CN107302038B - Method for realizing surface plasmon enhanced nano-structure thin-film solar cell - Google Patents
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- H10K30/87—Light-trapping means
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Abstract
A method for realizing a surface plasmon enhanced nano-structure thin-film solar cell comprises the steps of sequentially preparing a silicon dioxide nanosphere array/silver nanoparticle composite nano-structure and a PIN or NIP type thin-film solar cell on a substrate. The silicon dioxide nanosphere array is prepared by adopting a dip-coating method and a plasma etching technology, and the preparation process of the silver nanoparticle structure is at least one of evaporation, sputtering, sol-gel, focused ion beam etching or electron beam etching technology; the thin film solar cell includes an inorganic thin film solar cell, an organic thin film solar cell, and a tandem solar cell composed of at least one of the above two types. The invention has the beneficial effects that: the introduction of the surface plasmon polaritons can obtain a nano microcavity structure with a localized high-energy electric field, so that the optical path expansion is enhanced, the photon cutting and modulation effects are improved, the charge collection performance is optimized, and the synchronous improvement of the optical and electrical characteristics of the battery is facilitated.
Description
Technical Field
The invention belongs to the field of thin film solar cells, and particularly relates to a method for realizing a surface plasmon enhanced nano-structure thin film solar cell.
Background
Solar cells must be efficient and low-cost to become the main energy source in the future, and the thinning is one of the most important trends. In addition, for the amorphous silicon thin film battery, the reduction of the thickness of the active layer is beneficial to reducing the light-induced degradation effect and improving the stability of the device. For the copper indium gallium selenide, cadmium telluride and other compound solar cells, the thickness is reduced, the use amount of toxic and trace elements can be reduced, and the improvement of the industrial competitiveness is also facilitated. However, the thinning of the material, due to its limited absorption coefficient (especially near the band gap), necessitates obtaining a thick "optical thickness" with a thin "physical thickness" by means of an efficient light management structure, achieving an efficient absorption of solar photons.
With the progress of solar cell research, the importance of efficient light management structures is gradually recognized. In recent years, solar cells based on three-dimensional nano-microcavity structures have received increasing attention due to their excellent performance. Incident photons can realize multiple scattering at the interface of the three-dimensional nanometer microcavity structure, multiple incident paths are provided for the photons, the constraint association between the absorption characteristic of the active layer and the incident angle distribution is greatly reduced, and high absorption performance can be obtained in a wide spectral range, which is disclosed in the literature: M.D. Kelzenberg, S.W. Boettcher, J.A. Petykiewicz, et al, Nature Mater, 9(2010) 239-44, J.Y. Jung, Z.Guo, S.W. Jee, et al, A stronganti-specific cellular prepared by silicon nanowines, Opt.Express 18(2010) A286-92. In addition, the nano-scale metal structure has the advantages that a large number of free electrons on the Surface of the metal structure can interact with photons to generate continuous common oscillation, a mixed excited state of the free electrons and the photons, which is called Surface Plasmon Polariton (SPP), is formed, and the nano-scale metal structure has remarkable far-field and near-field photoelectric characteristics. On one hand, the optical characteristics of the far field of the surface plasmon polariton of the nano metal structure are utilized, the optical waveguide transmission mode of photons is excited through the far field coupling effect of the nano metal structure and the photons, so that the good light trapping characteristics in the thin film solar cell are obtained, and the absorption of photons of the absorption limit accessory is obviously enhanced; on the other hand, by utilizing the near-field electrical characteristics of the nano metal structure, the excited surface plasmon polariton can change the electromagnetic field distribution characteristics of the surrounding space, so that the effective regulation and control of the work function of the electron transmission layer in the organic solar cell are obtained, and the efficient transmission of charges is realized, see the documents: H.A. Atwater, A. PolmanNature Materials9 (2010)205-213、S. Trost, T. Becker, K. Zilberberg, et al, Scientific Reports 5(2015)7765。
Based on the structure, the invention provides a solar cell with a surface plasmon polariton enhanced nano microcavity structure, which introduces the surface plasmon polariton effect of metal nanoparticles into a three-dimensional nano microcavity light trapping structure to obtain a nano microcavity structure with a localized high-energy electric field, so as to enhance optical path expansion, improve photon cutting and modulation effects, obtain a good light trapping effect and optimize charge collection performance.
