CN105609646A - Preparation method of perovskite solar cell - Google Patents
Preparation method of perovskite solar cell Download PDFInfo
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- CN105609646A CN105609646A CN201510999602.7A CN201510999602A CN105609646A CN 105609646 A CN105609646 A CN 105609646A CN 201510999602 A CN201510999602 A CN 201510999602A CN 105609646 A CN105609646 A CN 105609646A
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- H—ELECTRICITY
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/211—Changing the shape of the active layer in the devices, e.g. patterning by selective transformation of an existing layer
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
Abstract
The invention discloses a preparation method of a perovskite solar cell. The method comprises the following steps: dispersing a copper nanowire and a silver nanowire into an ethanol solution at equal molar ratio; coating conductive glass comprising a titanium dioxide compact layer with an ethanol dispersion liquid of the copper nanowire and the silver nanowire, transforming the copper nanowire into a copper oxide nanowire and firmly adhering the copper oxide nanowire and the silver nanowire to the conductive glass through thermal treatment; filling a gap between the copper oxide nanowire and the silver nanowire with zirconium dioxide quantum dot particles, drying the zirconium dioxide quantum dot particles and then carrying out thermal treatment in an argon atmosphere; and finally etching away the silver nanowire and the copper oxide nanowire in a sample step by step, filling a hole transport material and a perovskite precursor step by step, carrying out thermal treatment in the argon atmosphere and evaporating a gold or silver film to form the perovskite solar cell. The method disclosed by the invention is beneficial to improvement of the cell stability. Furthermore, the method can also be applied to preparation of the solar cell with an N-type and P-type linear semiconductor material-staggered mesh structure.
Description
Technical field
The present invention relates to chemical solar cell field of new, especially relate to perovskite solar-electricityThe preparation method in pond.
Background technology
Perovskite solar cell is a kind of novel solar battery, with organic-inorganic hybridized perovskiteFor light absorbing material, with wide bandgap semiconductor oxide electron transport material and organic molecule, conductionPolymer or inorganic hole mobile material composition composite solar battery. There is low cost, preparation technologySimply, photoelectric transformation efficiency high, therefore have a good application prospect, be expected to substitute existingExpensive solar cell.
Perovskite solar battery structure has material impact to its photoelectric properties and long-time stability. TraditionPlanar heterojunction perovskite solar cell is because electronics and hole will be through transferring material layer ability separatelyArrive external circuit. In transmitting procedure, electronics and hole are higher by compound probability, particularly calcium titaniumWhen ore bed and hole transmission layer are thicker, dark reaction is even more serious. Meanwhile, preparation planar heterojunction calcium titaniumOre deposit solar cell, electron transfer layer, calcium titanium ore bed and thickness of hole transport layer can be accurately controlled in requirementAnd flatness, thereby increase preparation technology's complexity.
Therefore, explore a kind of new calcium titanium ore solar battery structure, can adopt straightforward procedure preparation,Both can simplify preparation technology, can obtain again efficient and stable perovskite solar cell is such sunCan move towards practical key technology by battery. In efficient organic solar batteries preparation process, body is differentMatter structure is widely adopted, and this structure can improve to greatest extent light induced electron and separate and transfer rate.This structure is incorporated in perovskite solar cell, is expected to overcome the defect that planar heterojunction exists.
In view of this, inventor, on the basis through a series of research and test, develops onePerovskite material and hole mobile material are the new structure perovskite solar cell of wire staggered-meshAnd preparation method thereof, this case produces thus.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of perovskite solar cell, its preparation sideMethod is simple, and can obtain efficient and stable perovskite solar cell.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for perovskite solar cell, preparation process is as follows:
The first step, by commercially available draw ratio be 100～500 copper nano-wire and nano silver wire by etc. moleThan being dispersed in ethanolic solution, obtain the alcohol dispersion liquid of copper nano-wire and nano silver wire;
Second step, is coated to surface by the alcohol dispersion liquid of described copper nano-wire and nano silver wire and hasOn the electro-conductive glass of the titanium dioxide dense layer that 30～50nm is thick, 50～200 DEG C of heat places in air atmosphereReason 0.5～1.5h makes copper nano-wire be transformed into cupric oxide nano line and makes cupric oxide nano line and nano silver wireBe tightly adhered on this electro-conductive glass;
The 3rd step, between between the above cupric oxide nano line of described electro-conductive glass and described nano silver wireIn gap, filling particle diameter is the zirconium dioxide quantum dot particle of 2～5nm, 50～100 DEG C of bakings in air atmosphereAfter dry, be placed in 300～500 DEG C of heat treatment 0.5～1.5h under argon gas atmosphere; Particle diameter is the dioxy of 2～5nmChanging zirconium quantum dot can fully be filled in the gap of cupric oxide nano line and nano silver wire, after heat treatment, formsFine and close diaphragm, plays packaged battery effect, improves battery long-time stability;
The 4th step, carves the described cupric oxide nano line on described electro-conductive glass and described nano silver wire substepEating away, past wherein substep filling hole transferring material and perovskite presoma, through under argon gas atmosphere100-150 DEG C of heat treatment 0.5～1.5h, hole mobile material and perovskite presoma form respectively hole transportLayer and calcium titanium ore bed, then steam plated with gold or silverskin, form perovskite solar cell.
