CN116130531A - Quantum dot laminated solar cell and preparation method thereof - Google Patents

Quantum dot laminated solar cell and preparation method thereof Download PDF

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CN116130531A
CN116130531A CN202211098827.1A CN202211098827A CN116130531A CN 116130531 A CN116130531 A CN 116130531A CN 202211098827 A CN202211098827 A CN 202211098827A CN 116130531 A CN116130531 A CN 116130531A
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quantum dot
cell
transparent conductive
solar cell
film
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高益军
张惠民
张晓蕾
陈超
孙秀云
陈洁
王芳
李敏
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Dezhou University
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    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
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    • H01L31/035218—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
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Abstract

The invention relates to the technical field of photovoltaic devices and discloses a quantum dot laminated solar cell and a preparation method thereof, wherein the quantum dot laminated solar cell specifically comprises a front cell, a transparent conductive middle layer, a rear cell and a counter electrode; the front cell comprises a conductive substrate, an oxide semiconductor film and a semiconductor quantum dot film; the transparent conductive intermediate layer is an ITO film; the rear battery comprises an oxide semiconductor film and a semiconductor quantum dot film; the counter electrode is a metal electrode; the quantum dot laminated solar cell prepared by the invention utilizes the high-transparency ITO interlayer, so that the light energy utilization rate of the solar cell is greatly improved, and the photoelectric conversion efficiency of the cell is effectively improved.

