CN101540348B - Preparation technology of multi-purpose silicon micro-nano structure - Google Patents

Abstract

The invention relates to a multi-purpose silicon micro-nano structure preparation technology, which belongs to the technical field of new material preparation. The invention combines the metal-catalyzed silicon corrosion technology with the photolithography technology, and develops a method for preparing a large-area highly ordered silicon micro-nano structure array. That is to use electron beam or ultraviolet light exposure technology to accurately copy the microstructure pattern on the photolithography mask on the surface of the clean silicon wafer coated with photoresist, and then obtain the resist-protected pattern required for etching . Deposit a metal silver film on the surface of the treated silicon wafer by using high vacuum thermal evaporation and other technologies, and remove the resist on the surface of the silicon wafer and the silver film covering it, and then immerse the silicon wafer in hydrofluoric acid containing an oxidant for corrosion The solution is treated in an airtight container for 10-100 minutes to obtain a large-area ordered silicon micro-nano structure array. This large-area ordered silicon micro-nano structure has broad application prospects in the fields of solar cells, lithium battery anode materials, gas sensors, and active surface-enhanced Raman spectroscopy substrates.

Description

A multi-purpose silicon micro-nano structure preparation technology

technical field

The invention relates to a multi-purpose ordered silicon micro-nano structure preparation technology, which belongs to the field of new material technology and nanometer materials.

Background technique

Semiconductor micro-nanostructure materials have broad application prospects in nano-optoelectronics and new solar cell devices due to their unique structures and physical properties. Due to the important position of silicon materials in the traditional microelectronics industry, the research of one-dimensional silicon nanowires has received great attention. The current nano-silicon wire preparation methods mainly include chemical vapor deposition and oxide-assisted growth techniques. Due to the limitations of the growth mechanism, these methods usually require relatively high temperatures and some complicated equipment, resulting in high production costs. For example, the silicon wire growth temperature in patent 00117242.5 is as high as 1600-2000°C [refer to: Chinese patent 00117242.5, publication number 1277152, publication date 2000.12.20]. A recently proposed chemical etching technology can easily prepare large-area silicon nanowire arrays at room temperature [see: Chinese Patent CN1382626; Chinese Patent Application No. 2005100117533]. This technology does not require high temperature and complicated equipment. Although this technique can be applied to silicon substrates with different doping types, concentrations and orientations, and can control the length and crystallographic orientation of nanowires, it is difficult to obtain silicon nanowires with uniform diameter and orderly arrangement. Our research group recently used polystyrene nanosphere and silica nanosphere template technology to prepare silicon nanowires with uniform diameter and order [Kuiqing Peng, Mingliang Zhang, Aijiang Lu, NingBew Wong, Ruiqin Zhang, Shuit-Tong Lee .Ordered Si nanowire arrays via NanosphereLithography and Metal-induced etching.Applied Physics Letters 2007, 90, 163123], but the preparation of silicon nanowires using polystyrene nanosphere technology requires reactive ion etching (RIE), resulting in silicon nanostructures The preparation efficiency is seriously reduced and the cost is greatly increased. At the same time, it is difficult for these two technologies to realize the preparation of large-area silicon micro-nanostructures.

Contents of the invention

The object of the present invention is to provide a method for preparing a large-area silicon micro-nano structure array arranged in an orderly manner. The area of the silicon micro-nano wire is determined by the area of the silicon substrate used, so that the area of 4 inches or even larger can be realized. Fabrication of silicon micro-nanostructure arrays.

The present invention combines metal-catalyzed silicon corrosion technology with photolithography technology to develop a method for preparing a large-area highly ordered silicon micro-nano structure array; this large-area ordered silicon micro-nano structure is used in solar cells and lithium batteries The anode material and sensor structure have broad application prospects. The preparation technology of a multi-purpose silicon micro-nano structure array proposed by the present invention is characterized in that: the method is carried out in sequence as follows:

(1) Using photolithography technology to accurately copy the pattern with micro-nano structure on the photolithography mask on the surface of the clean silicon wafer coated with photoresist. Put the exposed sheet into the developer solution to dissolve away the unnecessary photoresist, so as to obtain the resist-protected pattern required for etching.

(2) Depositing a layer of silver (or gold) film on the surface of the silicon wafer treated in step (1) by using vacuum thermal evaporation technology. Then the obtained silicon wafer is immersed in a stripping solution to remove the resist on the surface of the silicon wafer and the silver or gold film covering it.

(3) Immerse the silicon wafer obtained in step (3) into an etching solution containing HF+H ₂ O ₂ +H ₂ O (you can also use Fe(NO ₃ ) ₃ and other oxidizing substances to replace H ₂ O ₂ in the etching solution) In an airtight container, process at 25-50 degrees Celsius for 4-150 minutes. Soak the sample in concentrated nitric acid solution for at least one hour to remove the residual silver on the surface of the silicon micro-nanostructure sample.

