CN106025072B - Based on Zn1‑xCdxPerovskite solar cell of S solid solution films and preparation method thereof - Google Patents
Based on Zn1‑xCdxPerovskite solar cell of S solid solution films and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses one kind and is based on Zn1‑xCdxS is dissolved the perovskite solar cell of film, and its structure includes basalis（1）, and in basalis（1）On set gradually：Transparency conducting layer（2）, electron transfer layer Zn1‑xCdxS layers（3）, calcium titanium ore bed（4）, hole transmission layer（5）And metal electrode layer（6）.Electron transfer layer Zn of the present invention1‑xCdxS, without high temperature preparation technology, and it can be regulated and controled by composition and keep energy band to match with perovskite absorbed layer.The methods of electron transfer layer can be by reacting radio frequency cosputtering or chemical thought obtains, and preparation technology is simple, and power consumption is few, is easy to be widely applied.
Description
Technical field
The invention belongs to green energy resource technical field, the sun being related to based on hybrid inorganic-organic perovskite material
Energy battery, more particularly to a kind of Zn1-xCdxPerovskite solar cell of S solid solution films and preparation method thereof.
Background technology
Solar-photovoltaic technology is the important component of green energy resource, in the solar cell of current various species,
Ca-Ti ore type solar cell with its high absorbance, high carrier mobility, the excellent characteristics such as cost is cheap, technique is simple, by
To the concern of numerous scientific research personnel, and it is considered as the novel photovoltaic battery of great development prospect.Ca-Ti ore type photovoltaic electric at present
The conversion efficiency in pond up to more than 20%, has reached business silion cell peer-level.
Ca-Ti ore type solar cell mainly uses two kinds of structures at present, and one kind is to be based on TiO2Plane or porous knot
Structure, another kind are to be based on PEDOT:The planar structure of the organic charge transport layer such as PSS and PCBM.Wherein, based on TiO2Structure
Perovskite battery needs the technological process of a high annealing crystallization, and annealing process power consumption is high, technique is cumbersome, and these are still restricted
The large-area applications of Ca-Ti ore type solar cell.
The content of the invention
In order to solve in background technology, Ca-Ti ore type solar cell preparation technology is complicated, charge transport layer cost is high asks
Topic, the present invention provide one kind and are based on Zn1-xCdxPerovskite solar cell of S solid solution films and preparation method thereof.The present invention's
Perovskite solar cell has the advantages of technique is simple, and electricity conversion is high, has huge industry application potential.
Specifically, the invention provides following technical scheme：
The present invention provides one kind and is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its structure includes basalis
(1), and on basalis (1) set gradually：Transparency conducting layer (2), electron transfer layer Zn1-xCdxS layers (3), calcium titanium ore bed
(4), hole transmission layer (5) and metal electrode layer (6).
The zinc cadmium sulphur solid solution film layer of the present invention is arranged on calcium titanium ore bed, as electron transfer layer, fully combines vulcanization
The characteristic of cadmium and zinc sulphide, the effect of excellent electric energy conducting can be given play to so that solar cell photoelectric of the invention turns
Change efficiency more preferably.Because simple CdS film energy gap is about 2.4eV, causes it in the light transmittance of visible ray and pay no attention to
Think；The energy gap of simple ZnS films is about 3.7eV, belongs to the semi-conducting material of broad-band gap, it is seen that and light light transmittance is high, but
Matched with perovskite conduction level bad.And Zn1-xCdxS solid solution films can have the characteristic of CdS and ZnS films concurrently, can be saturating
Optical property and obtain optimal overall photoelectric properties with perovskite absorbed layer level-density parameter etc..Zn1-xCdxS is dissolved film table
Face is smooth, mobility is high, preparation technology temperature is low, can substitute it is existing need high temperature (>450 DEG C) sintering TiO2Electric transmission
Layer, reduces the preparation energy consumption of perovskite solar cell, and the popularization and application to perovskite solar cell have great significance.
Further, the material of the basalis (1) is to meet heatproof more than 120 DEG C and smooth with good light permeability
Material.Preferably glass, polyimides or polyester film.The polyester film (PET) is with polyethylene terephthalate
For the macromolecule plastic film of raw material.Film described herein belong to those skilled in the art for polyester film product routine
Method, do not limit base thickness, it should be understood that to belong to the film general into the PET film for preparing solar cell needs is arbitrarily met
Product in thought.These materials meet the requirement of resistance to gentle light transmission, and surfacing can be used as the cell substrate of the present invention.
