CN109904319A - The flat crystal of large scale perovskite, calcium titanium ore bed preparation method and solar battery - Google Patents
The flat crystal of large scale perovskite, calcium titanium ore bed preparation method and solar battery Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of calcium titanium ore bed, comprising the following steps: and the first precursor solution 1) is configured, solution is spun in substrate and forms wet film, annealing cooling；2) the second precursor solution is configured, the second precursor solution is added dropwise in the method for using more drop coating layers on substrate wet film after the cooling period, carries out continuous heat, obtains calcium titanium ore bed；Additionally provide the preparation method of solar battery, comprising the following steps: 1) electro-conductive glass substrate is cleaned, and electron transfer layer is prepared in substrate；2) calcium titanium ore bed is prepared on the electron transport layer；3) hole transmission layer is prepared on calcium titanium ore bed and prepares metal electrode.Method provided by the invention increases perovskite crystal size, crystal diameter is mainly distributed on (1.4-2.8) μm, it is maximum 5 μm reachable, the calcium titanium ore bed surfacing formed by perovskite crystal is pin-free, so as to improve the power-conversion efficiencies (PCE) and long-time stability of the solar battery based on this perovskite crystal.
Description
Technical field
The present invention relates to perovskite solar battery technologies of preparing, belong to electronic material and devices field, and in particular to one
The preparation method and its solar battery of the kind flat Crystallization calcium titanium ore bed of large scale perovskite.
Background technique
The process of the industrial revolution, along with the consumption of the energy, the fossil fuels such as coal, petroleum, natural gas are answered extensively in succession
For in the vital movement of people.Along with the continuous development of social economy and being constantly progressive for human civilization, people are to the energy
Demand is increasing.However, these energy are substantially non-renewable, structure between limited reserves and the unlimited demand of the mankind
At implacable contradiction.Secondly as global warming phenomenon is got worse, discharge amount of the countries in the world to carbon dioxide
Take various measures.The use of these energy will also result in greenhouse effects, accelerate global warming, to the mankind and other
The existence of animals and plants constitutes huge challenge.Therefore, exploring new energy becomes the task of top priority, and clean renewable energy becomes weight
Point, solar energy are exactly the clean energy resource of human candidate.For solar energy as a kind of renewable energy, it is a kind of spoke from the sun
It penetrates, is converted into the widely used electric energy of the mankind, have been obtained rapidly develop and wide use in recent years.
In past more than 10 years, perovskite solar battery rapidly develops due to its very prominent advantage.It is fabricated to
This is lower, and manufacturing process is simple, can prepare flexible, transparent battery.Meanwhile it being also equipped with more suitable band gap width, it can pass through
Change its band gap width to control the color of battery, prepares colored battery.Compared with silion cell, perovskite inhales green light and blue light
Receipts obviously increase.And the crystallinity of perovskite crystal is very high, and Carrier recombination degree greatly reduces, carrier diffusion length with
Increase, the trap density of states reduce, it is closely related that perovskite solar battery can show excellent performance and these characteristics.
But perovskite solar battery still remains many problems, such as the stability of battery in wet condition, the service life of battery,
How large area preparation etc..Preparing Ca-Ti ore type solar battery preparation process mainly has solution spin coating, vacuum evaporation at present
The methods of, wherein more mature technique is exactly solution spin-coating method.Solution spin-coating method is that solution is directly applied to substrate surface, benefit
With the high speed rotation of sol evenning machine, a kind of technique of membrane interface is formed.Power using the solar battery of spin coating proceeding manufacture turns
Change efficiency (PCE) and reaches 22.1%.However, perovskite solar battery power-conversion efficiencies are not still very high, while air
Stability under humidity is also very poor, it is therefore desirable to spin coating proceeding is advanced optimized, to improve perovskite solar cell properties.
In Chinese patent " a method of promote perovskite crystalline " (publication number: CN106128954A) confirmation,
DMSO (dimethyl sulfoxide) solution can be used for delaying crystallization process, then form the perovskite thin film of high quality.It is annealing simultaneously
DMSO solution is also used in the process, and the stable problem under environment epidemic disaster environment can be improved.But obtained crystalline size
It is not still it is obvious that crystal diameter is mainly distributed on (0.5-1) μm in report, maximum crystal diameter is close to 2 μm.It is this to have
The size of limit be limit the long-term Moisture stability of power-conversion efficiencies and corresponding perovskite solar battery unfavorable factor it
One.
In existing literature, Yanhong Zhao et al. [Journal of Power Sources 359 (2017): 147-
156] a kind of mode of more drop coating layers is mentioned.When preparing perovskite bottom, the first spin coating first in a manner of singly drop spin coating in substrate
Precursor solution, spin coating machine speed 3000rpm, rotational time 30 seconds, the first precursor solution included lead iodide (PbI2) solution and
DMSO solution gets well spin coating containing PbI2The substrate of film saves 20 minutes under vacuum conditions.Then in the PbI of formation2Drop coating on film
Second precursor solution, after sol evenning machine is rotated with 4000rpm revolving speed, every two seconds 1 drops of drop drip altogether (2-12) drop, 150 DEG C of dryings 10
Minute, finally calcium titanium ore bed is formed after forty minutes in 120 DEG C of continuous heats.Crystal diameter is obtained in report to be mainly distributed on
(0.4-2) μm, crystal diameter increase limited, improved interface without especially smooth, and crystal boundary still has pin hole, limitation power conversion
Efficiency.
Summary of the invention
In view of the above existing problems in the prior art, the present invention provides a kind of flat Crystallization calcium titaniums of large scale perovskite
The preparation method and solar battery of ore bed, the power-conversion efficiencies of perovskite solar battery can be improved using this method,
And the stability under air humidity also increases.
To achieve the goals above, the present invention provides a kind of flat crystal of large scale perovskite, the crystal diameter masters
It is distributed in (1.4-2.8) μm, it is maximum up to 5 μm；The flat crystal accumulation of perovskite forms calcium titanium ore bed, the calcium titanium together
Ore bed surfacing is pin-free.
