CN102280590A - Solar cell by virtue of taking colloid quantum dots and graphene as light anode and manufacturing method thereof - Google Patents
Solar cell by virtue of taking colloid quantum dots and graphene as light anode and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a solar cell by virtue of taking colloid quantum dots and graphene as a light anode and a manufacturing method thereof and belongs to the field of photoelectric conversion, new energy materials and technologies. In the manufacturing method, ITO (indium tin oxide) is taken as a framework, and the graphene and the colloid quantum dots with the different grain sizes are deposited on the framework in sequence layer by layer to form a {graphene/quantum dots} laminated film which is taken as the light anode; mixtures of organic polymers are deposited on the light anode in a film spinning mode; and finally vacuum evaporation is carried out on an electrode on the organic polymer film to finish the manufacturing of a solar cell device. The solar cell is simple and low in structure and manufacturing and can absorb the most of light energy of incident sunlight. The light anode is provided with the graphene film with high carrier mobility, thus greatly improving the extraction of photon-generated carriers to the electrode and the transmission process, thereby improving the photoelectric conversion efficiency of the solar cell.
Description
Technical field
The present invention relates to a kind of is solar cell of light anode and preparation method thereof based on colloid quantum dot and Graphene, belongs to opto-electronic conversion, new energy materials and technical field.
Background technology
At present; the mankind are being faced with the serious problems that environment constantly worsens and the energy is day by day short; strengthen environmental protection and exploitation clean energy resource are the focuses that national governments show great attention to, and the research of the development and utilization of solar energy is received people's fervent concern always, and its progress is also very rapid.The photovoltaic device that sunlight is converted to electric energy is a promising technology, can obtain a large amount of electric energy.In present photovoltaic device market, reach based on amorphous silicon, the semi-conductive thin film solar cell of CdTe, CuInGaSe2 and III-V family in occupation of main share based on silicon sheet (monocrystalline and polycrystalline) solar cell.Yet the energy conversion efficiency of these photovoltaic devices is far below its theoretical prediction value and its preparation cost costliness.Although people have adopted the whole bag of tricks to make the conversion efficiency of solar cell obtain certain improvement, but it is increased substantially, find a kind of more effective approach or countermeasure, the actual energy conversion efficiency that makes solar cell becomes key subjects of Material Physics, photovoltaic device and energy science near its theoretical prediction value.
The energy range of solar spectrum is between 0.5～3.5eV, but main energy only concentrates on 1.8eV (near～700nm) the near infrared region.For this reason, it is particularly important how effectively utilizing the energy of this wave band.In fact, concerning present solar cell on the market, there is quite a few solar spectrum (the particularly spectrum of 600～1100nm wave band) to be absorbed seldom! The thickness of the solar cell of Here it is common based single crystal silicon chip is generally the reason of 180～300 μ m.But high efficiency solar cell requires the thickness of its minority carrierdiffusion length times over material, so that all photo-generated carriers can both be collected into, this requirement is easy to satisfy for hull cell.Optical absorption length and the opposed requirement of carrier collection length, the structural design and the material that impel us must consider solar cell carefully are selected.
We know, because quantum confined effect, semiconductor-quantum-point (or nano particle) has wide absorption spectrum, narrow transmitted bandwidth and big absorption cross-section.The quantum size effect of quantum dot makes people can obtain the quantum dot of different energy gaps and light emitting region according to the quantum dot that synthesizes different size.And these quantum dots have been opened up a kind of method of utilizing hot electron or utilizing single photon generation multi-photon.For example, (it can greatly increase power conversion efficiency to the many excitons generations in PbSe quantum dot that it has been found that and the PbS quantum dot for Multiple exciton generation, MEG) phenomenon.Adding Graphene itself has very high carrier mobility and (can reach 10
4Cm
2/ Vs), therefore, we can " intersperse quantum dot " on graphene film, and the laminated film that obtains like this can improve the generation efficient of electron-hole pair, also can improve the transmission course of charge carrier, provide possibility for obtaining efficient solar battery to two end electrodes.Method by electrophoretic deposition just can prepare the Graphene thin layer with the aqueous solution of electronation Graphene on ito glass, and and then the CdS quantum dot is prepared on the graphene layer as the light anode.Reported with Na in the document
2S is the solar cell of electrolyte, and its photoelectric conversion efficiency IPCE=16% and its optical responsivity are 1.08mA/cm
2(at 100mW/cm
2Under the illumination condition)----this be best result in relevant carbon/quantum dot (Carbon/QD) solar cell of bibliographical information so far! And also the someone has reported with semiconductor-quantum-point (TiO
2And ZnO) and metallic nano crystal (Au and Pt) " interspersing " to the method for carbon nano-tube and Graphene, confirm that Graphene can be used as a two-dimentional carrier that disperses semiconductor-quantum-point and metallic nano crystal fully.Therefore, the graphene film that we just can " intersperse " with metallic nano crystal and semiconductor-quantum-point as the light anode and with high conductive SOLID ORGANIC thin-film material (or polymer) as active layer, will obtain a kind of novel photovoltaic device of high-photoelectric transformation efficiency.
