CN106025074A - Perovskite solar cell and preparation method thereof - Google Patents

Perovskite solar cell and preparation method thereof Download PDF

Info

Publication number
CN106025074A
CN106025074A CN201610446345.9A CN201610446345A CN106025074A CN 106025074 A CN106025074 A CN 106025074A CN 201610446345 A CN201610446345 A CN 201610446345A CN 106025074 A CN106025074 A CN 106025074A
Authority
CN
China
Prior art keywords
layer
humid air
perovskite
hole transmission
solar cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610446345.9A
Other languages
Chinese (zh)
Other versions
CN106025074B (en
Inventor
李述体
张崇臻
袁松洋
夏超
戚明月
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China Normal University
Original Assignee
South China Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China Normal University filed Critical South China Normal University
Priority to CN201610446345.9A priority Critical patent/CN106025074B/en
Publication of CN106025074A publication Critical patent/CN106025074A/en
Application granted granted Critical
Publication of CN106025074B publication Critical patent/CN106025074B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0001Processes specially adapted for the manufacture or treatment of devices or of parts thereof
    • H01L51/0029Special provisions for controlling the atmosphere during processing
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/42Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture
    • H01L51/4206Metal-organic semiconductor-metal devices
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Abstract

The invention provides a perovskite solar cell and a preparation method thereof. The contact resistance is reduced and the electric conductivity is improved through humid air treatment on a hole transport layer thin film, so that current of the cell is improved; and the optical-electrical characteristics of the solar cell are improved. Meanwhile, better diffusion of oxygen in a hole transport layer and a perovskite layer is promoted by the treatment process; the trap density is reduced; the interface resistance and the charge recombination rate between the hole transport layer and the perovskite layer are reduced; and the charge collection and transmission capacity is improved, so that the current and voltage of the cell are improved; and the optical-electrical characteristic of the solar cell are improved. The fill factor of the perovskite solar cell prepared by the preparation method provided by the invention can reach over 0.7; the short-circuit current density can reach 15.24mA/cm<2>; the open-circuit voltage can reach 0.95V; the maximum photoelectric conversion efficiency can reach 10.42%; and the perovskite solar cell has good photoelectric property.