Preferential, the material of substrate is glass, and glass has the advantages of easily obtaining, cost is low, and stability is good.The good printing opacity is put down
Whole timber material refers to the material that light transmittance is more than 60%, and preferably greater than 80%, more preferably greater than 90%, preferably light transmittance are more than
92%.
Further, the material of the transparency conducting layer (2) is one in tin indium oxide (ITO) and fluorine doped tin oxide (FTO)
Kind or two kinds.When using two kinds of ITO and FTO as transparency conducting layer, any one method of the prior art can be used
Both are mixed with to the conductive layer (2) of composite.Have light transmittance high using tin indium oxide or fluorine doped tin oxide, resistance is low
Characteristic, more illumination can be made to reach absorbed layers, and reduce the series resistance of battery, improve solar cell power output system
Number.
Further, the electron transfer layer Zn1-xCdxThe thickness of S layers (3) is 30-500nm.
Further, the electron transfer layer Zn1-xCdxX=0.1~0.9 in S layers (3), in Zn1-xCdxThe preparation of S films
During, composition 0 can be obtained by controlling depositing operation<x<1 Zn1-xCdxS is dissolved film, and generally 60~
The Zn of good crystallinity can be obtained under 200 DEG C of depositing temperatures1-xCdxS is dissolved film, passes through the compound of zinc sulphide and cadmium sulfide
Using the property for changing electron transfer layer, the photovoltaic property of perovskite solar cell is optimized, it is most important that can be very
The producting process difficulty of good reduction solar cell.Preferably, x=0.4~0.7.Control the zinc and cadmium in electron transfer layer
Usage ratio so that when x=0.4-0.7, solar cell has more excellent photovoltaic property.
Further, the electron transfer layer Zn1-xCdxThe preparation method of S layers (3) is chemical thought (CBD), magnetic control
Sputtering sedimentation (MF), thermal evaporation, ald (ALD) and ullrasonic spraying thermally decompose any one in (USP) method.Certainly
A variety of in above method can also be combined application by those skilled in the art according to needs of production, should be considered as with
The equivalent of upper unitary system layer method.Described electron transfer layer Zn1-xCdxS layers (3) are also referred to as Zn1-xCdxS is dissolved
Film.
Further, the chemical general formula of the calcium titanium ore bed (4) is ABX3Structure.
Wherein A is methylamino (CH3NH3 +), first miaow base (HC (NH2)2 +), Cs+Cation or their three kinds of ions are with certain
Ratio mixes.
B is divalence Pb2+And Sn2+One or both of.
X is monovalence Cl-、Br-And I-In one or more.
The ABX that above-described calcium titanium ore bed composition is formed3Formula, when receiving illumination, can rapidly it absorb
Learn photon and produce electron-hole pair, simultaneously because the difference of perovskite exciton bind energy, carrier are converted into free carrier,
Finally realize photoelectric conversion.Meanwhile perovskite material has higher carrier mobility, more traditional organic semiconductor is higher by number
Times, carrier diffusion efficiency high, material property is good, long lifespan.
Further, the thickness of the calcium titanium ore bed (4) is 100-500nm.The thickness knot of currently preferred calcium titanium ore bed
Manufacturing experience selection 100-500nm thickness is closed so that solar absorption and conversion ratio keep optimal scope, reduce too
The internal resistance of positive energy battery, improves solar cell fan-out capability.
Further, the material of the hole transmission layer (5) is selected from spiro-OMeTAD, P3HT, PEDOT:PSS、CuI、
MoO3In any one.
Further, the thickness of the hole transmission layer is 30-200nm.Hole transmission layer has preferable electron, right
Electric current output in solar cell after photoelectric conversion plays an important roll, the hole transport layer material electricity that the present invention applies
Sub- cloud distribution is wide, easily loses electronics, the flowing for carrier has good impetus, with reference to calcium in solar cell
The material of titanium ore layer and the characteristic of electron transfer layer, cavitation layer thickness control are advisable in 30-200nm, and solar cell battery is defeated
Output capacity is good.
