CN106981572A - A kind of CeO for preparing surface modification2The method and product of nano material and application - Google Patents
A kind of CeO for preparing surface modification2The method and product of nano material and application Download PDFInfo
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- CN106981572A CN106981572A CN201710106269.1A CN201710106269A CN106981572A CN 106981572 A CN106981572 A CN 106981572A CN 201710106269 A CN201710106269 A CN 201710106269A CN 106981572 A CN106981572 A CN 106981572A
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Abstract
The invention discloses a kind of CeO for preparing surface modification2The method and product of nano material and application, belong to perovskite area of solar cell.Its method includes：S1 prepares the CeO of oleic acid parcel2Nano particle；The CeO that S2 wraps up oleic acid2Nano particle is dispersed in toluene solution；The CeO that S3 is wrapped up to oleic acid2Toluene solution in add basic solvent, carry out eccentric cleaning after the completion of desorption reaction enclosure, desorption, obtain the CeO of milk yellow2Particle；S4 utilizes CeO of the acetylacetone,2,4-pentanedione to milk yellow2Particle is modified；CeO modified to acetylacetone,2,4-pentanedione S52Solution carries out vacuum distillation, to remove the acetylacetone,2,4-pentanedione solvent of surplus.Present invention also offers the CeO being modified using acetylacetone,2,4-pentanedione2The method that nano material prepares different structure perovskite solar cell.The inventive method technique is simple, the modification CeO of preparation2Nano ZnO is excellent, can apply in perovskite solar cell.
Description
Technical field
The invention belongs to perovskite technical field of solar batteries, and in particular to prepare the CeO that surface is modified2Nano material
And the method for associated solar battery.
Background technology
Coal, oil, natural gas etc. are non-renewable energy resources, and it always has depleted one day.Continue to keep economical
Stable rapid growth, we will face the energy problem of sternness.Solar energy as earth energy main source, rich reserves,
Cleaning is renewable.National governments will all study the solar cell based on photoelectric conversion, especially cheap solar cell skill
Art, is also the important trend of new energy technology development as the important content of National Sustainable Development Strategies.
In recent years, perovskite solar cell was quickly grown, by the extensive concern of working energy person.Its highest photoelectricity
Transformation efficiency is more than 22%, and close to the efficiency of tradition silion cell, and raw material sources are extensive, preparation technology is simple so that calcium titanium
Ore deposit solar cell turns into a kind of novel green photovoltaic industry of great competitiveness.
Perovskite solar cell be using perovskite material as solar cell in light absorbent a class battery, calcium
Titanium ore material is stimulated generation electron-hole pair after sunshine irradiation, electronics is collected by electron transport material is transferred in follow
Ring anode, via outer circulation to interior circulation negative electrode, so as to be catalyzed the hole mobile material that hole has been collected in reduction, goes into complete return
Road.Transmission of the electron-hole pair in battery device is restricted by the electric conductivity and carrier mobility of electron transfer layer, its
Secondary, because titanium ore material is easily degenerated in water oxygen environment in itself, its stability is wrapped in its both sides boundary layer stability
Restriction, therefore, it is the key for developing perovskite solar cell to develop the inorganic charge transport layers with efficient stable.
At present, organic charge transport layer has efficient electric conductivity, but its carrier mobility is low, need to carry out extra
Ion doping, and its poor chemical stability, degenerate easily in water oxygen environment, in addition, its molecular structure is complicated, purifying technique is numerous
It is trivial, yield poorly, use cost it is high.Using sulphur cyanogen is cuprous and cuprous iodide as representative unformed inorganic charge transmission material, due to
The problems such as its crystallinity is not high, device efficiency is low, hysteresis phenomenon is serious, also limit it and is widely applied.With zinc oxide and oxygen
Change the inorganic charge transmission material that tin is representative, due to its intrinsic good dispersion, prevent it from being widely used in no electromechanics
Lotus transmission material, and be difficult to disperse in simple non-polar solven, even and if a small amount of polar solvent still has to calcium titanium ore bed
Corrosion function.
Cerium oxide has a high carrier mobility of inorganic oxide, good electric conductivity and mechanical performance, and it
Preparation method is simple, can greatly reduce material and prepare cost.In conventional cerium oxide preparation system, the oleic acid of cerium oxide is wrapped up
The hydro-thermal reaction of cerium oxide can be slowed down, synthesize monodispersed cerium oxide nanoparticles.But, it is wrapped in cerium oxide nano
The oleic acid on grain surface is long chain organic molecules, poorly conductive, and extremely difficult is eliminated.Oleic acid is by carboxyl strong adsorption in cerium oxide
Surface, can thoroughly desorption in alkaline solution.But, after desorption, cerium oxide nanoparticles are in various common solvents
Middle decentralization is very poor, is not suitable for directly preparing charge transport layer.
Therefore, develop cheap, applicability extensively, efficient stable and polarity and non-polar solven can be applied to simultaneously
Inorganic charge transmission material has great importance, while also very challenging property.
The content of the invention
For electron transfer layer carrier mobility in the prior art is low, poor chemical stability, easily moved back in water oxygen environment
The problem of change, cost great number, the present invention provides the high dispersive CeO that a kind of surface is modified2The preparation method and product of nano material
And application, the inventive method technique is simple, the CeO of preparation2Nano material conductance is high, carrier mobility is high, chemically stable
The good, energy level of property is matched with perovskite light absorbent, it is ensured that the photoelectric transformation efficiency of battery device, and device can be also greatly improved
Long-time stability.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of CeO for preparing surface modification2Nanometer
The method of material, it comprises the following steps：
S1：Prepare the CeO of oleic acid parcel2Nano particle,
S2：The CeO for the oleic acid parcel that step S1 is obtained2Nano particle is dispersed in by no more than 5 grams per milliliter mass concentrations
Non-polar solution, non-polar solution is preferably toluene, benzene, n-hexane, carbon tetrachloride or dichloromethane, obtains oleic acid parcel
CeO2Non-polar solution,
S3：To the CeO of the step S2 oleic acid parcels obtained2Non-polar solution in add basic solvent, regulation pH value to 6
~14, to carry out adding alcohols solvent progress eccentric cleaning after the completion of desorption reaction enclosure, desorption, obtain the CeO of milk yellow2
Particle,
S4：By the CeO of the step S3 milk yellows obtained2Particle adds levulinic by the mass concentration of no more than 5 grams per milliliters
In ketone, alternately stirring and ultrasonication continues 0.5~48 hour, and finally filtering obtains the modified CeO of acetylacetone,2,4-pentanedione2
Solution,
S5：The CeO modified to the acetylacetone,2,4-pentanedione of step S4 acquisitions2Solution carries out vacuum distillation, to remove the second of surplus
Acyl acetone solvent, obtains the modified CeO of acetylacetone,2,4-pentanedione2Nano material.
Further, basic solvent described in step S3 is selected from TBAH and TMAH.
According to the second aspect of the invention, a kind of CeO being modified using the surface that as above method is prepared also is provided2
Nano material.
According to the third aspect of the invention, a kind of CeO being modified using surface as described above is also provided2Nano material system
The method of standby formal planar structure solar cell, it comprises the following steps：
(1) preparation of electron transfer layer：At room temperature, in the conductive surface spin coating nano-ink of indium doped tin oxide electro-conductive glass
Water, dries at a temperature of indium doped tin oxide electro-conductive glass electric conductivity is not destroyed, is not more than 100nm's to prepare thickness
Dense oxide cerium electron transfer layer,
The nanometer ink refers to the CeO that surface is modified2Nano material is dispersed in polar solvent or nonpolar molten
The solution formed in agent, wherein, the CeO that the surface is modified2The mass concentration of nano material is not more than 3 grams per milliliters；
(2) preparation of perovskite light-absorption layer：Perovskite thin film is ABX3, A=methylamine ions (MA, CH3NH3 +), cesium ion
(Cs+) or both mixture, B=lead ions (Pb2+), stannous ion (Sn2+) or both mixture, X=chlorions (Cl-), bromine
Ion (Br-), iodide ion (I-) or both mixture.Wherein three's ionic radius meets certain tolerance factor and structure factor.