In addition, organic polymer itself has relatively large exciton bind energy and higher characteristics such as electron mobility.Therefore with semiconductor nano with organic (polymer) material is compound and prepare the organic and inorganic composite photoelectric to lead device be one of focus of present application study.This photoconductive device is the device that makes up the donor-acceptor heterojunction, requirement at the interface at two kinds of materials exists because the electrostatic force that the difference of electron affinity energy and ionization energy forms, this just requires the electron affinity of polymer molecule and ionization energy ratio nano crystalline substance to want big, so just can form internal electric field, thereby order about separation of charge.If potential energy difference is greater than exciton bind energy, these local internal electric fields can be very strong and the photoproduction exciton are dissociated.Because P3HT and PCBM widespread usage have good carrier transmission performance and higher light transfer characteristic in solar cell.Therefore, we also select for use the mixture of P3HT and PCBM to be used as active layer, the main luminous energy that absorbs visible light wave range in the solar spectrum, add based on the absorption of the light anode of colloid quantum dot and Graphene, thereby make the absorption spectrum of entire device expand to infrared band from visible light near infrared spectrum.Therefore, the photoelectric conversion efficiency of solar cell correspondingly can increase a lot.
Summary of the invention
The objective of the invention is in order to provide a kind of is solar cell of light anode and preparation method thereof based on colloid quantum dot and Graphene.Promptly utilize the PbS colloid quantum dot of different-grain diameter " to intersperse " to graphene film, make the light anode of multi-layer quantum point laminated construction, and further the mixture of organic polymer is made film on this basis, so, the absorption spectrum of the entire device that obtains will be extended to infrared band by visible light wave range, strengthened of the absorption of solar cell device, and then improved the photoelectric conversion efficiency of solar cell solar energy.
The objective of the invention is to be achieved through the following technical solutions.
Of the present invention a kind of be the solar cell of light anode based on colloid quantum dot and Graphene, comprise light anode, organic polymer active layer and electrode based on colloid quantum dot and Graphene; Wherein the light anode based on colloid quantum dot and Graphene is to be skeleton with the ito glass, and the colloid quantum dot of different-grain diameter is formed { Graphene/quantum dot } film as the light anode with the method for electrophoresis with Graphene and quantum dot layer by layer deposition successively; Wherein the organic polymer active layer is meant electric transmission polymeric material and hole transport polymer mixtures of material, and then the mixture of this organic polymer deposited on the light anode by the mode of getting rid of film, at last again on this thin polymer film the vacuum evaporation metal electrode finish the solar cell preparation of devices;
Above-mentioned colloid quantum dot is the low-gap semiconductor material of absworption peak at infrared band (wavelength is greater than 800nm), is preferably PbS or PbSe;
Above-mentioned organic polymer active layer is preferably the mixture of P3HT or MEH-PPV and PCBM.Wherein P3HT is poly (3-hexylthiophene), and MEH-PPV is Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], PCBM is [6,6]-Phenyl C
61Butyric acid methyl ester;
Above-mentioned electrode is metal electrode, multiple layer metal electrode or the metal alloy electrodes of work function smaller or equal to 4.3eV; Metal electrode is preferably the aluminium electrode, and the multiple layer metal electrode is preferably Ca/Al, and metal alloy electrodes is preferably the Mg/Ag alloy;
Can also comprise one deck hole transmission layer and one deck electron transfer layer in the above-mentioned solar battery structure.Usually, add one deck hole transmission layer between based on the light anode of colloid quantum dot and Graphene and organic polymer active layer, electron transfer layer is added between organic polymer active layer and the electrode.
