CN106960908A - A kind of cathodic modification type plane perovskite solar cell and preparation method thereof - Google Patents
A kind of cathodic modification type plane perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of cathodic modification type plane perovskite solar cell and preparation method thereof, include conductive substrates, hole transmission layer, calcium titanium ore bed, electron transfer layer, cathodic modification layer and metal successively from bottom to top to electrode, the material of described cathodic modification layer is acetylacetone,2,4-pentanedione titanium oxide (TOPD), the setting of cathodic modification layer reduces the contact berrier between cathodic metal electrode and electron transfer layer to a certain extent, reduce series resistance, fill factor, curve factor and current density are greatly enhanced, energy conversion efficiency is effectively improved；On the other hand, for using the inorganic embellishing cathode interface layer of hot evaporation, preparation technology is greatly simplified, reduction prepares cost.The commercialization that overall process of the present invention uses low temperature preparation technique to realize high-efficiency soft perovskite solar cell provides new approach and reliability.
Description
Technical field
The invention belongs to plane perovskite area of solar cell, and in particular to a kind of alcoholic solution embellishing cathode interface type is put down
Face perovskite solar cell and preparation method thereof.
Background technology
With the increasingly depleted of fossil fuel, development clean energy resource is the inevitable means that the mankind carry out sustainable development.Too
Positive energy battery, by the way that endlessly solar energy is changed into electric energy there is provided inexhaustible clean energy resource, is to seek
Seek the important countermeasure of sustainable development.
Current commercialized battery be mainly using silicon solar cell and its compound solar cell it is leading, material into
This and preparation cost are higher, constrain its development, therefore low cost, the simple novel solar battery of preparation technology turn into each
The focus that state is competitively studied.Especially perovskite solar cell is with low cost, and preparation technology is simple, 2009, Japanese
Miyasaka et al. quotes organic-inorganic mixing perovskite material MAPbI first3And MAPbBr3It is used to fire as dye sensitizing agent
Expect sensitization solar battery, substantially increase the performance of device.From this this organic-inorganic mixing perovskite material by extensive
Concern.In short several years, perovskite solar battery technology obtains the development advanced by leaps and bounds, efficiency from 3.8% drastically
22% is risen to, considerably beyond organic solar batteries (OPV), DSSC (DSSC) and the quantum dot sun
Energy battery, has reached the CuInGaSe thin-film solar cells levels of current comparative maturity, but the cost of core material is significantly
It is relatively low, operating procedure very simple, as a star most potential in third generation novel thin film solar cell.
At present, the structure of perovskite solar cell mainly has two kinds, and one kind is to be based on inorganic semiconductor oxide for light
The n-i-p type perovskite solar cells of anode, battery structure preparation technology usually requires high-temperature annealing process, another to be
Based on the p-i-n row perovskite solar cells that polymer semiconductor's hole transmission layer is light anode, the structure and preparation technology
Simply, it can at low temperature prepare, be that flexible solar cell development opens road, but the performance of such device is relative to drop
It is low.In order to which the performance present invention for improving the reverse plane perovskite solar cell of this p-i-n rows uses a kind of low cost process
Simple alcoholic solution embellishing cathode interface, reduces the contact berrier between negative electrode and electron transfer layer, subtracts to a certain extent
Small series resistance, greatly enhances fill factor, curve factor and current density, is effectively improved energy conversion efficiency.
The content of the invention
It is an object of the invention to provide a kind of cathodic modification type plane perovskite solar cell, make energy conversion efficiency
Effectively improved.
It is another object of the present invention to provide the preparation method of above-mentioned solar cell.
The object of the invention is realized by following technical measures：A kind of cathodic modification type plane perovskite solar cell,
Include conductive substrates, hole transmission layer, calcium titanium ore bed, electron transfer layer and metal successively from bottom to top to electrode, its feature exists
In：The electron transfer layer and metal between electrode provided with embellishing cathode interface layer, the material of described embellishing cathode interface layer
Matter is acetylacetone,2,4-pentanedione titanium oxide (TOPD).
