CN114686806A - High-absorption and wide-spectrum black silicon composite material and preparation method thereof - Google Patents
High-absorption and wide-spectrum black silicon composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- H—ELECTRICITY
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- 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
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
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- 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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic System
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
Abstract
The invention discloses a high-absorption and wide-spectrum black silicon composite material and a preparation method thereof. Carrying out black silicification treatment on a silicon substrate to obtain black silicon, wherein the surface of the black silicon is provided with a pointed cone array; and (4) sputtering and depositing TiN nano particles on the black silicon surface. The invention utilizes black silicification to form a uniform and large-area pointed cone-shaped black silicon structure on the surface of the traditional silicon; the TiN nano particles are deposited on the surface of the black silicon, so that the microstructure of the surface of the black silicon is more complex, the reflection times of light between the black silicon pointed cones are increased, and the material absorption rate is improved; meanwhile, TiN nano particles are deposited on the surface of the cone-shaped black silicon through magnetron sputtering, and the spectrum of the visible infrared band is widened by utilizing the plasmon resonance effect.
Description
Technical Field
The invention relates to the technical field of photoelectric detection, in particular to a high-absorption and wide-spectrum black silicon composite material and a preparation method thereof.
Background
With the rapid development of the near infrared enhanced detection technology, the method shows unique application advantages in the fields of remote sensing, early warning, guidance, night vision, medical diagnosis and the like, and is widely concerned by people. And the material with high absorption and broad spectrum characteristics is the basis for preparing the near infrared enhanced detector. The silicon material has the advantages of rich resources, low cost, easy doping and mature semiconductor processing technology based on the silicon material, so that the realization of high absorption and wide spectrum on the silicon-based material has important significance.
However, silicon materials have been associated with two major problems: firstly, the surface of the silicon material is smooth and has higher reflectivity to incident light, so that the light absorptivity of the silicon-based photoelectric detector is not high, and the response performance of the detector is not good; secondly, the silicon material is an indirect bandgap material, has a relatively large forbidden bandwidth, and basically does not absorb light below the forbidden bandwidth, and due to this problem, the conventional silicon-based photodetector is difficult to be used in two optical communication windows of 1310nm and 1550 nm. It is necessary to reduce the reflectivity of the surface of the silicon material and simultaneously widen the spectral absorption range of the silicon material in the near infrared. In order to solve the two problems of the silicon material, a black silicification method is mostly adopted at present, the photoelectric performance of the prepared black silicon photoelectric detector is greatly improved, and the black silicon photoelectric detector can also have practical application in a near infrared band. In recent years, a surface plasmon black silicon broad spectrum absorption material has emerged. If research is carried out by combining reactive ion etching with Au plasmons, the absorption rate of the plasmon black silicon material to light is relatively low, and the uniformity of the material is insufficient; meanwhile, a Schottky barrier formed by Au and Si is large, and under certain illumination, hot electrons formed in Au are difficult to enter semiconductor Si, so that the quantum efficiency of the material is not high.
Disclosure of Invention
The invention aims to solve the technical problems that the existing black silicification material has lower near infrared spectrum absorptivity and low quantum efficiency. Aims to provide a high-absorption and wide-spectrum black silicon composite material and a preparation method thereof, so as to solve the problems.
The invention is realized by the following technical scheme:
the invention aims to provide a preparation method of a high-absorption wide-spectrum black silicon composite material, which comprises the following steps:
carrying out black silicification treatment on the silicon substrate to obtain black silicon, wherein the surface of the black silicon is provided with a pointed cone array;
and (4) sputtering and depositing TiN nano particles on the black silicon surface.
Alternatively, the size of the TiN nano-particles deposited on the black silicon surface is 20nm-80 nm.
Optionally, the silicon substrate is intrinsic silicon with a resistivity of 3000-6000 Ω cm.
Optionally, the black silicidation process is performed using a femtosecond laser method.
Optionally, the silicon substrate is a substrate to be processed, and the processing process includes:
cleaning the silicon substrate by adopting an RCA standard cleaning method; after the completion of the cleaning, the cleaning solution is washed,
and (3) putting the cleaned silicon substrate into a hydrofluoric acid solution for soaking and cleaning, ultrasonically cleaning, and drying in a nitrogen atmosphere.
Optionally, the black silicidation process is:
putting a silicon substrate into a vacuum chamber, vacuumizing, and introducing SF6Gas, keeping the pressure of the gas in the cavity at 1 × 104Pa～10×104Pa；
Femtosecond laser scanning etching is carried out under the following conditions: luminous flux 1kJ/m2～10kJ/m2Scanning speed 1mm/s-10 mm/s, scanning interval 0.01 mm-0.04 mm, and spot radius 0.04 mm.