In addition, the present invention also provides a kind of calcium titanium ore bed of flat Crystallization of large scale perovskite, the perovskite
Layer preparation method the following steps are included:
1) the first precursor solution is configured, solution is spun in substrate and forms wet film, annealing cooling；
2) the second precursor solution is configured, more drop coating layers of DMSO additive auxiliary are used on substrate wet film after the cooling period
Mode is added dropwise the second precursor solution, carries out continuous heat later, obtain calcium titanium ore bed.
In the step 1), the first precursor solution used is PbI2Powder is dissolved in dimethylformamide (DMF)/DMSO
Mixed solution forms；
The mixed volume ratio 9.5:0.5, the PbI of the DMF/DMSO2The additional amount 1.3M of powder.
In the step 1), the first precursor solution is with (1000-2000) rpm spin coating (20-35) second, and at (50-100)
It anneals 1 minute at DEG C, forms PbI2Film.
In the step 2), the second precursor solution of use includes organic salt carbonamidine iodine (FAI), methylamine bromine (MABr) and first
Amine chlorine (MACl), solvent are isopropanol, and additive is DMSO solution, and DMSO solution shared concentration in the second precursor solution is
(0.1-30)μL mL-1；
The molar ratio of described organic salt FAI, MABr and MACl are 1:0.15:0.25, and the dosage of the isopropanol is 1mL.
In the step 2), there is PbI2The substrate of film takes (40-60) with (1000-2000) rpm continuous rotation (20-35) s
The second precursor solution of μ L, is added dropwise solution after substrate starts rotation dropwise, drips 1 time per (1-3) second, and drop (4-6) is secondary, forms second
Layer wet film.
In the step 2), by resulting second layer wet film in the surrounding air of 40-60% humidity, it is enterprising to be placed on thermal station
Row continuous heat is in a dustless, closed environment in annealing process, and thermal station temperature is (120-160) DEG C, heats (10-
25) calcium titanium ore bed is obtained after minute.
In addition, the present invention also provides a kind of preparation methods of perovskite solar battery, comprising the following steps:
1) electro-conductive glass substrate is cleaned, and electron transfer layer is prepared in substrate；
2) calcium titanium ore bed is prepared on the electron transport layer；
3) hole transmission layer is prepared on calcium titanium ore bed and prepares metal electrode.
Finally, the present invention provides a kind of perovskite solar batteries prepared using the method.
The principle of the present invention is:
The present invention proposes a kind of more drop coating layer methods of DMSO additive auxiliary to prepare calcium titanium ore bed, can according to this method
To prepare a kind of flat crystal of large scale perovskite, the calcium titanium ore bed by this flat Crystallization of large scale perovskite is more smooth
Smooth, interface is pin-free.The solar battery of preparation, which is positive, sets structure, coats PbI on the electron transport layer first2Precursor is molten
Liquid forms PbI2Film, annealing cooling；Secondly, the second precursor solution is coated in PbI2On film, finally by the quasi- double-deck expansion
Calcium titanium ore bed is formed after dissipating annealing.The present invention improves ingredient on the basis of original solution ratio, adds in the second precursor solution
DMSO solution, while using a kind of deposition method of more drop coating layers obtains a kind of flat Crystallization of large scale perovskite
Calcium titanium ore bed.The present invention uses more drop coating layer methods of DMSO additive auxiliary, and DMSO solution is be used to form interphase normal
With cosolvent, therefore the present invention adds DMSO solution in the solution.In annealing process, delay the molding time of crystal, crystal
It is grown into, size is gradually increased, therefore available large-sized perovskite crystal.In addition, by way of more drop coating layers
Crystalline size can be further adjusted, interface is optimized.The time that strict control of the present invention is added dropwise, under same time interval (1-3)
Solution is added dropwise in second.During drop coating solution, small perovskite grain dissolution deposits to gap between big perovskite crystal, makes
It is more compact to obtain perovskite crystal boundary.In the solution, since adjacent key is less, the molecular proportion interior molecules of perovskite particle surface
Active, big perovskite particle contains more interior molecules and less surface molecular than small perovskite particle, therefore more
Molecule is separated from small perovskite particle surface and is diffused into solution.When free molecular flow concentration increases in solution, free molecular flow
It will be redeposited in big perovskite particle surface.Therefore, by way of this more drop coating layers, it can be ensured that small perovskite
The dissolution of grain and the growth of big perovskite particle, generate the bigger flat crystal of large scale perovskite, when the flat crystal of perovskite
Aggregation molding, the gap of perovskite crystal to each other are reduced by this coating way, crystal boundaries passivation, pin hole, boundary knot
Close more compact, the calcium titanium ore bed of formation is more flat and smooth.
The calcium titanium ore bed being prepared by more drop coating layer methods that DMSO additive assists, internal perovskite crystal ruler
It is very little it is bigger, pattern is more flat, calcium titanium ore bed structure is more compact, more smooth so that the crystal boundary of calcium titanium ore bed is flat and smooth, interface without
Pin hole, therefore photo-generated carrier Compound Degree greatly reduces, carrier diffusion length increases therewith, and the trap density of states reduces, and has
Conducive to the transmission of charge, therefore the sorption enhanced of light can be promoted, to improve the efficiency of perovskite solar battery.
The beneficial effects of the present invention are:
1) found out by characterization, in such a way that the present invention makes calcium titanium ore bed, after continuous heat treatment process, the party
The available larger-sized crystal of method, while calcium titanium ore bed crystal face also improves, interface is pin-free, and crystalline size maximum can
Reach 5 μm.Many evidences show that the crystal boundary in polycrystalline perovskite thin film causes charge recombination due to existing defects in crystal
Increase.Therefore, by DMSO additive, the forming process of crystal can be delayed in conjunction with the method for more drop coating layers, control crystal ruler
It is very little, form the perovskite film of the lesser big crystal of crystal boundary.