Description

A kind of perovskite solaode and preparation method thereof
Technical field
The present invention relates to technical field of solar batteries, particularly to a kind of perovskite solaode and Preparation method.
Background technology
Solaode, also known as photovoltaic cell, is directly light by photoelectric effect or Photochemical effects The device of electric energy can be converted into.At present, based on silica-based solar cell on market, but it manufactures work Skill is complicated, and energy consumption is big, and cost is high, seriously constrains its large-scale promotion application.
Since two thousand nine, perovskite solaode by higher quantum efficiency, short-circuit current density, Open-circuit voltage etc. and receive much concern, it is mainly by having ABX3(A=CH3NH3 +, HC (NH2)2+ Deng;B=Pb2+, Sn2+Deng;X=Cl-, Br-, SCN-, I-Deng) photovoltaic material of perovskite structure realizes Opto-electronic conversion, has efficiency height, light weight, processing technology is simple, can be prepared as large area flexible device Etc. advantage with conspicuous characteristics.Its upside-down mounting basic structure be followed successively by from bottom to top glass substrate, transparent electrode layer, Electron transfer layer, perovskite material light-absorption layer, hole transmission layer, metal electrode, be similar to p-(pi)-i- (in) multiple structure of-n, is up to now, except silicon solar cell, the sun that unijunction efficiency is the highest Can battery.
But the perovskite material light-absorption layer of perovskite solaode is very sensitive to water, at the sky of high humidity Gas can cause battery performance to reduce with water generation chemical reaction and then destruction crystal structure.Therefore, calcium The preparation of titanium ore solaode and use all control under conditions of relative air humidity is less than 30%, this Greatly limit its application.
Summary of the invention
It is an object of the invention to provide a kind of perovskite solaode and preparation method thereof.System of the present invention The standby perovskite solaode obtained can be used for, in the air that relative humidity is high, having good photo electric Energy.
The invention provides the preparation method of a kind of perovskite solaode, described perovskite solar-electricity Electro-conductive glass that pond includes setting gradually, electron transfer layer, calcium titanium ore bed, hole transmission layer, photocathode Decorative layer and photocathode layer, carry out humid air process to described hole transmission layer.
Preferably, described humid air processes particularly as follows: before photocathode decorative layer coats, with moist empty Gas is to the sky in electro-conductive glass, electron transfer layer, calcium titanium ore bed and four layers of structure of composite membrane of hole transmission layer Jet in the surface of cave transport layer.
Preferably, the relative humidity of described humid air is 30~50%.
Preferably, the relative humidity of described humid air is 35~49%.
Preferably, the temperature of described humid air is 20~65 DEG C.
Preferably, the temperature of described humid air is 40~55 DEG C.
Preferably, the winding-up flow velocity of described humid air is 2~4L/min.
Preferably, the time that described humid air processes is 8~12h.
Preferably, the direction of described winding-up is for being perpendicular to hole transmission layer surface.
Present invention also offers perovskite solaode prepared by preparation method described in technique scheme.
The present invention, by processing the humid air of hole transport layer film, utilizes high relative humidity to dissolve Partial organic substances in thin film, acceleration material, in the transmission of interlayer, contributes to the process of reconstruction of thin film, enters And contribute to reducing the contact resistance of device, promote the carrier lifetime of thin film interlayer transmission, pass through battery Leakage current diminish, electrical conductance is improved, so promote battery current, improve solar cell photoelectric Characteristic;Meanwhile, air-flow processing procedure promotes oxygen and preferably expands in hole transmission layer and calcium titanium ore bed Dissipate so that thin-film material can preferably with air contact, improve hole transmission layer degree of oxidation and Crystallinity, decreases trap density, reduce interface resistance between hole transmission layer and calcium titanium ore bed and Charge recombination rate, is conducive to improving charge-trapping and transmittability, and then promotes battery current and voltage, Improve solar cell photoelectric characteristic.Test result indicate that, calcium prepared by the preparation method that the present invention provides Titanium ore solaode fill factor, curve factor is up to more than 0.7, and short-circuit current density is up to 15.24mA/cm2, open Road voltage reaches as high as 10.42% up to 0.95V, photoelectric transformation efficiency, has good photoelectric properties.
The preparation method that the present invention provides is simple to operate, mild condition, energy consumption are low, with low cost, technique Easily-controllable, suitable large-scale industry is promoted.
Accompanying drawing explanation
Fig. 1 is electro-conductive glass structural representation in comparative example of the present invention and embodiment;
Fig. 2 is comparative example and the performance test structural representation of embodiment perovskite solaode, wherein: 1-FTO electro-conductive glass;2-TiO2Electron transfer layer;3-perovskite CH3NH3PbIxCl3-xLight-absorption layer; 4-Spiro-OMeTAD hole transmission layer;5-MoO3Anode modification layer;6-Ag metal electrode;7-metal Wire;8-load or test device;9-incident illumination;
