CN109904329A - A kind of the blade coating structure and preparation method of modified high-efficient perovskite solar battery - Google Patents

A kind of the blade coating structure and preparation method of modified high-efficient perovskite solar battery Download PDF

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CN109904329A
CN109904329A CN201910118264.XA CN201910118264A CN109904329A CN 109904329 A CN109904329 A CN 109904329A CN 201910118264 A CN201910118264 A CN 201910118264A CN 109904329 A CN109904329 A CN 109904329A
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perovskite
blade coating
solar battery
modified
perovskite solar
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徐保民
王行柱
王登
曾峰
胡路遥
胡航
陈家邦
张罗正
周贤勇
田颜清
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Southwest University of Science and Technology
Southern University of Science and Technology
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    • 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
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention belongs to Materials Science and Engineering energy device optimisation technique fields, disclose the blade coating structure and preparation method of a kind of modified high-efficient perovskite solar battery, it replaces PDEOT:PSS to carry out the interface optimization of solar cell device using NiOx, and is spin-coated on electro-conductive glass；Dimethyl sulfoxide and dimethyl formyl are added in the precursor liquid of perovskite and regulates and controls DMSO and DMF accounting, carries out the optimization of perovskite solution solvent；By perovskite solution, at ambient temperature on the method coating solar cell device of blade coating；It is successively coated with fullerene derivate BCPM block copolymer B CP, silver electrode is plated, prepares perovskite solar battery PSC.The present invention passes through the modification of solvent in perovskite solution, and the change of hole transmission layer boundary material theoretically improves the efficiency of perovskite solar battery；Preparation method substantially increases preparation speed, and operation convenience using blade coating simultaneously.

Description

A kind of the blade coating structure and preparation method of modified high-efficient perovskite solar battery
Technical field
The invention belongs to Materials Science and Engineering energy device optimisation technique field more particularly to a kind of modified high-efficient calcium titaniums The blade coating structure and preparation method of mine solar battery.
Background technique
Currently, the prior art commonly used in the trade is such that
First cleaned conductive substrates, later in the glove box of nitrogen atmosphere (oxygen content≤5.0ppm, water content≤ It 0.1ppm) is operated, for example by hole mobile material: the aqueous solution PDEOT:PSS of high molecular polymer is revolved with certain speed It is applied in conductive substrates, prepares perovskite solution using DMF or other solvents, successively by perovskite solution, electron transport material Such as fullerene derivate PCBM, modifying interface material such as titanium dioxide (TiO2) with certain speed to be spin-coated to above-mentioned hole transport thin In film layer, last evaporation metal electrode.
Hybrid inorganic-organic perovskite solar battery (PSC) due to its economic advantages and flexibility, from develop for the first time with Just to cause extensive concern.Up to the present, the efficiency of laboratory Ca-Ti ore type solar battery has been increased to 23% More than.Regrettably, this efficient device is usually by being prepared in glove box using the method for spin coating.For For following business application, it is inevitable trend that PSC is prepared under the conditions of air environment, and can there is an urgent need to find Meet the spin coating substitute of the requirement of large-scale production.Compared with spin-coating method, scraper for coating method is a kind of simple, economical, effective Precursor solution rheological behavior and Drying Dynamics utilization technology.Particularly, blade coating technology is widely answered With because blade coating technology can be suitble to produce under the conditions of room temperature environment, and being easy to be changed into other continuous printing skills Art, such as roll-to-roll printing.
In addition, DMF dissolves perovskite precursor solution as most common solvent.But DMF boiling point approaches and calcium titanium The stabilization phase transition temperature of mine film, the evaporation process of perovskite precursor solution start from the ring of blade coating condition lower substrate The result of the shortcomings that border temperature, this technique result in the inhomogeneities of perovskite thin film.Due to dimethyl sulfoxide (DMSO) with The coordination ability of Pb is stronger, and boiling point is higher, therefore removal dimethyl sulfoxide (DMSO) is more difficult than DMF from presoma.Therefore, In order to obtain the perovskite thin film of uniform crystallinity high quality, it is contemplated that using DMSO as the addition of DMF base precursor solution Agent, with delayed crystallisation process.Therefore, under room temperature (RH~45%, RT~25 DEG C), high quality can be made using scraper for coating method Perovskite thin film, PSC efficiency can be increased to 13.80% from 10.98%.