Another object of the present invention is realized by following technical measures：A kind of cathodic modification type plane perovskite solar-electricity
The preparation method in pond, comprises the following steps：
(1) conductive substrates and etching pattern are chosen, the conductive substrates etched are obtained after cleaning；
(2) conductive substrates etched in step (1) are used after plasma treatment, then using spin-coating method deposition polymerization
Thing semiconductive hole transport material, hole transmission layer is obtained after annealing；
(3) perovskite precursor aqueous solution is prepared, the spin coating perovskite precursor aqueous solution on the hole transmission layer of step (2), in rotation
Anti-solvent is added during painting, spin coating after annealing obtains the perovskite thin film of densification after cooling；
(4) the spin coating fullerene derivate electron transfer layer solution on the fine and close perovskite thin film that step (3) is obtained, is obtained
Electron transfer layer；
It is characterized in that：Also include
(5) configuration interface decorative layer solution, spin coating embellishing cathode interface layer is molten on the electron transfer layer that step (4) is obtained
Liquid obtains a bed boundary decorative layer；
The modifying interface layer material is acetylacetone,2,4-pentanedione titanium oxide (TOPD), and it is configured to the second that solution is 2~5mg/ml
The aqueous isopropanol of acyl acetone oxidation titanium；
The spin coating speed of spin coating embellishing cathode interface layer is 2000~5000rpm/min, spin-coating time is 20~
40s, annealing temperature is 60~100 DEG C, and annealing time is 10~15min, and acquisition thickness is 5~15nm；
(6) the upper hot evaporation gold of embellishing cathode interface layer or silver electrode obtained in step (5), obtains efficient p-i-n types and puts down
Face perovskite solar cell.
Preferential, the present invention is configured to the aqueous isopropanol for the acetylacetone,2,4-pentanedione titanium oxide that solution is 3mg/ml；The spin coating
The spin coating speed of embellishing cathode interface layer is 3000rpm/min, and spin-coating time is 30s, and annealing temperature is 60 DEG C, and annealing time is
15min, acquisition thickness is 10nm.
Conductive substrates described in step (1) of the present invention are preferably FTO glass, ito glass or ITO/PET substrates.
Cleaning conductive substrates process is that, respectively with water-detergent solution, deionized water, acetone is different in step (1) of the present invention
Propyl alcohol is cleaned by ultrasonic 10~20min.
The time of plasma treatment is 10~20min in step (2) of the present invention, and hole transport layer material is PEDOT:PSS
Or Poly-TPD, spin coating 2000~5000rpm/min of speed, the 20~40s of spin-coating time of spin coating hole transport layer material, annealing
120~150 DEG C of temperature, 10~15min of annealing time, acquisition thickness of hole transport layer is 20~50nm.
Perovskite solution is the mixed solution of lead iodide and methylpyridinium iodide amine in step (3) of the present invention, wherein lead iodide and
The magnitude relation of the material of methylpyridinium iodide amine is 1:0.8~1.15, the solvent of the mixed solution for DMF and
The mixed solvent of dimethyl sulfoxide (DMSO), the volume ratio of the DMF and dimethyl sulfoxide (DMSO) is 6~9:1~4.
The spin coating speed of spin coating perovskite solution is 3000~5000rpm/min in step (3) of the present invention, and spin-coating time is
20~30s, anti-solvent is added dropwise at the 6th~10, and annealing temperature is 100~105 DEG C, and annealing time is 10~20min, obtains calcium
Titanium ore film thickness is 300~500nm.
The chlorine that fullerene derivate electron transfer layer solution described in step (4) of the present invention is fullerene derivate PCBM
Benzole soln, its concentration is 10~30mg/mL；During spin coating fullerene derivate electron transfer layer solution, spin speed be 1000~
3000rpm/min, spin-coating time is 20~40s, and spin coating thickness is 20~60nm.
Hot dip gold or during silver electrode in step (6) of the present invention, evaporation rate is in ladder distribution, the regularity of distribution：0.1~
0.3A/s speed evaporation 3~8min, 0.5~0.8A/s speed evaporation 7~12min, 1~1.2A/s speed evaporation 8~
15min, obtains gold or silver electrode that thickness is 50~120nm.
Compared with prior art, the invention has the advantages that：
(1) the inventive method is in electronics relative to the main technique difference of traditional reef knot plane perovskite solar cell
One layer of cathodic modification layer acetylacetone,2,4-pentanedione titanium oxide is introduced between transport layer and cathodic metal electrode, is reduced to a certain extent
Contact berrier between cathodic metal electrode and electron transfer layer, reduces series resistance, greatly enhance filling because
Son and current density, make energy conversion efficiency reach 13.48%, short-circuit current density is up to 20.7, and fill factor, curve factor is up to
76.35%, open-circuit voltage is up to 0.85V.