Of the present invention a kind of be the preparation method of the solar cell of light anode based on colloid quantum dot and Graphene, concrete steps are:
1) prepares one deck graphene film earlier in the surperficial method of ito glass, on graphene film, prepare one deck colloid quantum dot film again with the method for getting rid of film then by electrophoresis;
2) method according to step 1) prepares one or more layers graphene film and colloid quantum dot film once more; The light anode based on colloid quantum dot and Graphene of different near infrared bands is absorbed;
3) in step 2) prepare the organic polymer active layer by the mode of getting rid of film on the light anode that obtains, at last under vacuum condition on the organic polymer active layer electrode evaporation, obtaining based on colloid quantum dot and Graphene is the solar cell of light anode.
Step 1) and step 2) in the quantum point grain diameter of colloid quantum dot film of preparation be different; In addition, can also add one deck electron transfer layer and hole transmission layer respectively in the both sides of organic polymer active layer.Can further improve the photoelectric properties of solar cell like this.
This based on behind the absorption of the colloid quantum dot in the light anode of colloid quantum dot and the Graphene photon, the photo-generated carrier that disassociation produces is easy to be transferred on the Graphene by the colloid quantum dot, transport by graphene film again with high carrier mobility, so just realized the quick extraction of photo-generated carrier, can improve the photoelectric conversion efficiency of device to electrode.
With after PCBM mixes, the absorption spectrum of its mixed solution is the linear superposition of the absorption spectrum of single component material, can cover most of visible light wave range with P3HT.Add that the absorption spectrum of entire device expands to infrared band by whole visible light wave range after this absorption of PbS colloid quantum dot to infrared light based on different-grain diameter in the light anode of colloid quantum dot and Graphene.Therefore, this is that the solar cell of light anode significantly strengthens the absorbability of solar energy based on colloid quantum dot and Graphene, and photoelectric conversion efficiency significantly improves.
Beneficial effect
Solar battery structure of the present invention prepares simple, cheap; Can absorb most luminous energy of incident sunlight, the adding with graphene film of high carrier mobility has greatly improved extraction and the transport process of photo-generated carrier to electrode, thereby can increase the photoelectric conversion efficiency of solar cell; PbS colloid quantum dot " is interspersed " to graphene film, strengthens the interaction between them, helps effective separation of charge carrier, improves photo-generated carrier density; The use of PCBM and P3HT mixture can form good inierpeneirating network structure, makes the photoproduction exciton separate effectively and is transferred to Graphene or electrode fast, and recombination probability reduces greatly, improves energy conversion efficiency.
Description of drawings
Fig. 1 is the light anode construction schematic diagram based on colloid quantum dot and Graphene that can absorb near infrared band in the solar spectrum of embodiment 1 preparation;
Fig. 2 is that particle diameter is the abosrption spectrogram of PbS quantum dot solution, MEH-PPV solution and the PCBM solution of 3.9nm;
Fig. 3 is that particle diameter is the abosrption spectrogram of mixed solution of PbS solution, MEH-PPV solution and the PCBM solution of 3.9nm;
Fig. 4 is the structural representation of the whole solar cell of embodiment 1 preparation;
Fig. 5 is the structural representation of the whole solar cell of embodiment 2 preparations.
Embodiment
The present invention will be further described below in conjunction with drawings and Examples.
A kind of is the solar cell of light anode based on colloid quantum dot and Graphene, comprises light anode, organic polymer active layer and electrode based on colloid quantum dot and Graphene;
Above-mentioned colloid quantum dot is low energy gap colloid quantum dot PbS;
Above-mentioned organic polymer active layer is the mixture of P3HT and PCBM, and wherein the mass ratio of P3HT and PCBM is 1: 1; P3HT, PCBM have good energy level coupling, help the collection of electric charge;
Above-mentioned electrode is the aluminium electrode, and aluminium is stable in the air; Its work function is 4.28eV.