On the other hand, it is based on PEDOT using most of inversion planar heterojunction PSC prepared by blade coating technology: PSS is as hole transmission layer (HTL).However, PEDOT:PSS is unfavorable for device in environment item due to its highly acidity and hygroscopicity Long-time stability under part.Therefore, replace PEDOT:PSS in reverse phase PSC using different hole mobile materials, it is such as organic Material PTAA, TAPC and inorganic material NiOx.For NiOx, band gap is wide, transmissivity is good, chemical stability is good and with calcium titanium The level-density parameter of mine is convenient for hole collection and electronic blocking.In addition, NiOx film and the good wetability of perovskite precursor liquid are not Raw material can be only saved, and is conducive to the large-scale production of PSC.Replace PEDOT:PSS as hole transport using NiOx Layer prepares perovskite thin film using scraper for coating method under room temperature (RH~45%, RT~25 DEG C), convenient for meeting industrial production Requirement.The technique can obtain height-oriented calcium titanium ore bed, and crystallite dimension even can achieve 200nm.PSC efficiency is by original 13.83% come is further increased to 15.34%.The new work that the technology will combine Thermal inactive process to obtain rapid shaping Skill.It, which has, utilizes rapid shaping technique, then model needed for being formed in low temperature chamber recycles thermally induced phase separation by material The advantages of mutually being separated with solvent.
In conclusion problem of the existing technology is:
(1) manufacturing technology of existing high efficiency perovskite solar battery (PSC) is confined to the spin coating proceeding in glove box.
(2) in the blade coating technology of the prior art, wetability of the common PEDOT:PSS solution with respect to NiOx solution It is poor, be unfavorable for perovskite precursor solution PEDOT:PSS layers quickly sprawl, to be unfavorable for perovskite solution high quality Film forming, furthermore PEDOT:PSS is unfavorable for the long-time stability of device at ambient conditions due to its highly acidity and hygroscopicity.
(3) in the blade coating technology of the prior art, perovskite solution solvent uses DMF solution, due to its volatilization Property it is higher, cause grain growth uneven in the case where solvent volatilizees power and blade coatings stress collective effect, it is equal to be unfavorable for perovskite Even film forming.
(4) substrate auxiliary heating is not used in operation, is unable to control solvent evaporation rate and phase transformation for prior art processes Temperature is unfavorable for the film forming consistency of perovskite thin film.
(5) high cost, harsh environment, so that the prior art is difficult to be commercialized.
(6) spin-coating method that prior art preparation largely uses can not be suitable for large area perovskite solar battery Preparation is studied limited for the meaning of industrialization.
Solve the difficulty of above-mentioned technical problem:
(1) perovskite material stability is poor, easily oxygenolysis in air, for how to protect under high humility hyperoxic conditions Fast filming is crucial while demonstrate,proving into film uniformity.
(2) perovskite material has certain toxicity, and mating gas precautions are needed for operator.
(3) proper ratio of accuracy controlling DMSO and DMF is difficult, and a small amount of DMSO can slow down film forming speed and promote calcium Titanium ore solution at film uniformity, but excessive DMSO can inhibit the crystallization process of perovskite solution, and it is uniform to be unfavorable for film forming Property, therefore the ratio of suitable DMSO and DMF mixing becomes the key technology of preparation high quality perovskite thin film.
(4) method that auxiliary heating was not used in forefathers when being coated with calcium titanium ore bed, heating temperature are needed with preparing Journey and adjust.
(5) full blade coating, for the uniformity challenge pole of 100 square centimeters of solar energy in large area battery film forming Greatly, skilled operation degree is required high.