In above-mentioned the 4th step, the reagent that described step etching adopts is a group in following: ammonium chloride and ammoniaWater, ammonium chloride and ferric nitrate, sulfuric acid and nitric acid.
In prepared perovskite solar cell, hole transmission layer is filled in the oxidation in zirconium dioxide filmIn the nanotubes staying after copper nano-wire etching, calcium titanium ore bed is filled in the silver nanoparticle in zirconium dioxide filmIn the nanotubes staying after line etching, and hole transmission layer and calcium titanium ore bed formation wire staggered-mesh knotStructure.
In adopting after such scheme, the preparation method of a kind of perovskite solar cell of the present invention, preparation sideMethod is simple, and calcium titanium ore bed and hole transmission layer be wire staggered-mesh structure, can effectively improve photoproduction electricitySon separates and transfer rate; Calcium titanium ore bed and hole transmission layer are coated by zirconium dioxide dense film simultaneously, haveBe beneficial to raising stability test, for the preparation of efficient and stable perovskite solar cell provides simpleFeasible new method. In addition, the inventive method also can be used for preparing N-type and P molded line shape semiconductor materialMaterial staggered-mesh structure solar cell.
Detailed description of the invention
Embodiment mono-:
The preparation method of a kind of perovskite solar cell of the present invention, preparation process is as follows:
The first step, is commercially available draw ratio 300 copper nano-wire and nano silver wire and divides by equimolar ratioBe dispersed in ethanolic solution, obtain the alcohol dispersion liquid of copper nano-wire and nano silver wire, make this alcohol dispersion liquidThe molar concentration of middle copper nano-wire and nano silver wire is 5mol/L;
Second step, preparation surface has the electro-conductive glass of the titanium dioxide dense layer that 30～50nm is thick, willThe alcohol dispersion liquid of described copper nano-wire and nano silver wire is coated to has described dioxy on this electro-conductive glassChange the one side of titanium compacted zone, form thick copper nano-wire and the nano silver wire hybrid films of 0.8 μ m, at 150 DEG CIn air atmosphere heat treatment 1h make copper nano-wire be transformed into cupric oxide nano line and make cupric oxide nano line andNano silver wire is tightly adhered on this electro-conductive glass;
The 3rd step, between between the above cupric oxide nano line of described electro-conductive glass and described nano silver wireIn gap, spin coating average grain diameter is that 3nm concentration is the toluene dispersion liquid of the zirconium dioxide quantum dot of 1mol/L,After 100 DEG C of air atmospheres are dried, be placed in heat treatment 1h under 450 DEG C of argon gas atmosphere, make zirconium dioxideQuantum dot forms zirconium dioxide dense film, obtains sample;
The 4th step, at room temperature immerses this sample 24h in the aqueous ammonium chloride solution of 2.5mol/L, carvesEtching off cupric oxide nano line also leaves the first tubular form in described zirconium dioxide dense film, toward this firstThe P3HT of spin coating 5mg/mL in tubular form (poly-3-hexyl thiophene) o-dichlorobenzene solution; Afterwards, thenSample is immersed to 24h in the ammonia spirit of 2.5mol/L, etching is removed nano silver wire and in described titanium dioxideIn zirconium dense film, leave the second tubular form, after 80 DEG C of vacuum drying ovens dry 12h, toward this second pipeThe PbI that in shape template, spin coating concentration is 1.5mol/L2The CH of (lead iodide) and 1.5mol/L3NH3I (firstBase ammonium iodide) DMSO (dimethyl sulfoxide (DMSO)) mixed solution. Through heat under 100 DEG C of argon gas atmosphereProcess 0.5h, then steam plated with gold film, form perovskite solar cell. This battery is in AM1.5 and 100mW·cm-2Under standard sunshine, test, photoelectric transformation efficiency reaches 14.3%.