Optionally, the black silicon is cleaned before sputter deposition, and the cleaning process is as follows: and (3) cleaning the black silicon in hydrofluoric acid, ultrasonically cleaning, and drying by nitrogen to obtain a black silicon sample.
Optionally, the process of sputtering and depositing TiN nanoparticles on the black silicon surface is as follows: placing a black silicon sample in a thermal evaporation instrument, and performing vacuum evaporation to sputter TiN nano particles, wherein the vacuum evaporation conditions are as follows: the vacuum evaporation chamber has an air pressure of 10-3Pa, average deposition rate of
The deposition time is 400-800 s, and TiN nano-particles with the size of 20-80 nm are formed on the surface of the black silicon through deposition.
The second purpose of the invention is to provide a black silicon composite material prepared by the preparation method.
The invention has the following advantages and beneficial effects:
the invention utilizes black silicification to form a uniform and large-area pointed cone-shaped black silicon structure on the surface of the traditional silicon; the TiN nano particles are deposited on the surface of the black silicon, so that the microstructure of the surface of the black silicon is more complex, the reflection times of light between the black silicon pointed cones are increased, and the material absorption rate is improved; under the irradiation of certain light, the TiN nano particles can generate a large number of hot electrons to cross the contact between TiN and black silicon to form a Schottky barrier, so that the probability of the hot electrons entering the semiconductor black silicon is improved, and the quantum efficiency of the material is increased. Meanwhile, TiN nano particles are deposited on the surface of the cone-shaped black silicon through magnetron sputtering, and the visible infrared band spectrum is widened by utilizing the plasmon resonance effect. In addition, compared with the high cost of metal Au, the cost of TiN is obviously reduced.
Drawings
In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and that for those skilled in the art, other related drawings can be obtained from these drawings without inventive effort. In the drawings:
fig. 1 is a schematic cross-sectional view of a black silicon material prepared by an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of a black silicon composite plasma material prepared according to an embodiment of the present invention.
FIG. 3 is a graph of simulated absorption rate of a black silicon composite plasma material obtained in example 1 of the present invention;
wherein fig. 3a, 3b, 3c, 3d, 3e represent simulated absorbance curves for the materials of ordinary black silicon, comparative example 1, example 2, example 3, respectively.
FIG. 4 is a graph showing the simulated electric field intensity distribution of the black silicon composite plasma material obtained in example 1 of the present invention under the irradiation of the incident light with the wavelength of 1550 nm;
wherein fig. 4a, 4b, 4c, 4d, 4e represent simulated electric field intensity distribution plots of the materials of the general black silicon, comparative example 1, example 2, example 3, respectively.
In the drawing, reference numeral 1 represents a silicon substrate, reference numeral 2 represents a pointed cone array of a black silicon surface, and reference numeral 3 represents TiN nanoparticles deposited on the black silicon surface.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limiting the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that: it is not necessary to employ these specific details to practice the present invention. In other instances, well-known materials or methods have not been described in detail in order to avoid obscuring the present invention.
Firstly, material preparation
Example 1:
(1) substrate material selection: selecting intrinsic silicon with the crystal orientation of 111 and the resistivity of 3000 omega cm as a substrate material;
(2) cleaning of the silicon substrate 1: cleaning the silicon substrate by adopting an RCA standard cleaning method; after cleaning, soaking and cleaning the silicon substrate in 5% hydrofluoric acid solution for 1 minute, ultrasonically washing the silicon substrate for 10 minutes by using deionized water, and finally drying the silicon substrate in a nitrogen atmosphere with the purity of 99.99% to remove oxides and pollutants on the surface of the silicon wafer;
(3) femtosecond laser scanning and etching: putting the cleaned silicon substrate 1 into a vacuum chamber, pumping out air in the chamber, and introducing SF6Gas, keeping the pressure of the gas in the cavity at 2X 104Pa. Turning on the femtosecond laser to control the luminous flux of the femtosecond laser to be 2kJ/m2The scanning speed is 1mm/s, the scanning interval is 0.01mm, and the spot radius is 0.04 mm. And obtaining the etched silicon substrate material, namely black silicon, wherein the surface of the black silicon is provided with a pointed cone array 2 of a microstructure.
(4) Cleaning a black silicon sample: and (3) cleaning the prepared black silicon in hydrofluoric acid with the concentration of 5% for 5 minutes, then ultrasonically cleaning the black silicon for 10 minutes by using deionized water, and finally drying the black silicon by using nitrogen with the purity of 99.99% to remove oxides and pollutants on the surface of the black silicon wafer sample.