Solve the meaning of above-mentioned technical problem:
(1) allow whole process under the conditions of high humility is high oxygen-containing (humidity >=45%, oxygen content >=21%) into Row operation.
(2) full blade coating, the perovskite solar battery of preparation large area that can be simple and quick are realized；
(3) uniformly, high-efficient, stability is good for the perovskite battery film forming prepared.
(4) NiOx material is cheap, and preparation cost is low, effectively facilitates the industrialization of perovskite solar battery.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of blade coatings of modified high-efficient perovskite solar battery Structure and preparation method.
The present invention for a kind of modified high-efficient perovskite solar battery blade coating structure preparation method the following steps are included:
Step 1 replaces PDEOT:PSS to carry out the interface optimization of solar cell device, and is applied to conduction using NiOx On glass FTO；
Step 2 is added dimethyl sulfoxide DMSO and dimethylformamide DMF and is regulated and controled in the precursor liquid of perovskite DMSO and DMF accounting, wherein the volume accounting of DMSO is respectively 0,15%, 30% and 45%, and perovskite is dissolved and carries out calcium titanium Mineral solution solvent optimization；
Step 3, by perovskite solution described in step 2, at ambient temperature described in the method application step one with blade coating On solar cell device；
Step 4, fullerene derivate PCBM is successively coated in step 3, and (concentration 20mg/ml, 40 μ L of total amount, is first used 0.45 μm of PTFE filter filtering), compound BCP solution (concentration 0.5mg/ml, 80 μ l of total amount, be dissolved in isopropanol).Finally Silver electrode is plated, the perovskite solar battery that area is 1.5cmX1.5cm is prepared.
Further, in step 1, PEDOT:PSS volume ratio is 1:1.
Further, step 2 specifically includes:
It is filtered, 150 DEG C of annealing 20min, then is applied in FTO layers of substrate with polytetrafluoroethylene PTFE filter, preparation is different Ratio DMSO:DMF precursor liquid, wherein the volume accounting of DMSO is respectively 0,15%, 30% and 45%, and perovskite is dissolved will Perovskite dissolution.
Further, step 3 specifically includes: carrying out calcium titanium ore bed blade coating, 90 DEG C of annealing 15min, by PCBM layers and isopropyl Alcohol 0.5mg/ml and 80ul BCP mixing, are coated on PCBM to obtain BCP layers.
Further, in step 3,25 DEG C of ambient room temperature, humidity 45%.
Further, step 4 specifically includes:
Silver electrode is deposited with vapour deposition method；
NiOx is prepared, the PEDOT:PSS layer in script PCS is replaced with NiOx layer film, repeats step 1 to step 3.
Another object of the present invention is to provide kind of a blade coating structures for the utilization modified high-efficient perovskite solar battery The blade coating structure of the modified high-efficient perovskite solar battery of preparation method preparation, the modified high-efficient perovskite solar battery Blade coating structure be successively compounded with from top to bottom:
FTO layers, NiOXLayer, calcium titanium ore bed, PCBM layers, BCP layers, silver electrode
The current density of the perovskite solar battery (PSC) is 19.98mA/cm2, open-circuit voltage 1.123V, effect Rate is 15.34%.
In conclusion advantages of the present invention and good effect are as follows:
The present invention takes under environmental condition (RH~45%, RT~25 DEG C) and is added two in perovskite precursor solution Methyl sulfoxide (DMSO) has delayed the method for the crystallization rate of perovskite, obtains uniform perovskite thin film by blade coating, Realize the large area blade coating preparation of modified high-efficient perovskite solar battery.The perovskite thin film of preparation has up to 100 μm of big domain.With the solar battery of these film preparations, current density is from 17.22mA/cm2It is increased to 19.98mA/cm2, efficiency is increased to 13.83% from 10.98%.It is lower (only 0.908V) for open-circuit voltage, using oxidation Nickel (NiOX) improved for hole mobile material.That is nickel oxide (NiOX) it is that hole mobile material replaces poly- 3,4- ethylene dioxy Thiophene/poly styrene sulfonate (PEDOT:PSS) prepares the perovskite thin film of high quality using blade coating at normal temperature. There is the perovskite thin film of preparation preferable orientation and up to 200 μm of big domain, open-circuit voltage to be increased to from 0.908 1.123V, efficiency are increased to 15.34% from 13.83%.Successfully developing one kind can prepare greatly under the conditions of air environment The controllable doctor blade technique of the perovskite solar battery (PSC) of area efficient.