The perovskite precursor solution configured is revolved on the dense oxide cerium electron transfer layer that Tu is obtained in step (1), Ran Hou
70~150 DEG C are made annealing treatment, and obtain perovskite light-absorption layer；
(3) preparation of hole transmission layer：(can be Spiro-MeOTAD, CuI, CuSCN by the hole transport solution configured
Deng hole mobile material), it is spin-coated on step (2) and obtains on described perovskite light-absorption layer, forms 10nm~1000nm holes and pass
Defeated layer.So far, the intermediate semi-finished products with electron transfer layer, perovskite light-absorption layer and hole transmission layer are obtained；
(4) preparation of the metal to electrode：The intermediate semi-finished products that step (3) is obtained are inserted in vacuum evaporation coating film device,
The gold electrode that a layer thickness is 50nm~300nm is deposited on hole transmission layer.
According to the fourth aspect of the invention, a kind of CeO being modified using surface as described above is also provided2Nano material system
The method of the trans planar structure solar cell of standby single layer electronic transport layer, it comprises the following steps：
(1) preparation of hole transmission layer：At 300 DEG C~600 DEG C, by for example nickel source solution configured, pass through thermal jet
The method of painting deposits one layer in fluorine doped tin oxide electro-conductive glass conductive surface and is not more than the thick nickel magnesia lithium hole transmission layers of 50nm；
(2) preparation of perovskite light-absorption layer：The perovskite precursor solution configured is revolved into Tu nickel magnesia in step (1)
On lithium hole transmission layer, then in 70~150 DEG C of annealings, perovskite light-absorption layer is obtained；
(3) preparation of electron transfer layer：At room temperature, the perovskite extinction layer surface spin coating nanometer ink in step (2),
Dried at a temperature of not destroying perovskite light-absorption layer performance, to obtain the dense oxide cerium electric transmission that thickness is not more than 1000nm
Layer,
The nanometer ink refers to the CeO that surface is modified2Nano material is dispersed in polar solvent or nonpolar molten
The solution formed in agent, wherein, the CeO that the surface is modified2The mass concentration of nano material is not more than 3 grams per milliliters, so far obtains
Obtain the intermediate semi-finished products with electron transfer layer, perovskite light-absorption layer and hole transmission layer；
(4) preparation of the metal to electrode：The intermediate semi-finished products that step (3) is obtained are inserted in vacuum evaporation coating film device,
Aluminium electrode or silver electrode that a layer thickness is 50nm~300nm is deposited.
Further, a kind of CeO being modified using surface as described above is also provided2It is anti-that nano material prepares double-layer electric sublayer
The method of formula planar structure solar cell, it comprises the following steps：
(1) preparation of hole transmission layer：At 300 DEG C~600 DEG C, by the nickel source solution configured, pass through thermal spraying
Method deposits one layer in fluorine doped tin oxide electro-conductive glass conductive surface and is not more than the thick nickel magnesia lithium hole transmission layers of 50nm；
(2) preparation of perovskite light-absorption layer：The perovskite precursor solution configured is revolved into Tu nickel magnesia in step (1)
On lithium hole transmission layer, then in 70 DEG C~150 DEG C annealings, perovskite light-absorption layer is obtained；
The preparation of (3) first electron transfer layers：At room temperature, the perovskite extinction layer surface spin coating Organic Electricity in step (2)
Sub- transport layer solution or inorganic electronic transport layer solution, are dried at a temperature of perovskite light-absorption layer performance is not destroyed, to obtain
The first electron transfer layer that thickness is not more than 1000nm is obtained,
(4) preparation of second layer electron transfer layer：At room temperature, the first electric transmission layer surface spin coating is received in step (3)
Meter Mo Shui, is dried at a temperature of perovskite light-absorption layer performance is not destroyed, to obtain the dense oxide that thickness is not more than 1000nm
Cerium electron transfer layer,
The nanometer ink refers to the CeO that surface is modified2Nano material is dispersed in polar solvent or nonpolar molten
The solution formed in agent, wherein, the CeO that the surface is modified2The mass concentration of nano material is not more than 3 grams per milliliters, so far obtains
Obtain the intermediate semi-finished products with electron transfer layer, perovskite light-absorption layer and hole transmission layer；
The electric conductivity of first electron transfer layer is better than the second layer electron transfer layer；
(5) preparation of the metal to electrode：The intermediate semi-finished products that step (4) is obtained are inserted in vacuum evaporation coating film device,
Aluminium electrode or silver electrode that a layer thickness is 50nm~300nm is deposited.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect：
In the inventive method, CeO is wrapped up or adsorbed using bipolarity organic molecule2Nano particle, so that the CeO2Nanometer
Material can be simultaneously dispersed in polar solvent and non-polar solven, then can using cerium oxide high carrier mobility, good
Good electric conductivity and mechanical performance and the easy advantage of preparation method, also overcoming oleic acid parcel causes CeO2Nano particle
Conductance is poor, treatment temperature is high and damages the shortcoming of perovskite light-absorption layer.
The modified CeO of the present invention2Nano material can be simultaneously dispersed in polar solvent and non-polar solven, may be used also
Reduce erosion of the solvent to successive functional layers in different structure battery.
Modified to cerium oxide nanoparticles with acetylacetone,2,4-pentanedione in the present invention, its strand is short, does not hinder electric charge and load
Transmission of stream between nano particle.The high dispersive material that this surface is modified, prepares with low cost, photovoltaic property well,
Charming performance and potential application value is presented in perovskite solar cell.
The CeO being modified using the inventive method2Nano material material can be effectively improved the stability of battery device, subtract
Lack battery device material cost, be conducive to the application of the extensive industrialization of the type battery.