The VA characteristic curve of the perovskite solaode that Fig. 3 is comparative example of the present invention and prepared by embodiment;
The PL spectrogram of the perovskite solaode that Fig. 4 is comparative example of the present invention and prepared by embodiment.
Detailed description of the invention
The invention provides the preparation method of a kind of perovskite solaode, described perovskite solar-electricity Electro-conductive glass that pond includes setting gradually, electron transfer layer, calcium titanium ore bed, hole transmission layer, photocathode Decorative layer and photocathode layer, carry out humid air process to described hole transmission layer.
In the present invention, described humid air processes and is preferably before photocathode decorative layer coats, by humidity Air is in electro-conductive glass, electron transfer layer, calcium titanium ore bed and four layers of structure of composite membrane of hole transmission layer Jet in the surface of hole transmission layer.
In the present invention, the preparation of described perovskite solaode preferably includes following steps:
(1) electron transfer layer, calcium titanium ore bed and hole transmission layer are coated successively at conductive glass surface, To four layers of structure of composite membrane;
(2) surface of hole transmission layer described in step (1) is carried out humid air process;
(3) the hole transmission layer surface after step (2) described process coats photocathode decorative layer successively With time basic unit, obtain perovskite solaode.
The present invention does not has special restriction to the kind of described electro-conductive glass, uses those skilled in the art ripe The electro-conductive glass known.In the present invention, described electro-conductive glass is preferably FTO electro-conductive glass or ITO Electro-conductive glass, more preferably FTO electro-conductive glass.In the present invention, the square of described FTO electro-conductive glass Resistance is preferably 6~8 Ω/sq, and more preferably 6.5~7.5 Ω/sq;The light transmittance of described FTO electro-conductive glass is excellent Elect as more than 85%, more preferably 88~95%;The etching area of described FTO electro-conductive glass is preferably total The 1/4~1/2 of area, more preferably 1/3;The area of described FTO electro-conductive glass is preferably 14~16mm × 14~16mm.In the present invention, described FTO electro-conductive glass, as light anode layer, has Good chemical stability and good photoelectric properties.
First the present invention carries out pretreatment to conductive glass surface.In the present invention, described pre-place Reason preferably includes treatment with ultraviolet light.In the present invention, the wavelength of described ultraviolet light is preferably 350~450nm; The intensity of described ultraviolet light is preferably 24~28mW/cm2.In the present invention, described treatment with ultraviolet light time Between be preferably 15~25min, more preferably 18~22min.In the present invention, described treatment with ultraviolet light is permissible Remove the organic impurities of conductive glass surface residual, improve conductive glass surface pattern.
After completing described pretreatment, the conductive glass surface that the present invention preferably obtains in described pretreatment is successively Coating electron transfer layer, calcium titanium ore bed and hole transmission layer, obtain four layers of structure of composite membrane.The present invention couple The preparation of described four layers of structure of composite membrane does not has special restriction, uses calcium well known to those skilled in the art The preparation method of four layers of structure of composite membrane in titanium ore solaode.
The present invention does not has special restriction to the material of described electron transfer layer, uses those skilled in the art Known to the material for electron transfer layer.In the present invention, described electron transfer layer is preferably TiO2 Or ZnO, more preferably TiO2.In the present invention, the thickness of described electron transfer layer is preferably 30~60nm, More preferably 40~50nm.In the present invention, described electron transfer layer forms Ohmic contact with calcium titanium ore bed, Can effectively transmit electronics, effectively stop hole transport simultaneously.
The present invention preferably coats electron transfer layer on electro-conductive glass, obtains two-layer compound membrane structure.At this In invention, the mode of described coating is preferably sputtering, deposition or spin coating;The present invention is more preferably by TiO2Before Drive liquid solution in the way of spin coating, be coated to conductive glass surface.In the present invention, the rotating speed of described spin coating It is preferably 6000~7000rpm, more preferably 6400~6600rpm.In the present invention, described spin coating is preferred Carry out in an inert atmosphere.
In the present invention, described TiO2The molar concentration of precursor solution is preferably 0.18~0.3mol/L, more It is preferably 0.2~0.25mol/L.In the present invention, described TiO2Precursor solution preferably by titanium source solution and Hydrochloric acid solution is mixed to get.In the present invention, described titanium source is preferably 0.18~0.3:1 with the mol ratio of hydrochloric acid, More preferably 0.2~0.25:1.In the present invention, described titanium source is preferably organic titanium source, is more preferably specially Isopropyl titanate.In the present invention, the solvent of described titanium source solution is preferably alcohols solvent, more preferably first One or more in alcohol, ethanol and propanol.In the present invention, the molar concentration of described titanium source solution is excellent Elect 0.4~0.5mol/L as, more preferably 0.43~0.48mol/L.In the present invention, described hydrochloric acid mole Concentration is preferably 1.5~2.5mol/L, more preferably 1.8~2.2mol/L.