Further, the material of the metal electrode layer (6) is the one or more in gold, silver, aluminium and copper.But it is not limited to
This, can also be the good metal material of other electric conductivities, such as nickel, titanium, chromium, molybdenum.It is preferred that gold, silver, aluminium and copper are applied, electricity
Hinder low, conducting effect is good, and the output to solar cell has good help.
It is provided by the invention to be based on Zn1-xCdxS is dissolved the perovskite solar cell preparation technology of film, including following step
Suddenly：
(1) substrate covered with transparency conducting layer is taken, and cleans the substrate covered with transparency conducting layer.
(2) electron transfer layer Zn is prepared over transparent conductive layer1-xCdxS layers, i.e. Zn1-xCdxS is dissolved film, preparation method
Thermally decomposed for chemical thought (CBD), magnetron sputtering deposition (MF), thermal evaporation, ald (ALD) and ullrasonic spraying
(USP) any one in method.According to needs of production, the combination of the above method can also be used to carry out preparation work, it is real
Structural Transformation in existing layer, composite force is broken through, the problems such as preparing difficulty.
(3) in Zn1-xCdxCalcium titanium ore bed is prepared on S solid solution films, preparation method is solution spin coating, solution spraying, evaporation
Any of method.
(4) hole transmission layer is prepared on calcium titanium ore bed, preparation method is in solution spin coating, solution spraying, evaporation
It is any.
(5) metal electrode layer is prepared using evaporation on hole transmission layer.
The present invention's prepares the technique of perovskite by kinds of processes connected applications together, according to the solar-electricity of the present invention
The property in pond have selected suitable preparation technology, sufficiently organically be incorporated in each Rotating fields of Ca-Ti ore type solar cell
Together, the effect of efficient photovoltaic is realized, preparation for solar cell and is respectively provided with applied to photoelectric conversion important
Meaning.
Compared with prior art, beneficial effects of the present invention：
1. use Zn in the solar battery structure of the present invention1-xCdxS is dissolved film as electron transfer layer, compared with
TiO2Electron transfer layer is compared, and its preparation temperature is low, and technique is simple, and photoelectric properties are good, the technique for advantageously reducing battery device
Complexity.Effectively solve that existing Ca-Ti ore type solar cell preparation technology is complicated, charge transport layer cost is high asks
Topic.
2. in the solar cell of the present invention, Zn1-xCdxS solid solution films are good with calcium titanium ore bed level-density parameter, particularly pass through
It is suitable to cross the proportionate relationship of zinc atom and cadmium atom in the zinc-cadmium sulfide optimized and revised, battery conversion efficiency can be effectively improved,
The photovoltaic energy conversion efficiency of Ca-Ti ore type solar cell prepared by the present invention reaches as high as 12.22%.
3. the conductive layer of the Ca-Ti ore type solar cell design of the present invention, electron transfer layer, calcium titanium ore bed, hole transport
The thickness of layer and electrode layer is suitable, coordinates cooperative effect good, and serving good collaboration in solar cell photovoltaic effect increases
Use is pretended, service life and product performance is more prominent compared with like product.
Brief description of the drawings：
Fig. 1 is the structural representation of the solar cell of the present invention.
Fig. 2 is Zn prepared by embodiment 11-xCdxThe surface topography photo of S film samples.
Fig. 3 is the Zn prepared by embodiment 11-xCdxThe transmittance curve that S film samples measure.
Fig. 4 is the i-v curve that the sample prepared by embodiment 1 measures.
Fig. 5 is the i-v curve that the sample prepared by embodiment 2 measures.
Fig. 6 is the i-v curve that the sample prepared by embodiment 3 measures.
Fig. 7 is the i-v curve that the sample prepared by embodiment 4 measures.
Fig. 8 is the i-v curve that the sample prepared by comparative example 1 measures.
Fig. 9 is the i-v curve that the sample prepared by comparative example 2 measures.
Embodiment
Part professional term is explained as follows：
spiro-OMeTAD：2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino]-fluorenes of 9,9'- spiral shells two, or
2,2',7,7'-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene.