(2) the inventive method using acetylacetone,2,4-pentanedione titanium oxide alcoholic solution as modifying interface, relative to using hot evaporation without
For machine embellishing cathode interface layer, greatly simplify preparation technology, reduction prepares cost, to prepare high efficient cryogenic planar flexible calcium
Titanium ore solar cell provides new approach and reliability；
Brief description of the drawings
Fig. 1 is the preparation flow of the reverse plane perovskite solar cell of alcoholic solution cathodic modification in the embodiment of the present invention
Figure；
Fig. 2 is the electricity of the reverse plane perovskite solar cell of alcoholic solution cathodic modification prepared in the embodiment of the present invention 1
Current density-voltage curve；
Fig. 3 is the contrast conventional method preparation of the embodiment of the present invention 1 without the reverse plane perovskite solar energy of cathodic modification
The current density voltage curve figure of battery；
Fig. 4 is the reverse plane perovskite solar cell (embodiment 1) of alcoholic solution cathodic modification and biography prepared by the present invention
Unite the contrast current density voltage curve figure of reverse plane perovskite solar cell (embodiment 2)；
Fig. 5 is the electricity of the reverse plane perovskite solar cell of alcoholic solution cathodic modification prepared in the embodiment of the present invention 2
Current density-voltage curve；
Fig. 6 is the electricity of the reverse plane perovskite solar cell of alcoholic solution cathodic modification prepared in the embodiment of the present invention 3
Current density-voltage curve；
Fig. 7 is the reverse plane perovskite solar cell Current density-voltage of alcoholic solution cathodic modification prepared by the present invention
Curve map with scanning direction change；
Fig. 8 is the reverse plane perovskite solar cell Current density-voltage of alcoholic solution cathodic modification prepared by the present invention
Curve map with sweep speed change；
In wherein Fig. 1：1 is conductive substrates, and 2 be hole transmission layer, and 3 be perovskite thin film, and 4 be electron transfer layer, and 5 be second
Acyl acetone oxidation Ti cathode decorative layer, 6 be metal Ag to electrode
Embodiment
Embodiment 1
As shown in figure 1, a kind of alcoholic solution embellishing cathode interface of the present embodiment prepares the plane perovskite of efficient unrestraint too
The method of positive energy battery, comprises the following steps successively：
(1) by transparent electro-conductive glass by laser ablation into required target pattern, then by the conduction etched
Substrate uses the standard detergent aqueous solution respectively, and deionized water, acetone and isopropanol are cleaned by ultrasonic 20 minutes successively, and then nitrogen blows
It is dry, obtain clean conductive substrates standby；
(2) handled 10 minutes using preceding plasma (plasma, using Conventional plasma cleaning machine) and parent is carried out to surface
Hydration process, is poly- 3,4-ethylene dioxythiophene and poly styrene sulfonate by polymer semiconductor's hole mobile material
(PEDOT:PSS) (model：PEDOT AL4083) it is spin-coated in conductive substrates, spin coating rotating speed is 3000rpm/min, spin-coating time
30s, moves back and is put in thermal station 120 DEG C and anneals 15 minutes, it is about 30nm hole transmission layers to obtain thickness；
(3) spin coating concentration is 1.25mol/L perovskites precursor aqueous solution (lead iodide (PbI after cooling2)：Methylpyridinium iodide amine
(CH3NH3I)=1:1, it is 7 to be dissolved in volume ratio:3 N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) (DMSO) mixing is molten
In agent), 70 DEG C of stirring 12h carry out two step spin coatings, and first step regulation spin speed is 500rpm, 5s, second step regulation rotation speed
Spend for 5000rpm, spin coating 25s, 1mL dry toluenes are added dropwise in the 10s of second step high speed spin coating, then by complete thin of spin coating
Film is annealed 10 minutes at 100 DEG C, obtains the perovskite thin film of densification, the thickness of gained perovskite thin film is 400nm；
(4) spin coating electron transport layer materials, electron transfer layer solution is the chlorobenzene solution of fullerene derivate (PCBM), its
Concentration is 20mg/mL, and spin speed is 1000rpm/min, and spin-coating time is 20s, obtains the electron transfer layer that thickness is 50nm.