2) in addition, the increased perovskite solar battery of crystalline solid degree also shows better power-conversion efficiencies and stabilization
Property.Based on the plane perovskite solar battery of the flat Crystallization calcium titanium ore bed of large scale perovskite, power-conversion efficiencies are aobvious
Improve to 20.63% (original perovskite solar battery is 16.02%).The unencapsulated flat crystal of large scale perovskite
Perovskite solar cell device is placed at room temperature, is stored under 40% relative humidity, its initial value is still maintained after 500 hours
93% power-conversion efficiencies.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the obtained perovskite solar battery of the present invention.
Fig. 2 is more drop coating layer methods of the present invention using DMSO additive auxiliary, makes the artwork of calcium titanium ore bed.
Fig. 3 is the current density and voltage (J-V) characteristic curve of four kinds of samples in the embodiment of the present invention 1, and cellar area is
0.1cm2。
Fig. 4 is the long-term stable experiment comparison diagram of the first sample and the 4th sample in the embodiment of the present invention 1；
Fig. 5 is that the embodiment of the present invention 1 is deposited on stannic oxide (SnO at different conditions2) perovskite thin film on substrate
Vertical view SEM image；It (1) is the first sample, using the film of more drop coating layer methods preparation of DMSO additive auxiliary；(2) it is
Second sample, using the film of more drop coating layer methods；It (3) is third sample, the film containing DMSO additive；It (4) is the 4th
Sample, without DMSO additive simultaneously also without using more drop coating layer methods.
Fig. 6 is that the embodiment of the present invention 1 is deposited on SnO at different conditions2The section SEM of perovskite thin film on substrate schemes
Picture；It (1) is the first sample, using the film of more drop coating layer methods preparation of DMSO additive auxiliary；(2) it is the second sample, adopts
With the film of more drop coating layer methods；It (3) is third sample, the film containing DMSO additive；(4) it is the 4th sample, is free of
DMSO additive is simultaneously also without using more drop coating layer methods.
In figure: 1, tin indium oxide (ITO) conductive glass layer, 2, SnO2Electron transfer layer, 3, calcium titanium ore bed, 4, hole transport
Layer, 5, metal gold electrode.
Specific embodiment
In order to make the objectives, technical solutions and advantages of the present invention clearer, below by accompanying drawings and embodiments, to this
Invention is further elaborated.However, it should be understood that described herein, specific examples are only used to explain the present invention, and
It is not used in and limits the scope of the invention.
Unless otherwise defined, all technical terms and scientific terms used herein are led with technology of the invention is belonged to
The normally understood meaning of the technical staff in domain is identical, and term as used herein in the specification of the present invention is intended merely to retouch
State the purpose of specific embodiment, it is not intended that in the limitation present invention.
The present invention provides a kind of preparation method of calcium titanium ore bed, this method strong operability, preparation process is stablized.Preparation
Battery device crystal growth size it is controllable, the transformation efficiency of solar battery is efficiently stablized.The present invention be perovskite too
The promotion of positive energy battery performance, provides a kind of effective process means, has broad application prospects.
The present invention provides a kind of solar battery prepared using the method, the solar battery structure such as Fig. 1 institutes
Show, supreme below successively includes indium tin oxide-coated glass layer 1, SnO2Electron transfer layer 2, calcium titanium ore bed 3, hole transmission layer 4
With metal gold electrode 5.
Embodiment 1
A kind of preparation method of solar battery, specifically includes the following steps:
1) preparation of substrate: first taking ito glass, is cut into the sample of 1cm × 1cm, successively use detergent, deionized water,
Acetone, isopropanol and ethyl alcohol successively wash 20 minutes, are cleaned by ultrasonic and dry, and then UV- ozone clean processing ITO substrate 25 is divided
Clock is then placed in drying for standby in nitrogen glove box to remove oxide layer and greasy dirt；
2) it prepares electron transfer layer: preparing SnO2Solution, by SnO2Colloid precursor solution is placed in reagent bottle, is added
Ionized water dilution, is ultrasonically treated 30min, is sufficiently mixed solution.Cleaned ito glass substrate is adsorbed on sol evenning machine,
SnO is added dropwise2Spin coating is carried out after solution.When spin coating, the revolving speed of sol evenning machine is 4000rpm, and rotational time is 30 seconds, then by substrate
It is transferred in thermal station, anneals 30 minutes at 150 DEG C；
3) calcium titanium ore bed is prepared:
1. the first precursor solution is prepared, by 1.3M PbI2It is molten that powder is dissolved in the mixing that DMF/DMSO volume ratio is 9.5:0.5
In agent, 30min is vibrated, mixed solution is obtained.The first precursor solution is taken, single drop is added dropwise in SnO2On compacted zone, pass through spin coating
Machine spin-coating film, spin coating machine speed 1500rpm, rotational time are 30 seconds, anneal 1 minute in 70 DEG C of thermal station, then will contain
PbI2The substrate of film puts cooling in dustless, closed environment, obtains PbI2Film；
2. prepare the second precursor solution, by organic salt FAI, MABr and MACl according to molar ratio be 1:0.15:0.25, be placed in
In reagent bottle, 1mL isopropanol is added, 30min is vibrated, dissolves organic salt sufficiently, add DMSO solution, DMSO in the solution
Solution shared concentration in the second precursor solution is 25 μ L mL-1, 30min is vibrated again, obtains the second precursor solution, spin coating
Two precursor solutions: in PbI2Spin coating solution on film, spin coating machine speed 1400rpm, rotation spin-coating time are 30 seconds, take about 60 μ L
Second precursor solution, is added dropwise dropwise, drips 1 time at interval of 1 second, drips 5 times, gained film is transferred to the environment of 40-60% humidity
It in air, is placed in thermal station and carries out continuous heat, a dustless, closed environment is in annealing process, thermal station temperature is
150 DEG C, heating obtained calcium titanium ore bed after 16 minutes；
4) it prepares hole transmission layer: preparing 2,2', 7,7'- tetra--(dimethoxy diphenylamines)-spiro fluorene (Spiro-OMeTAD)
Solution takes the spiro-OMeTAD powder of 87.8mg that reagent bottle is added, successively adds 1mL chlorobenzene, double trifluoro methylsulphurs of 19.5 μ L
Imide (Li-TFSI), the 4- tert .-butylpyridine (TBP) of 8 μ L cobalt complexes (FK209) and 35.5 μ L vibrate 30min,
It dissolves it sufficiently, obtains mixed solution.Spiro-OMeTAD solution list drop drop is taken on the calcium titanium ore bed of step 3), then
Spin coating, spin coating machine speed 4000rpm are carried out, rotational time is 20 seconds, shifts kept dry in drying box later.