It is also an advantage that
The optimization of perovskite solution solvent；
Hole transmission layer interface optimization；
In air under environmental condition (humidity~45%, temperature~25 DEG C), 1.5cm*1.5cm is completed with blade coating Perovskite battery (PSC) preparation；
There is efficient stable using the large area perovskite battery (PSC) that blade coating technology obtains.
The present invention passes through the modification of solvent in perovskite solution, and the change of hole transmission layer boundary material theoretically mentions The high efficiency of perovskite solar battery；Preparation method substantially increases preparation speed using blade coating technology simultaneously Degree and operation convenience；The uniform high-efficient perovskite of film forming can be still prepared under room temperature and the higher environment of humidity too It is positive can battery (PSC), solve the limitation that can only be operated in glove box under vacuum conditions for a long time.
Detailed description of the invention
Fig. 1 is the blade coating structure preparation method principle of modified high-efficient perovskite solar battery provided in an embodiment of the present invention Figure.
In figure: 1, FTO layers；2, PEDOT:PSS modified solution；3, calcium titanium ore bed；4, PCBM layers；5, BCP layers；6, silver electricity Pole；7,NiOXLayer.
Fig. 2 is the blade coating structure preparation method process of modified high-efficient perovskite solar battery provided in an embodiment of the present invention Figure.
Fig. 3 is the properties of perovskite solar battery (PSC) provided in an embodiment of the present invention.(a) in precursor solution Current density-voltage (J-V) characteristic of PSC with different DMSO contents；(b) external quantum efficiency (EQE) and current density, JSC The figure of function of wavelength as the PSC with different DMF and DMSO contents；(c) dependence of the various photovoltaic parameters to DMSO content Property.
Fig. 4 be (a) provided in an embodiment of the present invention by scratch different precursor solutions preparations perovskite thin film it is ultraviolet- Visible absorption spectra；(b) pass through X-ray diffraction (XRD) spectrum of the perovskite thin film of the different precursor liquids preparations of blade coating.
Fig. 5 is that the SEM of the perovskite thin film provided in an embodiment of the present invention prepared by blade coating difference precursor liquid schemes Picture: DMSO (a) is free of；(b) contain 15%DMSO；(c) contain 30%DMSO；(d) contain 45%DMSO.
Fig. 6 is X-ray diffraction (XRD) spectrum of (a) provided in an embodiment of the present invention NiOx film；(b) top view of NiOx film SEM figure；(c) the cross section SEM figure of typical NiOx based perovskite solar battery；(d) each functional layer in perovskite device Energy diagram.
Fig. 7 is the J-V curve of the best device of (a) provided in an embodiment of the present invention based on PEDOT:PSS and NiOx HTL； (b) the EQE spectrum and integration current density of the best device based on PEDOT:PSS and NiOx HTL；(c) it is based on PEDOT:PSS It is distributed with the transfer efficiency of 25 devices of NiOx HTL；(d) purple of the perovskite thin film based on PEDOT:PSS and NiOx HTL Outside-visible absorption spectra, (e) XRD spectrum and (f) stable state luminescence generated by light (PL)
Fig. 8 is that (a, b) provided in an embodiment of the present invention drops onto connecing for perovskite precursor on PEDOT:PSS and NiOx layer Feeler；(c) diagram that solution drips before blade coating；(d) SEM image of the perovskite film prepared on NiOx layer.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
The manufacturing technology of existing high efficiency perovskite solar battery (PSC) is confined to the spin coating proceeding in glove box, and And it is not yet commercialized.In the blade coating technology of the prior art, PEDOT:PSS is unfavorable for device due to its highly acidity and hygroscopicity The long-time stability of part at ambient conditions.
