CN106981572B - It is a kind of to prepare the modified CeO in surface2The method and product of nano material and application - Google Patents
It is a kind of to prepare the modified CeO in surface2The method and product of nano material and application Download PDFInfo
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Abstract
The modified CeO in surface is prepared the invention discloses a kind of2The method and product of nano material and application belong to perovskite area of solar cell.Its method includes: the CeO that S1 prepares oleic acid package2Nano 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 basic solvent is added, carry out desorption reaction enclosure, eccentric cleaning after the completion of desorption obtains the CeO of milk yellow2Particle；S4 is using acetylacetone,2,4-pentanedione to the CeO of milk yellow2Particle is modified；S5 CeO modified to acetylacetone,2,4-pentanedione2Solution is evaporated under reduced pressure, to remove superfluous acetylacetone,2,4-pentanedione solvent.The present invention also provides the CeOs modified using acetylacetone,2,4-pentanedione2The method that nano material prepares different structure perovskite solar battery.The method of the present invention simple process, the modification CeO of preparation2Nano ZnO is excellent, can apply in perovskite solar battery.
Description
Technical field
The invention belongs to perovskite technical field of solar batteries, and in particular to the modified CeO in preparation surface2Nanometer material
The method of material and associated solar battery.
Background technique
Coal, petroleum, natural gas etc. are non-renewable energy resources, always have depleted one day.Continue to keep economical
Stablize rapid growth, we will face severe energy problem.Main source of the solar energy as earth energy, rich reserves,
It cleans renewable.National governments will all study the solar battery based on photoelectric conversion, especially cheap solar battery skill
Art, the important trend that important content and new energy technology as National Sustainable Development Strategies develop.
In recent years, perovskite solar battery was quickly grown, the extensive concern by 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 process is simple, so that calcium titanium
Mine solar battery becomes a kind of novel green photovoltaic industry of great competitiveness.
Perovskite solar battery be using perovskite material as solar battery in light absorbent a kind of battery, calcium
Titanium ore material is stimulated after sunlight irradiation and generates electron-hole pair, and electronics is transferred to interior follow by electron transport material collection
Ring anode, via outer circulation to interior circulation cathode, to be catalyzed the hole mobile material that hole has been collected in reduction, row is returned at complete
Road.Transmission of the electron-hole pair in battery device is restricted by the electric conductivity and carrier mobility of electron transfer layer,
Secondary, since titanium ore material itself is easily degenerated in water oxygen environment, stability is wrapped in its two sides boundary layer stability
It restricts, therefore, developing the inorganic charge transport layers with efficient stable is the key that develop perovskite solar battery.
Currently, organic charge transport layer has efficient electric conductivity, however its carrier mobility is low, need to carry out additional
Ion doping, and its poor chemical stability, easily degenerate in water oxygen environment, in addition, its molecular structure is complicated, purifying technique is numerous
Trivial, low output, use cost are high.Using sulphur cyanogen is cuprous and cuprous iodide is the unformed inorganic charge transmission material of representative, due to
The problems such as its crystallinity is not high, device efficiency is low, hysteresis phenomenon is serious, also limits it and is widely applied.With zinc oxide and oxygen
Change the inorganic charge transmission material that tin is representative prevents it from being widely used in no electromechanics due to its intrinsic good dispersion
Lotus transmission material, and be difficult to disperse in simple nonpolar solvent, even and if a small amount of polar solvent still has calcium titanium ore bed
Corrosion function.
High carrier mobility of the cerium oxide with inorganic oxide, good electric conductivity and mechanical performance, and it
Preparation method is simple, can greatly reduce material preparation cost.In common cerium oxide preparation system, the oleic acid of cerium oxide is wrapped up
The hydro-thermal reaction that cerium oxide can be slowed down synthesizes 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 removed.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 dispersion degree is very poor, is not suitable for directly preparing charge transport layer.
Therefore, develop cheap, applicability extensively, efficient stable and polarity and nonpolar solvent can be suitable for simultaneously
Inorganic charge transmission material has great importance, while also very challenging property.
Summary of the invention
For electron transfer layer carrier mobility in the prior art low, poor chemical stability, easily moved back in water oxygen environment
The problem of change, cost great number, the present invention provide a kind of high dispersive CeO that surface is modified2The preparation method and product of nano material
And application, the method for the present invention simple process, the CeO of preparation2Nano material conductivity is high, carrier mobility is high, chemical stabilization
The good, energy level of property is matched with perovskite light absorbent, it is ensured that device can be also greatly improved in the photoelectric conversion efficiency of battery device
Long-time stability.
To achieve the above object, according to one aspect of the present invention, a kind of CeO for preparing surface and being modified is provided2Nanometer
The method of material comprising following steps:
S1: the CeO of oleic acid package is prepared2Nano particle,
S2: the CeO for the oleic acid package 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 are preferably toluene, benzene, n-hexane, carbon tetrachloride or methylene chloride, obtain oleic acid package
CeO2Non-polar solution,
S3: the CeO that the oleic acid obtained to step S2 wraps up2Non-polar solution in be added basic solvent, adjust pH value to 6
~14, to carry out desorption reaction enclosure, alcohols solvent is added after the completion of desorption and carries out eccentric cleaning, obtains the CeO of milk yellow2
Particle,
S4: by the CeO of the step S3 milk yellow obtained2Particle presses the mass concentration addition levulinic 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 modified CeO of acetylacetone,2,4-pentanedione that step S4 is obtained2Solution is evaporated under reduced pressure, to remove superfluous second
Acyl acetone solvent obtains the modified CeO of acetylacetone,2,4-pentanedione2Nano material.
Further, basic solvent described in step S3 is selected from tetrabutylammonium hydroxide and tetramethylammonium hydroxide.
The second aspect according to the invention also provides a kind of CeO that the surface prepared using method as above is modified2
Nano material.