Brief description of the drawings
Fig. 1 is non-modified CeO2The Flied emission transmission electron microscope figure of nano particle；
Fig. 2 (a), Fig. 2 (b) are non-modified CeO2The high resolution transmission electron microscopy of nano particle and constituency are spread out
Penetrate figure；
Fig. 3 is non-modified CeO2The XRD diffraction patterns of nano particle；
CeO in Fig. 4 embodiment of the present invention2The modification theory figure of nano particle；
Fig. 5 is the CeO of different phase in the Process of Surface Modification of embodiment one2The infrared spectrum comparison diagram of nano particle, bag
Include the oxidation of the oleic acid parcel after oleic acid (Oleic acid) solvent, acetylacetone,2,4-pentanedione (Acetylacetine) solvent, ethanol cleaning
The modified cerium oxide of cerium oxide (Desorption), acetylacetone,2,4-pentanedione after cerium (Rinsed), basic solvent desorption
(Redispersion) infrared spectrum comparison diagram, the CeO of each different phase is distinguished according to the English word in figure2Nanometer
Grain；
Fig. 6 is the CeO of different phase in the Process of Surface Modification of embodiment two2The optics that nano particle disperses in a solvent shines
Piece；
Fig. 7 is the modified CeO of embodiment two2The front scan electron microscope picture of film prepared by nano particle；
Fig. 8 is the modified CeO of embodiment two2The atomic force microscopy diagram of film prepared by nano particle；
Fig. 9 is the modified CeO of embodiment two2The transmission spectrogram of film prepared by nano particle；
Figure 10 is the modified CeO of embodiment two2Nano particle prepares the fluorescence spectra of film；Wherein, emission peak
(Fluorescence peak), at 440 nanometers, 470 nanometers are xenon lamp peak (Xenon lamp peak), and 630 nanometers are drawing
Man Feng (Raman peak)；
Figure 11 is the modified CeO of embodiment two2Nano particle prepare film ultraviolet photoelectron spectroscopy (UPS,
Ultroviolet Photoelectron Spectrometer) figure；
Figure 12 is the modified CeO of embodiment two2Nano particle prepares energy gap (Bandgap) figure of film；
Figure 13 is the modified CeO of embodiment two2X-ray photoelectron spectroscopy (XPS, the X-ray of film prepared by nano particle
Photoelectron Spectrometer) figure；
Figure 14 is the modified CeO of embodiment two2The high-resolution X-ray photoelectricity of the Ce elements of film prepared by nano particle
Sub- spectrogram；
Figure 15 is the modified CeO of embodiment two2The high-resolution X-ray photoelectricity of the oxygen element of film prepared by nano particle
Sub- spectrogram；
Figure 16 is the battery device structure chart of the formal plane perovskite solar cell of embodiment three, wherein, 1 is indium-doped oxygen
Change tin (ITO, Indium doped tin oxide) electro-conductive glass, 2 be modified cerium oxide electron transfer layer, and 3 be calcium titanium
Ore deposit light-absorption layer, 4 be hole transmission layer, and 5 be gold electrode；
Figure 17 is photovoltaic of the formal plane perovskite solar cell device of embodiment three under a standard sun light intensity
Curve；
Figure 18 is the battery device structure of the battery device of the trans single layer electronic transport layer plane battery structure of example IV
Figure.Wherein, 6 be fluorine doped tin oxide (FTO, Fluorine doped tin oxide) electro-conductive glass, and 7 be that nickel magnesia lithium hole is passed
Defeated layer, 3 be perovskite light-absorption layer, and 8 be the cerium oxide electron transfer layer of oleic acid parcel, and 9 be silver electrode；
Figure 19 is the battery device of the trans single layer electronic transport layer plane battery structure of example IV in a standard sun
Photovoltaic curve under light intensity；
Figure 20 is the battery device structure of the battery device of the trans single layer electronic transport layer plane battery structure of embodiment five
Figure, wherein, 6 be fluorine doped tin oxide electro-conductive glass, and 7 be nickel magnesia lithium hole transmission layer, and 3 be perovskite light-absorption layer, and 2 be modified
Cerium oxide electron transfer layer, 9 be silver electrode；
Figure 21 is the battery device of the trans single layer electronic transport layer plane battery structure of embodiment five in a standard sun
Photovoltaic curve under light intensity；
Figure 22 is the battery device structure of the battery device of the trans single layer electronic transport layer plane battery structure of embodiment six
Figure.Wherein, 6 be fluorine doped tin oxide electro-conductive glass, and 7 be nickel magnesia lithium hole transmission layer, and 3 be perovskite light-absorption layer, and 10 be organic
Electron transfer layer, 9 be silver electrode；
Figure 23 is the battery device of the trans single layer electronic transport layer plane battery structure of embodiment six in a standard sun
Photovoltaic curve under light intensity；
Figure 24 is the structure chart of the battery device of the trans two-layer electronic transport layer plane battery structure of embodiment seven.Wherein, 6
It is fluorine doped tin oxide electro-conductive glass, 7 be nickel magnesia lithium hole transmission layer, and 3 be perovskite light-absorption layer, and 10 be organic electron transport layer
(namely first electron transfer layer), 2 be modified cerium oxide as upper strata electron transfer layer (namely second electron transfer layer),
9 be silver electrode；
Figure 25 is the battery device of the trans two-layer electronic transport layer plane battery structure of embodiment seven in a standard sun
Photovoltaic curve under light intensity；
Figure 26 is the external quantum efficiency figure of the battery device of the trans two-layer electronic transport layer plane battery structure of embodiment seven；
Figure 27 is the steady-state current output of the battery device of the trans two-layer electronic transport layer plane battery structure of embodiment seven
Figure；
Figure 28 is the battery device of the trans two-layer electronic transport layer plane battery structure of embodiment seven under air atmosphere
Long term stability tests figure.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
Fig. 1 is non-modified CeO2The Flied emission transmission electron microscope figure of nano particle；Fig. 2 (a), Fig. 2 (b) are not
Modified CeO2The high resolution transmission electron microscopy and selected diffraction figure of nano particle；Fig. 3 is non-modified CeO2Receive
The XRD diffraction patterns of rice grain, three figure more than, modified monodispersed CeO used2The self assembly of nano particle crystal formation is arranged
Row, main exposure interplanar distance is 0.262 nanometer, belongs to (200) crystal face, and plane of crystal activity can be high compared with other crystal faces, favorably
In the progress of particle surface modification, CeO2Nano particle belongs to cubic system, and the position of five characteristic peaks is 28.549 °,
33.077 °, 47.483 °, 56.342 ° and 69.416 °, in corresponding (111) respectively, (200), (220), (311) and (400) etc. five
Individual crystal face.
Fig. 4 is CeO in the embodiment of the present invention2The modification theory figure of nano particle, as seen from the figure, it is seen that CeO2Nano particle
Surface parcel organic molecule be the longer oleic acid organic molecule of carbon chain lengths, the clean nanometer obtained after oleic acid desorption
Grain, is then carried out after surface modification treatment, and the shorter acetylacetone,2,4-pentanedione organic molecule of carbon chain lengths is adsorbed in CeO2Nano particle table
Face, obtains modified CeO2Nano particle.
Fig. 5 is the CeO of different phase in Process of Surface Modification in the embodiment of the present invention2The infrared spectrum contrast of nano particle
Figure, as seen from the figure in Process of Surface Modification different phase CeO2The adsorption state of nano particle, original CeO2Nanometer
Grain can significantly see the characteristic peak of oleic acid, with the desorption reaction enclosure of basic solvent, it can be seen that light wave number 2925 and light
See that the characteristic peak of oleic acid is weakened at wave number 2855, but the characteristic peak at light wave number 1737 has been wholly absent, receiving now
Rice grain is the cerium oxide nanoparticles wrapped up without oleic acid, can be in light wave number after the surface modification treatment of acetylacetone,2,4-pentanedione
3000~2500 is interval interior it can be seen that the characteristic peak peak type of acetylacetone,2,4-pentanedione, the skew of peak position is probably due to the two of acetylacetone,2,4-pentanedione
Plant with position isomer and CeO2The combination of nano particle.
In order to further illustrate modified CeO of the invention2Nano particle and products thereof, enters with reference to specific embodiment
One step is illustrated.