(5) spin coating embellishing cathode interface layer material, embellishing cathode interface layer solution is acetylacetone,2,4-pentanedione titanium oxide (TOPD)
Aqueous isopropanol, its concentration is 3mg/mL, and spin coating speed is 3000rpm/min, spin-coating time 30min, 60 DEG C of annealing 15min,
Obtain the embellishing cathode interface layer that thickness is 10nm.
(6) Ag electrodes are finally deposited with, during hot dip silver electrode, evaporation rate is in ladder distribution, and the regularity of distribution is, 0.2A/s's
Speed is deposited with 5min, 0.6A/s speed evaporation 8min, 1A/s speed evaporation 12min, obtains the silver electricity that thickness is about 120nm
Pole.
Above-mentioned that a kind of cathodic modification type plane perovskite solar cell is made, structure from bottom to top is followed successively by ITO linings
Bottom, hole transmission layer, calcium titanium ore bed, electron transfer layer, embellishing cathode interface layer and metal are to electrode.To obtained plane calcium titanium
Ore deposit solar cell I-V test result is up to 13.48% as shown in Fig. 2 obtaining energy conversion efficiency, and short-circuit current density is up to
20.7mA/cm2, fill factor, curve factor is up to 76.35%, and open-circuit voltage is up to 0.85V, the higher current density having and filling because
Component is in the embellishing cathode interface of the present invention.
Contrast test is carried out to above-described embodiment 1, reverse plane perovskite solar cell is prepared using conventional method, is had
Body is as follows：
(1) by transparent electro-conductive glass by laser ablation into required target pattern, then by the conduction etched
Substrate uses the standard detergent aqueous solution respectively, and deionized water, acetone and isopropanol are cleaned by ultrasonic 20 minutes successively, and then nitrogen blows
It is dry, obtain clean conductive substrates standby；
(2) handled 10 minutes using preceding plasma (plasma, using Conventional plasma cleaning machine) and parent is carried out to surface
Hydration process, is poly- 3,4-ethylene dioxythiophene and poly styrene sulfonate by polymer semiconductor's hole mobile material
(PEDOT:PSS) (model：PEDOT AL4083) it is spin-coated in conductive substrates, spin coating rotating speed is 3000rpm/min, spin-coating time
30s, moves back and is put in thermal station 120 DEG C and anneals 15 minutes, acquisitions thickness is 30nm hole transmission layers；
(3) spin coating concentration is 1.25mol/L perovskites precursor aqueous solution (lead iodide (PbI after cooling2)：Methylpyridinium iodide amine
(CH3NH3I)=1:1, it is 7 to be dissolved in volume ratio:3 N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) (DMSO) mixing is molten
In agent), 70 DEG C of stirring 12h carry out two step spin coatings, and first step regulation spin speed is 500rpm, 5s, second step regulation rotation speed
Spend for 5000rpm, spin coating 25s, 1mL dry toluenes are added dropwise in the 10s of second step high speed spin coating, then by complete thin of spin coating
Film is annealed 10 minutes at 100 DEG C, obtains the perovskite thin film of densification, the thickness of gained perovskite thin film is 400nm；
(4) spin coating electron transport layer materials, electron transfer layer solution is the chlorobenzene solution of fullerene derivate (PCBM), its
Concentration is 20mg/mL, and spin speed is 1000rpm/min, and spin-coating time is 20s, obtains the electron transfer layer that thickness is 50nm.
(5) Ag electrodes are finally deposited with, during hot dip silver electrode, evaporation rate is in ladder distribution, and the regularity of distribution is, 0.2A/s's
Speed is deposited with 5min, 0.6A/s speed evaporation 8min, 1A/s speed evaporation 12min, obtains the silver electricity that thickness is about 120nm
Pole.Obtained product does not set embellishing cathode interface layer, to the product I-V test results as shown in figure 3, obtaining energy conversion efficiency
Up to 7.67%, it is 13.93mA/cm2 that short-circuit current density, which reaches, and fill factor, curve factor is 69.54%, and open-circuit voltage is 0.80V.
The embodiment of the present invention one and the contrast current density voltage curve of conventional counter plane perovskite solar cell,
As shown in figure 4, by the I-V characteristic curve comparison for the battery for preparing embodiment one and conventional method, being repaiied by cathode interface
Decorations prepare Cell current density for 20.7mA/cm2 and fill factor, curve factor 76.35%, relative to traditional plane perovskite solar energy
The current density 13.93mA/cm2 and 69.54% of battery filling is greatly improved raising, illustrates that cathode interface layer can drop
Low electron transfer layer and interelectrode interface resistance, reduce Carrier recombination.