Embodiment bis-:
The preparation method of a kind of perovskite solar cell of the present invention, preparation process is as follows:
The first step, is commercially available draw ratio 500 copper nano-wire and nano silver wire and divides by equimolar ratioBe dispersed in ethanolic solution, obtain the alcohol dispersion liquid of copper nano-wire and nano silver wire, make this alcohol dispersion liquidThe molar concentration of middle copper nano-wire and nano silver wire is 5mol/L;
Second step, preparation surface has the electro-conductive glass of the titanium dioxide dense layer that 30～50nm is thick, willThe alcohol dispersion liquid of described copper nano-wire and nano silver wire is coated to has described dioxy on this electro-conductive glassChange the one side of titanium compacted zone, form thick copper nano-wire and the nano silver wire hybrid films of 1 μ m, at 100 DEG CIn air atmosphere, heat treatment 1.5h makes copper nano-wire be transformed into cupric oxide nano line and makes cupric oxide nano lineBe tightly adhered on this electro-conductive glass with nano silver wire;
The 3rd step, between between the above cupric oxide nano line of described electro-conductive glass and described nano silver wireIn gap, spin coating average grain diameter is that 5nm concentration is the cyclohexane dispersion of the zirconium dioxide quantum dot of 0.5mol/LLiquid, after 100 DEG C of air atmospheres are dried, is placed in heat treatment 1h under 450 DEG C of argon gas atmosphere, makes dioxyChange zirconium quantum dot and form zirconium dioxide dense film, obtain sample;
The 4th step, at room temperature immerses this sample 24h in the aqueous sulfuric acid of 2.5mol/L, etchingDeoxidation copper nano-wire also leaves the first tubular form in described zirconium dioxide dense film, toward this first pipeThe Spiro-MeOTAD{2 of spin coating 5mg/mL in shape template, 2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl)Amino]-9,9'-spiral shell two fluorenes } chlorobenzene solution; Afterwards, then sample is immersed in the salpeter solution of 2.5mol/L24h, etching is removed nano silver wire and leave the second tubular form in described zirconium dioxide dense film, process80 DEG C of vacuum drying ovens dry after 12h, the PbI that is 1.5mol/L toward spin coating concentration in this second tubular form2The CH of (lead iodide) and 1.5mol/L3NH3The DMSO (dimethyl sulfoxide (DMSO)) of I (methyl ammonium iodide)Mixed solution. Through heat treatment 0.5h under 100 DEG C of argon gas atmosphere, then steam plated with gold film, form calcium titaniumOre deposit solar cell. This battery is at AM1.5 and 100mWcm-2Under standard sunshine, test photoelectricityConversion efficiency reaches 15.7%.
Embodiment tri-:
The preparation method of a kind of perovskite solar cell of the present invention, preparation process is as follows:
The first step, is commercially available draw ratio 350 copper nano-wire and nano silver wire and divides by equimolar ratioBe dispersed in ethanolic solution, obtain the alcohol dispersion liquid of copper nano-wire and nano silver wire, make this alcohol dispersion liquidThe molar concentration of middle copper nano-wire and nano silver wire is 5mol/L;
Second step, preparation surface has the electro-conductive glass of the titanium dioxide dense layer that 30～50nm is thick, willThe alcohol dispersion liquid of described copper nano-wire and nano silver wire is coated to has described dioxy on this electro-conductive glassChange the one side of titanium compacted zone, form thick copper nano-wire and the nano silver wire hybrid films of 1.5 μ m, at 100 DEG CIn air atmosphere, heat treatment 1.5h makes copper nano-wire be transformed into cupric oxide nano line and makes cupric oxide nano lineBe tightly adhered on this electro-conductive glass with nano silver wire;
The 3rd step, between between the above cupric oxide nano line of described electro-conductive glass and described nano silver wireIn gap, spin coating average grain diameter is that 3nm concentration is the cyclohexane dispersion of the zirconium dioxide quantum dot of 0.5mol/LLiquid, after 100 DEG C of air atmospheres are dried, is placed in heat treatment 1h under 450 DEG C of argon gas atmosphere, makes dioxyChange zirconium quantum dot and form zirconium dioxide dense film, obtain sample;
The 4th step, at room temperature immerses this sample 24h in the aqueous ammonium chloride solution of 2.5mol/L, carvesEtching off cupric oxide nano line also leaves the first tubular form in described zirconium dioxide dense film, toward this firstThe CuSCN dithioglycol solution of spin coating 1mg/mL in tubular form; Immerse 2.5 afterwards, then by sample24h in the iron nitrate solution of mol/L, etching is removed nano silver wire and is stayed in described zirconium dioxide dense filmLower the second tubular form, after 80 DEG C of vacuum drying ovens dry 12h, toward spin coating in this second tubular formConcentration is the PbI of 1.5mol/L2The CH of (lead iodide) and 1.5mol/L3NH3I (methyl ammonium iodide)DMSO (dimethyl sulfoxide (DMSO)) mixed solution. Through heat treatment 0.5h under 100 DEG C of argon gas atmosphere,Steam again plated with gold film, form perovskite solar cell. This battery is at AM1.5 and 100mWcm-2Under standard sunshine, test, photoelectric transformation efficiency reaches 12.5%.
