layer, and thickness is 50nm.
Step 4: using double source coevaporation to prepare perovskite light absorbing zone on hole transmission layer, evaporation source is PbI2With CH3NH3I, amount ratio is 1:3.The two reaction forms CH3NH3PbI3Film thickness is 400nm.
Step 5: using magnetron sputtering to prepare TiO2 electron transfer layer on perovskite light absorbing zone, thickness is 150nm.
Step 6: using magnetron sputtering to prepare transparent conductive electrode on the electron transport layer, thickness is 100nm.
Step 7: use magnetron sputtering method to prepare Al electrode at the monocrystal silicon back side, thickness is 200nm.
Embodiment 3:
Step 1: using laser pulse irradiation p-type monocrystalline silicon surface to prepare crystalline cone structure, pulsewidth is 1-100ns, and wavelength is 870nm, power is 30mW, and radiation mode is mark continuously line by line, and the crystalline cone height of preparation is 0.05 μm, and halfwidth is 0.05 μ m。
Step 2: use corrosive liquid (HF:HNO3: H2O=3:2:3) monocrystal silicon and surface crystalline cone structure, scavenging period are cleaned For 120s.
Step 3: use magnetron sputtering to prepare NiO on crystalline cone surface2Thin film is as hole transmission layer, and thickness is 100nm.
Step 4: using double source coevaporation to prepare perovskite light absorbing zone on hole transmission layer, evaporation source is PbI2With CH3NH3I, amount ratio is 1:1.The two reaction forms CH3NH3PbI3Film thickness is 300nm.
Step 5: using magnetron sputtering to prepare TiO2 electron transfer layer on perovskite light absorbing zone, thickness is 200nm.
Step 6: using magnetron sputtering to prepare transparent conductive electrode on the electron transport layer, thickness is 50nm.
Step 7: use magnetron sputtering method to prepare Al electrode at the monocrystal silicon back side, thickness is 400nm.
Embodiment 4:
Step 1: using laser pulse irradiation p-type monocrystalline silicon surface to prepare crystalline cone structure, pulsewidth is 20-800fs, and wavelength is 532nm, power is 500mW, and radiation mode is mark continuously line by line, and the crystalline cone height of preparation is 100 μm, and halfwidth is 50 μm.
Step 2: use corrosive liquid (HF:HNO3: H2O=4:2:3) monocrystal silicon and surface crystalline cone structure, scavenging period are cleaned For 30s.
Step 3: use magnetron sputtering to prepare NiO on crystalline cone surface2Thin film is as hole transmission layer, and thickness is 200nm.
Step 4: using double source coevaporation to prepare perovskite light absorbing zone on hole transmission layer, evaporation source is PbI2With CH3NH3I, amount ratio is 1:3.The two reaction forms CH3NH3PbI3Film thickness is 100nm.
Step 5: using magnetron sputtering to prepare TiO2 electron transfer layer on perovskite light absorbing zone, thickness is 300nm.
Step 6: using magnetron sputtering to prepare transparent conductive electrode on the electron transport layer, thickness is 200nm.
Step 7: use magnetron sputtering method to prepare Al electrode at the monocrystal silicon back side, thickness is 30nm.
Embodiment 5:
Step 1: using metal catalytic chemical attack to prepare loose structure at p-type monocrystalline silicon surface, catalyst is 0.05mM HAuCl4Solution, corrosive liquid is HF and H2O2Deionized water solution (HF:H2O2: H2O=1:5:2), corrosion is in ultrasonic water bath In carry out, etching time 200s, the porous silicon degree of depth of preparation is 1000nm, and aperture is 300nm.
Step 2: use corrosive liquid (HF:HNO3: H2O=2:2:3) monocrystal silicon and surface crystalline cone structure, scavenging period are cleaned For 300s.
Step 3: use magnetron sputtering to prepare NiO on crystalline cone surface2Thin film is as hole transmission layer, and thickness is 300nm.
Step 4: using double source coevaporation to prepare perovskite light absorbing zone on hole transmission layer, evaporation source is PbI2With CH3NH3I, amount ratio is 1:2.The two reaction forms CH3NH3PbI3Film thickness is 600nm.
Step 5: using magnetron sputtering to prepare TiO2 electron transfer layer on perovskite light absorbing zone, thickness is 10nm.