Disclosure of Invention
The invention aims to further improve the performance of a solar cell and provides a method for realizing a surface plasmon enhanced nano-structure thin-film solar cell, which introduces the surface plasmon effect of nano silver particles into a silicon dioxide nanosphere array light trapping structure to obtain the thin-film solar cell with a nano microcavity structure of a localized high-energy electric field.
The technical scheme of the invention is as follows:
a method for realizing a surface plasmon enhanced nano-structure thin-film solar cell comprises the steps of sequentially preparing a silicon dioxide nano-sphere array/silver nano-particle composite nano-structure and a PIN or NIP type thin-film solar cell on a substrate, and is characterized in that: the thin film solar cell is directly deposited on the composite nano structure; the surface plasmon enhanced nano-structure thin film solar cell has a remarkable light absorption enhancement effect.
The silicon dioxide nanospheres in the silicon dioxide nanosphere array/silver nanoparticle composite nanostructure are prepared by adopting a dip-coating method and a plasma etching technology, and the preparation process of the silver nanoparticle structure is at least one of evaporation, sputtering, sol-gel, focused ion beam etching or electron beam etching.
The particle size of the silicon dioxide nanospheres is 100nm-2000nm, the particle size of the microspheres is modified by adopting a plasma etching process, and CF is selected4The duty ratio of the nanosphere array can be adjusted between 50% and 100% after etching for etching gas.
The silver nanoparticles have the particle size of 10nm-200nm and are directly deposited on the silicon dioxide nanospheres.
The thin film solar cell comprises a front electrode, a P-type hole transport layer, an I-type absorption layer, an N-type electron transport layer and a back electrode.
The front electrode is made of transparent conductive oxide material.
The thin film solar cell comprises an inorganic thin film solar cell, an organic thin film solar cell and a laminated solar cell formed by at least one of the two types of thin film solar cells.
The back electrode includes at least one conductive material of a transparent conductive oxide material or a metal electrode material.
The transparent conductive oxide material comprises ZnO, Al, ZnO, Ga, ZnO, H and In2O3:Sn，In2O3At least one of H materials is prepared by one or more of magnetron sputtering, thermal evaporation, electron beam evaporation or MOCVD.
The metal electrode material comprises at least one of Al, Ag and Au, and is prepared by adopting a magnetron sputtering or thermal evaporation technology.
The substrate material of the surface plasmon enhancement type nano-structure film solar is a hard substrate (such as a glass substrate) or a flexible substrate (such as stainless steel and polymer) material.
[ description of the drawings ]
Fig. 1 is a schematic structural diagram of a surface plasmon enhanced nano-structured PIN type thin film solar cell.
FIG. 2 shows the effect of different-scale composite nanostructures on the light absorption characteristics of an intrinsic amorphous silicon thin film.
Fig. 3 is an external quantum efficiency test curve of the surface plasmon polariton enhanced nano microcavity structure amorphous silicon thin film solar cell in example 1.
Fig. 4 is a current-voltage test curve of the surface plasmon enhanced nano microcavity structure amorphous silicon thin film solar cell in example 1.
[ detailed description ] embodiments
Example 1:
a method for realizing a surface plasmon enhanced nano-structure thin film solar cell comprises the following steps:
1) preparing a layer of monodisperse SiO with the particle size of 350 nm on a transparent glass substrate by adopting a dip-coating method2Nanospheres.
2) Plasma etching process is adopted to etch SiO2Dry etching the nanospheres, selecting CF4As etching reaction gas, the etching pressure is 1.0 Pa, the etching power is 50W, the etching time is 3 min, and SiO is obtained after etching2The particle size of the nanospheres is reduced to 260 nm, the distance is 115 nm, and the duty ratio is 69%.