Description

Quantum dot laminated solar cell and preparation method thereof
Technical Field
The invention relates to the technical field of photovoltaic devices, in particular to a quantum dot laminated solar cell and a preparation method thereof.
Background
Photovoltaic devices are semiconductor devices that absorb sunlight and convert the absorbed sunlight energy into electrical energy. Solar light spectrum is a mixed spectrum, each specific semiconductor material can only absorb light greater than a specific wavelength. In a single cell, unabsorbed sunlight is lost in the form of transmitted light or heat energy and cannot be absorbed and utilized; and heat loss occurs due to the band gap after the high energy light is absorbed. The efficiency of the single cell does not exceed 33.4% due to the low energy light transmission loss and the high energy light heat loss, i.e., the schottky limit.
The laminated battery combines two single batteries with different band gaps, so that the battery with a large band gap is used as a front battery to absorb high-energy light, and the battery with a low band gap is used as a rear battery to absorb low-energy light, thereby reducing energy loss and improving light energy utilization rate.
Quantum dots are semiconductor nanostructures that bind excitons in three spatial directions, generally spherical or spheroidal, typically between 2-20nm in diameter, and are an important low-dimensional semiconductor material, with common quantum dots consisting of elements IV, II-VI, IV-VI or III-V. The quantum dot has the characteristics of wide and continuous excitation spectrum, narrow and symmetrical emission spectrum, adjustable color, high photochemical stability, long fluorescence life and the like, and is widely applied to various photoelectronic devices including laminated batteries.
However, although some reports have been made on quantum dot stacked solar cells, the photoelectric conversion efficiency of the conventional quantum dot stacked solar cells is still low. Therefore, it is highly desirable to invent a quantum dot stacked solar cell with high photoelectric conversion efficiency.
Disclosure of Invention
In order to solve the technical problems, the invention provides a quantum dot laminated solar cell, which comprises a front cell, a transparent conductive middle layer, a rear cell and a counter electrode;
the front cell comprises a conductive substrate, an oxide semiconductor film and a semiconductor quantum dot film;
the transparent conductive intermediate layer is an ITO film;
the rear cell includes an oxide semiconductor thin film and a semiconductor quantum dot thin film.
Further, the oxide semiconductor film is a ZnO nanoparticle film; the semiconductor quantum dot film is a quantum dot-lead halide composite film.
Further, the quantum dot-lead halide composite film is a PbS quantum dot-lead halide composite film.
Further, the counter electrode is a metal electrode; the conductive substrate is conductive glass.
The invention also provides a preparation method of the quantum dot laminated solar cell, which comprises the following steps:
step S1, respectively coating an oxide semiconductor material, quantum dots and lead halide on the upper surface of a conductive substrate in the sequence of the oxide semiconductor material, the quantum dots and the lead halide to obtain a front battery;
step S2, coating a transparent conductive intermediate layer material on the front battery obtained in the step S1 to obtain a front battery covered with the transparent conductive intermediate layer;
step S3, coating oxide semiconductor materials, quantum dots and lead halide on the surface of the transparent conductive intermediate layer obtained in the step S2 in the sequence of the oxide semiconductor materials, the quantum dots and the lead halide to obtain a front battery-transparent conductive intermediate layer-rear battery compound;
and S4, depositing a metal electrode on the surface of the rear cell of the front cell-transparent conductive intermediate layer-rear cell composite to obtain the quantum dot laminated solar cell.
Further, the oxide semiconductor material is ZnO nano-particles; the quantum dots are PbS quantum dots; the lead halide is lead iodide; the transparent conductive intermediate layer material is ITO.
Further, in the step S1, the step S2 and the step S3, the coating is spin coating, the rotation speed of the spin coating is 2000rpm/min, and the time of the spin coating is 120S.
Further, in the step S2, the conditions for coating the transparent conductive intermediate layer material are as follows: a gas pressure of 1.5mTorr and an Ar gas atmosphere.
Further, in the step S4, the speed of the metal electrode deposition is 0.1nm/S.
Further, in the step S4, the metal electrode is a gold electrode with a thickness of 100nm.
Compared with the prior art, the beneficial effects of the method are as follows:
the invention provides a quantum dot laminated solar cell and a preparation method thereof, wherein the quantum dot laminated solar cell specifically comprises a front cell, a transparent conductive middle layer, a rear cell and a counter electrode; the front battery consists of a conductive substrate, an oxide semiconductor film and a semiconductor quantum dot film; the transparent conductive intermediate layer is an ITO film; the rear battery consists of an oxide semiconductor film and a semiconductor quantum dot film; the counter electrode is a metal electrode. The quantum dot laminated solar cell prepared by the invention utilizes the high-transparency ITO interlayer, so that the light energy utilization rate of the solar cell is greatly improved, and the photoelectric conversion efficiency of the cell is effectively improved.
Drawings
FIG. 1 is a graph showing the results of cell efficiency measurements for PbS quantum dot stacked solar cells prepared in examples 1-5 of the present invention;
fig. 2 is a measurement result of the cell efficiency of PbS quantum dot stacked solar cells prepared in example 3 and comparative example 1 of the present invention;
fig. 3 is a schematic structural diagram of the PbS quantum dot stacked solar cell of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