P3HT：Poly- (3- hexyl thiophenes -2,5- diyl), or Poly (3-hexylthiophene-2,5-diyl)
PEDOT:PSS, poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid), or poly (3,4-
ethylenedioxythiophene):poly(styrenesulfonate)
The title of part-structure level can use technical term title in the present invention, can also use popular technology art
Language, those skilled in the art can restructure the call of layer according to Conventional wisdom, have no effect on the reality of technical solution of the present invention
It is existing.Now it is exemplified below, basalis is also substrate；Transparency conducting layer is also conductive layer；Electron transfer layer Zn1-xCdxS layers (3) are also named
Zn1-xCdxS electron transfer layers, electron transfer layer, Zn1-xCdxS is dissolved film；Hole transmission layer is also transport layer；Metal electrode
Layer is also electrode, metal electrode, electrode layer.What difference occurred in technical term statement in part in the present invention can use described above
Uniformity understanding is carried out, has no effect on the realization of technical scheme in itself.
Further, step (1) cleaning process is cleaned using organic solvent, water etc. in preparation method of the invention, can
To clean once, can also clean several times.It can be cleaned, can also be used or not single solvent when being cleaned multiple times
Same solvent is cleaned.Preferably, cleaned in cleaning process using ultrasonic wave added.Above-mentioned organic solvent can be selected from following molten
One or more in agent：Acetone, butanone, methanol, ethanol, propyl alcohol, isopropanol, water, benzene,toluene,xylene, methyl acetate,
Ethyl acetate, propyl acetate, ether, petroleum ether, acetonitrile, pyridine, tetrahydrofuran, dioxane, rosin, carbon tetrachloride, chlorine
Imitative, dichloromethane, gasoline, hexane, hexamethylene.
Further, after the completion of step (1) is using solvent cleaning, dries or inert gas dries up.The inert gas is
The gas that the discord substrate known reacts, such as nitrogen, argon gas, are preferably dried up using nitrogen.
Further, after step (1) sample dries or dried up, sample is handled with one or both of ultraviolet or ozone,
Realize the activation of sample performance.Above-mentioned ultraviolet and/or ozone processing is referred to as to activate.Treated sample surfaces can carry
It is high, it is easier to reference to upper other functional layer structure layers.
Certainly, substrate sample of the invention or the substrate sample with part functional layer, can also without cleaning, it is living
Change, appropriate processing is selected according to the actual adhesive ability of sample surfaces.
Further, it is used to prepare Zn in preparation method step (2) of the present invention1-xCdxS is dissolved the mixing preformed solution of film
Include appropriate cadmium ion, zinc ion and element sulphur.Preferably, wherein the atomic ratio of cadmium and zinc is 0.1-0.9：0.9-0.1.
It is furthermore preferred that both ratios are 0.4~0.7：0.6-0.3.
Further, element sulphur exists in the form of thiocarbamide in above-mentioned mixing preformed solution.
Further, above-mentioned mixing preformed solution by caddy, zinc chloride, thiocarbamide, sodium tartrate, sodium citrate prepare and
Into.It can be appreciated that mixing preformed solution contains the ion after corresponding composition dissolving.
Further, 0.001-0.01mol/L caddy, 0.001-0.05mol are included in above-mentioned mixing preformed solution
Mol/L zinc chloride, 0.01-0.05mol/L thiocarbamide, 0.1-0.3mol/L sodium tartrates, 0.1-0.3mol/L citric acid
Sodium.
Further, calcium titanium ore bed uses one kind in solution spin coating, solution spraying, evaporation according to prior art, will
spiro-OMeTAD、P3HT、PEDOT:PSS、CuI、MoO3In one or more be mixed with to form corresponding calcium titanium ore bed.
The foregoing invention content of the present invention is described in further detail with reference to embodiment.But it should not incite somebody to action
This scope for being interpreted as the above-mentioned theme of the present invention is only limitted to following embodiments.The above-mentioned technological thought situation of the present invention is not being departed from
Under, according to ordinary skill knowledge and customary means, various replacements and change are made, the scope of the present invention all should be included in
It is interior.
Embodiment 1
Based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its structure is as shown in figure 1, wherein substrate (1) is
Glass, transparency conducting layer (2) are indium tin oxide films, and electron transfer layer (3) is Zn1-xCdxS is dissolved film, calcium titanium ore bed (4)
For CH3NH3PbI3, hole transmission layer (5) is organic material spiro-OMeTAD, and metal electrode (6) is gold.