In order to solve the above technical problems, below with reference to concrete scheme, the present invention is described in detail.
As Figure 1-Figure 2, the blade coating structure system of modified high-efficient perovskite solar battery provided in an embodiment of the present invention Preparation Method includes:
Step 1 replaces PDEOT:PSS to complete the interface optimization of solar cell device, and is spin-coated to conduction using NiOx On glass (FTO).
Step 2 is added dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) and is controlled in the precursor liquid of perovskite Wherein DMSO and DMF accounting is made, to complete the optimization of perovskite solution solvent.
Step 3, by perovskite solution described in step 2, (25 DEG C of room temperature and humidity 45%) uses blade coating at ambient temperature Method application step one described on device.
Step 4 is successively coated with fullerene derivate (BCPM) and compound (BCP) in step 3, plates silver electrode, Prepare the perovskite solar cell device (PSC) that area is 1.5cm*1.5cm.
In a preferred embodiment of the invention, the current density of perovskite solar battery (PSC) is 19.98mA/cm2, open Road voltage is 1.123V, efficiency 15.34%.
In preferred embodiment of the present invention step 1, PEDOT:PSS volume ratio is 1:1.
In a preferred embodiment of the invention, dimethyl sulfoxide DMSO and two is added in step 2 in the precursor liquid of perovskite Methylformamide DMF simultaneously regulates and controls DMSO and DMF accounting, and wherein the volume accounting of DMSO is respectively 0,15%, 30% and 45%.
In preferred embodiment of the present invention step 3, calcium titanium ore bed blade coating is carried out, 90 DEG C of annealing 15min, successively coating is rich Ene derivative PCBM (concentration 20mg/ml chlorobenzene solution, 40 μ L of total amount are filtered with 0.45 μm of PTFE filter) is strangled, is coated BCP solution (concentration 0.5mg/ml aqueous isopropanol, 80 μ l of total amount).
In a preferred embodiment of the invention, Ag electrode (or blade coating High-conductivity carbon slurry) is finally deposited in step 4.
Application principle of the invention is further described with reference to the accompanying drawing.
1) in the blade coating structure preparation method principle of modified high-efficient perovskite solar battery provided in an embodiment of the present invention, PEDOT:PSS modified solution layer 2 in Fig. 1 is used into NiOXLayer 7 replaces, and changes simultaneously the ratio of DMSO:DMF forerunner's agent in Fig. 2 To improve the film forming of improvement PSC and improve efficiency.
2) blade coating preparation process such as Fig. 2 of modified high-efficient perovskite solar battery provided in an embodiment of the present invention.
PEDOT:PSS modified solution layer 2 (volume ratio 1:1) in above-mentioned Fig. 1 is prepared, is filtered with polytetrafluoroethylene (PTFE) (PTFE) Device filtering, 150 DEG C of annealing 20min, then be applied in above-mentioned Fig. 1 in 1 substrate of FTO layer, prepare DMSO:DMF (different proportion) forerunner Perovskite is dissolved in wherein by liquid, then by 3 (MAPbl of calcium titanium ore bed3Layer) it scrapes and coats, then 90 DEG C of annealing 15min are successively applied Cloth PCBM layer 4 and BCP layer 5 deposit silver electrode 6 with vapour deposition method.
NiOx is prepared, the PEDOT:PSS film 2 in script PCS is replaced with above-mentioned NiOx layer film 7, repeats the above steps.
Experimental data of the invention is further described with reference to the accompanying drawing:
3) photovoltaic parameter is to the dependence of DMSO ratio as shown in figure 3, relevant performance parameter is as shown in table 1.