Embodiment 2
As shown in figure 1, a kind of alcoholic solution embellishing cathode interface of the present embodiment prepares the plane perovskite of efficient unrestraint too
The method of positive energy battery, comprises the following steps：
(1) by FTO transparent conducting glass by laser ablation into required target pattern, then by the conduction etched
Substrate uses the standard detergent aqueous solution respectively, and deionized water, acetone and isopropanol are cleaned by ultrasonic 20 minutes successively, and then nitrogen blows
It is dry, obtain clean conductive substrates standby；
(2) handled 10 minutes using preceding plasma (plasma, using Conventional plasma cleaning machine) and parent is carried out to surface
Hydration process, is poly- 3,4-ethylene dioxythiophene and poly styrene sulfonate by polymer semiconductor's hole mobile material
(PEDOT:PSS) (model：PEDOT AL4083) it is spin-coated in conductive substrates, spin coating rotating speed is 3000rpm/min, spin-coating time
30s, moves back and is put in thermal station 120 DEG C and anneals 15 minutes, it is about 30nm hole transmission layers to obtain thickness；
(3) spin coating concentration is 1.25mol/L perovskites precursor aqueous solution (lead iodide (PbI after cooling2)：Methylpyridinium iodide amine
(CH3NH3I)=1:1, it is 7 to be dissolved in volume ratio:3 N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) (DMSO) mixing is molten
In agent), 70 DEG C of stirring 12h carry out two step spin coatings, and first step regulation spin speed is 500rpm, 5s, second step regulation rotation speed
Spend for 5000rpm, spin coating 25s, 1mL dry toluenes are added dropwise in the 10s of second step high speed spin coating, then by complete thin of spin coating
Film is annealed 10 minutes at 100 DEG C, obtains the perovskite thin film of densification, the thickness of gained perovskite thin film is 400nm；
(4) spin coating electron transport layer materials, electron transfer layer solution is the chlorobenzene solution of fullerene derivate (PCBM), its
Concentration is 20mg/mL, and spin speed is 1000rpm/min, and spin-coating time is 20s, obtains the electron transfer layer that thickness is 50nm.
(5) spin coating embellishing cathode interface layer material, embellishing cathode interface layer solution is acetylacetone,2,4-pentanedione titanium oxide (TOPD)
Aqueous isopropanol, its concentration is 2mg/mL, and spin coating speed is 4000rpm/min, spin-coating time 40min, 60 DEG C of annealing 15min,
Obtain the embellishing cathode interface layer that thickness is 5nm.
(6) Ag electrodes are finally deposited with, during hot dip silver electrode, evaporation rate is in ladder distribution, and the regularity of distribution is, 0.2A/s's
Speed is deposited with 5min, 0.6A/s speed evaporation 8min, 1A/s speed evaporation 12min, obtains the silver electricity that thickness is about 120nm
Pole.
I-V test results to the present embodiment 2 are up to 9.12%, short circuit current flow as shown in figure 5, obtaining energy conversion efficiency
Density is up to 15.02mA/cm2, and fill factor, curve factor is up to 75.56%, and open-circuit voltage is up to 0.80V, relative to conventional method electric current
Density and fill factor, curve factor are increased, but in a slight decrease relative to the current density of embodiment one, and 15.02 are reduced to from 20.7,
Fill factor, curve factor slightly has reduction, comparative example 1 and 2, and reason is the TOPD cathodic modification layers thickness of the formation of embodiment 2 from 10nm
5nm is reduced to, causes current density to decrease, so as to cause efficiency to decrease.