For making TiO2Precursor solution covers uniformly at conductive glass surface, the present invention preferably complete described Preheat after spin coating.In the present invention, the temperature of described preheating is preferably 140~160 DEG C, more preferably 145~155 DEG C;The time of described insulation is preferably 5~15min, more preferably 8~12min.
After completing described preheating, the two-layer compound membrane structure heating that the present invention preferably will obtain after described preheating It is incubated to annealing temperature.In the present invention, the speed of described heating is preferably 8~12 DEG C/min;Institute State annealing temperature and be preferably 400~500 DEG C, more preferably 440~460 DEG C;The time of described insulation is preferably 1.5~2.5h, more preferably 1.8~2.2h.In the present invention, described annealing can improve the knot of titanium dioxide Brilliant degree.
After completing described annealing, the two-layer compound membrane structure obtained after described annealing is preferably carried out by the present invention Oxygen plasma processes.In the present invention, the time that described oxygen plasma processes is preferably 4~6min. In the present invention, described oxygen plasma processes can remove titanium dioxide layer sintering rear surface residue, Improve substrate pattern.
After completing the process of described oxygen plasma, the present invention is preferably at described electron transfer layer surface-coated calcium Titanium ore layer, obtains sandwich diaphragm structure.In the present invention, described calcium titanium ore bed is preferably CH3NH3PbIxCl3-x, 0 < x < 3, described x is more preferably 1~2.In the present invention, described calcium titanium ore bed Thickness be preferably 350~450nm, more preferably 380~420nm, most preferably 390~410nm.? In the present invention, described calcium titanium ore bed, as photoactive layer, can absorb ultraviolet-visible spectrum to greatest extent The photon in region, and then excite the transmission of separation of charge and carrier.
In the present invention, the mode of described coating calcium titanium ore bed is preferably double source coevaporation, gas phase assists molten Liquid or solution spin coating;Perovskite precursor solution is more preferably spin-coated on electron transfer layer surface by the present invention. In the present invention, the speed of described spin coating is preferably 2000~3000rpm, more preferably 2400~2600rpm. In the present invention, described spin coating is carried out the most in an inert atmosphere.
In the present invention, the mass concentration of described perovskite precursor solution is preferably 40~50wt%, more excellent Elect 44~46wt% as.The present invention is preferably by PbCl2、CH3NH3I mixes with solvent, and reacting by heating obtains Perovskite precursor solution.In the present invention, described PbCl2And CH3NH3The mol ratio of I is preferably 0.3~0.5:1.In the present invention, during described solvent is preferably dimethyl sulfoxide, acetonitrile and dimethylformamide One or more, the more preferably one in dimethyl sulfoxide, acetonitrile and dimethylformamide.
In the present invention, described mixing is carried out the most under agitation.In the present invention, described stirring It is preferably magnetic agitation;The speed of described stirring is preferably 700~900rpm, more preferably 750~850rpm; The time of described stirring is preferably 10~14h, more preferably 11~13h.In the present invention, described reaction Temperature is preferably 45~55 DEG C, more preferably 48~52 DEG C.
For improving the crystallization degree of calcium titanium ore bed, the present invention preferably anneals after completing described spin coating, Obtain sandwich diaphragm structure.In the present invention, the temperature of described annealing is preferably 100~120 DEG C, more excellent Elect 105~115 DEG C as;The time of described annealing is preferably 40~60min, more preferably 45~55min.
After obtaining sandwich diaphragm structure, the present invention is preferably at the calcium titanium ore bed of described sandwich diaphragm structure Surface-coated hole transmission layer, obtains four layers of structure of composite membrane.The present invention material to described hole transmission layer Material does not has special restriction, uses the material for hole transmission layer well known to those skilled in the art. In the present invention, described hole transmission layer is preferably 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) ammonia Base]-9,9'-spiral shell two fluorenes (i.e. Spiro-OMeTAD), the polymer (i.e. P3HT) of 3-hexyl thiophene, 4,4- Azo double (4-cyanopentanoic acid) (i.e. PTAA), CuSCN or CuI, can be specially in the present invention Spiro-OMeTAD.In the present invention, the thickness of described hole transmission layer is preferably 100~300nm, more It is preferably 180~220nm.In the present invention, described hole transmission layer can form ohm with calcium titanium ore bed Contact, effective transporting holes and can effectively stop the transmission of electronics.
In the present invention, the mode of described coating hole transmission layer is preferably deposition or spin coating;The present invention is more Preferably hole transmission layer precursor solution is spin-coated on calcium titanium ore bed surface.In the present invention, described spin coating Speed be preferably 3500~4500rpm, more preferably 3800~4200rpm.In the present invention, described rotation It is coated with and carries out the most in an inert atmosphere.