Preparation method：
A) substrate of glass that will be covered with tin indium oxide is washed 30 minutes with detergent, acetone, EtOH Sonicate successively, uses nitrogen
Air gun dries up, and carries out UV-ozone processing 5min.
b)Zn1-xCdxThe preparation of S electron transfer layers：
Prepared using the method for chemical thought.Chemical deposition solution is prepared at normal temperatures, is included in solution
0.005mol/L caddy, 0.02mol mol/L zinc chloride, 0.025mol/L thiocarbamide, 0.1mol/L sodium tartrates,
0.1mol/L sodium citrate.Sample after a) handling is put into deposition solution, and heating water bath solution deposits to 80 DEG C
60min。
The composition of (XRF) sample is analyzed using X-ray fluorescence spectra, the result of acquisition is that Zn/Cd atomic ratios are 0.68/
0.32.
The Zn of acquisition1-xCdxThe surface scan electromicroscopic photograph of S electron transfer layers is as shown in Figure 2.
Zn is detected using ultraviolet-uisible spectrophotometer1-xCdxThe visible light transmissivity of S layers, test wavelength scope 200~
900nm, as a result as shown in Figure 3.
C) preparation of calcium titanium ore bed
Prepared using the method for solution spin coating.By 1.35mmol CH3NH3I and 1.35mmol PbI2Powder is dissolved into 1mL
Into dimethylformamide (DMF) solution, then 50 μ L are taken toward 100 μ L dimethyl sulfoxide (DMSO)s (DMSO) solution are added in solution again
The solution drops in Zn1-xCdxS electric transmission layer surfaces, make its sufficient drawout, then rotary sample, then exists sample
Anneal 10min at 100 DEG C, the film thickness about 400nm of acquisition.
D) preparation of hole transmission layer
Prepared using the method for solution spin coating.70mg spiro-OMeTAD, 9.2mg tBP, 7mg Li-TFSI is molten
Among 1ml chlorobenzene, take the 50 μ L solution to drop in calcium titanium ore bed surface, make its sufficient drawout, then under 4000rpm
Rotary sample 30s, that is, obtain the thick hole transmission layers of about 300nm.
E) preparation of metal electrode
Gold electrode, thickness of electrode about 80nm are prepared using the method for thermal evaporation in hole transport layer surface.
Current-voltage scanning analysis are carried out to battery device using Keithley2400 digital sourcemeters, battery is placed in
AM1.5G, intensity of illumination 1000W/m2AAA levels solar simulator under the conditions of, the i-v curve result of acquisition is such as
Shown in Fig. 4, the photovoltaic parameter of extraction is open-circuit voltage 1.02V, short circuit current 15.9mA/cm2, fill factor, curve factor 0.65, photoelectricity energy
Measure conversion efficiency 10.62%.
Embodiment 2
Based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and structure is：Substrate (1) is poly terephthalic acid second
Diol ester (abbreviation PET), transparency conducting layer (2) are indium tin oxide films, and (3) are Zn1-xCdxS electron transfer layers, calcium titanium ore bed
(4) it is CH3NH3PbI3, hole transmission layer (5) is organic material spiro-OMeTAD, and metal electrode (6) is gold.
Preparation method：
A) PET base that will be covered with tin indium oxide is cleaned 5 minutes with deionized water, ethanol successively, is dried up with nitrogen gun；
b)Zn1-xCdxThe preparation of S electron transfer layers：
Prepared using the method for chemical thought.Chemical deposition solution is prepared at normal temperatures, is included in solution
0.005mol/L caddy, 0.01mol mol/L zinc chloride, 0.025mol/L thiocarbamide, 0.1mol/L sodium tartrates,
0.1mol/L sodium citrate.Sample after a) handling is put into deposition solution, and heating water bath solution deposits to 75 DEG C
60min。
The composition of (XRF) sample is analyzed using X-ray fluorescence spectra, the result of acquisition is that Zn/Cd atomic ratios are 0.57/
0.43。
Other step preparation methods are the same as embodiment 1.
Current Voltage test is carried out to the battery device that obtains in aforementioned manners, i-v curve result as shown in figure 5,
The photovoltaic parameter of extraction is open-circuit voltage 1.01V, short circuit current 14.1mA/cm2, fill factor, curve factor 0.49, photovoltaic energy conversion effect
Rate 7.01%.