5) it prepares electrode: the gold electrode of 100nm being deposited by vacuum coating equipment.
Perovskite crystal size and solar cell properties analysis:
In the present invention, the first sample is the sample of the more drop coating layer methods assisted using DMSO additive；Second sample
For using the sample of more drop coating layer methods；Third sample is the sample containing DMSO additive；4th sample is to add without DMSO
Add agent while also without the sample using more drop coating ways.
Crystal diameter size comparison obtained in the present embodiment 1: as shown in Figure 5, Figure 6, respectively the vertical view of Sample crystals,
Section SEM figure, it can be seen that the size of crystal.First Sample crystals diameter is mainly distributed on (1.4-2.8) μm, maximum up to 5 μ
m；Second Sample crystals diameter is mainly distributed on (0.75-1.6) μm, maximum up to 2.4 μm；Third Sample crystals diameter mainly divides
Cloth is at (0.6-1.8) μm, and maximum is up to 2 μm；4th Sample crystals diameter is mainly distributed on (0.2-0.8) μm, maximum up to 1.2
μm.Main distribution refers to 90% or more distribution.We can see that when also no using more drops simultaneously without DMSO additive
When coating way, crystal diameter size is minimum；When using DMSO additive or more drop coating layer methods, crystal diameter size has
Increased, but average largest diameter is no more than 2 μm；When using more drop coating layer methods of DMSO additive auxiliary, crystal
Size it is bigger, a big chunk crystal diameter be mainly distributed above 2 μm, full-size is up to 5 μm.
The performance for the solar battery that the present invention obtains is as shown in Figure 3, Figure 4.Fig. 3 fits the current density and electricity of sample
Characteristic curve is pressed, Fig. 4 reflects the stability of sample.Summary data is as shown in table 1 below: the power-conversion efficiencies of the first sample are
20.63%, while the stability of device is greatly enhanced, under ambient humidity, still there are also 90% or more effects after 500h
Rate.Second sample power transformation efficiency is 18.09%, and the second sample has dropped 12% than the first sample, and stability decreases.
Third sample power transformation efficiency is 19.73%, and third sample has dropped 4% than the first sample, and stability decreases.4th
Sample power transformation efficiency is 16.02%, and the 4th sample has dropped 22% than the first sample, and stability is poor.
Thus we have observed that, when using DMSO additive auxiliary more drop coating layer methods after, to the crystal ruler of calcium titanium ore bed
It is very little all to have a great impact, crystalline size can be expanded, improve interface, improve power-conversion efficiencies.But works as and take this hair
Bright mode, after more drop coating layer methods using DMSO additive auxiliary, crystalline size obtains further perfect, and interface is smooth
It is pin-free, it is possible to reduce charge recombination promotes the power-conversion efficiencies of device, improves device stability.
The various properties of sample testing results of above-described embodiment 1 are as shown in table 1 below.
The performance test results of various samples in 1 embodiment 1 of table
Embodiment 2
A kind of preparation method of the flat Crystallization calcium titanium ore bed of perovskite, specifically includes the following steps:
1) preparation of substrate: first taking ito glass, is cut into the sample of 1cm × 1cm, successively use detergent, deionized water,
Acetone, isopropanol and ethyl alcohol successively wash 20 minutes, are cleaned by ultrasonic and dry, and then UV- ozone clean processing ITO substrate 25 is divided
Clock is then placed in drying for standby in nitrogen glove box to remove oxide layer and greasy dirt；
2) calcium titanium ore bed is prepared:
1. the first precursor solution is prepared, by 1.3M PbI2It is molten that powder is dissolved in the mixing that DMF/DMSO volume ratio is 9.5:0.5
In agent, 30min is vibrated, the first precursor solution is obtained, take the first precursor solution, single drop is added dropwise in SnO2On compacted zone, pass through
Sol evenning machine spin-coating film, spin coating machine speed 1000rpm, rotational time are 20 seconds, are annealed 1 minute in 50 DEG C of thermal station, then
PbI will be contained2The substrate of film puts cooling in dustless, closed environment, obtains PbI2Film；
2. prepare the second precursor solution, by organic salt FAI, MABr and MACl according to molar ratio be 1:0.15:0.25, be placed in
In reagent bottle, 1mL isopropanol is added, 30min is vibrated, dissolves organic salt sufficiently, add DMSO solution, DMSO in the solution
Solution shared concentration in the second precursor solution is 15 μ L mL-1, 30min is vibrated again, mixed solution is obtained, before spin coating second
Liquid solution: in PbI2Spin coating solution on film, spin coating machine speed 1200rpm, rotation spin-coating time are 35 seconds, take about 40 μ L second
Precursor solution is added dropwise dropwise, drips 1 time at interval of 3 seconds, drips 4 times, gained film is transferred to surrounding air (40-60% humidity)
In, it is placed in thermal station and carries out continuous heat, a dustless, closed environment is in annealing process, thermal station temperature is 160
DEG C, heating obtains calcium titanium ore bed after ten minutes.
In the present invention, the 5th sample is the sample using traditional single drop coating layer, by the direct drop coating of solution in substrate,
It is then spin coated onto film；6th sample is the sample of the more drop coating layer methods assisted using DMSO additive, molten after substrate is rotated
Liquid dropwise drips in substrate, drips 4 drops altogether, final to form a film.