(5) Sputtering and depositing nano particles: placing the black silicon sample in a thermal evaporation instrument, wherein the air pressure of a vacuum evaporation chamber is 10- 3Pa, average deposition rate of
The deposition time is 800s, and TiN nano-particles 3 with the size of about 40nm are formed on the surface of the black silicon through deposition, so that the black silicon composite plasma is obtained.
Example 2:
(1) substrate material selection: selecting intrinsic silicon with the crystal orientation of 111 and the resistivity of 3000 omega cm as a substrate material;
(2) cleaning of the silicon substrate 1: cleaning the silicon substrate by adopting an RCA standard cleaning method; after cleaning, placing the silicon substrate in a 5% hydrofluoric acid solution for soaking and cleaning for 1 minute, then ultrasonically washing for 10 minutes by using deionized water, and finally drying in a nitrogen atmosphere with the purity of 99.99% to remove oxides and pollutants on the surface of the silicon wafer;
(3) femtosecond laser scanning and etching: putting the cleaned silicon substrate 1 into a vacuum chamber, pumping out air in the chamber, and introducing SF6Gas, keeping the pressure of the gas in the cavity at 8.5 × 104Pa. The femtosecond laser is turned on, and the luminous flux of the femtosecond laser is controlled to be 4.5kJ/m2The scanning speed is 2mm/s, the scanning interval is 0.02mm, and the spot radius is 0.04 mm. And obtaining the etched silicon substrate material, namely black silicon, wherein the surface of the black silicon is provided with a pointed cone array 2 of a microstructure.
(4) Cleaning a black silicon sample: and (3) cleaning the prepared black silicon in hydrofluoric acid with the concentration of 5% for 5 minutes, then ultrasonically cleaning the black silicon for 10 minutes by using deionized water, and finally drying the black silicon by using nitrogen with the purity of 99.99% to remove oxides and pollutants on the surface of the black silicon wafer sample.
(5) Sputtering deposition of nano particles: placing the black silicon sample in a thermal evaporation instrument, wherein the air pressure of a vacuum evaporation chamber is 10- 3Pa, average deposition rate of
The deposition time is 600s, TiN nano-particles 3 with the size of about 60nm are formed on the surface of the black silicon through deposition, and the black silicon composite plasma is obtained.
Example 3:
(1) substrate material selection: selecting intrinsic silicon with the crystal orientation of 111 and the resistivity of 3000 omega cm as a substrate material;
(2) cleaning of the silicon substrate 1: cleaning the silicon substrate by adopting an RCA standard cleaning method; after cleaning, placing the silicon substrate in a 5% hydrofluoric acid solution for soaking and cleaning for 1 minute, then ultrasonically washing for 10 minutes by using deionized water, and finally drying in a nitrogen atmosphere with the purity of 99.99% to remove oxides and pollutants on the surface of the silicon wafer;
(3) femtosecond laser scanning and etching: putting the cleaned silicon substrate 1 into a vacuum chamber, pumping out air in the chamber, and introducing SF6Gas, keeping the pressure of the gas in the cavity at 9 x 104Pa. Turning on the femtosecond laser to control the luminous flux of the femtosecond laser to 9kJ/m2The scanning speed is 5mm/s and the scanning distance is 0.04mmThe spot radius is 0.04 mm. And obtaining the etched silicon substrate material, namely black silicon, wherein the surface of the black silicon is provided with a pointed cone array 2 of a microstructure.
(4) Cleaning a black silicon sample: and (3) cleaning the prepared black silicon in hydrofluoric acid with the concentration of 5% for 5 minutes, then ultrasonically cleaning the black silicon for 10 minutes by using deionized water, and finally drying the black silicon by using nitrogen with the purity of 99.99% to remove oxides and pollutants on the surface of the black silicon wafer sample.
(5) Sputtering and depositing nano particles: placing the black silicon sample in a thermal evaporation instrument, wherein the air pressure of a vacuum evaporation chamber is 10- 3Pa, average deposition rate of
The deposition time is 800s, TiN nano-particles 3 with the size of about 80nm are formed on the surface of the black silicon through deposition, and the black silicon composite plasma is obtained.
Comparative example 1:
(1) selecting a P-type monocrystalline silicon wafer with the thickness of 675 microns, the crystal orientation of 100 microns and the resistivity of 10-15 omega cm, placing the silicon wafer into a dilute hydrofluoric acid solution with the concentration of 2% for treatment for 1 minute, then placing the silicon wafer into deionized water for cleaning for 10 minutes, removing oxides and pollutants on the surface of the silicon wafer, and placing the silicon wafer into a spin dryer for treatment for 10 minutes at 1200 revolutions per minute.