In the present invention, the molar concentration of described hole transmission layer precursor solution is preferably 0.15~0.2mol/L.The present invention is preferably by Spiro-OMeTAD, 4-tert .-butylpyridine (i.e. TBP), lithium The acetonitrile solution of salt (i.e. Li-TFSI) and solvent mixing, obtain hole transmission layer precursor solution.At this In invention, described solvent is preferably chlorobenzene or chloroform.
After obtaining four layers of structure of composite membrane, the hole transmission layer of described four layers of structure of composite membrane is entered by the present invention Row humid air processes.In the present invention, described humid air processes preferably particularly as follows: repair at photocathode Before decorations layer coating, with humid air, is jetted in the hole transmission layer surface in four layers of structure of composite membrane. In the present invention, the direction of described winding-up is preferably normal to hole transmission layer.
In the present invention, the relative humidity of described humid air is preferably 30~50%, more preferably 35~49%;The temperature of described humid air is preferably 20~65 DEG C, more preferably 40~55 DEG C;Described tide The flow velocity of humid air is preferably 2~4L/min.In the present invention, the time that described humid air processes is preferred It is 8~12h.
Complete humid air process after, the present invention preferably described humid air process after hole transmission layer Surface-coated photocathode decorative layer, obtains five layers of structure of composite membrane.The present invention is to described photocathode decorative layer Material there is no special restriction, use the material for photocathode decorative layer well known to those skilled in the art Expect.In the present invention, described photocathode decorative layer is preferably MoO3.In the present invention, described light The thickness of cathodic modification layer is preferably 5~10nm.In the present invention, described photocathode decorative layer promotes hole Preferably transmission.
In the present invention, the mode of described coating is preferably vacuum evaporation.In the present invention, described vacuum The vacuum of evaporation is preferably more than 3.5 × 10-4Pa, more preferably 3.6~4 × 10-4Pa;Described vacuum evaporation Evaporation rate be preferably
After completing the coating of described photocathode decorative layer, the present invention is preferably on described photocathode decorative layer surface Coating photocathode layer, obtains perovskite solaode.In the present invention, described photocathode layer is preferably Au or Ag, more preferably Ag.In the present invention, the thickness of described photocathode layer is preferably 80~120nm, More preferably 90~110nm.In the present invention, the mode of described coating is preferably vacuum evaporation.At this In bright, the vacuum of described vacuum evaporation is preferably more than 3.5 × 10-4Pa, more preferably 3.6~4 × 10-4Pa; The evaporation rate of described vacuum evaporation is preferably
In order to further illustrate the present invention, the perovskite solar energy present invention provided below in conjunction with embodiment The preparation method of battery is described in detail, but can not be interpreted as them to scope Limit.
Comparative example:
1. in the titanium isopropoxide solution of 0.46mol/L, dropwise instill the HCl solution of equal-volume 2mol/L, Join molar concentration is the TiO of 0.23mol/L2Precursor solution;
2. according to PbCl2:CH3NH3The ratio mixing of I:DMF=1.2mmol:3mmol:1mL, at 50 DEG C Lower magnetic agitation 12h, prepared mass concentration is the perovskite precursor solution of 45wt%;
3. press 72.3g Spiro-OMeTAD, 28.8uL 4-tert .-butylpyridine (TBP), 17.5uL lithium salts (Li-TFSI), be dissolved in the ratio of 1mL chlorobenzene solvent, join molar concentration is the hole of 0.17mol/L Transport layer precursor solution;
4. using surface square resistance is 7 Ω/sq, and light transmittance is more than 85%, and etching area is the gross area The FTO electro-conductive glass of 1/3 is as substrate and transparency electrode 1, as shown in Figure 1;
5. using intensity is 26mW/cm2UV treatment with ultraviolet light substrate surface 20min after, use turn Speed is 6500rpm spin coating TiO2Precursor solution, 150 DEG C are first heated 10min, immediately in atmosphere It is warming up at 450 DEG C heat 2h, afterwards its oxygen plasma is processed surface 5min, prepare film thickness TiO for 30nm2Compacted zone is as electron transfer layer 2;
6. the perovskite presoma using spin-coating method spin coating concentration on electron transfer layer 2 to be 45wt% is molten Liquid, rotating speed is 2500rpm, rotational time 45s, and then anneal at 105 DEG C 50min, obtains layer Thickness be the perovskite thin film of 400nm as light-absorption layer, this process need to be carried out in atmosphere of inert gases;
7. use spin-coating method hole transmission layer presoma of spin coating concentration 0.17mol/L on light-absorption layer 3 molten Liquid, rotating speed is 4000rpm, and rotational time 45s obtains the hole transmission layer that film thickness is 100nm, This process need to be carried out in atmosphere of inert gases;
8. device is moved on to relative humidity less than standing 10h (for NRT group) under the normal temperature and pressure of 30%;
9. use vacuum thermal evaporation method, be 3.7 × 10 in vacuum-4Under Pa, respectively withWith Evaporation rate prepare 8nm MoO3And the photocathode layer of 100nm Ag.