Crystalline size comparative analysis: the 5th Sample crystals diameter is mainly distributed on (0.8-1.65) μm；6th Sample crystals
Diameter is mainly distributed on (1.0-2.2) μm.
In the present embodiment, the 5th sample can be seen that crystal by SEM phenogram by the way of traditional single drop spin coating
Size, crystal diameter are mainly distributed on (0.8-1.65) μm, it can be seen that calcium titanium ore bed interface is less smooth, there is pin hole between crystal
In the presence of will affect device power transformation efficiency, stability can also be influenced.6th sample is more using DMSO additive auxiliary
Drop coating layer method, it can be seen that crystal diameter is mainly distributed on (0.8-1.65) μm, and it is more flat to be formed by calcium titanium ore bed interface
It is whole, almost without pin hole presence.Thus we have observed that, the more drop coating layer methods assisted using DMSO additive can delay crystalline substance
Body growth time, so that crystal molding time is longer, the dissolution of small crystals obtains larger sized crystalline substance with the formation of big crystal
Body, in this way available more smooth crystal boundary.
Embodiment 3
A kind of preparation method of the calcium titanium ore bed of the flat Crystallization of perovskite, comprising the following steps:
1) preparation of substrate: first taking ito glass, is cut into the sample of 1cm × 1cm, successively use detergent, deionized water,
Acetone, isopropanol and ethyl alcohol successively wash 20 minutes, are cleaned by ultrasonic and dry, and then UV- ozone clean processing ITO substrate 25 is divided
Clock is then placed in drying for standby in nitrogen glove box to remove oxide layer and greasy dirt；
2) calcium titanium ore bed is prepared:
1. the first precursor solution is prepared, by 1.3M PbI2It is molten that powder is dissolved in the mixing that DMF/DMSO volume ratio is 9.5:0.5
In agent, 30min is vibrated, mixed solution is obtained, take the first precursor solution, single drop is added dropwise in SnO2On compacted zone, pass through spin coating
Machine spin-coating film, spin coating machine speed 2000rpm, rotational time are 35 seconds, anneal 1 minute in 50 DEG C of thermal station, then will contain
PbI2The substrate of film puts cooling in dustless, closed environment, obtains PbI2Film；
2. prepare the second precursor solution, by organic salt FAI, MABr and MACl according to molar ratio be 1:0.15:0.25, be placed in
In reagent bottle, 1mL isopropanol is added, 30min is vibrated, dissolves organic salt sufficiently, add DMSO solution, DMSO in the solution
Solution shared concentration in the second precursor solution is 28 μ L mL-1, 30min is vibrated again, mixed solution is obtained, before spin coating second
Liquid solution: in PbI2Spin coating solution on film, spin coating machine speed 1800rpm, rotation spin-coating time are 25 seconds, take about 50 μ L second
Precursor solution is added dropwise dropwise, drips 1 time at interval of 2 seconds, drips 5 times, gained film is transferred to the surrounding air of 40-60% humidity
In, it is placed in thermal station and carries out continuous heat, a dustless, closed environment is in annealing process, thermal station temperature is 130
DEG C, heating obtained calcium titanium ore bed after 25 minutes.
In the present invention, the 7th sample is the sample using traditional single drop coating layer, by the direct drop coating of solution in substrate,
It is then spin coated onto film；8th sample is the sample of the more drop coating layer methods assisted using DMSO additive, molten after substrate is rotated
Liquid dropwise drips in substrate, drips 5 drops altogether, final to form a film.
Crystalline size comparative analysis: the 7th Sample crystals diameter is mainly distributed on (1.1-1.8) μm；8th Sample crystals are straight
Diameter is mainly distributed on (1.3-2.65) μm.
In the present embodiment, the 7th sample can be seen that crystal by SEM phenogram by the way of traditional single drop spin coating
Size, crystal diameter are mainly distributed on (1.1-1.8) μm, it can be seen that calcium titanium ore bed interface is less smooth, there is pin hole between crystal
In the presence of will affect device power transformation efficiency, stability can also be influenced.8th sample is more using DMSO additive auxiliary
Drop coating layer method, it can be seen that crystal diameter is mainly distributed on (1.3-2.65) μm, and it is more flat to be formed by calcium titanium ore bed interface
It is whole, almost without pin hole presence.Thus we have observed that, the more drop coating layer methods assisted using DMSO additive can delay crystalline substance
Body growth time, so that crystal molding time is longer, the dissolution of small crystals obtains larger sized crystalline substance with the formation of big crystal
Body, in this way available more smooth crystal boundary.
Embodiment 4
A kind of preparation method of the calcium titanium ore bed of the flat Crystallization of perovskite, comprising the following steps:
1) preparation of substrate: first taking ito glass, is cut into the sample of 1cm × 1cm, successively use detergent, deionized water,
Acetone, isopropanol and ethyl alcohol successively wash 20 minutes, are cleaned by ultrasonic and dry, and then UV- ozone clean processing ITO substrate 25 is divided
Clock is then placed in drying for standby in nitrogen glove box to remove oxide layer and greasy dirt；
2) calcium titanium ore bed is prepared:
1. the first precursor solution is prepared, by 1.3M PbI2It is molten that powder is dissolved in the mixing that DMF/DMSO volume ratio is 9.5:0.5
In agent, 30min is vibrated, mixed solution is obtained, take the first precursor solution, single drop is added dropwise in SnO2On compacted zone, pass through spin coating
Machine spin-coating film, spin coating machine speed 1600rpm, rotational time are 25 seconds, anneal 1 minute in 100 DEG C of thermal station, then will contain
PbI2The substrate of film puts cooling in dustless, closed environment, obtains PbI2Film；
2. prepare the second precursor solution, by organic salt FAI, MABr and MACl according to molar ratio be 1:0.15:0.25, be placed in
In reagent bottle, 1mL isopropanol is added, 30min is vibrated, dissolves organic salt sufficiently, add DMSO solution, DMSO in the solution
Solution shared concentration in the second precursor solution is 20 μ L mL-1, 30min is vibrated again, mixed solution is obtained, before spin coating second
Liquid solution: in PbI2Spin coating solution on film, spin coating machine speed 1000rpm, rotation spin-coating time are 20 seconds, take about 60 μ L second
Precursor solution is added dropwise dropwise, drips 1 time at interval of 2 seconds, drips 6 times, gained film is transferred to surrounding air (40-60% humidity)
In, it is placed in thermal station and carries out continuous heat, a dustless, closed environment is in annealing process, thermal station temperature is 120
DEG C, heating obtained calcium titanium ore bed after 25 minutes.