(2) And (2) placing the silicon wafer processed in the step (1) on a wafer feeding table of a reactive ion etcher, setting the gas pressure to be 800mTorr, the radio frequency power to be 800w, the argon flow to be 100 standard milliliters per minute, the sulfur hexafluoride flow to be 60 standard milliliters per minute, the oxygen flow to be 55 standard milliliters per minute, and the introduced cooling gas helium flow to be 10 torr to control the temperature of the substrate, wherein in order to prevent overhigh radio frequency inductance temperature caused by continuous work, a cyclic etching method of starting the radio frequency for 120 seconds to perform plasma etching and stopping the radio frequency for 15 seconds to perform gap adjustment is adopted to process the silicon wafer for 270 seconds. And finally, introducing excessive helium gas to cool the cavity, and taking out the silicon wafer after the cavity recovers the standard atmospheric pressure.
(3) Putting the black silicon prepared in the step (2) into a dilute hydrofluoric acid solution with the concentration of 2% again for treating for 1 minute, and then putting the black silicon into deionized waterAnd (3) cleaning the black silicon wafer in water for 10 minutes, removing oxides and pollutants on the surface of the black silicon wafer, and placing the black silicon wafer into a spin dryer to treat the black silicon wafer for 10 minutes at 1200 revolutions per minute. Putting black silicon into a thermal evaporation instrument, and adjusting the air pressure of a vacuum evaporation chamber to 10-3To 10-4Pa, controlling the average deposition rate to
The deposition time is 400s, a 40nm gold film is deposited on the black silicon surface and then taken out, and due to the shadow effect, gold can be attached to the nano hills on the rough black silicon surface etched by the reactive ions.
II, experimental results:
1. simulated absorption rate study
As shown in fig. 1, the black silicon obtained in the above embodiments 1 to 3 is ablated by femtosecond laser, so as to form a uniform and large-area pointed cone-shaped black silicon structure on the surface of the conventional silicon substrate, and the whole black silicon structure is a pointed cone array. The black silicon composite plasma material shown in fig. 2 is formed after the nano particles are sputtered on the surface of the black silicon. And forming TiN nano-particles with the size of 20nm-80nm on the formed black silicon rough surface pointed cone due to the shadow effect.
The results of the simulated absorption rate test of the surface plasmon black silicon materials obtained in examples 1 to 3 and comparative example 1 are shown in fig. 3. The specific test method is to establish a black silicon composite plasma model by using simulation software FDTD Solutions, and simulate and test the absorptivity. The absorption of light at different wavelengths was investigated for the materials of examples and comparative example 1. The materials of examples 1 to 3 respectively and correspondingly simulated that the Number of TiN nanoparticles is 400, 800 and 1200. The material of comparative example 1 corresponds to a simulated number of TiN nanoparticles of 400. Meanwhile, a simulated absorption rate test is also carried out on common black silicon, the common black silicon is the black silicon obtained in the embodiment 1, and TiN nano-particles are not sputtered and deposited on the surface of the black silicon.
As can be seen from fig. 3, the absorption rates of the materials of embodiments 1 to 3 (corresponding to 3a, 3b, and 3c in fig. 3, respectively) are significantly improved from 400nm, and all have high absorption rates, the average absorption rate reaches 81.1%, and the phenomenon of broad spectrum absorption enhancement occurs in the infrared band. The absorbance of the material of comparative example 1 was significantly lower than that of the examples, and the spectral absorption performance in the infrared band was also significantly poor. The absorptivity and spectral absorption performance of the common black silicon are worse. Therefore, the performance of the materials of examples 1-3 is greatly improved compared with the surface plasmon black silicon material prepared by the existing method such as comparative example 1.
2. Simulation electric field intensity distribution research
The simulated electric field intensity distribution conditions of different interfaces under the irradiation of 1550nm wavelength incident light are studied on the materials obtained in the examples 1 to 3 and the comparative example 1 and the common black silicon.
The specific test method is to establish a black silicon composite plasma model by utilizing simulation software FDTD Solutions and simulate and test the electric field intensity distribution. The Number of TiN nanoparticles simulated in examples 1 to 3 was 400, 800 and 1200, respectively, and the Number of TiN nanoparticles simulated in comparative example 1 was 400, and the results are shown in FIG. 4.