Fig. 3 a shows PSC in solar simulating radiation AM1.5g (100mW/cm2) under Current density-voltage (J-V) it is special Property；Device in perovskite precursor solution by using the DMSO/DMF of different proportion to prepare by blade coating.Photovoltaic parameter As shown in Figure 3c to the dependence of DMSO ratio, relevant performance parameter is as shown in table 1.It is not added in perovskite solution DMSO and the parametric device prepared, power conversion efficiency (PCE) are 10.98%, open-circuit voltage (VOC) it is 0.872V, short circuit electricity Current density (JSC) it is 17.22mA/cm2, fill factor (FF) is 73.09%.When DMSO content is 15vol% in precursor liquid (DMF:DMSO=8.5:1.5) when, the PCE of obtained device is significantly increased, PCE 13.83%, and Voc 0.908V, Jsc are 19.98mA/cm2, FF 76.26%.Compared with the device of no addition DMSO, prepared with the perovskite solution of 15%DMSO Device, the average value of all photovoltaic parameters, especially JSCIt is improved with FF.However, DMSO content further increases simultaneously Do not improve equipment performance.Therefore, 15% DMSO ratio is selected further to analyse in depth as the device of preparation.Best device External quantum efficiency (EQE) spectrum (Fig. 3 b) confirms the short-circuit current density ratio of the device by the perovskite solution preparation for adding DMSO The short-circuit current density for not adding the device of DMSO is much higher.In addition, adding the EQE of the device of DMSO in entire visibility region Value is higher than the EQE value of the not device of DMSO.These are the result shows that the addition of DMSO improves perovskite thin film quality, to change It is apt to its electron transport, facilitates the balance that charge-carrier in device transports.
4) uv-visible absorption spectra in Fig. 4 a shows all perovskite thin films based on scraper coating, in perovskite The different proportion of DMSO and DMF in solution shows strong absorption to the wavelength of visible-range (400 to 700nm).It is worth note Meaning, within the scope of 700-800nm, the absorptivity of all perovskite thin films is all decreased obviously, this is surveyed with EQE shown in Fig. 3 b Magnitude coincide very well.Although adding the perovskite thin film object phase having the same of DMSO, crystal structure domain and film morphology Differ greatly, lead to the variation of its photo absorption performance.X-ray diffraction (XRD) pattern in Fig. 4 b confirms that additive DMSO exists Effect in perovskite crystal growth.In the case where pure DMF, there is strongest diffraction maximum at 14.14 ° in XRD spectrum, corresponds to (110) diffraction.But in the presence of DMSO, the intensity highest of 20 ° of diffraction maximums, and other peaks almost can be ignored.Reason It may be that the boiling point of solvent and polarity are changed, the stress joint effect of different volatilization driving mechanics and blade causes Crystal orientation changes.
5) in order to illustrate influence of the additive DMSO to perovskite precursor solution, we have evaluated covering for perovskite thin film Lid rate and pattern are mainly influenced by nucleation and crystal growth kinetics.Fig. 5 shows the perovskite prepared by blade coating Scanning electron microscope (SEM) image of film.All perovskite thin films based on PEDOT:PSS all have fine and close, fine and close Domain has coffee cyclic structure, shows to prepare using the blade coating of DMSO, facilitates nucleation at ambient conditions.Very Obviously, for the perovskite thin film (Fig. 5 a) of no addition DMSO, the size of domain is non-uniform.This is because solvent is waved Hair driving force and the collective effect of scraper coating stress cause grain growth uneven.For containing 15% in precursor solution With the perovskite thin film (Fig. 5 b and 5c) of 30%DMSO, they have good surface smoothness and almost the same size, about 100 μm domain.In contrast, the former grain boundary defects are less.DMSO content is further increased to 45%, the crystallization of perovskite Journey is suppressed instead, because crystallization process delay is too long, Fig. 5 d shows that film has lesser domain size.In short, brilliant Farmland is bigger, and uniformity of film is better, and domain defect is fewer, and electron-transport efficiency is higher, and absorbing properties are better.