PbS quantum dots are semiconductor nanocrystals, and the diameter is generally below 40nm. Because the Bohr exciton radius of the PbS material is relatively large, the quantum confinement effect is relatively easy to generate, the energy level is split, and the band gap is generated. And the size of the band gap of the PbS nanocrystalline can be regulated and controlled by controlling the size of the PbS nanocrystalline: the diameter of the nano-crystal is reduced, and the band gap of the nano-crystal is increased; increasing the diameter of the nanocrystals reduces their band gap. This feature of quantum dots provides convenience for the stacked cell in one step of selecting materials. The embodiment discloses a preparation method of a PbS quantum dot laminated solar cell, which comprises the following steps:
step S1, preparing a pre-battery:
s1-1: ultrasonically cleaning the ITO glass of the lead substrate by using a detergent, water, ethanol and acetone respectively for 30min;
s1-2: spin-coating ZnO nano-particles on ITO glass by using a spin coater, wherein the spin-coating speed is 2000rpm/min, and the spin-coating time is 120s;
s1-3: spin-coating PbS quantum dots with band gap of 1.5eV on the ZnO film to obtain the ZnO film, wherein the spin-coating rotating speed is 2000rpm/min, and the spin-coating time is 120s; immediately soaking the semi-finished battery piece in DMF (dimethyl formamide) solution of PbI2 after spin coating, wherein the concentration of the solution is 4.6mg/ml; after soaking, acetonitrile is used for cleaning, and then the battery is manufactured after the battery is dried.
Step S2, preparing a transparent conductive intermediate layer on the front cell:
and (3) performing magnetron sputtering on the front battery obtained in the step (1) to form an ITO film with the thickness of 20nm under the Ar environment and the pressure of 1.5mTorr, thereby completing the preparation of the transparent conductive intermediate layer.
Step 3, preparing a front battery-transparent conductive middle layer-rear battery compound:
s3-1: spin-coating ZnO nano particles on the transparent conductive intermediate layer obtained in the step S2 by using a spin-coating machine to obtain a ZnO film, wherein the spin-coating speed is 2000rpm/min, and the spin-coating time is 120S;
s3-2: spin-coating PbS quantum dots with band gap of 1.2eV on the ZnO film, wherein the spin-coating rotating speed is 2000rpm/min, and the spin-coating time is 120s; immediately soaking the semi-finished battery piece in DMF (dimethyl formamide) solution of PbI2 after spin coating, wherein the concentration of the solution is 4.6mg/ml; after soaking, acetonitrile is used for cleaning, and then the mixture is dried to obtain the front battery-transparent conductive intermediate layer-rear battery compound.
Step S4, preparing a counter electrode on the front cell-transparent conductive middle layer-rear cell composite:
and evaporating a gold electrode with the thickness of 100nm on the surface of the rear cell of the front cell-transparent conductive intermediate layer-rear cell composite at the speed of 0.1nm/s to obtain the PbS quantum dot laminated solar cell.
Example 2
The embodiment discloses a preparation method of a PbS quantum dot laminated solar cell, which is the same as that of embodiment 1, and the only difference is that in the step S2, an ITO film is magnetically sputtered on a front cell, and the thickness is 80nm.
Example 3
The embodiment discloses a preparation method of a PbS quantum dot laminated solar cell, which is the same as that of embodiment 1, and the only difference is that in the step S2, an ITO film is magnetically sputtered on a front cell, and the thickness is 100nm.
Example 4
The embodiment discloses a preparation method of a PbS quantum dot laminated solar cell, which is the same as that of embodiment 1, and the only difference is that in the step S2, an ITO film is magnetically sputtered on a front cell, and the thickness is 140nm.
Example 5
The embodiment discloses a preparation method of a PbS quantum dot laminated solar cell, which is the same as that of embodiment 1, and the only difference is that in the step S2, an ITO film is magnetically sputtered on a front cell, and the thickness is 200nm.
Comparative example 1
The embodiment discloses a preparation method of a PbS quantum dot laminated solar cell, which is the same as that of embodiment 3, and the only difference is that in the step S3-2, pbS quantum dots with the band gap of 1.5eV are spin-coated on a ZnO film.
Test example 1
The PbS quantum dot stacked solar cell efficiencies prepared in examples 1-5 and comparative example 1 were measured.
FIG. 1 is a graph of IV of a cell with ITO interlayers of different thicknesses, wherein curve 1 of IV is the corresponding cell efficiency for an ITO interlayer with a thickness of 20nm, and the cell efficiency is 4.2%; IV curve 2 is the battery efficiency corresponding to the ITO intermediate layer with the thickness of 80nm, and the battery efficiency is 5.2%; IV curve 3 is the battery efficiency corresponding to the ITO intermediate layer with the thickness of 100nm, and the battery efficiency is 6.2%; IV curve 4 is the battery efficiency corresponding to an ITO intermediate layer with a thickness of 1400nm, and the battery efficiency is 4.3%; IV curve 5 is the cell efficiency for an ITO interlayer thickness of 200nm, which is 3.4%. As can be seen from the graph of FIG. 1, the optimal ITO thickness is 100nm, and the cell efficiency produced by this thickness is highest.
Fig. 2 shows the results of the battery efficiency measurement of example 3 and comparative example 1, specifically: FIG. 2 is a graph comparing IV curves of a single band gap and a large band gap matched cell, wherein curve 1 is the IV curve of a comparative example 1 and a band gap cell (the band gap of the front and back cells is 1.5 eV), and the corresponding efficiency is 5.1%; curve 2 is the IV curve for the cell of example 3 with a large bandgap match (front cell bandgap 1.5eV, rear cell bandgap 1.2 eV), corresponding to an efficiency of 6.2%.
Fig. 3 is a schematic structural diagram of a PbS quantum dot stacked solar cell.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and substitutions can be made by those skilled in the art without departing from the technical principles of the present invention, and these modifications and substitutions should also be considered as being within the scope of the present invention.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and substitutions can be made by those skilled in the art without departing from the technical principles of the present invention, and these modifications and substitutions should also be considered as being within the scope of the present invention.