(4) Depositing a discontinuously distributed platinum or gold nanoparticle film on the surface of the n-type silicon micro-nano structure obtained in step (3) by using electroless plating or vacuum thermal evaporation technology. n-type silicon micro-nanostructures coated with thin films of platinum or gold nanoparticles can be used as photoelectrodes for high-efficiency photoelectrochemical solar cells.

(5) The ordered silicon micro-nanostructure material obtained in step (3) can be used as a high-performance lithium battery negative electrode material.

(6) The ordered silicon micro-nanostructure material obtained in step (3) can be used as a highly sensitive gas-sensitive material.

(7) Depositing a Raman-active metal nanoparticle film such as silver or gold on the surface of the silicon micro-nano structure obtained in step (3) by using electroless plating or vacuum thermal evaporation technology. Silicon micro-nanostructures coated with thin films of Raman-active metal nanoparticles such as silver can be used as substrates for active surface-enhanced Raman spectroscopy.

(8) Phosphorus (or boron) is diffused on the surface of the p-type (or n-type) ordered silicon micro-nanostructure material obtained in step (3) to form a pn junction, and a monolithic silicon nanostructure is obtained after the electrodes are drawn out on both sides. wire solar cells.

(9) Deposit n-type (or p-type) semiconductor materials such as amorphous silicon etc. on the surface of the p-type (or n-type) ordered silicon micro-nanostructure material obtained in step (3) to form a pn junction, after the electrodes are drawn on both sides A monolithic silicon nanowire solar cell is obtained.

(10) After depositing an intrinsic amorphous silicon film on the surface of the p-type (or n-type) ordered silicon micro-nanostructure material obtained in step (3), then depositing an n-type (or p-type) amorphous silicon film, In this way, a PIN (or NIP) structure is formed, and a monolithic silicon nanowire HIT solar cell is obtained after the electrodes are drawn out on both sides.

In the preparation method of the above-mentioned silicon nanowire array, the concentration range of hydrofluoric acid in the step 4 is between 0.2mol/l-10mol/l, the concentration range of hydrogen peroxide is 0.02-2mol/L, and the concentration range of ferric nitrate is 0.01 -0.50mol/L.

In the present invention, the morphology of silicon micro-nano structure is determined by the pattern of micro-nano structure on the photolithography mask. Deposit a silver (or gold) film on the silicon surface after photolithography by vacuum thermal evaporation technology, and use a photoresist stripping solution to remove the resist on the surface of the silicon wafer and the silver (or gold) film covering it. A periodic silver (or gold) film structure can be formed. Using this silver (or gold) film with a periodic structure as a silicon corrosion catalyst in HF+H ₂ O ₂ +H ₂ O solution, after a suitable etching time, a large area of silicon microparticles arranged in an orderly manner can be formed. array of nanostructures. The preparation method has simple conditions, and can successfully prepare large-area silicon micro-nano structure arrays arranged in order, such as silicon micro-nano wire arrays.

Description of drawings

Fig. 1 is the scanning electron microscope morphology of the silicon nanowire array prepared in the present invention.

Detailed ways

The invention combines metal-catalyzed silicon corrosion technology with photolithography technology to realize the preparation of a large-area and highly ordered silicon micro-nano structure array on the surface of a silicon wafer; this large-area ordered silicon micro-nano structure is used in solar cells and lithium battery negative electrodes It has potential application prospects in the fields of materials and sensors.

The present invention will be further described below in conjunction with embodiment:

Example 1

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 100nm. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately thereafter, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25° C. for 10 minutes. An array of silicon nanostructures is obtained. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface.

Example 2

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 200nm. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface.

Example 3

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 800nm. After depositing a 100nm-thick metal silver film on the surface of the treated silicon wafer using high vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface.

Example 4

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 800nm. After depositing a 100nm-thick metal silver film on the surface of the treated silicon wafer using high vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 30 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface.

Example 5

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 1 micron. After using high vacuum thermal evaporation technology to deposit a layer of 200nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain a silicon micro-nano structure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface.

Example 6

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 1 micron. After using high vacuum thermal evaporation technology to deposit a layer of 200nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 20 minutes to obtain a silicon micro-nano structure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface.

Example 7

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 2 microns. After using high vacuum thermal evaporation technology to deposit a layer of 200nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain a silicon microstructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface.

Example 8

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 2 microns. After depositing a 100nm-thick metal silver film on the surface of the treated silicon wafer using high vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain a silicon microstructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. Electroless plating is used to deposit discontinuously distributed platinum nanoparticle films on the surface of n-type silicon microstructures. Platinum-coated n-type silicon micro-nanostructures can be used as photoelectrodes for high-efficiency photoelectrochemical solar cells.