6) limitation of the PEDOT:PSS as hole mobile material is considered, we are come using NiOx instead of PDEOT:PSS Improve the performance of device.The diffraction maximum of NiOx is cubic structure in Fig. 6 a, and there are three features at 37.2 °, 43.1 ° and 62.6 ° Peak respectively corresponds (111), (200) and (220) face.The top view SEM image of NiOx is shown very smooth and equal in Fig. 6 b Even surface topography, this facilitates the formation of perovskite film.As fig. 6 c, cross sectional Scanning Electron microscope (SEM) image Fine and close, the uniform perovskite thin film of thickness 500nm is showed on NiOx film；The energy level alignment of functional layer such as Fig. 6 d institute Show, wherein NiOx, MAPbI3, PC61The energy level of BM, BCP and Ag are quoted from document.
7) Fig. 7 a shows the J-V curve of the best device based on PEDOT:PSS and NiOx HTLs, the photovoltaic ginseng of device Ordered series of numbers is in table 2.Device based on PEDOT:PSS HTL has the V of 0.908VOCValue, 19.98mA/cm2JSCWith 76.261% FF, PCE value be 13.83%.For using the device of NiOx HTL, when reverse scan, obtains 15.34% significant PCE, JSCFor 20.031mA/cm2, VOCFor 1.113V, FF 68.78%.Obviously, two devices all show insignificant lag, this It is common for reversed PSC.Compared with the device based on PEDOT:PSS, NiOx base device has higher VOC, can return Because in the valence band (VB) and perovskite (MAPbI of NiOx3) orientation.The EQE spectrum and integration current density such as Fig. 7 b of best device It is shown.Within the scope of 300-450nm, the EQE of NiOx base device persistently rises, and the EQE value of PEDOT:PSS base device then goes out Existing peak.The integral J determined by EQE spectrum (table 2)SCValue and the value that is obtained by J-V curve it is very close, thus to a certain degree On demonstrate PCE value.PCE distribution based on PEDOT:PSS and NiOx is as shown in Figure 7 c.As a result, the device based on NiOx is shown Better photovoltaic performance and fabulous reproducibility out.Similar variation is observed that from ultraviolet-visible spectrum, such as Fig. 7 d institute Show.The XRD spectrum of Fig. 7 e presents the similar features peak of perovskite on PEDOT:PSS and NiOx, shows that the variation of HTLs is several The phase of perovskite cannot be changed.It is the perovskite thin film of the scraper coating of matrix preparation in 400~800nm using different HTLs Higher light absorption is all had in range, this is consistent with EQE result.In addition, measuring the perovskite thin film deposited on different layers Luminescence generated by light (PL) spectrum, acquired results are as depicted in fig. 7f.The reduction of maximum intensity shows NiOx within the scope of 750-800nm HTL more effectively extracts charge from calcium titanium ore bed.
8) formation of perovskite presoma is the same, in addition to energy level difference, it is maximum the difference is that NiOx film and The wetability of PEDOT:PSS film and perovskite presoma.Fig. 7 a and 7b show infiltration of the perovskite precursor solution on NiOx layer Permeability can be better than PEDOT:PSS layers: infiltration angle of the presoma on NiOx is only 32.45 °, and presoma is on PEDOT:PSS Infiltration angle be 56.8 °.This good infiltration enhances coating of the precursor solution on NiOx, to facilitate in environment Under the conditions of formed high quality perovskite film nucleation and lattice driving force.In addition, as shown in Figure 7 c, identical 30 microlitres of forerunners Liquid solution is enough to cover the surface NiOx, this helps to improve the utilization rate of industrial production chinese raw materials.From Fig. 7 d, we note that It arrives, in the perovskite thin film of NiOx upper blade coating, maximum domain (> 200um) is almost that PEDOT:PSS cutter applies Twice of the perovskite thin film of cloth.In addition, carrying out the calcium titanium of blade coating on NiOx HTL compared with PEDOT:PSS HTL Mine film is more uniform, has better crystalline orientation, and show less crystal defect.Bigger domain, preferably Crystal orientation and higher uniformity lead to more effective charge transmission and effective light absorption.