Embodiment 3
As shown in figure 1, a kind of alcoholic solution embellishing cathode interface of the present embodiment prepares the plane perovskite of efficient unrestraint too
The method of positive energy battery, comprises the following steps：
(1) by transparent electro-conductive glass by laser ablation into required target pattern, then by the conduction etched
Substrate uses the standard detergent aqueous solution respectively, and deionized water, acetone and isopropanol are cleaned by ultrasonic 20 minutes successively, and then nitrogen blows
It is dry, obtain clean conductive substrates standby；
(2) handled 10 minutes using preceding plasma (plasma, using Conventional plasma cleaning machine) and parent is carried out to surface
Hydration process, is poly- 3,4-ethylene dioxythiophene and poly styrene sulfonate by polymer semiconductor's hole mobile material
(PEDOT:PSS) (model：PEDOT AL4083) it is spin-coated in conductive substrates, spin coating rotating speed is 3000rpm/min, spin-coating time
30s, moves back and is put in thermal station 120 DEG C and anneals 15 minutes, it is about 30nm hole transmission layers to obtain thickness；
(3) spin coating concentration is 1.25mol/L perovskites precursor aqueous solution (lead iodide (PbI after cooling2)：Methylpyridinium iodide amine
(CH3NH3I)=1:1, it is 7 to be dissolved in volume ratio:3 N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) (DMSO) mixing is molten
In agent), 70 DEG C of stirring 12h carry out two step spin coatings, and first step regulation spin speed is 500rpm, 5s, second step regulation rotation speed
Spend for 5000rpm, spin coating 25s, 1mL dry toluenes are added dropwise in the 10s of second step high speed spin coating, then by complete thin of spin coating
Film is annealed 10 minutes at 100 DEG C, obtains the perovskite thin film of densification, the thickness of gained perovskite thin film is 400nm；
(4) spin coating electron transport layer materials, electron transfer layer solution is the chlorobenzene solution of fullerene derivate (PCBM), its
Concentration is 20mg/mL, and spin speed is 1000rpm/min, and spin-coating time is 20s, obtains the electron transfer layer that thickness is 50nm.
(5) spin coating embellishing cathode interface layer material, embellishing cathode interface layer solution is acetylacetone,2,4-pentanedione titanium oxide (TOPD)
Aqueous isopropanol, its concentration is 5mg/mL, and spin coating speed is 4000rpm/min, spin-coating time 30min, 60 DEG C of annealing 15min,
Obtain the embellishing cathode interface layer that thickness is 15nm.
(6) Ag electrodes are finally deposited with, during hot dip silver electrode, evaporation rate is in ladder distribution, and the regularity of distribution is, 0.2A/s's
Speed is deposited with 5min, 0.6A/s speed evaporation 8min, 1A/s speed evaporation 12min, obtains the silver electricity that thickness is about 120nm
Pole.
The I-V test results of the present embodiment 3 are up to 10.44%, short circuit current flow as shown in fig. 6, obtaining energy conversion efficiency
Density is up to 17.13mA/cm2, and fill factor, curve factor is up to 75.15%, and open-circuit voltage is up to 0.81V, relative to conventional method electric current
Density and fill factor, curve factor have large increase, but are slightly reduced to 17.13 from 20.7 relative to the current density of embodiment one, fill out
Fill the factor and slightly have reduction, comparative example 1 and 3, reason is the TOPD cathodic modification layers thickness of the formation of embodiment 3 from 10nm liters
Height arrives 15nm, causes current density to decrease, causes efficiency also to decrease.
The inhibitory action of the alcoholic solution cathodic modification perovskite solar cell prepared for the checking present invention, to embodiment 3
Product is made to be tested, the current density voltage curve figure of gained battery is prepared with scanning direction change such as Fig. 7 and scanning speed
The change of rate (sweep speed is respectively 1.4v/s, 1.12v/s, 0.7v/s, 0.42v/s, I-V test results during 0.14v/s)
As shown in figure 8, I-V curve is almost without significant change in the case of positive surface sweeping and reverse scan, while respectively with difference
Sweep speed 1.4v/s, 1.12v/s, 0.7v/s, 0.42v/s, 0.14v/s in the case of I-V curve almost overlap, illustrate this
Perovskite solar cell properties test prepared by invention is not influenceed by scanning direction and sweep speed, therefore prepared by the present invention
Inhibitory action is not present in perovskite solar cell.Other embodiment can also measure similar result, not repeat one by one.
Although the present invention is disclosed as above with embodiment, it is not limited to protection scope of the present invention, any ripe
Those skilled in the art are known, in the change and retouching made without departing from the spirit and scope of the invention, this hair all should be belonged to
Bright protection domain.
Claims (10)
1. a kind of cathodic modification type plane perovskite solar cell, include successively from bottom to top ITO substrates, hole transmission layer,
Calcium titanium ore bed, electron transfer layer and metal are to electrode, it is characterised in that：The electron transfer layer and metal between electrode to being provided with
Embellishing cathode interface layer, the material of described embellishing cathode interface layer is acetylacetone,2,4-pentanedione titanium oxide.