Solar cell properties characterization parameter mainly has short circuit current (JSC), open-circuit voltage (VOC), fill out Fill the factor (FF) and photoelectric transformation efficiency (PCE).Wherein, photoelectric transformation efficiency is to characterize solar energy The most critical index of battery, is also the industrial standard weighing solar cell properties, representation unit area Peak power P of output on batterymWith incident power PiRatio, i.e. PCE=Pm/Pi=(JSC*VOC*FF) /Pi;The peak power output of fill factor, curve factor representation unit light-receiving area and JSC*VOCRatio, FF is the biggest, Represent that solar cell properties is the best, so the raising of solaode fill factor, curve factor, for device photoelectric Conversion efficiency promotes significant.Above-mentioned several parameters of perovskite solaode are surveyed by the present invention Fixed.
Perovskite solar cell device comparative example prepared is placed under standard solar simulator, With 3M test clip by transparency electrode and metal electrode connecting test instrument, test, test structural representation As shown in Figure 2.
In air at room temperature, use 100mW/cm2Solar simulator (Newport) AM1.5G illumination Under, use current-voltage tester (Keithley2400) to record current-voltage value, measurement result such as Fig. 3 Shown in.Read open-circuit voltage VOC, short-circuit current density JSCValue, and calculate fill factor, curve factor FF, photoelectricity Conversion efficiency PCE and series resistance RS, parallel resistance RSH, as shown in table 1.
The perovskite solaode preparing comparative example carries out PL spectrum test, and result is as shown in Figure 4.
Embodiment 1:
1. in the titanium isopropoxide solution of 0.46mol/L, it is added dropwise over the HCl solution of equal-volume 2mol/L, Magnetic agitation 10h under 800rpm speed, obtains the TiO that molar concentration is 0.23mol/L2Presoma is molten Liquid;
2. according to PbCl2:CH3NH3The ratio mixing of I:DMF=1.2mmol:3mmol:1mL, at 50 DEG C Magnetic agitation 12h under 800rpm speed, prepared mass concentration is the perovskite precursor solution of 45wt%;
3. press 72.3g Spiro-OMeTAD, 28.8uL4-tert .-butylpyridine (TBP), 17.5uL lithium salts (Li-TFSI), the ratio being dissolved in 1mL chlorobenzene solvent mixes, magnetic agitation 10h under 800rpm speed, Obtain the hole transmission layer precursor solution that molar concentration is 0.17mol/L;
4. using surface square resistance is 7 Ω/sq, and light transmittance is more than 85%, and etching area is the gross area The FTO electro-conductive glass of 1/3 is as substrate and transparency electrode 1, as shown in Figure 1;
5. using intensity is 26mW/cm2UV treatment with ultraviolet light substrate surface 20min after, use turn Speed is 6500rpm spin coating TiO2Precursor solution, 150 DEG C are first heated 10min in atmosphere, immediately with 10 DEG C/min ramp heats 2h at 450 DEG C, afterwards its oxygen plasma is processed surface 5min, Prepared film thickness is the TiO of 30nm2Compacted zone is as electron transfer layer 2;
6. the perovskite presoma using spin-coating method spin coating concentration on electron transfer layer 2 to be 45wt% is molten Liquid, rotating speed is 2500rpm, rotational time 45s, and anneal at 110 DEG C 50min, and obtaining thickness is 400nm Perovskite thin film as light-absorption layer, this process need to be carried out in atmosphere of inert gases;
7. use spin-coating method hole transmission layer presoma of spin coating concentration 0.17mol/L on light-absorption layer 3 molten Liquid, rotating speed is 4000rpm, and rotational time 45s obtains the hole transmission layer that film thickness is 100nm, This process need to be carried out in atmosphere of inert gases;
The most at ambient pressure, use flow velocity 3L/min, relative humidity be 48% 25 DEG C of air draughts stablize vertical Blow to the samples devices 10h after depositing hole transmission layer (for ART enforcement group);
9. use vacuum thermal evaporation method, be 3.7 × 10 in vacuum-4Under Pa, respectively withWith Evaporation rate prepare 8nm MoO3And the photocathode layer of 100nm Ag.
The perovskite solaode using the method identical with comparative example to prepare the present embodiment is carried out Test, test result is respectively as shown in Fig. 3, Fig. 4 and Biao 1.
Embodiment 2:
Use method same as in Example 1, step 8 replaced with: at ambient pressure, use flow velocity 3L/min, Relative humidity be 48% 45 DEG C of air draughts the most vertically blow to the sample device after depositing hole transmission layer Part 10h (for Air T45 enforcement group).
The perovskite solaode using method same as in Example 1 to prepare the present embodiment enters Row test, test result is respectively as shown in Fig. 3, Fig. 4 and Biao 1.
Embodiment 3:
Use method same as in Example 1, step 8 replaced with: at ambient pressure, use flow velocity 3L/min, Relative humidity be 48% 65 DEG C of air draughts the most vertically blow to the sample device after depositing hole transmission layer Part 10h (for Air T65 enforcement group).
The perovskite solaode using method same as in Example 1 to prepare the present embodiment enters Row test, test result is respectively as shown in Fig. 3, Fig. 4 and Biao 1.
The volt-ampere performance parameter of table 1 perovskite solaode
As can be seen from the above embodiments, the perovskite sun prepared by the preparation method provided according to the present invention The PCE of battery can reach as high as 10.42%, fill factor, curve factor up to more than 0.7, open-circuit voltage VOCWith short Road electric current JSCRespectively up to 0.95V and 15.24mA/cm2
The above is only the preferred embodiment of the present invention, and the present invention not makees any pro forma limit System.It should be pointed out that, for those skilled in the art, without departing from the principle of the invention On the premise of, it is also possible to making some improvements and modifications, these improvements and modifications also should be regarded as the present invention's Protection domain.