In the present invention, the 9th sample is the sample using traditional single drop coating layer, by the direct drop coating of solution in substrate,
It is then spin coated onto film；Tenth sample is the sample of the more drop coating layer methods assisted using DMSO additive, molten after substrate is rotated
Liquid dropwise drips in substrate, drips 6 drops altogether, final to form a film.
Crystalline size comparative analysis: the 9th Sample crystals diameter is mainly distributed on (1.1-1.75) μm；Tenth Sample crystals
Diameter is mainly distributed on (1.25-2.6) μm.
In the present embodiment, the 9th sample can be seen that crystal by SEM phenogram by the way of traditional single drop spin coating
Size, crystal diameter are mainly distributed on (1.1-1.75) μm, it can be seen that calcium titanium ore bed interface is less smooth, there is pin hole between crystal
In the presence of will affect device power transformation efficiency, stability can also be influenced.Tenth sample is more using DMSO additive auxiliary
Drop coating layer method, it can be seen that crystal diameter is mainly distributed on (1.25-2.6) μm, and it is more flat to be formed by calcium titanium ore bed interface
It is whole, almost without pin hole presence.Thus we have observed that, the more drop coating layer methods assisted using DMSO additive can delay crystalline substance
Body growth time, so that crystal molding time is longer, the dissolution of small crystals obtains larger sized crystalline substance with the formation of big crystal
Body, in this way available more smooth crystal boundary.
Embodiment 5
A kind of preparation method of the flat Crystallization calcium titanium ore bed of perovskite, comprising the following steps:
1) preparation of substrate: first taking ito glass, is cut into the sample of 1cm × 1cm, successively use detergent, deionized water,
Acetone, isopropanol and ethyl alcohol successively wash 20 minutes, are cleaned by ultrasonic and dry, and then UV- ozone clean processing ITO substrate 25 is divided
Clock is then placed in drying for standby in nitrogen glove box to remove oxide layer and greasy dirt；
2) calcium titanium ore bed is prepared:
1. the first precursor solution is prepared, by 1.3M PbI2It is molten that powder is dissolved in the mixing that DMF/DMSO volume ratio is 9.5:0.5
In agent, 30min is vibrated, mixed solution is obtained, take the first precursor solution, single drop is added dropwise in SnO2On compacted zone, pass through spin coating
Machine spin-coating film, spin coating machine speed 1800rpm, rotational time are 25 seconds, anneal 1 minute in 70 DEG C of thermal station, then will contain
PbI2The substrate of film puts cooling in dustless, closed environment, obtains PbI2Film；
2. prepare the second precursor solution, by organic salt FAI, MABr and MACl according to molar ratio be 1:0.15:0.25, be placed in
In reagent bottle, 1mL isopropanol is added, 30min is vibrated, dissolves organic salt sufficiently, add DMSO solution, DMSO in the solution
Solution shared concentration in the second precursor solution is 25 μ L mL-1, 30min is vibrated again, mixed solution is obtained, before spin coating second
Liquid solution: in PbI2Spin coating solution on film, spin coating machine speed 1600rpm, rotation spin-coating time are 30 seconds, take about 50 μ L second
Precursor solution is added dropwise dropwise, drips 1 time at interval of 1 second, drips 5 times, gained film is transferred to surrounding air (40-60% humidity)
In, it is placed in thermal station and carries out continuous heat, a dustless, closed environment is in annealing process, thermal station temperature is 140
DEG C, heating obtains calcium titanium ore bed after twenty minutes.
In the present invention, the tenth a sample is the sample of the more drop coating layer methods assisted using DMSO additive, by substrate
After rotation, solution dropwise drips in substrate, drips 5 drops altogether, final to form a film, and adds in the second precursor solution used micro
DMSO solution, DMSO solution shared concentration in the second precursor solution is 0.1 μ L mL-1；12nd sample is to use more drop coating layers
The sample of method, after substrate is rotated, solution dropwise drips in substrate, drips 5 drops altogether, final to form a film, before used second
Micro DMSO solution is added in liquid solution, DMSO solution shared concentration in the second precursor solution is 25 μ L mL-1。
Crystalline size comparative analysis: the tenth a sample crystal diameter is mainly distributed on (0.85-1.65) μm；12nd sample
Crystal diameter is mainly distributed on (1.3-2.4) μm.
In the present embodiment, for the tenth a sample by the way of more drop coating layers, it is molten that the second precursor solution contains micro DMSO
Liquid can be seen that crystalline size, crystal diameter are mainly distributed on (0.85-1.65) μm by SEM phenogram, be formed by calcium titanium
Interface of ore layer out-of-flatness with the presence of pin hole, therefore will affect device power transformation efficiency.12nd sample is equally added using DMSO
The more drop coating layer methods for adding agent to assist, it can be seen that crystal diameter is mainly distributed on (1.3-2.4) μm, and calcium titanium ore bed interface is more
Smooth, crystalline size is larger, and almost pin-free presence, all has an impact to device power transformation efficiency and stability between crystal.By
This we have observed that, using DMSO additive assist more drop coating layer methods, crystal growth time can be delayed so that crystal form
Time is longer, and the dissolution of small crystals obtains larger sized crystal with the formation of big crystal, available in this way
More smooth crystal boundary.When be practically free of DMSO solution crystal molding it is too fast, the size of formation is also smaller, thus between crystal between
Gap increases, and crystal boundary is also just less smooth.