Embodiment 1, comprises the following steps：
(1) it is 17mmol/L to weigh six water cerous nitrates and be dissolved in distilled water configuration concentration, under conditions of ice-water bath by
Be added dropwise to tert-butylamine to PH be 8；
(2) take in the reactor that 150 milliliters of steps (1) solution adds 500 milliliters, add oleic acid, configuration oleic acid with
Cerium ion mol ratio is 10:The precursor solution of 1 oleic acid protection, the precursor solution protected by oleic acid is with volume of toluene ratio
1:1 adds toluene (can replace toluene with benzene, n-hexane, carbon tetrachloride or dichloromethane), and standing is not stirred；
(3) reactor by step (2) filling about 60% is moved into the baking oven of 180 degrees Celsius of constant temperature, reaction 24
Room temperature is cooled to after hour, is taken out, takes upper strata brown clear liquid to obtain the toluene solution of the cerium oxide of oleic acid parcel；
(4) toluene solution of cerium oxide and 30mL absolute ethyl alcohol that the oleic acid described in 30 milliliters of steps (3) is wrapped up is taken to mix
Close, stirring, ultrasound make it fully separate out, centrifugation obtains the cerium oxide of auburn oleic acid parcel and received under 8000r/min speed
Rice grain；
(5) repeat step (4) three times is to remove oleic acid excessive in solution, and the cerium oxide for obtaining the oleic acid parcel of brown is received
Rice grain；
(6) cerium oxide particle of 2 grams of steps (5) oleic acid parcel is taken to be dispersed in again in 20 milliliters of toluene solvant,
Configure the CeO of 0.1g/mL oleic acid parcel2Toluene solution, ultrasound makes its fully dispersed；
(7) 40% aqueous solution of TBAH is taken, the cerium oxide of the oleic acid parcel described in step (6) is added dropwise
Toluene solution in, regulation pH value is to 10, and vibration, ultrasound make it fully react, to carry out desorption；
(8) absolute ethyl alcohol is added in the solution described in step (7), reacted solution is fully transferred to 100 milliliters
In centrifuge tube.Under 6000r/min speed, three layers of product being separated from each other are obtained, supernatant liquor is removed, take milk yellow to sink
Form sediment.Cleaned repeatedly by above-mentioned steps three times with absolute ethyl alcohol, it is ensured that remaining without impurity product.Obtain scattered pure cerium oxide
Nano particle；
(9) the scattered pure cerium oxide nanoparticles described in 2 grams of steps (8) are weighed, acetylacetone,2,4-pentanedione is added, CeO is configured2
Mass concentration is 0.1g/mL solution, and vibration, ultrasound make it be dispersed to without obvious particle；
(10) solution described in step (9) is stirred repeatedly, ultrasound 48 hours after, stirring and ultrasonication alternately,
The acetylacetone,2,4-pentanedione solution of cerium oxide is obtained by 220 nanometers of the membrane filtration in aperture；
(11) solution after step (10) described filtering is added into revolving instrument to remove superfluous acetylacetone,2,4-pentanedione.Revolving
Instrument water temperature is controlled at 40~100 degrees Celsius, and the millipascal of air pressure 0~80 obtains kermesinus slurry.So far, acetylacetone,2,4-pentanedione is obtained to change
The CeO of property2Nano material.
Embodiment 2, comprises the following steps：
(1) configuration step of modified cerium oxide solution：By the cerium oxide slurry point described in the step of embodiment 1 (11)
It is dispersed in alcohol solvent, obtains modified cerium oxide solution.
(2) cleaning step：It is 5~25 ohm, indium doped tin oxide (ITO) glass of transmitance 70%~90% to select sheet resistance
Glass is substrate, is then cleaned successively with liquid detergent, distilled water, ethanol and acetone, and nitrogen is handled after drying with oxygen plasma beam
10 minutes；
(3) preparation of modified ceria film：The solution described in 70 microlitres of steps (1) is taken to be spin-coated on step (2) institute
Indium doped tin oxide (ITO) surface stated, after 5000 rpms of speed spin coating solution 30 seconds, is placed on 80 degrees Celsius of heat
Heated 10 minutes on platform, obtain modified ceria film.
Fig. 6 is the CeO of different phase in the Process of Surface Modification of embodiment two2The light of nano particle dispersity in a solvent
Photo comparison's figure is learned, as seen from the figure, clean cerium oxide is more difficult scattered in a solvent, it is necessary to carry out surface Modified lift material
Dispersiveness, the modified CeO in surface2Nano material equal energy in the different solvent of two kinds of polarity is good to be disperseed, and obtains color
Slightly discrepant clarification, clear solution；
Fig. 7 is the modified CeO in the surface of embodiment two2The front scan electron microscope of film prepared by nano particle
Figure, as seen from the figure, by modified CeO2Film prepared by nano particle is continuous, smooth, pin-free, the modified CeO in surface2
Nano particle is improved due to dispersiveness in a solvent, improves the modified CeO in surface2The machine of film prepared by nano particle
Tool performance；
Fig. 8 is the modified CeO in the surface of embodiment two2The atomic force microscopy diagram of film prepared by nano particle, by scheming
Understand, the modified CeO in surface2Film prepared by nano particle is very smooth, and local roughness is only 0.26 nanometer, can be with
Reduce the influence that boundary layer rises and falls to planar structure perovskite solar battery efficiency；
Fig. 9 is the modified CeO in the surface of embodiment two2The transmission spectrogram of film prepared by nano particle, as seen from the figure,
The modified CeO in surface2The light transmission rate of film prepared by nano particle is high, and satisfaction is used as perovskite window layer of solar battery
Requirement；
Figure 10 is the modified CeO in the surface of embodiment two2Nano particle prepares the fluorescence spectra of film, as seen from the figure,
The modified CeO in surface2Film prepared by nano particle has obvious fluorescent effect in ultraviolet region, can will have broken to perovskite
The ultraviolet light of bad effect is converted into the visible ray that can be absorbed by perovskite, and perovskite is improved while perovskite light-absorption layer is protected
The external quantum efficiency of solar cell.
Figure 11 is the modified CeO in the surface of embodiment two2Nano particle prepare film ultraviolet photoelectron spectroscopy (UPS,
Ultroviolet Photoelectron Spectrometer) figure, as seen from the figure, modified CeO2Nano particle is natural
N-type semiconductor, the modified CeO in surface2The work function value of nano particle is -4.12 electron-volts (eV), i.e. Fermi's energy
Level position is -4.12 electron-volts, the modified CeO in surface apart from vacuum level2The maximum valence band location of nano particle is
3.44 electron-volts (eV), i.e. top of valence band position (VB) are 3.44 electron-volts apart from the position of fermi level, can be calculated
The valence band location of cerium oxide is -7.56 electron-volts (eV)；
Figure 12 is the modified CeO in the surface of embodiment two2Nano particle prepares energy gap (Bandgap) figure of film,
As seen from the figure, the modified CeO in surface2The energy gap of nano particle is the conduction band position of 3.5 electron-volts (eV), i.e. cerium oxide
It is 3.5 electron-volts to put with the distance of valence band location, and the conduction band positions that can calculate cerium oxide are -4.06 electron-volts
(eV)；
Figure 13 is the modified CeO in the surface of embodiment two2Nano particle prepare film x-ray photoelectron spectroscopy (XPS,
X-ray Photoelectron Spectrometer) figure, as seen from the figure, the modified CeO in surface2Prepared by nano particle thin
The combination energy position of the Ce elements of film is between 880eV 920eV, and the combination energy position of O elements is between 530eV 540eV；
Figure 14 is the modified CeO in the surface of embodiment two2The high-resolution X-ray of the Ce elements of film prepared by nano particle
Photoelectron spectrogram, as seen from the figure, 3d5/2The Ce elements of track can be divided by two kinds of valence states of trivalent cerium and quadrivalent cerium, wherein trivalent cerium
Go out u ' (v ') and u0(v0) two tracks, quadrivalent cerium can divide three tracks of u " ' (v " '), u " (v ") and u (v), by song
Line integral, the atom accounting that can obtain trivalent cerium and quadrivalent cerium is respectively 60.28at.% and 39.72at.%；
Figure 15 is the modified CeO in the surface of embodiment two2The high-resolution X-ray of the oxygen element of film prepared by nano particle
Photoelectron spectrogram, as seen from the figure, the oxygen element of 1s tracks have three characteristic peaks, wherein, combined with the cerium of three valence states, with four valence states
Cerium combine and the combination of particle surface carbon-oxygen bond can be respectively at 536.85,534.55 and 532.05 electron-volts, this enters one
Step illustrates the surface state of particle, there is the acetylacetone,2,4-pentanedione Molecular Adsorption that carbon chain lengths are shorter.