As can be seen from FIG. 4, when TiN nanoparticles are irradiated to cover the (X-Z) section and the (X-Y) section of the black silicon of the pointed cone by the incident light with the wavelength of 1550nm, it is found that in examples 1 to 3 (corresponding to 4a, 4b and 4c in FIG. 4 respectively), as the number of TiN increases, more hot spots are distributed on the surface of the pointed cone, and the hot spots limit the incident light collection on the side wall surface of the black silicon, which indicates that the incident light with the wavelength of 1550nm is significantly absorbed. Compared with the material obtained in the comparative example 1, the hot spot distribution of the surface of the common black silicon is less. The results show that the TiN nanoparticles of the materials of embodiments 1-3 can generate a large number of hot electrons to cross the contact between TiN and black silicon to form a Schottky barrier, and the probability of the hot electrons entering semiconductor black silicon is improved, so that the quantum efficiency of the materials is increased.
The reagents used in the above embodiments can be obtained by commercially available or existing technologies, the instruments and devices involved in the process all adopt known devices, and the methods and the like not mentioned in the process all adopt known technologies, and are not described herein again.
The invention uses femtosecond laser to ablate black silicon, and forms uniform and large-area taper-shaped black silicon structure on the surface of the traditional silicon; SF introduced during ablation6And an impurity energy level is introduced into a silicon band gap by gas, so that the limitation of the forbidden band width of the traditional silicon material is broken through. TiN nano-particles are deposited on the surface of the cone-shaped black silicon through magnetron sputtering, and the visible infrared band spectrum is widened by utilizing the plasmon resonance effect. Therefore, by utilizing a two-step process of 'femtosecond laser ablation of black silicon' and 'deposition of TiN nano-particles on the surface of the black silicon', the surface microstructure of the black silicon is more complex, the reflection times of light between black silicon pointed cones are increased, the material absorptivity is improved, and the average absorptivity reaches 81.1%; under certain light irradiation, more hot spots appear in the electric field distribution near the black silicon pointed cone by introducing TiN nano particles, more hot electrons are generated, and the hot electrons cross a Schottky barrier formed by the contact of TiN and black silicon, so that the probability of the hot electrons entering the semiconductor black silicon is increased, and the quantum efficiency of the material is increased.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a high-absorption and wide-spectrum black silicon composite material is characterized by comprising the following steps:
carrying out black silicification treatment on the silicon substrate to obtain black silicon, wherein the surface of the black silicon is provided with a pointed cone array;
and (4) sputtering and depositing TiN nano particles on the black silicon surface.
2. The method of claim 1, wherein the size of the TiN nanoparticles deposited on the black silicon surface is 20nm-80 nm.
3. The method of claim 1 for preparing a high absorption, broad spectrum black silicon composite, wherein:
the silicon substrate is intrinsic silicon with the resistivity of 3000-6000 omega cm.
4. The method of claim 1, wherein the black silicon is formed by a femtosecond laser method.
5. The method of claim 1, wherein the silicon substrate is a substrate to be processed, and the processing comprises:
cleaning the silicon substrate by adopting an RCA standard cleaning method; after the completion of the cleaning, the cleaning solution is washed,
and (3) placing the cleaned silicon substrate into a hydrofluoric acid solution for soaking and cleaning, ultrasonically cleaning, and drying in a nitrogen atmosphere.
6. The method for preparing a high-absorption broad-spectrum black silicon composite material as claimed in claim 1, wherein the black silicification process comprises:
putting a silicon substrate into a vacuum chamber, vacuumizing, and introducing SF6Gas, keeping the pressure of the gas in the cavity at 1 × 104Pa～10×104Pa；
Femtosecond laser scanning etching is carried out under the following conditions: luminous flux 1kJ/m2～10kJ/m2The scanning speed is 1 mm/s-10 mm/s, the scanning interval is 0.01 mm-0.04 mm, and the spot radius is 0.04 mm.
7. The method for preparing a high-absorption broad-spectrum black silicon composite material as claimed in claim 1, wherein the black silicon is cleaned before sputter deposition, and the cleaning process is as follows: and (3) cleaning the black silicon in hydrofluoric acid, ultrasonically cleaning, and drying by nitrogen to obtain a black silicon sample.
8. The method for preparing the black silicon composite material with high absorption and broad spectrum according to claim 7, wherein the process of sputtering and depositing TiN nano-particles on the black silicon surface comprises the following steps: subjecting the black silicon sample to heatIn the evaporation instrument, vacuum evaporation is carried out to sputter TiN nano particles, and the conditions of the vacuum evaporation are as follows: the vacuum evaporation chamber has an air pressure of 10-3Pa, average deposition rate of
The deposition time is 400-800 s, and TiN nano-particles with the size of 20-80 nm are formed on the surface of the black silicon through deposition.
9. The black silicon composite plasma material obtained by the preparation method according to any one of claims 1 to 8.
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