Embodiment 3
Based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and structure is：Substrate (1) is glass, electrically conducting transparent
Layer (2) is indium tin oxide films, and (3) are Zn1-xCdxS electron transfer layers, calcium titanium ore bed (4) are CH3NH3PbI3, hole transport
Layer (5) is organic material spiro-OMeTAD, and metal electrode (6) is gold.
Preparation method：
b)Zn1-xCdxThe preparation of S electron transfer layers：
Prepared using the method for chemical thought.Chemical deposition solution is prepared at normal temperatures, is included in solution
0.005mol/L caddy, 0.01mol mol/L zinc chloride, 0.025mol/L thiocarbamide, 0.1mol/L sodium tartrates,
0.1mol/L sodium citrate.Sample after a) handling is put into deposition solution, and heating water bath solution deposits to 75 DEG C
60min。
Other step preparation methods are the same as embodiment 1.
Current Voltage test is carried out to the battery device that obtains in aforementioned manners, i-v curve result as shown in fig. 6,
The photovoltaic parameter of extraction is open-circuit voltage 1.06V, short circuit current 18.1mA/cm2, fill factor, curve factor 0.64, photovoltaic energy conversion effect
Rate 12.22%.
Embodiment 4
Based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and structure is：Substrate (1) is glass, electrically conducting transparent
Layer (2) is indium tin oxide films, and (3) are Zn1-xCdxS electron transfer layers, calcium titanium ore bed (4) are CH3NH3PbI3, hole transport
Layer (5) is organic material P3HT, and metal electrode (6) is gold.
Preparation method：
D) preparation of hole transmission layer：
Prepared using the method for solution spin coating.20mg P3HT materials are dissolved among 1ml chlorobenzene, take the 50 μ L solution
Calcium titanium ore bed surface is dropped in, makes its sufficient drawout, then rotary sample 30s under 2000rpm, that is, obtains P3HT hole transports
Layer.
Other step preparation methods are the same as embodiment 3.
Current Voltage test is carried out to the battery device that obtains in aforementioned manners, i-v curve result as shown in fig. 7,
The photovoltaic parameter of extraction is open-circuit voltage 0.94V, short circuit current 16.0mA/cm2, fill factor, curve factor 0.54, photovoltaic energy conversion effect
Rate 8.14%.
Comparative example 1
Based on the perovskite solar cell of pure ZnS films, structure is：Substrate (1) is glass, and transparency conducting layer (2) is
Indium tin oxide films, (3) are ZnS electron transfer layers, and calcium titanium ore bed (4) is CH3NH3PbI3, hole transmission layer (5) is organic material
Expect spiro-OMeTAD, metal electrode (6) is gold.
Preparation method：
B) preparation of ZnS electron transfer layers：
Prepared using the method for chemical thought.Chemical deposition solution is prepared at normal temperatures, is included in solution
0.025mol/L zinc acetate zinc, 0.03mol/L thiocarbamide, 0.072mol/L sodium tartrates, 0.02mol/L sodium citrate.
Sample after a) handling is put into deposition solution, and heating water bath solution deposits 60min to 80 DEG C.
Other step preparation methods are the same as embodiment 1.
Current Voltage test is carried out to the battery device that obtains in aforementioned manners, i-v curve result as shown in figure 8,
The photovoltaic parameter of extraction is open-circuit voltage 0.98V, short circuit current 2.3mA/cm2, fill factor, curve factor 0.44, photovoltaic energy conversion efficiency
0.98%.
Comparative example 2
Based on the perovskite solar cell of low temperature TiO2 films, structure is：Substrate (1) is glass, transparency conducting layer (2)
For indium tin oxide films, (3) are TiO2 electron transfer layers, and calcium titanium ore bed (4) is CH3NH3PbI3, hole transmission layer (5) is to have
Machine material spiro-OMeTAD, metal electrode (6) are gold.
Preparation method：
B) preparation of TiO2 electron transfer layers：
Prepared using the method for solution spin coating.0.2mmol isopropyl titanate materials are dissolved in 1ml aqueous isopropanol, taken
The 50 μ L solution are dropped on transparency conducting layer (2), then rotary sample 30s under 4000rpm, subsequent sample condition at 100 DEG C
Lower dry 20min, that is, obtain TiO2 electron transfer layers.