Embodiment 3, the battery device for preparing formal plane perovskite solar cell, comprises the following steps：
(1) cleaning step：It is 5~25 ohm, indium doped tin oxide (ITO) glass of transmitance 70%~90% to select sheet resistance
Glass is substrate, is then cleaned successively with liquid detergent, distilled water, ethanol and acetone, and nitrogen is handled after drying with oxygen plasma beam
10 minutes；
(2) preparation of electron transfer layer solution：Cerium oxide slurry described in the step of Example 1 (11) is dense by quality
5 milligrams every milliliter of degree is dispersed in chlorobenzene solvent, is stirred under normal temperature to all scattered, is obtained the chlorobenzene solution of cerium oxide.
(3) preparation of electron transfer layer：The solution described in step (2) is taken to be spin-coated in the ITO substrate described in step (1),
After 5000 rpms of speed spin coating solution 30 seconds, it is placed in 80 degrees Celsius of thermal station and heats 10 minutes, obtain about 20
The dense oxide cerium electron transfer layer of nanometer thickness.
(4) preparation process of perovskite solution：By PbI2Mixture, wherein PbI are mixed to form with MAI2Accounting for mol ratio is
70%, DMF and DMSO in the mixed solvents are dissolved in, it is 80% that wherein DMF, which accounts for volume ratio,.It is stirred at room temperature, until all molten
Solution, obtains MAPbI3Perovskite solution；
(5) preparation of calcium titanium ore bed：The perovskite solution configured is spin-coated on cerium oxide electron transfer layer, with 6000
Rpm speed spin coating solution after 30 seconds, be placed in 100 degrees Celsius of thermal station and heat 10 minutes, formed after solvent volatilization
The perovskite light-absorption layer of one layer of about 350 nanometer thickness；
(6) preparation process of hole transmission layer solution：80 milligrams of Spiro-OMeTAD powder are taken, 30 microlitres of tricresyl phosphates are added
Butyl ester (TBP), the acetonitrile solution and 1 milliliter of chlorobenzene of 35 microlitre of two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI), vibration makes it
Dissolving is complete, is aoxidized 12 hours in dry air, obtains Spiro-OMeTAD chlorobenzene solution.
(7) preparation of hole transmission layer：The Spiro-OMeTAD solution configured is spin-coated on perovskite light-absorption layer, shape
Into about 100 nanometer thickness hole transmission layers.
(8) preparation process of the metal to electrode：Using vacuum evaporation coating film device, one is deposited on the hole transport layer
Thickness degree is 100nm gold electrode, obtains the formal plane perovskite solar cell of solid-state.
Figure 16 is the battery device structure chart of the formal plane perovskite solar cell of embodiment three, and Figure 17 is embodiment three
Formal photovoltaic curve of the plane perovskite solar cell device under a standard sun light intensity, two figure more than, table
The modified CeO in face2Film prepared by nano particle is applied as Window layer in formal plane perovskite solar cell, is obtained
Beneficial to its high transmittance, prepared formal plane solar energy battery has very high short circuit current flow.
Embodiment 4, comprises the following steps：
(1) cleaning step：It is 5~25 ohm, fluorine doped tin oxide (FTO) glass of transmitance 70%~90% to select sheet resistance
Glass is substrate, is then cleaned successively with liquid detergent, distilled water, ethanol and acetone, and nitrogen is handled after drying with oxygen plasma beam
10 minutes；
(2) preparation process of hole transmission layer solution：At room temperature, weigh a certain amount of nickel acetylacetonate, lithium acetate and
Magnesium acetate, according to stoichiometric proportion Ni:Li:Mg=80:5:15 mixing, are dissolved in acetonitrile solution, obtaining nickel molar concentration is
0.02 mole every liter of precursor liquid.
(3) preparation of hole transmission layer：Electro-conductive glass after step (1) processing is placed on 600 degrees Centigrades upward
On platform, using the precursor solution described in oxygen pressing atomization steps (2), continuously 50 milliliters of precursor solutions are sprayed into successively
The conductive surface of high temperature, deposits rapidly fine and close, continuous nickel magnesium lithia (NiMgLiO) compacted zone, thickness is about 20 nanometers.Spray
Apply and complete follow-up continuous annealing 60 minutes at such a temperature；
(4) preparation process of calcium titanium ore bed solution：It is identical with the step of embodiment 2 (4)；
(5) preparation of calcium titanium ore bed：The perovskite solution configured is spin-coated on nickel magnesia lithium electron transfer layer, with
6000 rpms of speed spin coating solution was placed in 100 degrees Celsius of thermal station and heated 10 minutes after 30 seconds, after solvent volatilization
Form the perovskite light-absorption layer of one layer of about 350 nanometer thickness；
(6) preparation process of electron transfer layer solution：The solution described in step (6) in embodiment 1 is pressed with toluene solvant
5 milligrams of every milliliter of dilutions of mass concentration, obtain the toluene solution that oleic acid wraps up cerium oxide；
(7) preparation of electron transfer layer：The solution described in step (6) is taken to be spin-coated on the calcium titanium ore bed described in step (5),
After 5000 rpms of speed spin coating solution 30 seconds, it is placed in 80 degrees Celsius of thermal station and heats 10 minutes, obtain about 50
The cerium oxide electron transfer layer of the oleic acid parcel of nanometer thickness.
(8) preparation process of the metal to electrode：Using vacuum evaporation coating film device, one is deposited on the hole transport layer
Thickness degree is 100nm silver electrode, obtains the trans plane perovskite solar cell of the full-inorganic boundary layer of solid-state.
Figure 18 is the battery device structure of the battery device of the trans single layer electronic transport layer plane battery structure of example IV
Figure, Figure 19 is the battery device of the trans single layer electronic transport layer plane battery structure of example IV under a standard sun light intensity
Photovoltaic curve, two figure more than, oleic acid parcel cerium oxide prepare film as electron transfer layer in trans individual layer
Applied in electron transfer layer plane battery, excessive intermolecular distance blocks migration of the electric charge in electron transfer layer, greatly reduction
The photovoltaic performance of solar cell, obtains strange " S " type photovoltaic property curve.
Embodiment 5, comprises the following steps：
First five step, i.e. step (1)~step (5) are same as Example 4.
(6) preparation process of electron transfer layer solution：Cerium oxide slurry described in the step of Example 1 (11), by matter
5 milligrams every milliliter of concentration of amount is dispersed in chlorobenzene solvent, is stirred under normal temperature to all scattered, is obtained the chlorobenzene solution of cerium oxide；
(7) preparation of electron transfer layer：The solution described in step (6) is taken to be spin-coated on the calcium titanium ore bed described in step (5),
After 5000 rpms of speed spin coating solution 30 seconds, it is placed in 80 degrees Celsius of thermal station and heats 10 minutes, obtain about 50
The dense oxide cerium electron transfer layer of nanometer thickness.
(8) preparation process of the metal to electrode：Using vacuum evaporation coating film device, one is deposited on the hole transport layer
Thickness degree is 100nm silver electrode, obtains the trans plane perovskite solar cell of the full-inorganic boundary layer of solid-state.
Figure 20 is the battery device structure of the battery device of the trans single layer electronic transport layer plane battery structure of embodiment five
Figure, Figure 21 is the battery device of the trans single layer electronic transport layer plane battery structure of embodiment five under a standard sun light intensity
Photovoltaic curve, two figure more than, the modified CeO in surface2Film prepared by nano particle exists as electron transfer layer
Applied in trans single layer electronic transport layer plane battery, intermolecular distance shortens in electron transfer layer, be conducive to electric charge to be passed in electronics
The migration of defeated layer, lifts the photovoltaic performance of solar cell.