A kind of is the preparation method of the solar cell of light anode based on colloid quantum dot and Graphene, and concrete steps are:
1) at first uses absorbent cotton and washing agent wiping ito glass repeatedly, and rinse well with deionized water, and then used deionized water, acetone and isopropyl alcohol respectively each ultrasonic 15 minutes, all ito glass is dried up before the back ultrasonic cleaning whenever carrying out with nitrogen, after ultrasonic cleaning is intact ito glass is put into the ozone treatment machine and carried out ozone treatment 15 minutes, after cooling with standby; Ito surface (4cm with the ito glass that obtains
2) and gauze platinum electrode (5cm
2) to form spacing be the parallel-plate electrode of 3mm, be positioned in the electrophoretic deposition pond.In being the graphene aqueous solution of 0.2mg/mL, concentration remains on 0.5mA/cm
2Electrophoretic deposition graphene film under the current density can obtain the graphene film layer that thickness is 30nm through behind the 75s.Method by getting rid of film is at graphene film surface spin coating one deck colloid quantum dot thin layer then, like this, just obtained the graphene film that one deck point is embroidered with the colloid quantum dot.Wherein transmitance is greater than 85% in visible light and near-ultraviolet range for ito glass, and its square resistance is 10 Ω/;
2) according to the method for step 1), prepare the graphene film that six layers of point are embroidered with the colloid quantum dot of other particle diameter, form laminated construction.Prepare one deck point at every turn and be embroidered with after the graphene film of colloid quantum dot, all will carry out drying.The light anode based on colloid quantum dot and Graphene of different infrared bands is absorbed; As shown in Figure 1, each layer point is embroidered with the Graphene laminated construction schematic diagram of different-grain diameter colloid quantum dot.The Graphene of different colours represents that with quantum dot the quantum point grain diameter size on this graphene layer is different, and it is representing the light (from top to bottom, Dui Ying optical wavelength is elongated gradually) that can absorb different wave length (color) separately;
3) in step 2) prepare the mixture film of one layer of polymeric P3HT and PCBM on the light anode that obtains by the mode of getting rid of film, its thickness is 100nm.At last on the organic polymer active layer 4 * 10
-3The aluminium electrode that evaporation 150nm is thick under the vacuum condition of Pa, promptly obtaining based on colloid quantum dot and Graphene is the solar cell of light anode, as shown in Figure 4.
Remove outside the absorption spectrum of organic polymer active layer in visible-range step 1) and step 2) in the pairing absorption spectrum of different-grain diameter quantum dot of colloid quantum dot film of preparation and the near infrared spectrum in the solar spectrum be complementary.
A kind of is the solar cell of light anode based on colloid quantum dot and Graphene, comprises light anode, PEDOT:PSS hole transmission layer, organic polymer active layer, PCBM electron transfer layer and electrode based on colloid quantum dot and Graphene;
Above-mentioned colloid quantum dot is low energy gap colloid quantum dot PbS;
Above-mentioned organic polymer active layer is the mixture of P3HT and PCBM, and wherein the mass ratio of P3HT and PCBM is 1: 1; P3HT, PCBM have good energy level coupling, help the collection of electric charge;
Above-mentioned electrode is the aluminium electrode; Its work function is 4.28eV.
