CN110634966B - Ultrathin sunlight black silicon wave absorber and preparation method thereof - Google Patents
Ultrathin sunlight black silicon wave absorber and preparation method thereof Download PDFInfo
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- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
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- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides an ultrathin sunlight black silicon wave absorber and a preparation method thereof. The ultrathin sunlight black silicon wave absorber comprises a substrate layer and a super-surface structure layer, wherein the super-surface structure layer is connected to the upper surface of the substrate layer; the base layer and the super-surface structure layer are made of silicon, the thickness of the super-surface structure layer is 120-200 nanometers, and the super-surface structure layer comprises a plurality of concave cavities with different sizes and irregularities; the different sizes and the irregularity mean that the area of the concave cavities changes from 10 square nanometers to 500 square nanometers, the depth of the concave cavities changes from 10 nanometers to 280 nanometers, and the interval between the adjacent concave cavities changes from 10 nanometers to 100 nanometers. The super-surface structure layer has a series of irregular cavities that form a model with different resonant modes in different wavelength ranges. Near-complete anti-reflection absorption (efficiency > 97%) is achieved in the full solar radiation spectral range of 280-2500 nm.
Description
Technical Field
The invention relates to a silicon material, in particular to a black silicon wave absorber and a preparation method thereof.
Background
With the rapid development of modern science and technology, the effective utilization of solar energy is receiving wide attention of people. The ultra-wideband perfect optical absorber is one of necessary devices for realizing efficient absorption of solar energy spectrum and broadband photoelectric detection, can realize efficient absorption of sunlight in a range from visible light to near infrared wave bands, and generally has the principle that the phenomena of surface plasmon resonance, fabry-Perot resonant cavity and spectrum phase coupling or coherence and the like cause the absorption or capture phenomenon of resonance induced light of light waves.
In recent years, various wave-absorbing structures have been designed, such as planar metal/dielectric structures, reflective metal grating structures, metamaterial structures, and surface plasmon-based structures. There are many schemes for realizing total absorption based on a plasmon metamaterial system, and a metal particle-dielectric layer-metal layer metamaterial system is one of typical structures for realizing super absorption. Compared with the traditional method, the system has the characteristic of subwavelength, and the overall thickness of the general system is only a few hundredths of the working wavelength. In addition, these absorber systems have some drawbacks, such as narrow absorption band, low absorption efficiency, complex structure and the need to use noble metal materials. In addition, the metamaterial structure and the novel wave-absorbing structure of the surface plasmon have great potential application value in the fields of designing selective heat emitters, biosensors, solar energy collecting systems and the like by virtue of the characteristics of nearly perfect absorption efficiency, insensitivity along with angle polarization, small structural units, light weight and the like. Therefore, designing a high-efficiency wide-spectrum wave-absorbing structure with good thermal stability, wide working wave band and low cost still remains a great challenge in the field.
The metamaterial electromagnetic wave absorber was first proposed in 2008 by the Landy project group of boston institute of america and was verified in the microwave band (Physical Review Letter 100, 207402 (2008)). The surface type double-layer structure is formed by the dielectric substrate coated with metal on the two sides, the upper layer is an open resonant ring, the bottom layer is a cut metal wire, and the open resonant ring and the cut metal wire form a resonant ring structure, so that electromagnetic waves incident on the absorber structure form resonance and absorb consumption, the purpose of perfect absorption is achieved, and the absorption efficiency of nearly 88% is realized at the 11.5GHz accessory. However, this structure can only absorb single polarization electromagnetic wave, and the middle dielectric insulating film layer is a low dielectric material. After that, researchers at home and abroad put forward more metal-medium-metal layered resonance metamaterial structures. However, the metamaterial electromagnetic wave absorber for realizing multiband or broadband is often complex in structural design and poor in repeatability. This limits the applications of most electromagnetic wave absorbers in photoelectric detection devices, optoelectronic functional devices, etc.
Therefore, the design and realization of perfect absorption only depend on a metal-medium composite system which is simple and easy to operate and can be produced by a large-area process, and the method has very important practical significance and application value for the difficult problem of the solar absorber.
Disclosure of Invention
The invention provides an ultrathin sunlight black silicon wave absorber and a preparation method thereof, aiming at solving the problems of narrow working frequency band, complex structural design and high manufacturing cost of an electromagnetic wave absorber.
The invention provides an ultrathin sunlight black silicon wave absorber which comprises a substrate layer and a super-surface structure layer, wherein the super-surface structure layer is connected to the upper surface of the substrate layer; the base layer and the super-surface structure layer are made of silicon, the thickness of the super-surface structure layer is 120-200 nanometers, and the super-surface structure layer comprises a plurality of concave cavities with different sizes and irregularities; the different sizes and the irregularity mean that the area of the concave cavities changes from 10 square nanometers to 500 square nanometers, the depth of the concave cavities changes from 10 nanometers to 280 nanometers, and the interval between the adjacent concave cavities changes from 10 nanometers to 100 nanometers. The super-surface structure layer comprises a plurality of concave cavities, the concave cavities are different in size, and the arrangement interval is irregular. Electromagnetic waves are incident to the super-surface structure layer, and have different resonance modes in different wavelength ranges due to the effect of the irregular concave cavities.