Embodiment 6, comprises the following steps：
First five step, i.e. step (1)~step (5) are same as Example 4.
(6) preparation process of electron transfer layer solution：At room temperature, a certain amount of PCBM powder is weighed, it is dense according to quality
20 milligrams every milliliter of degree is dissolved in chlorobenzene solution, is stirred under 40 degrees Celsius to being completely dissolved, is obtained PCBM chlorobenzene solution；
(7) solution described in step (6) is taken to be spin-coated on the calcium titanium ore bed described in step (5), with 5000 rpms
After speed spin coating solution 30 seconds, it is placed in 80 degrees Celsius of thermal station and heats 10 minutes, obtain the PCBM lower floors of about 50 nanometer thickness
Electron transfer layer.
(8) preparation process of the metal to electrode：Using vacuum evaporation coating film device, one is deposited on the hole transport layer
Thickness degree is 100nm silver electrode, obtains the trans plane perovskite solar cell of the bielectron transport layer of solid-state.
Figure 22 is the battery device structure of the battery device of the trans single layer electronic transport layer plane battery structure of embodiment six
Figure, Figure 23 is the battery device of the trans single layer electronic transport layer plane battery structure of embodiment six under a standard sun light intensity
Photovoltaic curve, two figure more than, film prepared by PCBM is flat in trans single layer electronic transport layer as electron transfer layer
Applied in the battery of face, PCBM conductance is better than the modified CeO in surface2Nano particle, but due to PCBM conduction band positions mistake
Height, the contact with silver electrode is Schottky contacts, there is strong non-radiative recombination on both interfaces, reduces solar-electricity
The photovoltaic performance in pond, obtains class " S " type photovoltaic property curve.
Embodiment 7, comprises the following steps：
The first seven step, i.e. step (1)~step (7) are same as Example 6.
(8) preparation process of upper strata electron transfer layer solution：Cerium oxide slurry described in the step of Example 1 (11),
By mass concentration, 5 milligrams every milliliter is dispersed in methanol solvate, stirs to whole and disperses under normal temperature, the methanol for obtaining cerium oxide is molten
Liquid.
(9) under 6000 rpms of speed, by the solution described in 150 microlitres of steps (7) dropwise drop coating in step (7)
On described PCBM electron transfer layers, it is placed in 80 degrees Celsius of thermal station and heats 10 minutes, obtain the oxidation of about 50 nanometer thickness
Cerium upper strata electron transfer layer.
(10) preparation process of the metal to electrode：Using vacuum evaporation coating film device, it is deposited on the hole transport layer
A layer thickness is 100nm silver electrode, obtains the trans plane perovskite solar cell of the bielectron transport layer of solid-state.
Figure 24 is the structure chart of the battery device of the trans two-layer electronic transport layer plane battery structure of embodiment seven, Tu25Shi
Photovoltaic of the battery device of the trans two-layer electronic transport layer plane battery structure of embodiment seven under a standard sun light intensity is bent
Line, Figure 26 is the external quantum efficiency figure of the battery device of the trans two-layer electronic transport layer plane battery structure of embodiment seven, by with
Knowable to upper three figure, the modified CeO in surface2Film prepared by nano particle (that is to say the second electricity as upper strata electron transfer layer
Sub- transport layer) to be applied in trans two-layer electronic transport layer plane battery, two-layer electronic transport layer not only increases electric charge in electricity
Transmission speed in sub- transport layer, while eliminating the Schottky contacts on interface, greatly improved the outer quantum effect of battery device
Should so that the photovoltaic performance of solar cell gets a promotion；
Figure 27 is the steady-state current output of the battery device of the trans two-layer electronic transport layer plane battery structure of embodiment seven
Figure, Figure 28 is that the battery device of the trans two-layer electronic transport layer plane battery structure of embodiment seven is long-term steady under air atmosphere
Qualitative test figure, two figure more than, the modified CeO in surface2Film prepared by nano particle, due to surface acetylacetone,2,4-pentanedione
Organic molecule enhances intermolecular force, and the compactness lifting of film not only stops the organic of battery device inside perovskite
The loss of molecule, also blocks corrosion function of the extraneous water oxygen to battery device, and the output of maximum power point electric current is more stable, in sky
Long-time stability under atmosphere is enclosed also get a promotion.
The step of embodiment 8, this implementation, is identical with embodiment 1, and simply parameter area is different, is not all specifically：
(1) configuration concentration be 1mmol/L cerous nitrate solutions, be added dropwise under conditions of ice-water bath ammoniacal liquor to PH be 9；
(2) in the precursor solution of oleic acid protection, oleic acid is no more than 20 with cerium ion mol ratio:1, protected by oleic acid
Precursor solution is 2 with volume of toluene ratio:1 adds toluene；
(3) reactor loading is 50%, and in the baking oven for moving into 240 degrees Celsius of constant temperature, reaction is cooled to room after 48 hours
Temperature；
(6) configuration is not more than the CeO of 5g/mL oleic acid parcel2Toluene solution, ultrasound makes its fully dispersed；
(7) TMAH is taken to add in the toluene solution of the cerium oxide of oleic acid parcel, regulation pH value to 14；
(9) CeO is configured2Mass concentration is no more than 5g/mL solution；
(10) stirring, ultrasonic time are after 24 hours repeatedly.
The step of embodiment 9, this implementation, is identical with embodiment 1, and simply parameter area is different, is not all specifically：
(1) configuration concentration be 50mmol/L cerous nitrate solutions, be added dropwise under conditions of ice-water bath ammoniacal liquor to PH be 4；
(2) in the precursor solution of oleic acid protection, oleic acid is no more than 20 with cerium ion mol ratio:1, protected by oleic acid
Precursor solution is 1 with volume of toluene ratio:20 add toluene；
(3) reactor loading is 80%, and in the baking oven for moving into 160 degrees Celsius of constant temperature, reaction is cooled to room after 12 hours
Temperature；
(6) configuration is not more than the CeO of 5g/mL oleic acid parcel2Toluene solution, ultrasound makes its fully dispersed；
(7) TMAH is taken to add in the toluene solution of the cerium oxide of oleic acid parcel, regulation pH value to 6；
(9) CeO is configured2Mass concentration is no more than 5g/mL solution；
(10) stirring, ultrasonic time are after 0.5 hour repeatedly.
Embodiment 10, the battery device for preparing formal plane perovskite solar cell, the step of it includes and reality
Apply that example 3 is identical, simply parameter area is different, is not all specifically：
(2) preparation of electron transfer layer solution：The chlorobenzene that the mass concentration of configuration cerium oxide is not more than 3 grams every milliliter is molten
Liquid；
(3) preparation of electron transfer layer：Heated 10 minutes in 70 degrees Celsius of thermal station, obtain the cause of about 100 nanometer thickness
Close cerium oxide electron transfer layer；
(5) preparation of calcium titanium ore bed：The perovskite solution configured is spin-coated on cerium oxide electron transfer layer, is placed on
Heated 10 minutes in 150 degrees Celsius of thermal station, the perovskite light-absorption layer of one layer of about 300 nanometer thickness is formed after solvent volatilization；
(7) preparation of hole transmission layer：Form about 1000 nanometer thickness hole transmission layers；
(8) preparation process of the metal to electrode：Evaporation a layer thickness is electric for 300nm gold on the hole transport layer
Pole.
Embodiment 11, the battery device for preparing formal plane perovskite solar cell, the step of it includes and reality
Apply that example 3 is identical, simply parameter area is different, is not all specifically：
(2) preparation of electron transfer layer solution：The chlorobenzene that the mass concentration of configuration cerium oxide is not more than 3 grams every milliliter is molten
Liquid.