3) In SiO2Preparing nano Ag particles on the nanospheres by adopting a radio frequency magnetron sputtering technology, and adopting Ar gas as a sputtering gas source, wherein the gas pressure is 0.13Pa, the power is 50W, the time is 20 s, and the substrate temperature is 50 DEGoAnd C, obtaining nano Ag particles with the particle size of 10 nm.
4) A layer of ZnO-Al transparent conductive film is deposited on the composite nano structure by adopting a radio frequency magnetron sputtering technology, the thickness is 500 nm, and the square resistance is 15 omega/□.
5) And (3) preparing the PIN type amorphous silicon thin film solar cell by adopting a PECVD (plasma enhanced chemical vapor deposition) technology, wherein the thickness of a p/i/n layer is 15 nm/250 nm/15 nm respectively.
6) And preparing a ZnO/Ag back electrode on the n-type a-Si: H, wherein the ZnO back electrode adopts an MOCVD technology and has the thickness of 100nm, and the Ag back electrode adopts a thermal evaporation technology and has the thickness of 120 nm.
And (3) displaying an application result: compared with the amorphous silicon thin film battery only provided with the planar ZnO-Al front electrode, the surface plasmon enhanced nano microcavity structure amorphous silicon thin film solar battery has the integrated current of 11.64 mA/cm in the wavelength range of 350 nm-800 nm2Lifting to 14.07 mA/cm2The external quantum efficiency is improved by 20.87 percent, and the efficiency is improved by4.72 percent is improved to 6.63 percent, and the light absorption and carrier collection enhancement effects are obvious.
Example 2:
a method for realizing a surface plasmon enhanced nano-structure thin film solar cell comprises the following steps:
1) preparing a layer of monodisperse SiO with the grain diameter of 1500 nm on a polyimide substrate by adopting a dipping and pulling method2Nanospheres.
2) Plasma etching process is adopted to etch SiO2Dry etching the nanospheres, selecting CF4As etching reaction gas, the etching pressure is 8.0 Pa, the etching power is 90W, the etching time is 10 min, and SiO is obtained after etching2The particle size of the nanospheres is reduced to 1100 nm, the distance is 800 nm, and the duty ratio is 55%.
3) In SiO2Preparing nano Ag particles on the nanospheres by adopting a thermal evaporation technology, wherein the thermal evaporation technology is adopted, the substrate temperature is 60 ℃, and the background vacuum is 9.8 х 10-4pa, evaporation rate of 1 Å/s, and equivalent thickness of 5 nm detected on line by adopting a crystal probe to obtain nano Ag particles with particle size of 25 nm.
4) A layer of ZnO transparent conductive film is deposited on the composite nano structure by adopting the MOCVD technology, the thickness is 100nm, and then a silver electrode material is deposited by adopting the thermal evaporation technology, the thickness is 100nm, so that a back electrode is formed.
5) And preparing the NIP type microcrystalline thin film solar cell by adopting a PECVD (plasma enhanced chemical vapor deposition) technology, wherein the thickness of an n/i/p layer is 15 nm/250 nm/15 nm respectively.
6) Preparing In on p-type muc-Si: H by adopting thermal evaporation technology2O3A front electrode of Sn with a thickness of 120 nm.
And (3) displaying an application result: compared with the microcrystalline silicon thin film cell only provided with the planar ZnO/Ag back electrode, the surface plasmon enhanced type microcrystalline silicon thin film solar cell with the nanometer microcavity structure has the integrated current of 23.28 mA/cm in the wavelength range of 350 nm-1100 nm2Lifting to 27.61 mA/cm2The external quantum efficiency is improved by 18.60%, and the light absorption and carrier collection enhancement effects are obvious.