Step 6: using magnetron sputtering to prepare transparent conductive electrode on the electron transport layer, thickness is 100nm.
Step 7: use magnetron sputtering method to prepare Al electrode at the monocrystal silicon back side, thickness is 500nm.
Embodiment 6:
Step 1: using metal catalytic chemical attack to prepare loose structure at p-type monocrystalline silicon surface, catalyst is 0.05mM HAuCl4Solution, corrosive liquid is HF and H2O2Deionized water solution (HF:H2O2: H2O=1:5:2), corrosion is in ultrasonic water bath In carry out, etching time 180s, the porous silicon degree of depth of preparation is 500nm, and aperture is 800nm.
Step 2: use corrosive liquid (HF:HNO3: H2O=4:2:3) monocrystal silicon and surface crystalline cone structure, scavenging period are cleaned For 200s.
Step 3: use magnetron sputtering to prepare NiO on crystalline cone surface2Thin film is as hole transmission layer, and thickness is 10nm.
Step 4: using double source coevaporation to prepare perovskite light absorbing zone on hole transmission layer, evaporation source is PbI2With CH3NH3I, amount ratio is 1:1.The two reaction forms CH3NH3PbI3Film thickness is 100nm.
Step 5: using magnetron sputtering to prepare TiO2 electron transfer layer on perovskite light absorbing zone, thickness is 150nm.
Step 6: using magnetron sputtering to prepare transparent conductive electrode on the electron transport layer, thickness is 200nm.
Step 7: use magnetron sputtering method to prepare Al electrode at the monocrystal silicon back side, thickness is 300nm.
The micron-sized crystalline cone structure that the present invention is formed by the melted of laser pulse and corrasion at monocrystalline silicon surface, And the nano level loose structure prepared by the chemical corrosion method of metal catalytic, by incident illumination in micro-nano structure Multiple reflections produces and repeatedly absorbs, and can reduce the luminous reflectance loss of solar cell greatly, improve absorptivity.This anti-reflection Penetrating effect is the absorption number of times realization by increasing incident illumination, therefore the incident illumination of any one wavelength is all had effect, It is a kind of wide spectrum antireflective mechanism.
Prepare crystalline cone or porous micro-nano structure on monocrystalline substrate surface, and form hetero-junctions with perovskite light absorbing zone Structure, using calcium titanium ore bed as side to light, first passes through incident illumination in the reflection suction of the repeatedly interface of perovskite/silica-based micro-nano structure Receive, the optical absorption of calcium titanium ore bed can be increased；Secondly micro-nano structure is by increasing the area of hetero-junctions, improves photoproduction further The generation rate of carrier；Finally, the hetero-junctions that perovskite/silica-based micro-nano structure is formed can realize segmentation and inhale solar spectrum Receiving, perovskite energy gap (Eg) is 1.5eV, can effectively absorb solar spectrum medium wavelength less than 800nm in 400nm thickness Incident illumination, monocrystal silicon Eg is 1.1eV, can continue absorbing wavelength more than 800nm and the incident illumination that can not be absorbed by perovskite, Thus expand the absorption spectrum of perovskite solar cell, improve photoproduction photoproduction carrier concentration and photogenerated current density further.

Claims (10)

1. a perovskite solar cell based on silica-based micro-nano structure, it is characterised in that: include the monocrystalline with light trapping structure Silicon, this monocrystal silicon forms heterojunction structure with perovskite light absorbing zone, and described perovskite absorbed layer is as side to light.
A kind of perovskite solar cell based on silica-based micro-nano structure the most according to claim 1, it is characterised in that: described Light trapping structure is crystalline cone structure or the loose structure using chemical attack to remove surface damage.
A kind of perovskite solar cell based on silica-based micro-nano structure the most according to claim 2, it is characterised in that: described Crystalline cone structure is that quasi-sequence is distributed at monocrystalline silicon surface, described crystalline cone structure be the conical structure formed by laser pulse irradiation or Class conical structure.
A kind of perovskite solar cell based on silica-based micro-nano structure the most according to claim 2, it is characterised in that: described Loose structure is randomly distributed in monocrystalline silicon surface, and described loose structure is the poroid knot formed by the chemical attack of metal catalytic Structure.