(3) preparation of electron transfer layer：Heated 10 minutes in 70 degrees Celsius of thermal station, obtain the densification of about 10 nanometer thickness
Cerium oxide electron transfer layer.
(5) preparation of calcium titanium ore bed：The perovskite solution configured is spin-coated on cerium oxide electron transfer layer, is placed on
Heated 10 minutes in 70 degrees Celsius of thermal station, the perovskite light-absorption layer of one layer of about 300 nanometer thickness is formed after solvent volatilization.
(7) preparation of hole transmission layer：Form about 10 nanometer thickness hole transmission layers.
(8) preparation process of the metal to electrode：The gold electrode that evaporation a layer thickness is 50nm on the hole transport layer.
Embodiment 12, the battery device of layer plane perovskite solar cell, bag are transmitted for preparing trans single layer electronic
Include following steps：
(1) preparation of hole transmission layer：The thick holes of one layer of 50nm are deposited in fluorine doped tin oxide electro-conductive glass conductive surface
Transport layer；
(2) preparation of perovskite light-absorption layer：The perovskite precursor solution configured is revolved into Tu hole in step (1) to pass
On defeated layer, then in 70 DEG C of annealings, perovskite light-absorption layer is obtained；
(3) preparation of electron transfer layer：At room temperature, the perovskite extinction layer surface spin coating nanometer ink in step (2),
Dried at a temperature of not destroying perovskite light-absorption layer performance, to obtain thickness 1000nm dense oxide cerium electron transfer layer, institute
State the CeO of surface modification2The mass concentration of nano material is 3 grams per milliliters；
(4) preparation of the metal to electrode：The intermediate semi-finished products that step (3) is obtained are inserted in vacuum evaporation coating film device,
The aluminium electrode that evaporation a layer thickness is 50nm on the electron transport layer.
Embodiment 13, the battery device of layer plane perovskite solar cell, bag are transmitted for preparing trans single layer electronic
Include following steps：
(1) preparation of hole transmission layer：The thick holes of one layer of 10nm are deposited in fluorine doped tin oxide electro-conductive glass conductive surface
Transport layer；
(2) preparation of perovskite light-absorption layer：The perovskite precursor solution configured is revolved into Tu hole in step (1) to pass
On defeated layer, then in 150 DEG C of annealings, perovskite light-absorption layer is obtained；
(3) preparation of electron transfer layer：At room temperature, the perovskite extinction layer surface spin coating nanometer ink in step (2),
Dried at a temperature of not destroying perovskite light-absorption layer performance, it is described to obtain thickness 10nm dense oxide cerium electron transfer layer
The CeO that surface is modified2The mass concentration of nano material is not more than 3 grams per milliliters；
(4) preparation of the metal to electrode：The intermediate semi-finished products that step (3) is obtained are inserted in vacuum evaporation coating film device,
The aluminium electrode that evaporation a layer thickness is 300nm on the electron transport layer.
Embodiment 14, for preparing the trans planar structure solar cell of double-layer electric sublayer, it is characterised in that it is included such as
Lower step：
(1) preparation of hole transmission layer：The thick holes of one layer of 50nm are deposited in fluorine doped tin oxide electro-conductive glass conductive surface
Transport layer；
(2) preparation of perovskite light-absorption layer：The perovskite precursor solution configured is revolved into Tu hole in step (1) to pass
On defeated layer, then in 70 DEG C of annealings, perovskite light-absorption layer is obtained；
The preparation of (3) first electron transfer layers：At room temperature, the perovskite extinction layer surface spin coating Organic Electricity in step (2)
Sub- transport layer solution or inorganic electronic transport layer solution, are dried at a temperature of perovskite light-absorption layer performance is not destroyed, to obtain
The first electron transfer layer that thickness is 1000nm is obtained,
(4) preparation of second layer electron transfer layer：At room temperature, the first electric transmission layer surface spin coating is received in step (3)
Meter Mo Shui, is dried at a temperature of perovskite light-absorption layer performance is not destroyed, to obtain dense oxide cerium electricity of the thickness as 1000nm
Sub- transport layer, the CeO that the surface is modified2The mass concentration of nano material is not more than 3 grams per milliliters, first electric transmission
The electric conductivity of layer is better than the second layer electron transfer layer,
(5) preparation of the metal to electrode：The intermediate semi-finished products that step (4) is obtained are inserted in vacuum evaporation coating film device,
It is 50nm aluminium electrodes that a layer thickness is deposited on the second electron transfer layer.
Embodiment 15, for preparing the trans planar structure solar cell of double-layer electric sublayer, it is characterised in that it is included such as
Lower step：
(1) preparation of hole transmission layer：The thick holes of one layer of 10nm are deposited in fluorine doped tin oxide electro-conductive glass conductive surface
Transport layer；
(2) preparation of perovskite light-absorption layer：The perovskite precursor solution configured is revolved into Tu hole in step (1) to pass
On defeated layer, then in 150 DEG C of annealings, perovskite light-absorption layer is obtained；
The preparation of (3) first electron transfer layers：At room temperature, the perovskite extinction layer surface spin coating Organic Electricity in step (2)
Sub- transport layer solution or inorganic electronic transport layer solution, are dried at a temperature of perovskite light-absorption layer performance is not destroyed, to obtain
The first electron transfer layer that thickness is 10nm is obtained,
(4) preparation of second layer electron transfer layer：At room temperature, the first electric transmission layer surface spin coating is received in step (3)
Meter Mo Shui, is dried at a temperature of perovskite light-absorption layer performance is not destroyed, to obtain dense oxide cerium electronics of the thickness as 10nm
Transport layer, the CeO that the surface is modified2The mass concentration of nano material is not more than 3 grams per milliliters, first electron transfer layer
Electric conductivity be better than the second layer electron transfer layer,
(5) preparation of the metal to electrode：The intermediate semi-finished products that step (4) is obtained are inserted in vacuum evaporation coating film device,
It is 300nm aluminium electrodes that a layer thickness is deposited on the second electron transfer layer.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (8)
1. a kind of CeO for preparing surface modification2The method of nano material, it is characterised in that it comprises the following steps：
S1：Prepare the CeO of oleic acid parcel2Nano particle,
S2：The CeO for the oleic acid parcel that step S1 is obtained2Nano particle is dispersed in non-pole by no more than 5 grams per milliliter mass concentrations
Property solution, non-polar solution is preferably toluene, benzene, n-hexane, carbon tetrachloride or dichloromethane, obtain oleic acid parcel CeO2's
Non-polar solution,
S3：To the CeO of the step S2 oleic acid parcels obtained2Non-polar solution in add basic solvent, regulation pH value to 6~14,
To carry out adding alcohols solvent progress eccentric cleaning after the completion of desorption reaction enclosure, desorption, the CeO of milk yellow is obtained2Particle,
S4：By the CeO of the step S3 milk yellows obtained2Particle is added in acetylacetone,2,4-pentanedione by the mass concentration of no more than 5 grams per milliliters,
Alternately stirring and ultrasonication, continue 0.5~48 hour, and finally filtering obtains the modified CeO of acetylacetone,2,4-pentanedione2Solution,
S5：The CeO modified to the acetylacetone,2,4-pentanedione of step S4 acquisitions2Solution carries out vacuum distillation, to remove the acetylacetone,2,4-pentanedione of surplus
Solvent, obtains the modified CeO of acetylacetone,2,4-pentanedione2Nano material.
2. the CeO that surface is modified is prepared as claimed in claim 12The method of nano material, it is characterised in that institute in step S3
State basic solvent and be selected from the organic amine solvent easily removed, preferably TBAH, TMAH, ethamine, second
Diamines or tert-butylamine.