9) Tables 1 and 2 summarize the PSC performance parameter comparison of different DMSO contents respectively and based on PEDOT:PSS and The photovoltaic parameter of the two class devices of NiOx HTL compares.
The PSC performance parameter of 1 difference DMSO content of table
The photovoltaic parameter of 2 liang of class devices of table
Fig. 8 is that (a, b) provided in an embodiment of the present invention drops onto connecing for perovskite precursor on PEDOT:PSS and NiOx layer Feeler；(c) diagram that solution drips before blade coating；(d) SEM image of the perovskite film prepared on NiOx layer.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (8)

1. a kind of blade coating structure preparation method of modified high-efficient perovskite solar battery, which is characterized in that the modified high-efficient The blade coating structure preparation method of perovskite solar battery the following steps are included:
Step 1 replaces PDEOT:PSS to carry out the interface optimization of solar cell device, and is spin-coated to electro-conductive glass using NiOx On FTO；
Step 2, in the precursor liquid of perovskite be added dimethyl sulfoxide DMSO and dimethylformamide DMF and regulate and control DMSO and DMF accounting carries out the optimization of perovskite solution solvent, and wherein the volume accounting of DMSO is respectively 0,15%, 30% and 45%；
Perovskite solution described in step 2 is used the sun described in the method application step one of blade coating by step 3 at ambient temperature On energy battery device；
Step 4 is successively coated with fullerene derivate PC61BM chlorobenzene solution on perovskite thin film in step 3, and block is total Polymers BCP solution on PC61BM film, plates silver electrode with 4000rpm rotary coating, prepares perovskite solar battery PSC。
2. the blade coating structure preparation method of modified high-efficient perovskite solar battery as described in claim 1, which is characterized in that In step 1, PEDOT:PSS volume ratio is 1:1.
3. the blade coating structure preparation method of modified high-efficient perovskite solar battery as described in claim 1, which is characterized in that Step 2 specifically includes:
It is filtered, then is applied in FTO layers of substrate with polytetrafluoroethylene PTFE filter, 150 DEG C of annealing 20min prepare different proportion DMSO:DMF, wherein the volume accounting of DMSO is respectively 0,15%, 30% and 45%, and perovskite is dissolved.
4. the blade coating structure preparation method of modified high-efficient perovskite solar battery as described in claim 1, which is characterized in that Step 3 specifically includes: after carrying out calcium titanium ore bed blade coating, it is molten to be coated with fullerene derivate PC61BM chlorobenzene by 90 DEG C of annealing 15min Liquid is on perovskite thin film, and block copolymer B CP solution is with 4000rpm rotary coating on PC61BM film.
5. the blade coating structure preparation method of modified high-efficient perovskite solar battery as described in claim 1, which is characterized in that In step 3,25 DEG C of ambient room temperature, humidity 45%.
6. the blade coating structure preparation method of modified high-efficient perovskite solar battery as described in claim 1, which is characterized in that In step 4, fullerene derivate PC61BM chlorobenzene solution is concentration 20mg/ml, is filtered with 0.45 μm of PTFE filter, total amount 40μL；
Copolymer BCP solution concentration is 0.5mg/ml, and 80 μ l of dosage is dissolved in isopropanol.
7. the blade coating structure preparation method of modified high-efficient perovskite solar battery as described in claim 1, which is characterized in that Step 4 specifically includes:
Silver electrode is deposited with vapour deposition method；
NiOx is prepared, the PEDOT:PSS layer in script PCS is replaced with NiOx layer film, repeats step 1 to step 3.
8. prepared by a kind of blade coating structure preparation method using modified high-efficient perovskite solar battery described in claim 1 changes The blade coating structure of the efficient perovskite solar battery of property, which is characterized in that the modified high-efficient perovskite solar battery is scraped Structure is applied successively to be compounded with from top to bottom:
FTO layers, NiOXLayer, calcium titanium ore bed, PCBM layers, BCP layers, silver electrode.
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