Claims (10)

1. A quantum dot stacked solar cell, wherein the cell comprises a front cell, a transparent conductive interlayer, a rear cell and a counter electrode;
the front cell comprises a conductive substrate, an oxide semiconductor film and a semiconductor quantum dot film;
the transparent conductive intermediate layer is an ITO film;
the rear cell includes an oxide semiconductor thin film and a semiconductor quantum dot thin film.
2. The quantum dot stacked solar cell of claim 1, wherein the oxide semiconductor thin film is a ZnO nanoparticle thin film; the semiconductor quantum dot film is a quantum dot-lead halide composite film.
3. The quantum dot stack solar cell of claim 2, wherein the quantum dot-lead halide composite film is a PbS quantum dot-lead halide composite film.
4. The quantum dot stack solar cell of claim 1, wherein the counter electrode is a metal electrode; the conductive substrate is conductive glass.
5. The preparation method of the quantum dot laminated solar cell is characterized by comprising the following steps of:
step S1, respectively coating an oxide semiconductor material, quantum dots and lead halide on the upper surface of a conductive substrate in the sequence of the oxide semiconductor material, the quantum dots and the lead halide to obtain a front battery;
step S2, coating a transparent conductive intermediate layer material on the front battery obtained in the step S1 to obtain a front battery covered with the transparent conductive intermediate layer;
step S3, coating oxide semiconductor materials, quantum dots and lead halide on the surface of the transparent conductive intermediate layer obtained in the step S2 in the sequence of the oxide semiconductor materials, the quantum dots and the lead halide to obtain a front battery-transparent conductive intermediate layer-rear battery compound;
and S4, depositing a metal electrode on the surface of the rear cell of the front cell-transparent conductive intermediate layer-rear cell composite to obtain the quantum dot laminated solar cell.
6. The method according to claim 5, wherein the oxide semiconductor material is ZnO nanoparticles; the quantum dots are PbS quantum dots; the lead halide is lead iodide; the transparent conductive intermediate layer material is ITO.
7. The method according to claim 5, wherein in the step S1, the step S2 and the step S3, the coating is spin coating, the spin coating is performed at a rotation speed of 2000rpm/min, and the spin coating is performed for 120S.
8. The method according to claim 5, wherein in the step S2, the conditions for coating the transparent conductive intermediate layer material are: a gas pressure of 1.5mTorr and an Ar gas atmosphere.
9. The method according to claim 5, wherein in the step S4, the metal electrode is deposited at a rate of 0.1nm/S.
10. The method according to claim 5 or 9, wherein in the step S4, the metal electrode is a gold electrode having a thickness of 100nm.
CN202211098827.1A 2022-09-07 2022-09-07 Quantum dot laminated solar cell and preparation method thereof Pending CN116130531A (en)

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Citations (3)

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CN103346176A (en) * 2013-06-18 2013-10-09 天津理工大学 Laminated solar cell based on different-grain-diameter PbS quantum dots and preparation method
KR20140091623A (en) * 2012-12-27 2014-07-22 에스케이이노베이션 주식회사 Quantum Dot Solar Cell and the Fabrication Method Thereof
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CN102097509A (en) * 2010-11-24 2011-06-15 北京航空航天大学 Design of five-layered structure of tandem thin-film amorphous silicon solar cell
CN108281501B (en) * 2018-01-29 2019-09-13 华中科技大学 Based on Sb2S3Push up the overlapping thin film solar battery and preparation method thereof of battery
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CN103346176A (en) * 2013-06-18 2013-10-09 天津理工大学 Laminated solar cell based on different-grain-diameter PbS quantum dots and preparation method
KR20210026476A (en) * 2019-08-30 2021-03-10 한국전력공사 Quantum dot solar cells and manufacturing method thereof

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