Further, a metal layer is included, which may be made of gold, silver, copper or aluminum. The metal layer may be formed on the super-surface structure layer by a plating technique. The metal layer is connected to the upper surface of the super-surface structure layer, electromagnetic waves enter the metal layer, and the metal layer is evaporated on the basis of irregular concave cavities in the super-surface structure layer, so that the metal layer can also have corresponding irregular cavities, and has different strong near-field coupling modes in different wavelength ranges. Therefore, the metal layer can realize more perfect anti-reflection absorption and realize photoelectric response and hot electron excitation and collection.
Furthermore, the thickness of the metal layer is 10-30 nanometers.
The preparation method of the ultrathin sunlight black silicon wave absorber comprises the following steps:
and 4, immersing the silicon wafer containing the metal particle layer into an etching solution for etching, so that the metal particle layer disappears, and irregular concave cavities with different sizes are formed on the surface of the silicon wafer, thereby obtaining the ultrathin sunlight black silicon absorber.
Furthermore, the coating technology is a magnetron sputtering method, an electron beam evaporation method, a pulse laser deposition method or an atomic layer deposition method.
Further, the metal film is made of gold.
Further, the granulation treatment is to granulate the metal film by using a heat treatment technology.
Further, the etching is chemical etching, and the etching solution is hydrogen fluoride solution.
Further, the method also comprises the following steps:
and 5, forming a metal layer on one side of the silicon wafer containing the concave cavity by using a coating technology, wherein the metal layer is made of gold, silver, copper or aluminum.
The invention has the following beneficial effects: the ultrathin sunlight black silicon wave absorber has only two-layer structure, is simpler than the electromagnetic wave absorber with three or more layers, and realizes near-perfect anti-reflection absorption (the efficiency is more than 97%) in the full solar radiation spectral range of 280-2500 nm. In addition, reflection suppression or antireflection operation can be performed on the wave band of 280-2500 nm, and the method has wide application in the fields of antireflection film layers and the like. The sizes and the shapes of the concave cavities in the super-surface structural layer have individual differences, and the concave cavities with the individual differences can provide more resonance absorption modes in a spectral range, so that light absorption of a wider wave band is realized; in addition, the coupling absorption of light can be further enhanced and the absorption spectral bandwidth can be widened by the near-field coupling effect between the cavities. The structure not only has optical characteristics, but also has the advantages of simple structure, large-area manufacturing and low cost.
Drawings
Fig. 1 is a schematic perspective view of an ultra-thin sunlight black silicon wave absorber according to the present invention.
Fig. 2 is a schematic cross-sectional structure diagram of the ultra-thin sunlight black silicon wave absorber of the present invention.
FIG. 3 is a SEM image of the surface of an experimental sample of example 1 of the present invention.
FIG. 4 is an absorption spectrum chart corresponding to the experimental samples of examples 1 to 4 of the present invention.
FIG. 5 is a graph showing the absorption spectrum of solar energy corresponding to the experimental sample of example 1 of the present invention.
Fig. 6 is a photograph of experimental samples of the black silicon wave absorber obtained after metal films with different thicknesses (2, 4, 7, 10, and 13 nm, respectively) are deposited in the preparation step 2 (examples 1, 2, 3, 4, and 5).
FIG. 7 is a reflection spectrum of the experimental samples of examples 5, 6, 7, 8 and 9 of the present invention.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
The ultrathin sunlight black silicon wave absorber can be prepared according to the following steps:
and 4, immersing the SI-AuNPs sample into a newly prepared etching solution for etching, so that a metal particle layer on the surface of the silicon wafer disappears, and concave cavities with different sizes and irregularities are formed on the surface of the silicon wafer, thereby obtaining the ultrathin sunlight black silicon absorber.
The thickness of the metal film can be regulated and controlled by changing the film plating condition. The average size of the metal particles, the average inter-particle distance and the morphology of the particles can be controlled by changing the thickness of the metal film layer and the conditions (e.g., temperature, time) of the heat treatment. The etching is chemical etching, the etching solution is a hydrogen fluoride solution, and the preparation ratio of the etching solution is hydrofluoric acid to hydrogen peroxide to deionized water = 3. The concave cavities on the surface of the silicon wafer are related to the size, the spacing and the morphology of metal particles.
In the prepared ultrathin sunlight black silicon absorber, the layer where the concave cavities with different sizes and irregularities are located is called a super-surface structural layer (upper layer), and the silicon layer below the super-surface structural layer is called a substrate layer (lower layer). As shown in fig. 1 and fig. 2, the super-surface structure layer 2 is connected to the upper surface of the substrate layer 1, and the super-surface structure layer 2 has a plurality of concave cavities 3 with different shapes and sizes, and the concave cavities 3 are irregularly arranged. The area size of the hollow cavity 3 is 10 to 500 square nanometers, the depth is 10 to 280 nanometers, and the interval between the adjacent hollow cavities is 10 to 100 nanometers.