A kind of perovskite solar cell based on silica-based micro-nano structure the most according to claim 4, it is characterised in that: described Chemical corrosion liquid used by metal catalytic is the Fluohydric acid. deionized water solution with hydrogen peroxide of tetra chlorauric acid catalysis, tetrachloro gold Acid: hydrogen peroxide: the volume ratio of water is 1:5:2.
A kind of perovskite solar cell based on silica-based micro-nano structure the most according to claim 1, it is characterised in that: this calcium The concrete structure of titanium ore solar cell is: monocrystalline substrate surface is followed successively by: hole transmission layer (2), perovskite light absorbing zone (3), electron transfer layer (4) and transparency conductive electrode (5), the monocrystalline substrate back side is metal electrode (6).
A kind of perovskite solar cell based on silica-based micro-nano structure the most according to claim 6, it is characterised in that: described Hole transmission layer (2) is inorganic, metal oxide nickel oxide, molybdenum oxide, chromium oxide or ruthenium-oxide thin film；Described perovskite light is inhaled Receiving layer (3) is methylamino lead iodine compound；Described electron transfer layer be fine and close titanium deoxid film or aluminium sesquioxide thin Film or zirconia film or zinc-oxide film.
8. the preparation method of a perovskite solar cell based on silica-based micro-nano structure, it is characterised in that: in monocrystalline substrate Light trapping structure is prepared on surface, then forms heterojunction structure, using calcium titanium ore bed as side to light with perovskite light absorbing zone.
The preparation method of a kind of perovskite solar cell based on silica-based micro-nano structure the most according to claim 8, it is special Levy and be, specifically include following steps:
(1) laser pulse irradiation is used to prepare crystalline cone structure at monocrystalline silicon surface or use metal catalytic to corrode at monocrystal silicon table Loose structure is prepared in face；
(2) using chemical attack to remove the surface damage of monocrystal silicon, corrosive liquid is the deionized water solution of Fluohydric acid. and nitric acid, its In, Fluohydric acid. excess, etching time 30-300s；
(3) magnetron sputtering or ald is used to prepare the hole transmission layer that thickness is 10-300nm at monocrystalline silicon surface, empty Cave transport layer is NiO2、MoO3、Cr2O3Or RuO2Thin film；
(4) using double source coevaporation method to prepare perovskite light absorbing zone, evaporation source is PbI2Or PbCl2Or PbBr2Or HC (NH2)2I Or HC (NH2)2Br and CH3NH3I, mass ratio is 1:1-1:3, forms CH after reaction3NH3PbI3Light absorbing zone or CH3NH3PbI3- xClxAbsorbed layer or CH3NH3PbI3-xBrxAbsorbed layer or CH3NH3SnxPb1-xI3Absorbed layer or HC (NH2)2PbI3Absorbed layer or HC (NH2)2PbBr3Absorbed layer, thickness is 100-600nm；
(5) being sequentially prepared electron transfer layer and transparency conductive electrode with magnetron sputtering, wherein, the target of electron transfer layer is TiO2 Or Al2O3Or ZrO or ZnO, thickness is 10-300nm；The thickness of transparency conductive electrode is 50-200nm；
(6) using magnetron sputtering or thermal evaporation to prepare argent or aluminum electrode layer at the monocrystalline substrate back side, thickness is 30- 500nm。
The preparation method of a kind of perovskite solar cell based on silica-based micro-nano structure the most according to claim 9, it is special Levying and be: in step (1), the crystalline cone height of described crystalline cone structure is 0.05-100 μm, and halfwidth is 0.05-50 μm, preparation crystalline substance The monocrystal silicon after cone surface reflectivity fall not higher than 6% in 380nm-1100nm wave band；The porous silicon of described loose structure The degree of depth is 20-1000nm, and aperture is 50-800nm, prepares the table in 380nm-1100nm wave band of the monocrystal silicon after loose structure Face reflectance fall not higher than 5%.
CN201610519030.2A 2016-07-04 2016-07-04 A kind of perovskite solar cell based on silica-based micro-nano structure and preparation method thereof Pending CN106159094A (en)

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CN111697138A (en) * 2020-06-24 2020-09-22 山西大学 Based on TiO2Perovskite battery model of nanocone array
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