In terms of third according to the invention, a kind of CeO modified using surface as described above is also provided2Nano material system
The method of standby formal planar structure solar battery comprising 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, do not destroy indium-doped tin oxide electro-conductive glass electric conductivity at a temperature of it is dry, to prepare thickness no more than 100nm's
Dense oxide cerium electron transfer layer,
The nanometer ink refers to the modified CeO in surface2Nano material is dispersed in polar solvent or nonpolarity is molten
The solution formed in agent, wherein the modified CeO in the surface2The mass concentration of nano material is not more than 3 grams per milliliters；
(2) preparation of perovskite light-absorption layer: perovskite thin film ABX3, A=methylamine ion (MA, CH3NH3 +), cesium ion
(Cs+) or both mixture, B=lead ion (Pb2+), stannous ion (Sn2+) or both mixture, X=chloride ion (Cl-), bromine
Ion (Br-), iodide ion (I-) or both mixture.Wherein three's ionic radius meets certain tolerance factor and structure factor.
On the dense oxide cerium electron transfer layer that configured perovskite precursor solution rotation Tu is obtained in step (1), then exist
70~150 DEG C are made annealing treatment, and perovskite light-absorption layer is obtained；
(3) preparation of hole transmission layer: by configured hole transport solution (can for Spiro-MeOTAD, CuI,
The hole mobile materials such as CuSCN), it is spin-coated on step (2) and obtains on the perovskite light-absorption layer, it is empty to form 10nm~1000nm
Cave transport layer.So far, obtain while having the intermediate semi-finished products of electron transfer layer, perovskite light-absorption layer and hole transmission layer；
(4) preparation of the metal to electrode: in the intermediate semi-finished products merging vacuum evaporation coating film device that step (3) are obtained,
The gold electrode that vapor deposition a layer thickness is 50nm~300nm on the hole transport layer.
4th aspect according to the invention, also provides a kind of CeO modified using surface as described above2Nano material system
The method of the standby trans- planar structure solar battery of single layer electronic transport layer comprising following steps:
(1) preparation of hole transmission layer: at 300 DEG C~600 DEG C, by configured for example nickel source solution, pass through thermal jet
The method of painting deposits one layer of nickel magnesia lithium hole transport for being not more than 50nm thickness in fluorine-doped tin oxide electro-conductive glass conductive surface
Layer；
(2) configured perovskite precursor solution the preparation of perovskite light-absorption layer: is revolved into Tu nickel magnesium in step (1)
It on oxygen lithium hole transmission layer, is then made annealing treatment at 70~150 DEG C, obtains 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),
Do not destroy it is dry at a temperature of perovskite light-absorption layer performance, to obtain the dense oxide cerium electron-transport that thickness is not more than 1000nm
Layer,
The nanometer ink refers to the modified CeO in surface2Nano material is dispersed in polar solvent or nonpolarity is molten
The solution formed in agent, wherein the modified CeO in the surface2The mass concentration of nano material is not more than 3 grams per milliliters, so far obtains
Obtain the intermediate semi-finished products simultaneously with electron transfer layer, perovskite light-absorption layer and hole transmission layer；
(4) preparation of the metal to electrode: in the intermediate semi-finished products merging vacuum evaporation coating film device that step (3) are obtained,
The aluminium electrode or silver electrode that a layer thickness is 50nm~300nm is deposited.
Further, a kind of CeO 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 battery comprising following steps:
(1) preparation of hole transmission layer: at 300 DEG C~600 DEG C, by configured nickel source solution, pass through thermal spraying
Method deposits one layer of nickel magnesia lithium hole transmission layer for being not more than 50nm thickness in fluorine-doped tin oxide electro-conductive glass conductive surface；
(2) configured perovskite precursor solution the preparation of perovskite light-absorption layer: is revolved into Tu nickel magnesium in step (1)
It on oxygen lithium hole transmission layer, is then made annealing treatment at 70 DEG C~150 DEG C, obtains perovskite light-absorption layer；
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, do not destroy perovskite light-absorption layer performance at a temperature of it is dry, 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 electron-transport layer surface spin coating is received in step (3)
Meter Mo Shui, do not destroy perovskite light-absorption layer performance at a temperature of it is dry, to obtain the dense oxide that thickness is not more than 1000nm
Cerium electron transfer layer,
The nanometer ink refers to the modified CeO in surface2Nano material is dispersed in polar solvent or nonpolarity is molten
The solution formed in agent, wherein the modified CeO in the surface2The mass concentration of nano material is not more than 3 grams per milliliters, so far obtains
Obtain the intermediate semi-finished products simultaneously 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: in the intermediate semi-finished products merging vacuum evaporation coating film device that step (4) are obtained,
The aluminium electrode or silver electrode that a layer thickness is 50nm~300nm is deposited.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
In the method for the present invention, CeO is wrapped up or adsorbed using bipolarity organic molecule2Nano particle, so that the CeO2Nanometer
Material can be evenly dispersed in polar solvent and nonpolar solvent simultaneously, then can utilize the high carrier mobility, good of cerium oxide
The simple advantage of the electric conductivity and mechanical performance and preparation method got well, also overcoming oleic acid package leads to CeO2Nano particle
Conductivity is poor, treatment temperature is high and the shortcomings that damaging perovskite light-absorption layer.
The modified CeO of the present invention2Nano material can be evenly dispersed in polar solvent and nonpolar solvent simultaneously, may be used also
Reduce erosion of the solvent to successive functional layers in different structure battery.
In the present invention, modified to cerium oxide nanoparticles with acetylacetone,2,4-pentanedione, strand is short, does not hinder charge and load
Transmission of stream between nano particle.The modified high dispersive material in this surface, preparation cost is cheap, photovoltaic property is good,
Charming performance and potential application value are presented in perovskite solar battery.
Using the modified CeO of the method for the present invention2Nano material material can effectively improve the stability of battery device, subtract
Lack battery device material cost, is conducive to the application of the extensive industrialization of the type battery.
Detailed description of the invention
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 pattern 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 one Process of Surface Modification of embodiment2The infrared spectrum comparison diagram of nano particle, packet
The oxidation of oleic acid package after including oleic acid (Oleic acid) solvent, acetylacetone,2,4-pentanedione (Acetylacetine) solvent, ethyl alcohol cleaning
Cerium oxide (Desorption), the modified cerium oxide of acetylacetone,2,4-pentanedione after cerium (Rinsed), basic solvent desorption
(Redispersion) infrared spectrum comparison diagram distinguishes the CeO of each different phase according to the English word in figure2Nanometer
Grain；
Fig. 6 is the CeO of different phase in two Process of Surface Modification of embodiment2The 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 the film of nano particle preparation；
Fig. 8 is the modified CeO of embodiment two2The atomic force microscopy diagram of the film of nano particle preparation；
Fig. 9 is the modified CeO of embodiment two2The film of nano particle preparation penetrates spectrogram；
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 to draw
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 forbidden bandwidth (Bandgap) figure of film；
Figure 13 is the modified CeO of embodiment two2X-ray photoelectron spectroscopy (XPS, the X-ray of the film of nano particle preparation
Photoelectron Spectrometer) figure；
Figure 14 is the modified CeO of embodiment two2The high-resolution X-ray photoelectricity of the Ce elements of the film of nano particle preparation
Sub- spectrogram；
Figure 15 is the modified CeO of embodiment two2The high-resolution X-ray photoelectricity of the oxygen element of the film of nano particle preparation
Sub- spectrogram；
Figure 16 is the battery device structure chart of the formal plane perovskite solar battery of embodiment three, wherein 1 is indium-doped
Tin oxide (ITO, Indium doped tin oxide) electro-conductive glass, 2 be modified cerium oxide electron transfer layer, and 3 be calcium
Titanium ore 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 passes
Defeated layer, 3 be perovskite light-absorption layer, and 8 be the cerium oxide electron transfer layer of oleic acid package, 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 afterwards, 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 layer 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.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
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 the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
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 CeO2It receives
The XRD diffraction pattern of rice grain, by above three figure it is found that modified monodispersed CeO used2Nano particle crystal form self assembly row
Column, main exposure interplanar distance is 0.262 nanometer, belongs to (200) crystal face, and plane of crystal activity can be compared with other crystal faces height, 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 respectively corresponding (111), (200), and (220), (311) and (400) etc.
Five crystal faces.
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 package organic molecule be the longer oleic acid organic molecule of carbon chain lengths, the clean nanometer obtained after oleic acid desorption
Grain, after then carrying out surface modification treatment, the shorter acetylacetone,2,4-pentanedione organic molecule of carbon chain lengths is adsorbed on 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 spectroscopy of nano particle compares
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 completely disappeared, receiving at this time
Rice grain is that the cerium oxide nanoparticles of no oleic acid package can be in light wave number after the surface modification treatment of acetylacetone,2,4-pentanedione
It can be seen that the characteristic peak peak type of acetylacetone,2,4-pentanedione, the offset of peak position may be due to the two of acetylacetone,2,4-pentanedione in 3000~2500 sections
Kind is the same as position isomer and CeO2The combination of nano particle.
Modified CeO in order to further illustrate the present invention2Nano particle and products thereof, below with reference to specific embodiment into
One step illustrates.
Embodiment 1, includes the following steps:
(1) weighing cerium nitrate hexahydrate and being dissolved in distilled water configuration concentration is 17mmol/L, under conditions of ice-water bath by
Be added dropwise to tert-butylamine to PH be 8；
(2) take 150 milliliters of steps (1) solution to be added in 500 milliliters of reaction kettle, be added oleic acid, configuration oleic acid with
The precursor solution that the oleic acid that cerium ion molar ratio is 10:1 is protected, the precursor solution by oleic acid protection are with volume of toluene ratio
Toluene (can replace toluene with benzene, n-hexane, carbon tetrachloride or methylene chloride) is added in 1:1, and standing does not stir；
(3) reaction kettle of step (2) filling about 60% is moved into 180 degrees Celsius of constant temperature of baking oven, reaction 24
It is cooled to room temperature, takes out after hour, upper layer brown clear liquid is taken to obtain the toluene solution of the cerium oxide of oleic acid package；
(4) toluene solution for the cerium oxide for taking oleic acid described in 30 milliliters of steps (3) to wrap up and the dehydrated alcohol of 30mL are mixed
It closes, it is precipitated sufficiently in stirring, ultrasound, and the cerium oxide that centrifugation obtains auburn oleic acid package under 8000r/min speed is received
Rice grain；
(5) step (4) are repeated three times to remove excessive oleic acid in solution, the cerium oxide for obtaining the oleic acid package of brown is received
Rice grain；
(6) cerium oxide particle of 2 grams of steps (5) oleic acid package is taken to be dispersed in 20 milliliters of toluene solvant again,
Configure the CeO of 0.1g/mL oleic acid package2Toluene solution, ultrasound keeps its fully dispersed；
(7) cerium oxide of the package of oleic acid described in step (6) is added dropwise in 40% aqueous solution for taking tetrabutylammonium hydroxide
Toluene solution in, adjust pH value to 10, oscillation, ultrasound react it sufficiently, to carry out desorption；
(8) dehydrated alcohol is added in the solution described in step (7), and the solution after reaction is fully transferred to 100 milliliters
In centrifuge tube.Under the speed of 6000r/min, three layers of product being separated from each other are obtained, supernatant liquor is removed, takes milk yellow heavy
It forms sediment.It is cleaned repeatedly three times with dehydrated alcohol by above-mentioned steps, it is ensured that remaining without impurity product.The pure cerium oxide dispersed
Nano particle；
(9) the pure cerium oxide nanoparticles of dispersion described in 2 grams of steps (8) are weighed, acetylacetone,2,4-pentanedione is added, configure CeO2
Mass concentration is the solution of 0.1g/mL, and oscillation, ultrasound make it be dispersed to no obvious particle；
(10) it after being stirred solution described in step (9) repeatedly, being 48 hours ultrasonic, stirs with ultrasonication alternately,
The acetylacetone,2,4-pentanedione solution of cerium oxide is obtained by 220 nanometers of the membrane filtration in aperture；
(11) step (10) the filtered solution is added into revolving instrument to remove superfluous acetylacetone,2,4-pentanedione.Revolving
Instrument water temperature is controlled at 40~100 degrees Celsius, and 0~80 millipascal of air pressure obtains kermesinus slurry.So far, acetylacetone,2,4-pentanedione is obtained to change
The CeO of property2Nano material.
Embodiment 2, includes the following steps:
(1) configuration step of modified cerium oxide solution: by cerium oxide slurry described in 1 step of embodiment (11) point
It is dispersed in alcohol solvent, obtains modified cerium oxide solution.
(2) cleaning step: selecting sheet resistance is 5~25 ohm, indium-doped tin oxide (ITO) glass of transmitance 70%~90%
Glass is substrate, is then successively cleaned with dish washing liquid, distilled water, ethyl alcohol and acetone, is handled after nitrogen is dry with oxygen plasma beam
10 minutes；
(3) preparation of modified ceria film: solution described in 70 microlitres of steps (1) is taken to be spin-coated on step (2) institute
The surface indium-doped tin oxide (ITO) stated is placed on 80 degrees Celsius of heat after speed spin coating solution 30 seconds of 5000 rpms
It is heated 10 minutes on platform, obtains modified ceria film.
Fig. 6 is the CeO of different phase in two Process of Surface Modification of embodiment2The light of nano particle dispersity in a solvent
Learn photo comparison's figure, as seen from the figure, clean cerium oxide more difficult dispersion in a solvent, it is necessary to carry out surface Modified lift material
Dispersibility, the modified CeO in surface2Nano material good dispersion of energy in the different solvent of two kinds of polarity, obtains color
Slightly discrepant clarification, clear solution；
Fig. 7 is the modified CeO in two surface of embodiment2The front scan electron microscope of the film of nano particle preparation
Figure, as seen from the figure, by modified CeO2The film of nano particle preparation is continuous, smooth, pin-free, the modified CeO in surface2
Nano particle improves the modified CeO in surface since dispersibility in a solvent improves2The machine of the film of nano particle preparation
Tool performance；
Fig. 8 is the modified CeO in two surface of embodiment2The atomic force microscopy diagram of the film of nano particle preparation, by scheming
It is found that the modified CeO in surface2The film of nano particle preparation 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 two surface of embodiment2The film of nano particle preparation penetrates spectrogram, as seen from the figure,
The modified CeO in surface2The light transmission rate of the film of nano particle preparation is high, meets and is used as perovskite window layer of solar battery
Requirement；
Figure 10 is the modified CeO in two surface of embodiment2Nano particle prepares the fluorescence spectra of film, as seen from the figure,
The modified CeO in surface2The film of nano particle preparation has apparent fluorescent effect in ultraviolet region, can will have to perovskite broken
The ultraviolet light of bad effect is converted into the visible light that can be absorbed by perovskite, improves perovskite while protecting perovskite light-absorption layer
The external quantum efficiency of solar battery.
Figure 11 is the modified CeO in two surface of embodiment2Nano 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 apart from vacuum level, the modified CeO in surface2The maximum valence band location of nano particle is
3.44 electron-volts (eV), i.e. the position of top of valence band position (VB) apart from fermi level is 3.44 electron-volts, can be calculated
The valence band location of cerium oxide is -7.56 electron-volts (eV)；
Figure 12 is the modified CeO in two surface of embodiment2Nano particle prepares forbidden bandwidth (Bandgap) figure of film,
As seen from the figure, the modified CeO in surface2The forbidden bandwidth of nano particle is 3.5 electron-volts (eV), the i.e. conduction band of cerium oxide
Position is 3.5 electron-volts at a distance from valence band location, and the conduction band positions that cerium oxide can be calculated are -4.06 electron-volts
(eV)；
Figure 13 is the modified CeO in two surface of embodiment2Nano particle preparation film x-ray photoelectron spectroscopy (XPS,
X-ray Photoelectron Spectrometer) figure, as seen from the figure, the modified CeO in surface2Nano particle is prepared thin
The combination energy position of the Ce element of film is between 880eV 920eV, and the combination energy position of O element is between 530eV 540eV；
Figure 14 is the modified CeO in two surface of embodiment2The high-resolution X-ray of the Ce elements of the film of nano particle preparation
Photoelectron spectrogram, as seen from the figure, 3d5/2The Ce elements of track are by two kinds of valence states of trivalent cerium and quadrivalent cerium, and wherein trivalent cerium can divide
U ' (v ') and u out0(v0) two tracks, quadrivalent cerium can divide out u " ' (v " '), three tracks of u " (v ") and u (v), by song
The atom accounting of line integral, available trivalent cerium and quadrivalent cerium is respectively 60.28 at.% and 39.72at.%；
Figure 15 is the modified CeO in two surface of embodiment2The high-resolution X-ray of the oxygen element of the film of nano particle preparation
Photoelectron spectrogram, as seen from the figure, there are three characteristic peaks for the oxygen element of 1s track, wherein in conjunction 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 is into 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 is used to prepare the battery device of formal plane perovskite solar battery, includes the following steps:
(1) cleaning step: selecting sheet resistance is 5~25 ohm, indium-doped tin oxide (ITO) glass of transmitance 70%~90%
Glass is substrate, is then successively cleaned with dish washing liquid, distilled water, ethyl alcohol and acetone, is handled after nitrogen is dry with oxygen plasma beam
10 minutes；
(2) preparation of electron transfer layer solution: cerium oxide slurry described in 1 step of Example (11) is dense by quality
5 milligrams every milliliter of degree is dispersed in chlorobenzene solvent, and stirring obtains the chlorobenzene solution of cerium oxide to whole dispersions under room temperature.
(3) preparation of electron transfer layer: taking solution described in step (2) to be spin-coated in ITO substrate described in step (1),
After speed spin coating solution 30 seconds of 5000 rpms, 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 step of perovskite solution: by PbI2It is mixed to form mixture with MAI, wherein PbI2Accounting for molar ratio is
70%, it is dissolved in DMF and DMSO in the mixed solvent, 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: configured perovskite solution is spin-coated on cerium oxide electron transfer layer, with 6000
Rpm speed spin coating solution 30 seconds after, be placed in 100 degrees Celsius of thermal station and heat 10 minutes, solvent volatilization after formed
The perovskite light-absorption layer of one layer of about 350 nanometer thickness；
(6) preparation step of hole transmission layer solution: taking 80 milligrams of Spiro-OMeTAD powder, and 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), oscillation make it
Dissolution completely, aoxidizes 12 hours in dry air, obtains the chlorobenzene solution of Spiro-OMeTAD.
(7) preparation of hole transmission layer: configured Spiro-OMeTAD solution is spin-coated on perovskite light-absorption layer, shape
At about 100 nanometer thickness hole transmission layers.
(8) preparation step of the metal to electrode: vacuum evaporation coating film device is used, one is deposited on the hole transport layer
Layer obtains solid formal plane perovskite solar battery with a thickness of the gold electrode of 100nm.
Figure 16 is the battery device structure chart of the formal plane perovskite solar battery of embodiment three, and Figure 17 is embodiment
Photovoltaic curve of the three formal plane perovskite solar cell devices under a standard sun light intensity, by above two figure it is found that
The modified CeO in surface2The film of nano particle preparation is applied in formal plane perovskite solar battery as Window layer,
Have benefited from its high transmittance, prepared formal plane solar energy battery has very high short circuit current.
Embodiment 4, includes the following steps:
(1) cleaning step: selecting sheet resistance is 5~25 ohm, fluorine-doped tin oxide (FTO) glass of transmitance 70%~90%
Glass is substrate, is then successively cleaned with dish washing liquid, distilled water, ethyl alcohol and acetone, is handled after nitrogen is dry with oxygen plasma beam
10 minutes；
(2) preparation step of hole transmission layer solution: at room temperature, weigh a certain amount of nickel acetylacetonate, lithium acetate and
Magnesium acetate is mixed according to stoichiometric ratio Ni:Li:Mg=80:5:15, is dissolved in acetonitrile solution, obtaining nickel molar concentration is
0.02 mole every liter of precursor liquid.
(3) preparation of hole transmission layer: by step (1), treated that electro-conductive glass is placed on 600 degrees Centigrades upward
On platform, using precursor solution described in oxygen pressing atomization steps (2), successively continuously 50 milliliters of precursor solutions are sprayed into
The conductive surface of high temperature deposits rapidly fine and close, continuous nickel magnesium lithia (NiMgLiO) compacted zone, and film thickness is about 20 nanometers.Spray
It applies and completes subsequent continuous annealing 60 minutes at such a temperature；
(4) preparation step of calcium titanium ore bed solution: identical as embodiment 2 step (4)；
(5) preparation of calcium titanium ore bed: configured perovskite solution is spin-coated on nickel magnesia lithium electron transfer layer, with
It behind speed spin coating solution 30 seconds of 6000 rpms, is placed in 100 degrees Celsius of thermal station and heats 10 minutes, after solvent volatilization
Form the perovskite light-absorption layer of one layer of about 350 nanometer thickness；
(6) preparation step of electron transfer layer solution: 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 of oleic acid package cerium oxide；
(7) preparation of electron transfer layer: taking solution described in step (6) to be spin-coated on calcium titanium ore bed described in step (5),
After speed spin coating solution 30 seconds of 5000 rpms, 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 package of nanometer thickness.
(8) preparation step of the metal to electrode: vacuum evaporation coating film device is used, one is deposited on the hole transport layer
Layer obtains the trans- plane perovskite solar battery of solid full-inorganic boundary layer with a thickness of the silver electrode of 100nm.
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, by above two figure it is found that oleic acid package cerium oxide preparation film as electron transfer layer in trans- single layer
It is applied in electron transfer layer plane battery, excessive intermolecular distance blocks charge in the migration of electron transfer layer, greatly reduces
The photovoltaic performance of solar battery obtains strange " S " type photovoltaic property curve.
Embodiment 5, includes the following steps:
First five step, i.e. step (1)~step (5) are same as Example 4.
(6) preparation step of electron transfer layer solution: cerium oxide slurry described in 1 step of Example (11), by matter
5 milligrams every milliliter of concentration of amount is dispersed in chlorobenzene solvent, and stirring obtains the chlorobenzene solution of cerium oxide to whole dispersions under room temperature；
(7) preparation of electron transfer layer: taking solution described in step (6) to be spin-coated on calcium titanium ore bed described in step (5),
After speed spin coating solution 30 seconds of 5000 rpms, 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 step of the metal to electrode: vacuum evaporation coating film device is used, one is deposited on the hole transport layer
Layer obtains the trans- plane perovskite solar battery of solid full-inorganic boundary layer with a thickness of the silver electrode of 100nm.
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, by above two figure it is found that the modified CeO in surface2The film of nano particle preparation exists as electron transfer layer
It is applied in trans- single layer electronic transport layer plane battery, intermolecular distance shortens in electron transfer layer, is conducive to charge and passes in electronics
The migration of defeated layer promotes the photovoltaic performance of solar battery.
Embodiment 6, includes the following steps:
First five step, i.e. step (1)~step (5) are same as Example 4.
(6) preparation step of electron transfer layer solution: at room temperature, weighing a certain amount of PCBM powder, dense according to quality
20 milligrams every milliliter of degree is dissolved in chlorobenzene solution, and the chlorobenzene solution that PCBM is obtained to being completely dissolved is stirred under 40 degrees Celsius；
(7) solution described in step (6) is taken to be spin-coated on 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 layer of about 50 nanometer thickness
Electron transfer layer.
(8) preparation step of the metal to electrode: vacuum evaporation coating film device is used, one is deposited on the hole transport layer
Layer obtains the trans- plane perovskite solar battery of solid bielectron transport layer with a thickness of the silver electrode of 100nm.
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, by above two figure it is found that PCBM preparation film put down as electron transfer layer in trans- single layer electronic transport layer
It is applied in the battery of face, the conductivity of PCBM is better than the modified CeO in surface2Nano particle, but due to the conduction band positions mistake of PCBM
Height, the contact with silver electrode reduce solar-electricity there are strong non-radiative recombination on the two interface for Schottky contacts
The photovoltaic performance in pond obtains class " S " type photovoltaic property curve.
Embodiment 7, includes the following steps:
The first seven step, i.e. step (1)~step (7) are same as Example 6.
(8) preparation step of upper layer electron transfer layer solution: cerium oxide slurry described in 1 step of Example (11),
It is dispersed in methanol solvate by 5 milligrams every milliliter of mass concentration, to whole dispersions, the methanol for obtaining cerium oxide is molten for stirring under room temperature
Liquid.
(9) under 6000 rpms of speed, by solution described in 150 microlitres of steps (7) dropwise drop coating in step (7)
On the PCBM electron transfer layer, it is placed in 80 degrees Celsius of thermal station and heats 10 minutes, obtain the oxidation of about 50 nanometer thickness
Cerium upper layer electron transfer layer.
(10) preparation step of the metal to electrode: vacuum evaporation coating film device is used, is deposited on the hole transport layer
A layer thickness is the silver electrode of 100nm, obtains the trans- plane perovskite solar battery of solid bielectron transport layer.
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 are the external quantum efficiency figures of the battery device of the trans- two-layer electronic transport layer plane battery structure of embodiment seven, by with
Upper three figure is it is found that the modified CeO in surface2The film of nano particle preparation (that is to say the second electricity as upper layer electron transfer layer
Sub- transport layer) it is applied in trans- two-layer electronic transport layer plane battery, two-layer electronic transport layer not only increases charge in electricity
Transmission speed in sub- transport layer, while the Schottky contacts on interface are eliminated, the outer quantum effect of battery device greatly improved
It answers, so that the photovoltaic performance of solar battery 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 are 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, by above two figure it is found that the modified CeO in surface2The film of nano particle preparation, due to surface acetylacetone,2,4-pentanedione
Organic molecule enhances intermolecular force, and the compactness of film is promoted, and 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 only parameter area is different, specific different are as follows:
(1) configuration concentration be 1mmol/L cerous nitrate solution, be added dropwise under conditions of ice-water bath ammonium hydroxide to PH be 9；
(2) in the precursor solution of oleic acid protection, oleic acid and cerium ion molar ratio are no more than 20:1, by oleic acid protection
Precursor solution and volume of toluene ratio are that toluene is added in 2:1；
(3) reaction kettle loading is 50%, is moved into 240 degrees Celsius of constant temperature of baking oven, and reaction was cooled to room after 48 hours
Temperature；
(6) CeO of the configuration no more than 5g/mL oleic acid package2Toluene solution, ultrasound keeps its fully dispersed；
(7) it takes tetramethylammonium hydroxide to be added in the toluene solution of the cerium oxide of oleic acid package, adjusts PH value to 14；
(9) CeO is configured2Mass concentration is the solution no more than 5g/mL；
(10) stirring, ultrasonic time are after 24 hours repeatedly.
The step of embodiment 9, this implementation, is identical with embodiment 1, and only parameter area is different, specific different are as follows:
(1) configuration concentration be 50mmol/L cerous nitrate solution, be added dropwise under conditions of ice-water bath ammonium hydroxide to PH be 4；
(2) in the precursor solution of oleic acid protection, oleic acid and cerium ion molar ratio are no more than 20:1, by oleic acid protection
Precursor solution and volume of toluene ratio are that toluene is added in 1:20；
(3) reaction kettle loading is 80%, is moved into 160 degrees Celsius of constant temperature of baking oven, and reaction was cooled to room after 12 hours
Temperature；
(6) CeO of the configuration no more than 5g/mL oleic acid package2Toluene solution, ultrasound keeps its fully dispersed；
(7) it takes tetramethylammonium hydroxide to be added in the toluene solution of the cerium oxide of oleic acid package, adjusts PH value to 6；
(9) CeO is configured2Mass concentration is the solution no more than 5g/mL；
(10) stirring, ultrasonic time are after 0.5 hour repeatedly.
Embodiment 10 is used to prepare the battery device of formal plane perovskite solar battery comprising the step of and reality
Apply that example 3 is identical, and only parameter area is different, it is specific different are as follows:
(2) preparation of electron transfer layer solution: the mass concentration for configuring cerium oxide is molten no more than 3 grams every milliliter of chlorobenzene
Liquid；
(3) it the preparation of electron transfer layer: is heated 10 minutes in 70 degrees Celsius of thermal station, obtains the cause of about 100 nanometer thickness
Close cerium oxide electron transfer layer；
(5) preparation of calcium titanium ore bed: configured perovskite solution is spin-coated on cerium oxide electron transfer layer, is placed on
It is heated 10 minutes in 150 degrees Celsius of thermal station, forms the perovskite light-absorption layer of one layer of about 300 nanometer thickness after solvent volatilization；
(7) about 1000 nanometer thickness hole transmission layers the preparation of hole transmission layer: are formed；
(8) the gold electricity that a layer thickness is 300nm preparation step of the metal to electrode: is deposited on the hole transport layer
Pole.
Embodiment 11 is used to prepare the battery device of formal plane perovskite solar battery comprising the step of and reality
Apply that example 3 is identical, and only parameter area is different, it is specific different are as follows:
(2) preparation of electron transfer layer solution: the mass concentration for configuring cerium oxide is molten no more than 3 grams every milliliter of chlorobenzene
Liquid.
(3) it the preparation of electron transfer layer: is heated 10 minutes in 70 degrees Celsius of thermal station, obtains the cause of about 10 nanometer thickness
Close cerium oxide electron transfer layer.
(5) preparation of calcium titanium ore bed: configured perovskite solution is spin-coated on cerium oxide electron transfer layer, is placed on
It is heated 10 minutes in 70 degrees Celsius of thermal station, forms the perovskite light-absorption layer of one layer of about 300 nanometer thickness after solvent volatilization.
(7) about 10 nanometer thickness hole transmission layers the preparation of hole transmission layer: are formed.
(8) the gold electricity that a layer thickness is 50nm preparation step of the metal to electrode: is deposited on the hole transport layer
Pole.
Embodiment 12 is used to prepare the battery device of trans- single layer electronic transmission layer plane perovskite solar battery, packet
Include following steps:
(1) preparation of hole transmission layer: the hole of one layer of 50nm thickness is deposited in fluorine-doped tin oxide electro-conductive glass conductive surface
Transport layer；
(2) configured perovskite precursor solution the preparation of perovskite light-absorption layer: is revolved into Tu hole in step (1)
It in transport layer, is then made annealing treatment at 70 DEG C, obtains 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),
Do not destroy it is dry at a temperature of perovskite light-absorption layer performance, to obtain the dense oxide cerium electron transfer layer of thickness 1000nm, institute
State the modified CeO in surface2The mass concentration of nano material is 3 grams per milliliters；
(4) preparation of the metal to electrode: in the intermediate semi-finished products merging vacuum evaporation coating film device that step (3) are obtained,
The aluminium electrode that vapor deposition a layer thickness is 50nm on the electron transport layer.
Embodiment 13 is used to prepare the battery device of trans- single layer electronic transmission layer plane perovskite solar battery, packet
Include following steps:
(1) preparation of hole transmission layer: the hole of one layer of 10nm thickness is deposited in fluorine-doped tin oxide electro-conductive glass conductive surface
Transport layer；
(2) configured perovskite precursor solution the preparation of perovskite light-absorption layer: is revolved into Tu hole in step (1)
It in transport layer, is then made annealing treatment at 150 DEG C, obtains 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),
Do not destroy it is dry at a temperature of perovskite light-absorption layer performance, it is described to obtain the dense oxide cerium electron transfer layer of thickness 10nm
The modified CeO in surface2The mass concentration of nano material is not more than 3 grams per milliliters；
(4) preparation of the metal to electrode: in the intermediate semi-finished products merging vacuum evaporation coating film device that step (3) are obtained,
The aluminium electrode that vapor deposition a layer thickness is 300nm on the electron transport layer.
Embodiment 14 is used to prepare the trans- planar structure solar battery of double-layer electric sublayer, which is characterized in that it includes such as
Lower step:
(1) preparation of hole transmission layer: the hole of one layer of 50nm thickness is deposited in fluorine-doped tin oxide electro-conductive glass conductive surface
Transport layer；
(2) configured perovskite precursor solution the preparation of perovskite light-absorption layer: is revolved into Tu hole in step (1)
It in transport layer, is then made annealing treatment at 70 DEG C, obtains perovskite light-absorption layer；
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, do not destroy perovskite light-absorption layer performance at a temperature of it is dry, to obtain
The first electron transfer layer with a thickness of 1000nm is obtained,
(4) preparation of second layer electron transfer layer: at room temperature, the first electron-transport layer surface spin coating is received in step (3)
Meter Mo Shui, do not destroy perovskite light-absorption layer performance at a temperature of it is dry, to obtain the dense oxide cerium electricity with a thickness of 1000nm
Sub- transport layer, the modified CeO in the surface2The mass concentration of nano material is not more than 3 grams per milliliters, first electron-transport
The electric conductivity of layer is better than the second layer electron transfer layer,
(5) preparation of the metal to electrode: in the intermediate semi-finished products merging vacuum evaporation coating film device that step (4) are obtained,
It is 50nm aluminium electrode that a layer thickness is deposited on the second electron transfer layer.
Embodiment 15 is used to prepare the trans- planar structure solar battery of double-layer electric sublayer, which is characterized in that it includes such as
Lower step:
(1) preparation of hole transmission layer: the hole of one layer of 10nm thickness is deposited in fluorine-doped tin oxide electro-conductive glass conductive surface
Transport layer；
(2) configured perovskite precursor solution the preparation of perovskite light-absorption layer: is revolved into Tu hole in step (1)
It in transport layer, is then made annealing treatment at 150 DEG C, obtains perovskite light-absorption layer；
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, do not destroy perovskite light-absorption layer performance at a temperature of it is dry, to obtain
The first electron transfer layer with a thickness of 10nm is obtained,
(4) preparation of second layer electron transfer layer: at room temperature, the first electron-transport layer surface spin coating is received in step (3)
Meter Mo Shui, do not destroy perovskite light-absorption layer performance at a temperature of it is dry, to obtain the dense oxide cerium electronics with a thickness of 10nm
Transport layer, the modified CeO in the surface2The 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: in the intermediate semi-finished products merging vacuum evaporation coating film device that step (4) are obtained,
It is 300nm aluminium electrode 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, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (8)
1. a kind of prepare the modified CeO in surface2The method of nano material, which is characterized in that it includes the following steps:
S1: the CeO of oleic acid package is prepared2Nano particle,
S2: the CeO for the oleic acid package 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 be toluene, benzene, n-hexane, carbon tetrachloride or methylene chloride, obtain oleic acid package CeO2Non- pole
Property solution,
S3: the CeO that the oleic acid obtained to step S2 wraps up2Non-polar solution in be added basic solvent, adjust pH value to 6~14,
To carry out desorption reaction enclosure, alcohols solvent is added after the completion of desorption and carries out eccentric cleaning, obtains the CeO of milk yellow2Particle,
S4: by the CeO of the step S3 milk yellow obtained2Particle is pressed in the mass concentration addition acetylacetone,2,4-pentanedione 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 modified CeO of acetylacetone,2,4-pentanedione that step S4 is obtained2Solution is evaporated under reduced pressure, to remove superfluous acetylacetone,2,4-pentanedione
Solvent obtains the modified CeO of acetylacetone,2,4-pentanedione2Nano material.
2. the modified CeO in preparation surface as described in claim 12The method of nano material, which is characterized in that institute in step S3
It states basic solvent and is selected from the organic amine solvent easily removed, be tetrabutylammonium hydroxide, tetramethylammonium hydroxide, ethamine, second two
Amine or tert-butylamine.
3. the modified CeO in preparation surface as claimed in claim 1 or 22The method of nano material, which is characterized 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, addition alkaline solution tune pH value to 4~9 forms solvent thermal reaction precursor solution,
S12: solvent thermal reaction precursor solution described in step S11 is added in autoclave, by oleic acid and cerium molar ratio
Oleic acid is added no more than 20, obtains the precursor solution of oleic acid protection, by the precursor solution and volume of toluene ratio of oleic acid protection
For 1:20~2:1 be added toluene so that in reaction kettle packed space 50%~80% reactant；
S13: reaction kettle described in step S12 being moved into 160 DEG C~240 DEG C of constant temperature of baking oven, after reaction 12 hours~48 hours
It is cooled to room temperature, takes upper layer brown clear liquid, obtain the toluene solution of the excessive cerium oxide of oleic acid；
S14: ethyl alcohol is added in the toluene solution of the excessive cerium oxide of the oleic acid described in step S13, obtains oil after eccentric cleaning
The CeO of acid package2Nano particle.
4. the modified CeO in preparation surface as claimed in claim 32The method of nano material, which is characterized in that the step S11
In alkaline solution be selected from tert-butylamine and ammonium hydroxide.
5. a kind of CeO modified using the surface prepared such as one of claim 1-4 method2Nano material.
6. a kind of CeO modified using surface as claimed in claim 52Nano material prepares formal planar structure solar battery
Method, which is characterized in that it includes 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,
Do not destroy it is dry at a temperature of 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 modified CeO in surface2Nano material is dispersed in shape in polar solvent or nonpolar solvent
At solution, wherein the modified CeO in the surface2The mass concentration of nano material is not more than 3 grams per milliliters；
(2) preparation of perovskite light-absorption layer: the densification that configured perovskite precursor solution rotation Tu is obtained in step (1)
It on cerium oxide electron transfer layer, is then made annealing treatment at 70~150 DEG C, obtains perovskite light-absorption layer；
(3) preparation of hole transmission layer: configured hole transport solution is spin-coated on step (2) and obtains the perovskite suction
On photosphere, formed 10nm~1000nm hole transmission layer, so far, obtain and meanwhile 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: in the intermediate semi-finished products merging vacuum evaporation coating film device that step (3) are obtained, in sky
The gold electrode that a layer thickness is 50nm~300nm is deposited in cave transport layer.
7. a kind of CeO modified using surface as claimed in claim 52Nano material prepares the trans- plane of single layer electronic transport layer
The method of structure solar battery, which is characterized in that it includes the following steps:
(1) preparation of hole transmission layer: one layer of sky for being not more than 50nm thickness is deposited in fluorine-doped tin oxide electro-conductive glass conductive surface
Cave transport layer；
(2) preparation of perovskite light-absorption layer: by configured perovskite precursor solution rotation Tu in step (1) hole-transporting layer
On, it is then made annealing treatment at 70~150 DEG C, obtains perovskite light-absorption layer；
(3) preparation of electron transfer layer: at room temperature, perovskite extinction layer surface spin coating nanometer ink, is not breaking in step (2)
It is dry 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 modified CeO in surface2Nano material is dispersed in shape in polar solvent or nonpolar solvent
At solution, wherein the modified CeO in the surface2The 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: in the intermediate semi-finished products merging vacuum evaporation coating film device that step (3) are obtained, in electricity
The aluminium electrode or silver electrode that a layer thickness is 50nm~300nm are deposited in sub- transport layer.
8. a kind of CeO modified using surface as claimed in claim 52Nano material prepares the trans- planar structure of double-layer electric sublayer
The method of solar battery, which is characterized in that it includes the following steps:
(1) preparation of hole transmission layer: one layer of sky for being not more than 50nm thickness is deposited in fluorine-doped tin oxide electro-conductive glass conductive surface
Cave transport layer；
(2) preparation of perovskite light-absorption layer: by configured perovskite precursor solution rotation Tu in step (1) hole-transporting layer
On, it is then made annealing treatment at 70~150 DEG C, obtains perovskite light-absorption layer；
The preparation of (3) first electron transfer layers: at room temperature, perovskite extinction layer surface spin coating organic electronic passes in step (2)
Defeated layer solution or inorganic electronic transport layer solution, do not destroy perovskite light-absorption layer performance at a temperature of it is dry, to obtain thickness
Degree is not more than the first electron transfer layer of 1000nm,
(4) preparation of second layer electron transfer layer: at room temperature, the first electron-transport layer surface spin coating nano-ink in step (3)
Water, do not destroy perovskite light-absorption layer performance at a temperature of it is dry, to obtain dense oxide cerium electricity of the thickness no more than 1000nm
Sub- transport layer,
The nanometer ink refers to the modified CeO in surface2Nano material is dispersed in shape in polar solvent or nonpolar solvent
At solution, wherein the modified CeO in the surface2The 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: in the intermediate semi-finished products merging vacuum evaporation coating film device that step (4) are obtained, the
The aluminium electrode or silver electrode that a layer thickness is 50nm~300nm are deposited on two electron transfer layers.
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Citations (2)
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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 |
| CN103553031A (en) * | 2013-11-06 | 2014-02-05 | 北京邮电大学 | Method for preparing reduced graphene oxide/cerium oxide nanoparticle composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN103553031A (en) * | 2013-11-06 | 2014-02-05 | 北京邮电大学 | Method for preparing reduced graphene oxide/cerium oxide nanoparticle composite |
Non-Patent Citations (2)
| Title |
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| 制备表面修饰油酸的CeO2纳米粒子;***，等;《化工质量》;20071231;第46-47页 |
| 纳米CeO2的表面改性及其在水介质中的分散性能;王明轩，等;《北京化工大学学报（自然科学版）》;20111231;第38卷(第4期);第6-11页 |
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