A kind of is the preparation method of the solar cell of light anode based on colloid quantum dot and Graphene, and concrete steps are:
1) at first uses absorbent cotton and washing agent wiping ito glass repeatedly, and rinse well with deionized water, and then used deionized water, acetone and isopropyl alcohol respectively each ultrasonic 15 minutes, all ito glass is dried up before the back ultrasonic cleaning whenever carrying out with nitrogen, after ultrasonic cleaning is intact ito glass is put into the ozone treatment machine and carried out ozone treatment 15 minutes, after cooling with standby; Ito surface (4cm with the ito glass that obtains
2) and gauze platinum electrode (5cm
2) to form spacing be the parallel-plate electrode of 3mm, be positioned in the electrophoretic deposition pond.In being the graphene aqueous solution of 0.2mg/mL, concentration remains on 0.5mA/cm
2Electrophoretic deposition graphene film under the current density can obtain the graphene film layer that thickness is 30nm through behind the 75s.Method by getting rid of film is at graphene film surface spin coating one deck colloid quantum dot thin layer then, like this, just obtained the graphene film that one deck point is embroidered with the colloid quantum dot.Wherein transmitance is greater than 85% in visible light and near-ultraviolet range for ito glass, and its square resistance is 10 Ω/;
2) according to the method for step 1), prepare the graphene film that six layers of point are embroidered with the colloid quantum dot of other particle diameter, form laminated construction.Prepare one deck point at every turn and be embroidered with after the graphene film of colloid quantum dot, all will carry out drying.The light anode based on colloid quantum dot and Graphene of different infrared bands is absorbed;
3) in step 2) mode by getting rid of film on the light anode that the obtains thick PEDOT:PSS hole transmission layer of preparation one deck 40nm earlier, prepare the mixture film of one layer of polymeric P3HT and PCBM then thereon, its thickness is 100nm.Then evaporation prepares the thick PCBM electron transfer layer of one deck 30nm on the organic polymer active layer; At last on electron transfer layer, 4 * 10
-3The aluminium electrode that evaporation 150nm is thick under the vacuum condition of Pa, promptly obtaining based on colloid quantum dot and Graphene is the solar cell of light anode, as shown in Figure 5.
Remove outside the absorption spectrum of organic polymer active layer in visible-range step 1) and step 2) in the pairing absorption spectrum of different-grain diameter quantum dot of colloid quantum dot film of preparation and the near infrared spectrum in the solar spectrum be complementary.
Comparative Examples 1
A kind of based on colloid quantum dot and Graphene be the solar cell and preparation method thereof of light anode with embodiment 1, the difference is that with MEH-PPV to replace P3HT that obtaining based on colloid quantum dot and Graphene at last is the efficient solar battery of light anode.
Comparative Examples 2
A kind of based on colloid quantum dot and Graphene be the solar cell and preparation method thereof of light anode with embodiment 2, the difference is that with MEH-PPV to replace P3HT that obtaining based on colloid quantum dot and Graphene at last is the efficient solar battery of light anode.
Comparative Examples 3
A kind of is that the solar cell and preparation method thereof of light anode is with embodiment 2 based on colloid quantum dot and Graphene, the difference is that with P3HT to replace PEDOT:PSS as hole transmission layer, making based on colloid quantum dot and Graphene at last is the efficient solar battery of light anode.
Comparative Examples 4
A kind of based on colloid quantum dot and Graphene be the solar cell and preparation method thereof of light anode with embodiment 2, the difference is that with C
60Replace PCBM as electron transfer layer, making based on colloid quantum dot and Graphene at last is the efficient solar battery of light anode.
PbS colloid quantum dot in the foregoing description 1, embodiment 2, Comparative Examples 1, Comparative Examples 2, Comparative Examples 3 and the Comparative Examples 4 can replace with PbSe colloid quantum dot, and making based on colloid quantum dot and Graphene at last is the solar cell of light anode.
Above-mentioned PEDOT:PSS is made of PEDOT and two kinds of materials of PSS, and PEDOT is the polymer of EDOT (3,4-enedioxy thiophene monomer), and PSS is a poly styrene sulfonate, and the mass ratio of PEDOT and PSS is 1: 2.5.
Particle diameter be 3.9nm PbS solution, MEH-PPV solution and PCBM solution abosrption spectrogram as shown in Figure 2.Fig. 3 is the absorption spectrum of mixed solution of PbS solution, MEH-PPV solution and the PCBM solution of 3.9nm for particle diameter among Fig. 2, and as seen, the absorption spectrum of this mixed solution is the linear superposition of the absorption spectrum of this PbS solution, MEH-PPV solution and PCBM solution.As a same reason, the absorption spectrum of the mixed solution of PbS colloid quantum dot solution, P3HT solution and PCBM solution also is the linear superposition of the absorption spectrum of PbS colloid quantum dot solution, P3HT solution and PCBM solution.