In summary, the present invention provides a method for realizing a surface plasmon enhanced nano-structure thin film solar cell, wherein a surface plasmon effect of nano silver particles is introduced into a silicon dioxide nanosphere array light trapping structure, so as to obtain a thin film solar cell with a localized high-energy electric field and a nano microcavity structure.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for realizing a surface plasmon enhanced nano-structure thin-film solar cell comprises the steps of sequentially preparing a silicon dioxide nano-sphere array/silver nano-particle composite nano-structure and a PIN or NIP type thin-film solar cell on a substrate, and is characterized in that: the thin film solar cell is directly deposited on the composite nano structure; the surface plasmon enhanced nano-structure thin-film solar cell has a remarkable light absorption enhancement effect, a silicon dioxide nanosphere array is prepared by adopting a dip-coating method and a plasma etching technology, a silver nano-particle structure preparation process is at least one of evaporation, sputtering, sol-gel, focused ion beam etching or electron beam etching, the particle size of the silicon dioxide nanospheres is 100-2000 nm, the particle size of microspheres is modified by adopting a plasma etching process, CF4 is selected as etching gas, the duty ratio of the nanosphere array after etching is adjustable between 50% and 100%, and the particle size of silver nanoparticles is 10-200 nm and is directly deposited on the silicon dioxide nanospheres.
2. The method of claim 1, wherein: the thin film solar cell comprises a front electrode, a P-type hole transport layer, an I-type absorption layer, an N-type electron transport layer and a back electrode.
3. The method of claim 2, wherein: the front electrode is a transparent conductive oxide material.
4. The method of claim 1, wherein: the thin film solar cell comprises an inorganic thin film solar cell and an organic thin film solar cell.
5. The method of claim 2, wherein: the back electrode includes at least one conductive material of a transparent conductive oxide material or a metal electrode material.
6. The method of claim 5, wherein: the transparent conductive oxide material comprises ZnO, Al, ZnO, Ga, ZnO, H and In2O3:Sn，In2O3At least one of H materials is prepared by one or more of magnetron sputtering, thermal evaporation, electron beam evaporation or MOCVD.
7. The method of claim 5, wherein: the metal electrode material comprises at least one of Al, Ag and Au, and is prepared by adopting magnetron sputtering or thermal evaporation technology.
8. The method of claim 1, wherein: the substrate material is a hard substrate or a flexible substrate material.
9. The method of claim 8, wherein: wherein the hard substrate is a glass substrate.
10. The method of claim 8, wherein: wherein the flexible substrate is stainless steel or a polymer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544177A (en) * | 2011-03-30 | 2012-07-04 | 郑州大学 | Plasma strengthening upconverter for solar cells and preparation method thereof |
| CN103890965A (en) * | 2011-10-26 | 2014-06-25 | 住友化学株式会社 | Photoelectric conversion element |
| CN104733554A (en) * | 2015-04-10 | 2015-06-24 | 上海电机学院 | Silicon based thin film solar cell with bottom provided with metal nanoparticle structure |
| CN106252519A (en) * | 2016-09-07 | 2016-12-21 | 中国科学院长春光学精密机械与物理研究所 | Organic solar batteries processing method |
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| WO2010107720A2 (en) * | 2009-03-18 | 2010-09-23 | Tuan Vo-Dinh | Up and down conversion systems for production of emitted light from various energy sources |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544177A (en) * | 2011-03-30 | 2012-07-04 | 郑州大学 | Plasma strengthening upconverter for solar cells and preparation method thereof |
| CN103890965A (en) * | 2011-10-26 | 2014-06-25 | 住友化学株式会社 | Photoelectric conversion element |
| CN104733554A (en) * | 2015-04-10 | 2015-06-24 | 上海电机学院 | Silicon based thin film solar cell with bottom provided with metal nanoparticle structure |
| CN106252519A (en) * | 2016-09-07 | 2016-12-21 | 中国科学院长春光学精密机械与物理研究所 | Organic solar batteries processing method |
Non-Patent Citations (1)
| Title |
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| SiO2、ZnO空心微球及SiO2/Ag复合微球的制备与性能研究;邓字巍;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20090315;第60页第2-3段、第62页第1段、第63页第1段第67页倒数第1段、第74页倒数第1段，图4.1、4.6、4.8 * |
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