Various properties of sample testing results in above-described embodiment are as shown in table 2 below.
The performance test results of various samples in 2 embodiment of table
The data in conjunction with described in the above table 2 are it is found that the present invention provides a kind of flat crystal of large scale perovskite, preparation method
And solar battery, the interface dimensions of plane perovskite solar battery are improved, the more drop coatings assisted by DMSO additive
Layer method promotes the flat Crystallization calcium titanium ore bed of large scale perovskite.By being added in embodiment one it is found that passing through comparison
DMSO solution and more drop coating ways, are become apparent using more drop coating layer method advantages that DMSO additive of the invention assists.
It can be seen that crystal diameter by the first sample to be mainly distributed on (1.4-2.8) μm, it is maximum up to 5 μm, and its in embodiment 1
He compares three samples, and maximum gauge can only be to 2.4 μm.Embodiment 2,3 and 4 is as can be seen that control more drop coating layers in experiment
Mode, for example, be added dropwise solution number, annealing time, molten number of drops etc. can all influence crystalline size, compared to tradition
Single drop coating way, crystalline size can be increased, crystal boundary is smooth pin-free.Thus it will be seen that using of the invention
More drop coating layer methods of DMSO additive auxiliary have very big advantage, can increase the size of crystal, optimize interface, obtain big ruler
The very little flat crystal of perovskite.
The present invention provides the preparation method and solar battery of a kind of flat Crystallization calcium titanium ore bed of large scale perovskite,
The interface dimensions for improving plane perovskite solar battery, the more drop coating layer methods assisted by DMSO additive promote big
The flat Crystallization calcium titanium ore bed of size perovskite.Interface is optimized, delays crystal molding time, the dissolution of small crystals is with big
The formation of crystal induces large scale perovskite crystal and forms calcium titanium ore bed.Simultaneously because crystal boundary is reduced, defect state is shown
It reduces, high-crystallinity has good strong light absorption and low Carrier recombination rate.Illustrate not only to want the dense of strict control DMSO solution
Degree, will also control the craft method of more drop coating layers, could improve the transformation efficiency of solar battery, corresponding power conversion in this way
Efficiency is promoted to 20.63% from original 16.02% is significant.Importantly, even if the perovskite solar-electricity not encapsulated
Pond also shows excellent stability, keeps 93% starting efficiency, and original dress after 500 hours in the air of 40% humidity
Setting only reduces about 65% in survival 256 hours.Therefore, which is the calcium titanium ore bed for preparing the flat crystal of large scale perovskite
Stable perovskite solar battery provides promising approach with high-performance.
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 modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
1. a kind of flat crystal of large scale perovskite, which is characterized in that the crystal diameter is mainly distributed on (1.4-2.8) μm,
It is maximum 5 μm reachable；The flat crystal accumulation of perovskite forms calcium titanium ore bed together, and the calcium titanium ore bed surfacing is pin-free.
2. a kind of preparation method of calcium titanium ore bed described in a kind of claim 1, which is characterized in that specifically includes the following steps:
1) the first precursor solution is configured, solution is spun in substrate and forms wet film, annealing cooling；
2) the second precursor solution, the side of the more drop coating layers assisted on substrate wet film after the cooling period using DMSO additive are configured
Formula is added dropwise the second precursor solution, then carries out continuous heat, obtains calcium titanium ore bed.
3. a kind of preparation method of calcium titanium ore bed according to claim 2, which is characterized in that in the step 1), use
The first precursor solution be PbI2The mixed solution that powder is dissolved in DMF/DMSO is formulated；
The mixed volume ratio of the DMF/DMSO is 9.5:0.5, the PbI2The additional amount 1.3M of powder.
4. a kind of preparation method of calcium titanium ore bed according to claim 2 or 3, which is characterized in that in the step 1),
First precursor solution is annealed 1 minute at (50-100) DEG C with (1000-2000) rpm spin coating (20-35) second, forms PbI2
Film.
5. a kind of preparation method of calcium titanium ore bed according to claim 2, which is characterized in that in the step 2), use
The second precursor solution include organic salt FAI, MABr and MACl, solvent is isopropanol, and additive is DMSO solution, DMSO solution
Shared concentration is (0.1-30) μ L mL in the second precursor solution-1；
The molar ratio of described organic salt FAI, MABr and MACl are 1:0.15:0.25, and the dosage of the isopropanol is 1mL.
6. a kind of preparation method of calcium titanium ore bed according to claim 2 or 5, which is characterized in that in the step 2), have
PbI2The substrate of film is taken (40-60) μ the second precursor solution of L, is opened in substrate with (1000-2000) rpm continuous rotation (20-35) s
Begin that solution is added dropwise dropwise after rotation, dripped 1 time per (1-3) second, drop (4-6) is secondary, forms second layer wet film.
7. a kind of preparation method of calcium titanium ore bed according to claim 6, which is characterized in that by second layer wet film in 40-
It in 60% humidity environment air, is placed in thermal station and carries out continuous heat, a dustless, closed ring is in annealing process
Border, thermal station temperature are (120-160) DEG C, and heating (10-25) obtains calcium titanium ore bed after minute.
8. a kind of preparation method of perovskite solar battery, which comprises the following steps:
1) electro-conductive glass substrate is cleaned, and electron transfer layer is prepared in substrate；
2) calcium titanium ore bed is prepared with any one of claim 2-7 the method on the electron transport layer；
3) hole transmission layer is prepared on calcium titanium ore bed and prepares metal electrode.