Claims (10)

1. a preparation method for perovskite solaode, described perovskite solaode includes successively Electro-conductive glass, electron transfer layer, calcium titanium ore bed, hole transmission layer, photocathode decorative layer and the light arranged Cathode layer, it is characterised in that described hole transmission layer is carried out humid air process.
Preparation method the most according to claim 1, it is characterised in that described humid air processes tool Body is: before photocathode decorative layer coats, with humid air to electro-conductive glass, electron transfer layer, calcium titanium Jet in the surface of the hole transmission layer in ore bed and four layers of structure of composite membrane of hole transmission layer.
Preparation method the most according to claim 2, it is characterised in that described humid air relative Humidity is 30~50%.
Preparation method the most according to claim 3, it is characterised in that described humid air relative Humidity is 35~49%.
5. according to the preparation method described in claim 3 or 4, it is characterised in that described humid air Temperature is 20~65 DEG C.
Preparation method the most according to claim 5, it is characterised in that the temperature of described humid air It it is 40~55 DEG C.
Preparation method the most according to claim 2, it is characterised in that the winding-up of described humid air Flow velocity is 2~4L/min.
Preparation method the most according to claim 1 and 2, it is characterised in that at described humid air The time of reason is 8~12h.
Preparation method the most according to claim 2, it is characterised in that the direction of described winding-up is vertical Straight in hole transmission layer surface.
10. the perovskite solaode that prepared by preparation method described in claim 1~9 any one.
CN201610446345.9A 2016-06-16 2016-06-16 A kind of perovskite solar cell and preparation method thereof Active CN106025074B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610446345.9A CN106025074B (en) 2016-06-16 2016-06-16 A kind of perovskite solar cell and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610446345.9A CN106025074B (en) 2016-06-16 2016-06-16 A kind of perovskite solar cell and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106025074A true CN106025074A (en) 2016-10-12
CN106025074B CN106025074B (en) 2018-03-16