These are only preferred embodiment of the present invention, not the restriction to protection scope of the present invention, allThe equivalent variations of doing according to the mentality of designing of this case, all falls into the protection domain of this case.
Claims (3)
1. a preparation method for perovskite solar cell, is characterized in that, preparation process is as follows:
The first step, by commercially available draw ratio be 100～500 copper nano-wire and nano silver wire by etc. moleThan being dispersed in ethanolic solution, obtain the alcohol dispersion liquid of copper nano-wire and nano silver wire;
Second step, is coated to surface by the alcohol dispersion liquid of described copper nano-wire and nano silver wire and hasOn the electro-conductive glass of the titanium dioxide dense layer that 30～50nm is thick, 50～200 DEG C of heat places in air atmosphereReason 0.5～1.5h makes copper nano-wire be transformed into cupric oxide nano line and makes cupric oxide nano line and nano silver wireBe tightly adhered on this electro-conductive glass;
The 3rd step, between between the above cupric oxide nano line of described electro-conductive glass and described nano silver wireIn gap, filling particle diameter is the zirconium dioxide quantum dot particle of 2～5nm, 50～100 DEG C of bakings in air atmosphereAfter dry, be placed in 300～500 DEG C of heat treatment 0.5～1.5h under argon gas atmosphere;
The 4th step, carves the described cupric oxide nano line on described electro-conductive glass and described nano silver wire substepEating away, past wherein substep filling hole transferring material and perovskite presoma, through under argon gas atmosphere100～150 DEG C of heat treatment 0.5～1.5h, hole mobile material and perovskite presoma form respectively hole and passDefeated layer and calcium titanium ore bed, then steam plated with gold or silverskin, form perovskite solar cell.
2. the preparation method of a kind of perovskite solar cell as claimed in claim 1, its feature existsIn: in above-mentioned the 4th step, the reagent that described step etching adopts is a group in following: ammonium chloride and ammoniaWater, ammonium chloride and ferric nitrate, sulfuric acid and nitric acid.
3. the preparation method of a kind of perovskite solar cell as claimed in claim 1, its feature existsIn: in prepared perovskite solar cell, hole transmission layer is filled in the cupric oxide in zirconium dioxide filmIn the nanotubes staying after nano wire etching, calcium titanium ore bed is filled in the nano silver wire in zirconium dioxide filmIn the nanotubes staying after etching, and hole transmission layer and calcium titanium ore bed formation wire staggered-mesh knotStructure.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112687805A (en) * | 2020-12-28 | 2021-04-20 | 华侨大学 | Perovskite solar cell electronic transmission layer and preparation method thereof |
Citations (4)
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| WO2015031944A1 (en) * | 2013-09-04 | 2015-03-12 | Dyesol Ltd | A photovoltaic device |
| CN104795498A (en) * | 2015-04-08 | 2015-07-22 | 华中科技大学 | Flexible perovskite solar cell production technology |
| US20150287852A1 (en) * | 2014-04-03 | 2015-10-08 | The Hong Kong Polytechnic University | Crystal Control and Stability for High-Performance Perovskite Solar Cell |
| CN105047822A (en) * | 2015-06-12 | 2015-11-11 | 苏州捷迪纳米科技有限公司 | Flexible fiber-shaped perovskite solar cell and manufacturing method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015031944A1 (en) * | 2013-09-04 | 2015-03-12 | Dyesol Ltd | A photovoltaic device |
| US20150287852A1 (en) * | 2014-04-03 | 2015-10-08 | The Hong Kong Polytechnic University | Crystal Control and Stability for High-Performance Perovskite Solar Cell |
| CN104795498A (en) * | 2015-04-08 | 2015-07-22 | 华中科技大学 | Flexible perovskite solar cell production technology |
| CN105047822A (en) * | 2015-06-12 | 2015-11-11 | 苏州捷迪纳米科技有限公司 | Flexible fiber-shaped perovskite solar cell and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112687805A (en) * | 2020-12-28 | 2021-04-20 | 华侨大学 | Perovskite solar cell electronic transmission layer and preparation method thereof |
| CN112687805B (en) * | 2020-12-28 | 2023-06-02 | 华侨大学 | Preparation method of perovskite solar cell electron transport layer |
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