3. the CeO that surface is modified is prepared as claimed in claim 1 or 22The method of nano material, it is characterised in that the step
S1 includes following sub-step：
S11：By Ce (NO3)3·6H2O presses 1mmol L-1~50mmol L-1Molar concentration is dissolved in distilled water, in ice-water bath
In, add alkaline solution and adjust pH value to 4~9, form solvent thermal reaction precursor solution,
S12：Solvent thermal reaction precursor solution described in step S11 is added in autoclave, by oleic acid and cerium mol ratio
No more than 20 add oleic acid, obtain the precursor solution of oleic acid protection, the precursor solution and volume of toluene ratio protected by oleic acid
For 1:20~2:1 add toluene so that in reactor packed space 50%~80% reactant；
S13：In the baking oven that reactor described in step S12 is moved into 160 DEG C~240 DEG C of constant temperature, after reacting 12 hours~48 hours
Room temperature is cooled to, upper strata brown clear liquid is taken, the toluene solution of the excessive cerium oxide of oleic acid is obtained；
S14：Oil is obtained after adding ethanol, eccentric cleaning in the toluene solution of the excessive cerium oxide of the oleic acid described in step S13
The CeO of acid parcel2Nano particle.
4. the CeO that surface is modified is prepared as claimed in claim 32The method of nano material, it is characterised in that the step S11
In alkaline solution be selected from tert-butylamine and ammoniacal liquor.
5. the CeO that a kind of surface prepared using such as one of claim 1-4 method is modified2Nano material.
6. a kind of CeO being modified using surface as claimed in claim 52Nano material prepares formal planar structure solar cell
Method, it is characterised in that it comprises the following steps：
(1) preparation of electron transfer layer：At room temperature, in the conductive surface spin coating nanometer ink of indium doped tin oxide electro-conductive glass,
Dried at a temperature of not destroying indium doped tin oxide electro-conductive glass electric conductivity, to obtain the dense oxide that thickness is not more than 100nm
Cerium electron transfer layer,
The nanometer ink refers to the CeO that surface is modified2Nano material is dispersed in shape in polar solvent or non-polar solven
Into solution, wherein, the CeO that the surface is modified2The mass concentration of nano material is not more than 3 grams per milliliters；
(2) preparation of perovskite light-absorption layer：The perovskite precursor solution configured is revolved into the densification that Tu is obtained in step (1)
On cerium oxide electron transfer layer, then made annealing treatment at 70~150 DEG C, obtain perovskite light-absorption layer；
(3) preparation of hole transmission layer：The hole transport solution configured is spin-coated on step (2) and obtains described perovskite suction
On photosphere, formed 10nm~1000nm hole transmission layers, so far, obtain simultaneously have electron transfer layer, perovskite light-absorption layer with
And the intermediate semi-finished products of hole transmission layer；
(4) preparation of the metal to electrode：The intermediate semi-finished products that step (3) is obtained are inserted in vacuum evaporation coating film device, in sky
The gold electrode that a layer thickness is 50nm~300nm is deposited in cave transport layer.
7. a kind of CeO being modified using surface as claimed in claim 52Nano material prepares the trans plane of single layer electronic transport layer
The method of structure solar cell, it is characterised in that it comprises the following steps：
(1) preparation of hole transmission layer：One layer, which is deposited, in fluorine doped tin oxide electro-conductive glass conductive surface is not more than the thick skies of 50nm
Cave transport layer；
(2) preparation of perovskite light-absorption layer：The perovskite precursor solution configured is revolved into Tu in step (1) hole-transporting layer
On, then in 70~150 DEG C of annealings, obtain perovskite light-absorption layer；
(3) preparation of electron transfer layer：At room temperature, the perovskite extinction layer surface spin coating nanometer ink in step (2), is not breaking
Dried at a temperature of bad perovskite light-absorption layer performance, to obtain the dense oxide cerium electron transfer layer that thickness is not more than 1000nm,
The nanometer ink refers to the CeO that surface is modified2Nano material is dispersed in shape in polar solvent or non-polar solven
Into solution, wherein, the CeO that the surface is modified2The mass concentration of nano material is not more than 3 grams per milliliters, so far obtains simultaneously
Intermediate semi-finished products with electron transfer layer, perovskite light-absorption layer and hole transmission layer；
(4) preparation of the metal to electrode：The intermediate semi-finished products that step (3) is obtained are inserted in vacuum evaporation coating film device, in electricity
Aluminium electrode or silver electrode that a layer thickness is 50nm~300nm are deposited in sub- transport layer.
8. a kind of CeO being modified using surface as claimed in claim 52Nano material prepares the trans planar structure of double-layer electric sublayer
The method of solar cell, it is characterised in that it comprises the following steps：
(1) preparation of hole transmission layer：One layer, which is deposited, in fluorine doped tin oxide electro-conductive glass conductive surface is not more than the thick skies of 50nm
Cave transport layer；
(2) preparation of perovskite light-absorption layer：The perovskite precursor solution configured is revolved into Tu in step (1) hole-transporting layer
On, then in 70~150 DEG C of annealings, obtain perovskite light-absorption layer；
The preparation of (3) first electron transfer layers：At room temperature, perovskite extinction layer surface spin coating organic electronic is passed in step (2)
Defeated layer solution or inorganic electronic transport layer solution, are dried at a temperature of perovskite light-absorption layer performance is not destroyed, to obtain thickness
Degree is not more than 1000nm the first electron transfer layer,
(4) preparation of second layer electron transfer layer：At room temperature, the first electric transmission layer surface spin coating nano-ink in step (3)
Water, is dried at a temperature of perovskite light-absorption layer performance is not destroyed, to obtain the dense oxide cerium electricity that thickness is not more than 1000nm
Sub- transport layer,
The nanometer ink refers to the CeO that surface is modified2Nano material is dispersed in shape in polar solvent or non-polar solven
Into solution, wherein, the CeO that the surface is modified2The mass concentration of nano material is not more than 3 grams per milliliters, so far obtains simultaneously
Intermediate semi-finished products with electron transfer layer, perovskite light-absorption layer and hole transmission layer；
The electric conductivity of first electron transfer layer is better than the second layer electron transfer layer；
(5) preparation of the metal to electrode：The intermediate semi-finished products that step (4) is obtained are inserted in vacuum evaporation coating film device, the
Aluminium electrode or silver electrode that a layer thickness is 50nm~300nm are deposited on two electron transfer layers.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110649160A (en) * | 2018-06-26 | 2020-01-03 | 华中科技大学鄂州工业技术研究院 | Inorganic charge transport layer, preparation method thereof and application of perovskite solar cell |
| CN115322121A (en) * | 2022-09-06 | 2022-11-11 | 华中科技大学鄂州工业技术研究院 | Organic hole transport material and perovskite solar cell prepared from same |
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| CN103387257A (en) * | 2013-07-19 | 2013-11-13 | 东华大学 | Method for preparing nano cerium dioxide material by utilizing tween-80 as surfactant |
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| CN103387257A (en) * | 2013-07-19 | 2013-11-13 | 东华大学 | Method for preparing nano cerium dioxide material by utilizing tween-80 as surfactant |
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| 王明轩，等: "纳米CeO2的表面改性及其在水介质中的分散性能", 《北京化工大学学报（自然科学版）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110649160A (en) * | 2018-06-26 | 2020-01-03 | 华中科技大学鄂州工业技术研究院 | Inorganic charge transport layer, preparation method thereof and application of perovskite solar cell |
| CN115322121A (en) * | 2022-09-06 | 2022-11-11 | 华中科技大学鄂州工业技术研究院 | Organic hole transport material and perovskite solar cell prepared from same |
| CN115322121B (en) * | 2022-09-06 | 2024-02-09 | 华中科技大学鄂州工业技术研究院 | Organic hole transport material and perovskite solar cell prepared from same |
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