Family

ID=57086976

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610446345.9A Active CN106025074B (en) 2016-06-16 2016-06-16 A kind of perovskite solar cell and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106025074B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107994118A (en) * 2017-11-13 2018-05-04 华中科技大学鄂州工业技术研究院 Perovskite solar cell, double-level-metal electrode and preparation method thereof
CN109524554A (en) * 2018-11-26 2019-03-26 西安交通大学 Perovskite/silicon lamination solar cell component deoxygenation packaging method of drying
CN109753678A (en) * 2018-11-17 2019-05-14 华中科技大学 A method of calibration solar battery VA characteristic curve
CN111490168A (en) * 2020-04-01 2020-08-04 中南大学 Preparation method of inorganic perovskite solar cell based on atmosphere control

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4593680B1 (en) * 2010-02-10 2010-12-08 昭和電工株式会社 Reprocessing method for metal working tools
CN104576930B (en) * 2015-01-06 2017-05-03 宁波大学 Perovskite solar cell and manufacturing method of perovskite solar cell

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107994118A (en) * 2017-11-13 2018-05-04 华中科技大学鄂州工业技术研究院 Perovskite solar cell, double-level-metal electrode and preparation method thereof
CN109753678A (en) * 2018-11-17 2019-05-14 华中科技大学 A method of calibration solar battery VA characteristic curve
CN109524554A (en) * 2018-11-26 2019-03-26 西安交通大学 Perovskite/silicon lamination solar cell component deoxygenation packaging method of drying
CN109524554B (en) * 2018-11-26 2020-07-28 西安交通大学 Dehumidification and oxygen removal packaging method for perovskite/silicon laminated solar cell module
CN111490168A (en) * 2020-04-01 2020-08-04 中南大学 Preparation method of inorganic perovskite solar cell based on atmosphere control

Also Published As

Publication number Publication date
CN106025074B (en) 2018-03-16

Similar Documents

Publication Publication Date Title
CN104134711B (en) A kind of preparation method of perovskite solar cell
Guchhait et al. Over 20% efficient CIGS–perovskite tandem solar cells
CN104091888B (en) A kind of Ca-Ti ore type solaode and preparation method thereof
TWI566450B (en) Materials for controlling the epitaxial growth of photoactive layers in photovoltaic devices
CN106025074B (en) A kind of perovskite solar cell and preparation method thereof
CN1579023A (en) Organic photovoltaic devices
JP2000285977A (en) Photoelectric conversion element and photocell
Yang et al. 28.3%-efficiency perovskite/silicon tandem solar cell by optimal transparent electrode for high efficient semitransparent top cell
CN107204379A (en) A kind of high-quality inorganic perovskite thin film and preparation method thereof and application in solar cells
CN105977386A (en) Perovskite solar cell of nano metal oxide hole transport layer and preparation method thereof
CN106953014A (en) A kind of hybrid solar cell structure and preparation method using CuPc as hole transmission layer
CN107123693A (en) A kind of efficient CdTe nanometer crystalline solar cell with high transparency window layer material processed based on solwution method and preparation method thereof
CN107369764A (en) A kind of perovskite solar cell and preparation method for adulterating lead acetate trihydrate
CN109065727A (en) A kind of preparation method of perovskite solar battery
US9040318B2 (en) Lamination as a modular approach for building organic photosensitive devices
US20110000542A1 (en) Hybrid photovoltaic modules
Zhang et al. Enhancing perovskite quality and energy level alignment of TiO2 nanorod arrays-based solar cells via interfacial modification
CN108011044A (en) Large area flexible perovskite solar cell and preparation method thereof
He et al. Interface engineering of BCP buffer layers in planar heterojunction perovskite solar cells with NiOx hole transporting layers
CN105304819A (en) Solar cell containing perovskite material and preparation method thereof
CN104937736A (en) Multijunction organic photovoltaics incorporating solution and vacuum deposited active layers
Wang et al. Crystallization process of PbI2 solution in two-step deposition of CH3NH3PbI3 for high-performance perovskite solar cells
Wu et al. Progress in blade-coating method for perovskite solar cells toward commercialization
Kim et al. Broad Spectrum Light Harvesting in TiO $ _2 $ Nanotube Array–Hemicyanine Dye–P3HT Hybrid Solid-State Solar Cells
CN105206749A (en) Perovskite solar cell and preparation process thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant