CN105304819A - Solar cell containing perovskite material and preparation method thereof - Google Patents
Solar cell containing perovskite material and preparation method thereof Download PDFInfo
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- CN105304819A CN105304819A CN201510827181.XA CN201510827181A CN105304819A CN 105304819 A CN105304819 A CN 105304819A CN 201510827181 A CN201510827181 A CN 201510827181A CN 105304819 A CN105304819 A CN 105304819A
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- H—ELECTRICITY
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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Abstract
The invention discloses a solar cell containing perovskite material and a preparation method thereof. The perovskite solar cell comprises a light transmission layer, a transparent electrode layer, a transition layer, an electron transport layer, a light absorption layer, an electron absorption layer, a hole transport layer, and a top electrode which are successively stacked. The transition layer is an oxide of nickel. The electron transport layer is a quaternary oxide. The light absorption layer is a material provided with perovskite structure. The electron absorption layer is formed by fullerene derivative. The hole transport layer is formed by a ternary oxide. The top electrode is formed by a material with good conductivity. The solar cell effectively utilizes the performance of the perovskite material, is increased in the photoelectric converting efficiency by over 20 percent, and is suitable for batch production.
Description
Technical field
The invention belongs to perovskite area of solar cell, particularly a kind of solar cell comprising perovskite material and preparation method thereof.
Background technology
Human use's solar energy has various ways, such as, utilize its thermal effect, luminous effect etc.Solar cell is the device directly light energy conversion being become electric energy by photoelectric effect or Photochemical effects, is also called photovoltaic cell.Prevailing silicon solar cell on current commercial solar cell market, namely using crystalline silicon as the material of photoelectric conversion.Perovskite solar cell is a class solar cell comparatively novel at present, mainly utilizes similar ABX (A=CHNH+ etc.; B=Pb2+, Sn2+ etc.; X=Cl-, Br-, I-etc.) there is the photovoltaic material of perovskite structure to realize opto-electronic conversion.In recent years, people study discovery, and this kind of cell photoelectric transformation efficiency is high, and cost is low.Promise to be the commercial solar cell of future generation of low cost.
Chinese invention patent CN104701023A discloses carbon electrode material of a kind of perovskite solar cell and preparation method thereof, sprayed on membrane method is adopted to prepare compact titanium dioxide film electron transfer layer in electrically conducting transparent substrate, then on compact titanium dioxide film, the organic metal halide of perovskite structure is prepared as light absorbing zone, then on perovskite thin film light absorbing zone, prepare hole transmission layer/carbon electrode layer by sprayed on membrane method, the C film obtained is the carbon electrode layer of perovskite solar cell.This invention adopts material with carbon element to substitute expensive noble metal as hole transport electrode material, reduces costs.Sprayed on membrane method that is simple, quick, that be produced on a large scale is adopted to further save cost; and solve that perovskite electrode of solar battery cost is high, the problem that metal electrode method is difficult to accomplish scale production is prepared in vacuum evaporation, be applicable to the electrode material of low-temperature growth large area perovskite solar cell.The transformation efficiency of the battery of this invention is lower than 7%.
Chinese invention patent CN104091889B discloses a kind of semiconductor perovskite solar cell and preparation method thereof, the invention belongs to area of solar cell, solve the problem of existing perovskite solar cell material costliness, complex process, keep higher photoelectric conversion efficiency simultaneously.A kind of semiconductor perovskite solar cell of the present invention; comprise substrate, conductive layer, hole blocking layer, mesoporous electron collection layer, mesoporous hole collection layer, mesoporous dorsum electrode layer from bottom to top successively, its preparation method comprises preparation electrode district, prepares hole blocking layer, prepares mesoporous electron collection layer, prepares mesoporous hole collection layer, prepares mesoporous dorsum electrode layer and injection perovskite light absorbent step; Another kind of semiconductor perovskite solar cell of the present invention, adds mesoporous insulating barrier, the mesoporous insulating barrier step of its preparation method corresponding increase preparation.The invention solves the existing material expensive of perovskite solar cell, the problem of complex process; All be improved in the open circuit voltage of battery, short circuit current and fill factor, curve factor several respects.Photoelectric conversion efficiency can reach 11.3%.
Chinese invention patent CN104576932A discloses perovskite photovoltaic cell of the mesoporous electron transfer layer of a kind of double-layer nanometer and preparation method thereof.This battery is made up of conductive substrates, double-deck electron transfer layer, perovskite light-absorption layer, hole transmission layer and metal electrode.Adopt the SnO2 of one-step method low-temperature epitaxy as electron transfer layer, instead of the TiO2 electron transfer layer of two-step method high temperature sintering, greatly simplify preparation flow.The mesoporous perovskite photovoltaic cell of this one-step method low-temperature growth, at the high-photoelectric transformation efficiency obtaining 13.82%, effectively reduces cost of manufacture simultaneously, improves the performance of battery and stability.But, its transformation efficiency is still lower than 15%.
Perovskite solar cell progressively constantly advances to industrialization by foregoing invention, and but, two conditions are depended in the industrialization of perovskite, and one is low cost of manufacture, but its transformation efficiency wants high, and at present its efficiency all also below 15%.Finding more high efficiency solar battery structure is the focus that people work.
Summary of the invention
Goal of the invention: in order to make full use of the character of perovskite material, preparation can be used for the perovskite solar cell produced, and the invention provides a kind of solar cell comprising perovskite material and preparation method thereof.Adopt battery material of the present invention and structure thereof, significantly can improve solar cell to the absorption of photon and transformation efficiency thereof, thus improve the electricity conversion of solar cell, improve device performance.
Technical scheme of the present invention is as follows:
1) adopt the glass of light transmittance more than 90% as photic zone;
2) adopt electro-conductive glass as transparent electrode layer;
3) transition zone is prepared: adopt spray pyrolysis technology to prepare the oxide skin(coating) of nickel at conductive glass surface.THICKNESS CONTROL is within the scope of 5-50nm;
4) prepare electron transfer layer: the then mixture of the sour acetone nickel of spin coating, lithium acetate, magnesium acetate 4 hydrate, dry (300 DEG C-400 DEG C), prepare electron transfer layer, THICKNESS CONTROL is between 10-100nm;
5) light-absorption layer is prepared:
A. prepare PbI2 solution, the concentration of PbI2 is 0.5-3.0Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 10mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer.By the concentration of control PbI2 and CH3NH3I reaction solution, control pattern and the thickness of perovskite, THICKNESS CONTROL is between 50-500nm;
6) Electron absorption layer is prepared:
Adopt the chlorobenzene solution of fullerene derivate to be spun on light-absorption layer, dry, obtain Electron absorption layer, control concentration and the coating thickness of solution, make the thickness of Electron absorption layer between 30-150nm;
7) hole transmission layer is prepared:
By mixing of titanium isopropoxide (or two (acetylacetone based) diisopropyl titanate precursor solution) and ethanol niobium, stir, be spun on Electron absorption layer;
8) preparation of top electrode:
Adopt the methods such as vacuum thermal evaporation, spraying, deposition, at conductive metal layer or the carbon-coating of device upper surface evaporation 50-300nm.
The material of perovskite solar cell transparent electrode layer of the present invention is transparent and the material that can conduct electricity composition, include but not limited to indium tin oxide (ITO, IndiumTinOxides), fluorine tin-oxide (FTO, fluorinedopedtinoxide) transparent electrode material that, aluminium zinc oxide (AZO, aluminium-dopedzincoxide) etc. are conventional.Transition zone is the oxide of Ni, including but not limited to NiO, NiO
2.Electron transfer layer is quaternary oxide, be made up of, and the mol ratio of Li/Mg is between 1:10 and 1:3 Ni, Mg, Li, O tetra-kinds of elements.Light-absorption layer is the material with perovskite structure, and the perovskite structure photovoltaic material adopted is the organic inorganic hybridization perovskite of ABX3 type crystal structure.Wherein, B is lead, tin, antimony, and X is halogens.Electron absorption layer is the derivative of fullerene, including but not limited to PCBM, PC71BM.Hole transmission layer is made up of ternary oxide, comprise Ti, Nb, O tri-kinds of elements, and the mol ratio of Nb/Ti is between 1:30 and 1:10.Top electrode is metal electrode or conductive carbon material electrode, as silver, gold, copper, graphite, Graphene etc.
Useful effect:
Adopt material of the present invention and structure, can make full use of the performance of perovskite material, and excavate its potential, form P-I-N heterojunction, fully absorb solar energy and improve its conversion ratio, its transformation efficiency reaches as high as more than 20%.Present invention employs the nickeliferous transition zone of nanoscale, P-I-N heterojunction can not only be promoted and flutter the ability obtaining absorb photons, and greatly improve the time stability of this battery.The present invention mainly adopts the rubbing method of industrial maturation, is applicable to the production of industrialization production large scale, low cost, high efficiency solar cell.But, the existing solar cell containing perovskite material not yet obtains the sample that large area can be used for producing, the invention solves this problem, the technology of inventing is suitable for preparing large area, high efficiency solar cell, and its cost only has 1/3rd of traditional silicon solar cell.
embodiment:
Below by 1 describing device of the present invention and preparation method thereof in detail with embodiment by reference to the accompanying drawings, but be not construed as limiting the invention.
accompanying drawing illustrates:
Fig. 1 is structural representation of the present invention.1 be photic zone in figure, 2 transparent electrode layers, 3 are transition zone, 4 be electron transfer layer, 5 be light-absorption layer, 6 be Electron absorption layer, 7 for hole transmission layer and 8 is for top electrode.
embodiment 1
1) adopt low iron glass as photic zone;
2) ITO(IndiumTinOxides is adopted) electro-conductive glass is as transparent electrode layer;
3) spray pyrolysis technology is adopted to prepare NiO2 layer at conductive glass surface, thickness 8nm;
4) according to the mixed solution of the sour acetone nickel of the proportional arrangement of mol ratio 2:1:6, lithium acetate, magnesium acetate 4 hydrate, be spun on transition zone, in 350 DEG C of oven dry, prepare electron transfer layer; Thickness 15nm;
5) light-absorption layer is prepared:
A. prepare PbI2 solution, concentration is 1.5Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 8.5mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer.Thickness 410nm;
6) Electron absorption layer is prepared
Adopt the chlorobenzene solution of PCBM to be spun on light-absorption layer, dry, obtain thickness 83nm and obtain Electron absorption layer;
7) hole transmission layer is prepared:
By titanium isopropoxide and ethanol niobium the mixing of ratio in 25:1, stir, be spun on Electron absorption layer, obtain hole transmission layer;
8) preparation of top electrode:
Adopt the silver layer of method evaporation 50nm on hole transmission layer of vacuum thermal evaporation.
Carry out battery performance test, adopt in experimentation and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 19.8%.
embodiment 2
1) adopt low iron glass as photic zone;
2) adopt aluminium zinc oxide AZO electro-conductive glass as transparent electrode layer;
3) spray pyrolysis technology is adopted to prepare NiO2 layer at conductive glass surface.Thickness 50nm;
4) according to the mixed solution of the sour acetone nickel of the proportional arrangement of mol ratio 1:1:3, lithium acetate, magnesium acetate 4 hydrate, be spun on transition zone, in 400 DEG C of oven dry, prepare electron transfer layer; Thickness 60nm;
5) light-absorption layer is prepared:
A. prepare PbI2 solution, concentration is 0.5Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 10mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer, thickness 500nm;
6) Electron absorption layer is prepared
Adopt the chlorobenzene solution of PC71BM to be spun on light-absorption layer, dry, obtain the Electron absorption layer of thickness 30nm;
7) hole transmission layer is prepared:
By titanium isopropoxide and ethanol niobium the mixing of ratio in 20:1, stir, be spun on Electron absorption layer, obtain hole transmission layer;
8) preparation of top electrode:
Adopt the silver layer of the method for hot evaporation evaporation 300nm on hole transmission layer.
Carry out battery performance test, adopt in experimentation and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 20.4%.
embodiment 3
1) adopt low iron glass as photic zone;
2) fluorine tin-oxide (FTO, fluorinedopedtinoxide) electro-conductive glass is adopted to make transparent electrode layer;
3) adopt spray pyrolysis technology at conductive glass surface NiO2 layer.Thickness 6nm;
4) according to the mixed solution of the sour acetone nickel of the proportional arrangement of mol ratio 1:1:10, lithium acetate, magnesium acetate 4 hydrate, be spun on transition zone, in 350 DEG C of oven dry, prepare electron transfer layer; Thickness 98nm;
5) light-absorption layer is prepared:
A. prepare PbI2 solution, concentration is 2.3Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 7.5mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer.Thickness 450nm;
6) Electron absorption layer is prepared
Adopt the chlorobenzene solution of PCBM to be spun on light-absorption layer, dry, obtain the Electron absorption layer of thickness 150nm;
7) hole transmission layer is prepared:
By two (acetylacetone based) diisopropyl titanate precursor solution and the mixing mixing the ratio in 10:1 of ethanol niobium, stir, be spun on Electron absorption layer, obtain hole transmission layer;
8) preparation of top electrode:
Adopt the silver layer of method evaporation 250nm on hole transmission layer of vacuum thermal evaporation.
Carry out battery performance test, adopt in experimentation and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 20.1%.
embodiment 4
1) adopt low iron glass as photic zone;
2) adopt ITO electro-conductive glass as transparent electrode layer;
3) spray pyrolysis technology is adopted to prepare NiO layer at conductive glass surface, thickness 35nm;
4) according to the mixed solution of the sour acetone nickel of the proportional arrangement of mol ratio 1:1:5, lithium acetate, magnesium acetate 4 hydrate, be spun on transition zone, in 300 DEG C of oven dry, prepare electron transfer layer; THICKNESS CONTROL is at 10nm;
5) light-absorption layer is prepared:
A. prepare PbI2 solution, concentration is 3.0Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 5mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer, thickness 50nm;
6) Electron absorption layer is prepared
Adopt the chlorobenzene solution of PCBM to be spun on light-absorption layer, dry, obtain the Electron absorption layer of thickness 60nm;
7) hole transmission layer is prepared:
By titanium isopropoxide and ethanol niobium the mixing of ratio in 30:1, stir, be spun on Electron absorption layer, obtain hole transmission layer;
8) preparation of top electrode:
Adopt the silver layer of method evaporation 150nm on hole transmission layer of vacuum thermal evaporation.
Carry out battery performance test, adopt in experimentation and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 19.5%.
embodiment 5
1) adopt low iron glass as photic zone;
2) adopt aluminium zinc oxide AZO electro-conductive glass as transparent electrode layer;
3) spray pyrolysis technology is adopted to prepare NiO layer at conductive glass surface; THICKNESS CONTROL is at 15nm;
4) according to the mixed solution of the sour acetone nickel of the proportional arrangement of mol ratio 2:1:3, lithium acetate, magnesium acetate 4 hydrate, be spun on transition zone, in 360 DEG C of oven dry, prepare electron transfer layer; Thickness 55nm;
5) light-absorption layer is prepared:
A. prepare PbI2 solution, concentration is 2.0Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 8mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer; Thickness 500nm;
6) Electron absorption layer is prepared
Adopt the chlorobenzene solution of PCBM to be spun on light-absorption layer, dry, obtain thickness 95nm and obtain Electron absorption layer;
7) hole transmission layer is prepared:
By titanium isopropoxide and ethanol niobium the mixing of ratio in 10:1, stir, be spun on Electron absorption layer, obtain hole transmission layer;
8) preparation of top electrode:
Adopt the carbon-coating of method evaporation 98nm on hole transmission layer of chemical deposition.
Carry out battery performance test, adopt in experimentation and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 18%.
The above is only some examples of embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. solar cell comprising perovskite material and preparation method thereof, the photic zone that this battery stacks gradually, transparent electrode layer, transition zone, electron transfer layer, light-absorption layer, Electron absorption layer, hole transmission layer and top electrode, wherein: described transition zone is the oxide of nickel; Electron transfer layer is quaternary oxide; Light-absorption layer is the material with perovskite structure; Described Electron absorption layer is made up of fullerene derivate; Described hole transmission layer is made up of ternary oxide, and described top electrode is made up of the material that electric conductivity is good.
2. a solar cell as claimed in claim 1, is characterized in that, the quaternary oxide of described electron transfer layer is made up of Ni, Mg, Li, O tetra-kinds of elements, and the mol ratio of Li/Mg is between 1:10 and 1:3; Described hole transmission layer is ternary oxide, be made up of, and the mol ratio of Nb/Ti is between 1:30 and 1:10 Ti, Nb, O tri-kinds of elements; Described electric transmission layer thickness is between 10-100nm, and described light-absorption layer thickness is between 50-500nm, and described Electron absorption layer thickness is between 30-150nm, and described top electrode thickness is between 50-300nm.
3. a solar cell as claimed in claim 1, is characterized in that, its preparation method comprises following steps:
1) photic zone adopts the glass of light transmittance more than 90%;
2) adopt electro-conductive glass as transparent electrode layer;
3) transition zone is prepared: adopt spray pyrolysis technology to prepare the oxide skin(coating) of nickel at conductive glass surface;
4) prepare electron transfer layer: the then mixture of the sour acetone nickel of spin coating, lithium acetate, magnesium acetate 4 hydrate, dry (300 DEG C-400 DEG C), prepare electron transfer layer, THICKNESS CONTROL is between 10-100nm;
5) light-absorption layer is prepared:
A. prepare PbI2 solution, the concentration of PbI2 is 0.5-3.0Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 5-10mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer; By the concentration of control PbI2 and CH3NH3I reaction solution, control pattern and the thickness of perovskite, THICKNESS CONTROL is between 50-500nm;
6) Electron absorption layer is prepared:
Adopt the chlorobenzene solution of fullerene derivate to be spun on light-absorption layer, dry, obtain Electron absorption layer, control concentration and the coating thickness of solution, make the thickness of Electron absorption layer between 30-150nm;
7) hole transmission layer is prepared:
By mixing of titanium isopropoxide (or two (acetylacetone based) diisopropyl titanate precursor solution) and ethanol niobium, stir, be spun on Electron absorption layer;
8) preparation of top electrode:
Adopt the methods such as vacuum thermal evaporation, spraying, deposition, at conductive metal layer or the carbon-coating of device upper surface evaporation 50-300nm.
4. solar cell as claimed in claim 1, it is characterized in that, the material of transparency electrode is transparent and the material that can conduct electricity composition, include but not limited to indium tin oxide (ITO, IndiumTinOxides), fluorine tin-oxide (FTO, fluorinedopedtinoxide), the transparent electrode material such as aluminium zinc oxide (AZO, aluminium-dopedzincoxide).
5. solar cell as claimed in claim 1, it is characterized in that, described perovskite structure photovoltaic material is the organic inorganic hybridization perovskite of ABX3 type crystal structure; Wherein, B is lead, tin, antimony, and X is halogen.
6. solar cell as claimed in claim 1, it is characterized in that, Electron absorption layer is the derivative of fullerene, including but not limited to PCBM, PC71BM.
7. solar cell as claimed in claim 1, it is characterized in that, described top electrode is metal electrode or material with carbon element electrode.
8. solar cell as claimed in claim 1, it is characterized in that, the thickness of transition zone is within the scope of 5-50nm.
9. solar cell as claimed in claim 1, it is characterized in that, described photic zone is the material that light transmittance is greater than 90%.
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Cited By (6)
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| CN106159094A (en) * | 2016-07-04 | 2016-11-23 | 陕西煤业化工技术研究院有限责任公司 | A kind of perovskite solar cell based on silica-based micro-nano structure and preparation method thereof |
| CN106711334A (en) * | 2017-02-17 | 2017-05-24 | 镇江皮埃纳米科技有限公司 | Solar battery containing perovskite material and preparation method of solar battery |
| CN106784333A (en) * | 2017-02-17 | 2017-05-31 | 镇江皮埃纳米科技有限公司 | A kind of perovskite solar cell of high stability and preparation method thereof |
| CN108580174A (en) * | 2018-06-30 | 2018-09-28 | 中国科学院上海硅酸盐研究所 | The coating process and device of perovskite light-absorption layer in a kind of perovskite solar cell |
| CN110518124A (en) * | 2019-07-26 | 2019-11-29 | 西安电子科技大学 | Using ternary quaternary oxide as the perovskite solar battery and preparation method of electron transfer layer |
| CN115745811A (en) * | 2021-09-03 | 2023-03-07 | 中国科学院大连化学物理研究所 | Undoped or stibium-doped non-lead-doped indium-based halogen perovskite material and synthesis and application thereof |
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