Other step preparation methods are the same as embodiment 1.
Current Voltage test is carried out to the battery device that obtains in aforementioned manners, i-v curve result as shown in figure 9,
The photovoltaic parameter of extraction is open-circuit voltage 0.79V, short circuit current 6.2mA/cm2, fill factor, curve factor 0.44, photovoltaic energy conversion efficiency
2.18%.
Claims (11)
1. one kind is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its structure includes basalis（1）, and in substrate
Layer（1）On set gradually：Transparency conducting layer（2）, electron transfer layer Zn1-xCdxS layers（3）, calcium titanium ore bed（4）, hole transport
Layer（5）And metal electrode layer（6）.
2. one kind according to claim 1 is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its feature exists
In：The basalis（1）Material be to meet heatproof more than 120 DEG C and the planarizing material with good light permeability.
3. one kind according to claim 1 is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its feature exists
In：The transparency conducting layer（2）Material be one or both of tin indium oxide and fluorine doped tin oxide.
4. one kind according to claim 1 is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its feature exists
In：The electron transfer layer Zn1-xCd xS layers（3）Thickness be 30-500nm.
5. one kind according to claim 1 is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its feature exists
In：The electron transfer layer Zn1-xCdxS layers（3）In x=0.1 ~ 0.9.
6. one kind according to claim 5 is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its feature exists
In：The electron transfer layer Zn1-xCdxS layers（3）In x=0.4 ~ 0.7.
7. one kind according to claim 1 is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its feature exists
In：The calcium titanium ore bed（4）Chemical general formula be ABX3Structure；
Wherein A is methylamino（CH3NH3 +）, first miaow base（HC(NH2)2 +）, Cs+Cation or their three kinds of ions are mixed with certain proportion
Conjunction forms；
B is divalence Pb2+And Sn2+One or both of；
X is monovalence Cl-、Br-And I-In one or more；
The calcium titanium ore bed（4）Thickness be 100-500nm.
8. one kind according to claim 1 is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its feature exists
In：The hole transmission layer（5）Material be selected from spiro-OMeTAD, P3HT, PEDOT:PSS、CuI、MoO3In it is any one
Kind.
9. one kind according to claim 1 is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its feature exists
In：The thickness of the hole transmission layer is 30-200nm.
10. one kind according to claim 1 is based on Zn1-xCdxS is dissolved the perovskite solar cell of film, and its feature exists
In：The metal electrode layer（6）Material be gold, silver, aluminium and copper in one or more.
11. one kind is based on Zn1-xCdxS is dissolved the perovskite solar cell preparation technology of film, comprises the following steps：
(1) substrate covered with transparency conducting layer is taken, and cleans the substrate covered with transparency conducting layer；
(2) electron transfer layer Zn is prepared over transparent conductive layer1-xCdxS layers, i.e. Zn1-xCdxS is dissolved film, and preparation method is change
Learn any one in water-bath deposition, magnetron sputtering deposition, thermal evaporation, ald and ultrasonic spray pyrolysis；
(3) in Zn1-xCdxCalcium titanium ore bed is prepared on S solid solution films, preparation method is in solution spin coating, solution spraying, evaporation
It is any；
(4) hole transmission layer is prepared on calcium titanium ore bed, preparation method is any in solution spin coating, solution spraying, evaporation
Kind；
(5) metal electrode layer is prepared using evaporation on hole transmission layer.
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| CN104037324A (en) * | 2014-06-24 | 2014-09-10 | 浙江大学 | Perovskite hybrid solar cell based on cadmium sulfide nanoarray |
| CN105591030A (en) * | 2016-03-11 | 2016-05-18 | 华中科技大学 | Semitransparent perovskite solar cell and preparation method thereof |
| CN105609634A (en) * | 2015-12-22 | 2016-05-25 | 成都新柯力化工科技有限公司 | Mesoporous nano quantum dot perovskite solar cell and preparation method thereof |
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| CN105609634A (en) * | 2015-12-22 | 2016-05-25 | 成都新柯力化工科技有限公司 | Mesoporous nano quantum dot perovskite solar cell and preparation method thereof |
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