2. the preparation method of cathodic modification type plane perovskite solar cell, comprises the following steps described in a kind of claim 1：
(1) conductive substrates and etching pattern are chosen, the conductive substrates etched are obtained after cleaning；
(2) conductive substrates etched in step (1) are used after plasma treatment, then using spin-coating method deposited polymer half
Hole transmission layer is obtained after conductor hole mobile material, annealing；
(3) perovskite precursor aqueous solution is prepared, the spin coating perovskite precursor aqueous solution on the hole transmission layer of step (2), spun
Anti-solvent is added in journey, spin coating after annealing obtains the perovskite thin film of densification after cooling；
(4) the spin coating fullerene derivate electron transfer layer solution on the fine and close perovskite thin film that step (3) is obtained, obtains electronics
Transport layer；
It is characterized in that：Also include
(5) configuration interface decorative layer solution, spin coating embellishing cathode interface layer solution is obtained on the electron transfer layer that step (4) is obtained
Obtain a bed boundary decorative layer；
The modifying interface layer material is acetylacetone,2,4-pentanedione titanium oxide, and it is configured to the acetylacetone,2,4-pentanedione that solution is 2~5mg/ml and aoxidized
The aqueous isopropanol of titanium；
The spin coating speed of the spin coating embellishing cathode interface layer is 2000~5000rpm/min, and spin-coating time is 20~40s, is moved back
Fiery temperature is 60~100 DEG C, and annealing time is 10~15min, and thickness is 5~15nm；
(6) the upper hot evaporation gold of embellishing cathode interface layer or silver electrode obtained in step (5), obtains p-i-n type plane perovskites
Solar cell.
3. preparation method according to claim 1, it is characterized in that：The acetyl that solution is 3mg/ml is configured in step (5)
The aqueous isopropanol of acetone oxidation titanium；The spin coating speed of the spin coating embellishing cathode interface layer is 3000rpm/min, spin-coating time
For 30s, annealing temperature is 60 DEG C, and annealing time is 15min, and acquisition thickness is 10nm.
4. preparation method according to claim 1, it is characterized in that：Conductive substrates described in step (1) are FTO glass,
Ito glass or ITO/PET substrates.
5. preparation method according to claim 1, it is characterized in that：Cleaning conductive substrates process is to use respectively in step (1)
Water-detergent solution, deionized water, acetone, isopropanol is cleaned by ultrasonic 10~20min.
6. preparation method according to claim 1, it is characterized in that：In step (2) time of plasma treatment be 10~
20min, hole transport layer material is PEDOT:PSS or Poly-TPD, revolve Tu hole transport layer material rotation Tu speed 2000~
5000rpm/min, revolves 20~40s of Tu time, and 120~150 DEG C of annealing temperature, 10~15min of annealing time obtains hole transport
Thickness degree is 20~50nm.
7. preparation method according to claim 1, it is characterized in that：In step (3) perovskite precursor aqueous solution be lead iodide and
The mixed solution of methylpyridinium iodide amine, the wherein magnitude relation of the material of lead iodide and methylpyridinium iodide amine are 1:0.8~1.15, it is described mixed
It is DMF and the mixed solvent of dimethyl sulfoxide (DMSO), the DMF and two to close the solvent of solution
The volume ratio of methyl sulfoxide is 6~9:1~4.
8. preparation method according to claim 1, it is characterized in that：The spin coating speed of spin coating perovskite solution in step (3)
For 3000~5000rpm/min, spin-coating time is 20~30s, is added dropwise anti-solvent at the 6th~10, annealing temperature is 100~
105 DEG C, annealing time is 10~20min, and it is 300~500nm to obtain perovskite thin film thickness.
9. preparation method according to claim 1, it is characterized in that：Fullerene derivate electronics described in step (4) is passed
Defeated layer solution is fullerene derivate PCBM chlorobenzene solution, and its concentration is 10~30mg/mL；Spin coating fullerene derivate electronics
During transport layer solution, spin speed be 1000~3000rpm/min, spin-coating time be 20~40s, spin coating thickness be 20~
50nm。
10. preparation method according to claim 1, it is characterized in that：Hot dip gold or during silver electrode in step (6), evaporation speed
Rate is distributed in ladder, and the regularity of distribution is：0.1~0.3A/s speed evaporation 3~8min, 0.5~0.8A/s speed evaporation 7~
12min, 1~1.2A/s speed are deposited with 8~15min, obtain gold or silver electrode that thickness is 50~120nm.
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