Different ultrathin sunlight black silicon wave absorbers can be obtained by changing the preparation conditions. The following table shows the preparation conditions and the dimensional parameters of the ultra-thin solar black silicon wave absorbers of examples 1 to 9.
FIG. 4 is a graph showing the reflection spectra of the ultra-thin solar black silicon absorber of examples 1-4. The curves in the figure are the reflectivity of different thickness super-surface structure layers, where the thickness of the super-surface structure layer varies from 120 nm to 200 nm. The results show that the curve has a significant red-shift over the wavelength range. A broadband reflection suppression range is obtained in a longer wavelength range. Furthermore, as the dimensions of the structures are scaled, the anti-reflection windows are scaled simultaneously.
Fig. 5 is a graph showing the solar light absorption spectrum of the ultra-thin solar light black silicon absorber of example 1. It is clearly seen therein that the average absorption reaches 97% over the full wavelength range of 280 to 2500nm, indicating a full spectrum absorber.
As shown in fig. 6, the experimental samples obtained after the step 3 and the step 4 have significant differences in the reflection rate performance when metal films with different thicknesses are deposited in the preparation step 2. It can be seen that controlling the thickness of the deposited film in step 2 can control the antireflective properties of the final sample.
As can be seen from fig. 7, as the chemical etching time increases from 2min to 7min, the reflection is significantly reduced due to the enhanced light trapping capability of the deep cavity, especially in the longer wavelength range, which is rapidly attenuated in the process; this is why larger and deeper cavity structures will produce resonant absorption and confinement for longer wavelength light waves. However, for shorter wavelength light, strong optical field coupling and absorption can be achieved by ultra-thin high refractive index media or semiconductors due to their low order and fundamental resonance. In addition, the maximum etch depth of the system is also less than 200nm, indicating that the system has a thinner antireflective film. These properties confirm the realization of a solar full spectrum antireflective absorber through ultra-thin surface structures, which may be more suitable for optoelectronic devices.
In conclusion, the invention provides the ultrathin sunlight black silicon wave absorber with the irregular medium cavity surface, which overcomes the defects of narrow working frequency band, complex structural design and high manufacturing cost; the preparation method has the advantages of realizing more efficient light absorption rate in the sunlight spectral range, being simple and practical in preparation technology, being easy to prepare in a large area, low in cost, high in quality and high in repeatability, and having wide application prospects in the fields of thermophotovoltaic technology, photoelectric detection, photoelectric conversion, photo-generated electron and hot electron generation and collection and the like.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (9)
1. An ultra-thin sunlight black silicon wave absorber which is characterized in that: the super-surface structure layer is connected to the upper surface of the substrate layer; the substrate layer and the super-surface structure layer are made of silicon, the thickness of the super-surface structure layer is 120-200 nanometers, and the super-surface structure layer comprises a plurality of concave cavities which are different in size and are irregular; the different sizes and the irregularity mean that the area of the concave cavities changes from 10 square nanometers to 500 square nanometers, the depth of the concave cavities changes from 10 nanometers to 280 nanometers, and the interval between the adjacent concave cavities changes from 10 nanometers to 100 nanometers.
2. The ultra-thin sunlight black silicon absorber of claim 1, wherein: and the metal layer is made of gold, silver, copper or aluminum.
3. The ultra-thin sunlight black silicon absorber of claim 2, wherein: the thickness of the metal layer is 10-30 nanometers.
4. The method for preparing the ultra-thin sunlight black silicon wave absorber according to claim 1, comprising the following steps:
step 1, preparing a clean silicon wafer;
step 2, forming a layer of metal film on the silicon wafer by using a film coating technology;
step 3, granulating the metal film to enable the metal film to become a metal particle layer, wherein the metal particles in the metal particle layer are different in size, and the radius of the metal particles is changed from 50 nanometers to 200 nanometers;
and 4, immersing the silicon wafer containing the metal particle layer into an etching solution for etching, so that the metal particle layer disappears, and irregular concave cavities with different sizes are formed on the surface of the silicon wafer, thereby obtaining the ultrathin sunlight black silicon absorber.
5. The method of claim 4, wherein: the coating technology is a magnetron sputtering method, an electron beam evaporation method, a pulse laser deposition method or an atomic layer deposition method.
6. The method of claim 4, wherein: the metal film is made of gold.
7. The method of claim 4, wherein: the granulation treatment is to granulate the metal film by using a heat treatment technology.
8. The method of claim 4, wherein: the etching is chemical etching, and the etching solution is hydrogen fluoride solution.
9. The method according to any one of claims 4 to 8, wherein: further comprising the steps of:
and 5, forming a metal layer on one side of the silicon wafer containing the concave cavity by using a coating technology, wherein the metal layer is made of gold, silver, copper or aluminum.
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