As can be known, this based on this mixed solution for organic polymer active layer preparation be that the efficient solar battery of light anode can absorb visible light wave range and infrared band based on colloid quantum dot and Graphene, its photoelectric conversion efficiency obviously improves.
Claims (7)
1. one kind is the solar cell of light anode based on colloid quantum dot and Graphene, it is characterized in that: comprise light anode, organic polymer active layer and electrode based on colloid quantum dot and Graphene;
The colloid quantum dot is that absworption peak is at the low-gap semiconductor material of infrared band wavelength greater than 800nm;
The organic polymer active layer is the mixture of P3HT and PCBM or the mixture of MEH-PPV and PCBM; Wherein P3HT is poly (3-hexylthiophene), and MEH-PPV is Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], PCBM is [6,6]-Phenyl C
61Butyric acid methyl ester;
Electrode is metal electrode, multiple layer metal electrode or the metal alloy electrodes of work function smaller or equal to 4.3eV.
2. according to claim 1 a kind of be the solar cell of light anode based on colloid quantum dot and Graphene, it is characterized in that: the colloid quantum dot is PbS or PbSe.
3. according to claim 1 a kind of be the solar cell of light anode based on colloid quantum dot and Graphene, it is characterized in that: metal electrode is the aluminium electrode.
4. according to claim 1 a kind of be the solar cell of light anode based on colloid quantum dot and Graphene, it is characterized in that: the multiple layer metal electrode is Ca layer and Al layer.
5. according to claim 1 a kind of be the solar cell of light anode based on colloid quantum dot and Graphene, it is characterized in that: metal alloy electrodes is Mg and Ag alloy.
6. according to claim 1 a kind of be the solar cell of light anode based on colloid quantum dot and Graphene, it is characterized in that: between based on the light anode of colloid quantum dot and Graphene and organic polymer active layer, add one deck hole transmission layer, and between organic polymer active layer and electrode, add one deck electron transfer layer.
7. one kind is the preparation method of the solar cell of light anode based on colloid quantum dot and Graphene, it is characterized in that concrete steps are:
1) prepares one deck graphene film earlier in the surperficial method of ito glass, on graphene film, prepare one deck colloid quantum dot film again with the method for getting rid of film then by electrophoresis;
2) method according to step 1) prepares one or more layers graphene film and colloid quantum dot film once more; The light anode based on colloid quantum dot and Graphene of different near infrared bands is absorbed;
3) in step 2) prepare the organic polymer active layer by the mode of getting rid of film on the light anode that obtains, at last under vacuum condition on the organic polymer active layer electrode evaporation, obtaining based on colloid quantum dot and Graphene is the solar cell of light anode;
Step 1) and step 2) in the quantum point grain diameter of colloid quantum dot film of preparation be different.
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| US9354465B2 (en) | 2013-07-24 | 2016-05-31 | Boe Technology Group Co., Ltd. | Color filter substrate, liquid crystal display panel and dispersing method of monocolor quantum dots |
| US9851601B2 (en) | 2013-07-24 | 2017-12-26 | Boe Technology Group Co., Ltd. | Color filter substrate, liquid crystal display panel and dispersing method of monocolor quantum dots |
| CN103904224A (en) * | 2014-03-05 | 2014-07-02 | 宁波大学 | Organic photovoltaic cell based on inorganic quantum dot and preparing method |
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| CN113120889A (en) * | 2020-01-16 | 2021-07-16 | 北京大学 | Method for improving third harmonic of graphene material |
| CN113120889B (en) * | 2020-01-16 | 2022-03-25 | 北京大学 | Method for improving third harmonic of graphene material |
| CN117809985A (en) * | 2024-02-29 | 2024-04-02 | 山东恒嘉高纯铝业科技股份有限公司 | Thin film electrode containing calcium hexaaluminate and preparation method and application thereof |
| CN117809985B (en) * | 2024-02-29 | 2024-05-10 | 山东恒嘉高纯铝业科技股份有限公司 | Thin film electrode containing calcium hexaaluminate and preparation method and application thereof |
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