9. a kind of perovskite solar battery prepared using claim 8 the method.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710785A (en) * | 2020-06-18 | 2020-09-25 | 浙江浙能技术研究院有限公司 | Non-pinhole large-area controllable perovskite growth film forming process |
| CN111883670A (en) * | 2020-08-03 | 2020-11-03 | 江苏集萃分子工程研究院有限公司 | Process for preparing perovskite thin film, perovskite thin film and solar cell |
| CN117729822A (en) * | 2024-02-07 | 2024-03-19 | 西安电子科技大学 | Large-area perovskite solar cell based on gas phase ion doping and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014180789A1 (en) * | 2013-05-06 | 2014-11-13 | Abengoa Research S.L | High performance perovskite-sensitized mesoscopic solar cells |
| CN104900810A (en) * | 2015-05-15 | 2015-09-09 | 西安交通大学 | Preparation method for uniform organic-inorganic perovskite film solar cell |
| CN105655490A (en) * | 2016-04-15 | 2016-06-08 | 厦门大学 | Preparation method of perovskite solar cell |
| CN105671640A (en) * | 2015-12-29 | 2016-06-15 | 东南大学 | Layered large-size hybridized perovskite microcrystal material and preparation method thereof |
| CN105957970A (en) * | 2016-05-30 | 2016-09-21 | 哈尔滨工业大学 | Preparation method of large-size mono-crystal perovskite film |
| CN106058060A (en) * | 2016-06-16 | 2016-10-26 | 厦门大学 | Method for preparing high-quality perovskite crystal thin film |
| CN106128954A (en) * | 2016-07-21 | 2016-11-16 | 电子科技大学 | A kind of method promoting perovskite crystalline |
| US20170098514A1 (en) * | 2015-10-05 | 2017-04-06 | Ut-Battelle, Llc | Hybrid perovskite films |
| CN106938854A (en) * | 2017-03-14 | 2017-07-11 | 电子科技大学 | A kind of preparation method of large scale lead halide caesium perovskite crystal |
| WO2018000294A1 (en) * | 2016-06-30 | 2018-01-04 | The University Of Hong Kong | An organolead halide perovskite film and the method of making the same |
| US20180194786A1 (en) * | 2015-06-25 | 2018-07-12 | Global Frontier Center for Multiscale Energy | Lead halide adduct compound and perovskite element using same |
| CN108649121A (en) * | 2018-05-11 | 2018-10-12 | 南京理工大学 | The method that dynamic spin coating prepares perovskite thin film |
| CN108682745A (en) * | 2018-04-23 | 2018-10-19 | 电子科技大学 | A method of perovskite thin film is prepared based on anti-solvent dynamic spin coating |
-
2019
- 2019-01-29 CN CN201910083459.5A patent/CN109904319B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014180789A1 (en) * | 2013-05-06 | 2014-11-13 | Abengoa Research S.L | High performance perovskite-sensitized mesoscopic solar cells |
| CN104900810A (en) * | 2015-05-15 | 2015-09-09 | 西安交通大学 | Preparation method for uniform organic-inorganic perovskite film solar cell |
| US20180194786A1 (en) * | 2015-06-25 | 2018-07-12 | Global Frontier Center for Multiscale Energy | Lead halide adduct compound and perovskite element using same |
| US20170098514A1 (en) * | 2015-10-05 | 2017-04-06 | Ut-Battelle, Llc | Hybrid perovskite films |
| CN105671640A (en) * | 2015-12-29 | 2016-06-15 | 东南大学 | Layered large-size hybridized perovskite microcrystal material and preparation method thereof |
| CN105655490A (en) * | 2016-04-15 | 2016-06-08 | 厦门大学 | Preparation method of perovskite solar cell |
| CN105957970A (en) * | 2016-05-30 | 2016-09-21 | 哈尔滨工业大学 | Preparation method of large-size mono-crystal perovskite film |
| CN106058060A (en) * | 2016-06-16 | 2016-10-26 | 厦门大学 | Method for preparing high-quality perovskite crystal thin film |
| WO2018000294A1 (en) * | 2016-06-30 | 2018-01-04 | The University Of Hong Kong | An organolead halide perovskite film and the method of making the same |
| CN106128954A (en) * | 2016-07-21 | 2016-11-16 | 电子科技大学 | A kind of method promoting perovskite crystalline |
| CN106938854A (en) * | 2017-03-14 | 2017-07-11 | 电子科技大学 | A kind of preparation method of large scale lead halide caesium perovskite crystal |
| CN108682745A (en) * | 2018-04-23 | 2018-10-19 | 电子科技大学 | A method of perovskite thin film is prepared based on anti-solvent dynamic spin coating |
| CN108649121A (en) * | 2018-05-11 | 2018-10-12 | 南京理工大学 | The method that dynamic spin coating prepares perovskite thin film |
Non-Patent Citations (4)
| Title |
|---|
| WENJING HOU等: ""Dimethyl sulfoxide and bromide methylamine co-treating inducing defect healing for effective and stable perovskite solar cells"", 《MATERIALS RESEARCH BULLETIN》 * |
| YANHGONG ZHAO等: ""Sequential multi-drop coating methode for large crystallized α-(NH2)2CHPbI3 and mixed-organic-cation perovskite films for highly efficient mesoscopic perovskite solar cells"", 《JOURNAL OF POWER SOURCES》 * |
| 李欣杭等: "两步旋涂沉积条件对钙钛矿薄膜形貌和电池性能的影响研究", 《功能材料》 * |
| 王亚琼等: "溶剂蒸汽退火对钙钛矿薄膜形貌和电池性能的影响", 《太原理工大学学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710785A (en) * | 2020-06-18 | 2020-09-25 | 浙江浙能技术研究院有限公司 | Non-pinhole large-area controllable perovskite growth film forming process |
| CN111710785B (en) * | 2020-06-18 | 2022-08-16 | 浙江浙能技术研究院有限公司 | Non-pinhole large-area controllable perovskite growth film forming process |
| CN111883670A (en) * | 2020-08-03 | 2020-11-03 | 江苏集萃分子工程研究院有限公司 | Process for preparing perovskite thin film, perovskite thin film and solar cell |
| CN117729822A (en) * | 2024-02-07 | 2024-03-19 | 西安电子科技大学 | Large-area perovskite solar cell based on gas phase ion doping and preparation method thereof |
| CN117729822B (en) * | 2024-02-07 | 2024-05-14 | 西安电子科技大学 | Large-area perovskite solar cell based on gas phase ion doping and preparation method thereof |
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