Example 9

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 1 micron. After depositing a 100nm-thick metal silver film on the surface of the treated silicon wafer using high vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 20 minutes to obtain a silicon micro-nano structure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. Electroless plating is used to deposit discontinuously distributed platinum nanoparticle films on the surface of n-type silicon microstructures. Platinum-coated n-type silicon microstructures can be used as photoelectrodes for high-efficiency photoelectrochemical solar cells.

Example 10

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 200 nanometers. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 20 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. A non-continuously distributed platinum nanoparticle film is deposited on the surface of n-type silicon nanostructures by electroless plating. Platinum-coated n-type silicon nanostructures can be used as photoelectrodes for high-efficiency photoelectrochemical solar cells.

Example 11

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 200 nanometers. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 30 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. The prepared ordered silicon nanostructure material can be used as a high-performance lithium battery negative electrode material.

Example 12

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 100 nanometers. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 20 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. The prepared ordered silicon nanostructure material can be used as a high-performance lithium battery negative electrode material.

Example 13

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 100 nanometers. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 20 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. Metal silver nanoparticle film is deposited on the surface of silicon nanostructure obtained by electroless plating. Silicon nanostructures coated with thin films of silver nanoparticles can be used as substrates for active surface-enhanced Raman spectroscopy.

Example 14

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 200 nanometers. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 30 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. The silver nanoparticle thin film is deposited on the surface of the silicon nanostructure obtained by electroless plating. Silicon nanostructures coated with thin films of silver nanoparticles can be used as substrates for active surface-enhanced Raman spectroscopy.

Example 15

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 600 nanometers. After depositing a 100nm-thick metal silver film on the surface of the treated silicon wafer using high vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 30 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. The silver nanoparticle thin film is deposited on the surface of the silicon nanostructure obtained by electroless plating. Silicon nanostructures coated with thin films of silver nanoparticles can be used as substrates for active surface-enhanced Raman spectroscopy.

Example 16

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 600 nanometers. After depositing a 100nm-thick metal silver film on the surface of the treated silicon wafer using high vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 30 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. A gold nanoparticle film is deposited on the silicon nanostructure surface obtained by electroless plating. Silicon nanostructures coated with thin films of gold nanoparticles can be used as substrates for active surface-enhanced Raman spectroscopy.

Example 17

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 600 nanometers. After depositing a 100nm-thick metal silver film on the surface of the treated silicon wafer using high vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 30 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. A pn junction is formed by phosphorus diffusion on the surface of the p-type ordered silicon nanostructure material, and a monolithic silicon nanowire solar cell is obtained after electrodes are drawn out on both sides.

Example 18

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 1 micron. After using high vacuum thermal evaporation technology to deposit a layer of 200nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain a silicon micro-nano structure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. A pn junction is formed by phosphorus diffusion on the surface of the p-type ordered silicon micro-nano structure material, and a monolithic silicon nanowire solar cell is obtained after the electrodes are drawn out on both sides.

Example 19

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 1 micron. After using high vacuum thermal evaporation technology to deposit a layer of 200nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain a silicon micro-nano structure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. A pn junction is formed by boron diffusion on the surface of the n-type ordered silicon micro-nano structure material, and a monolithic silicon nanowire solar cell is obtained after the electrodes are drawn out on both sides.

Example 20

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 2 microns. After using high vacuum thermal evaporation technology to deposit a layer of 200nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain an ordered silicon microstructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. A pn junction is formed by phosphorus diffusion on the surface of the p-type ordered silicon microstructure, and a monolithic silicon nanowire solar cell is obtained after the electrodes are drawn out on both sides.

Example 21

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 2 microns. After using high vacuum thermal evaporation technology to deposit a layer of 200nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain an ordered silicon microstructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. A pn junction is formed by depositing n-type amorphous silicon on the surface of the p-type ordered silicon microstructure, and a monolithic silicon nanowire solar cell is obtained after electrodes are drawn out on both sides.

Example 22

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 400 nm. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. By depositing n-type amorphous silicon on the surface of the p-type ordered silicon nanostructure material to form a pn junction, a monolithic silicon nanowire solar cell is obtained after electrodes are drawn out on both sides.

Example 23

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 1 micron. After using high vacuum thermal evaporation technology to deposit a layer of 200nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25° C. for 10 minutes to obtain an ordered silicon micro-nano structure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. A pn junction is formed by depositing n-type amorphous silicon on the surface of the p-type ordered silicon micro-nano structure material, and a monolithic silicon nanowire solar cell is obtained after electrodes are drawn out on both sides.

Example 24

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 1 micron. After using high vacuum thermal evaporation technology to deposit a layer of 200nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. After depositing the intrinsic non-crystalline silicon film on the surface of the p-type ordered silicon microstructure array, and then depositing the n-type amorphous silicon film, a PIN structure is formed, and a monolithic silicon nanowire HIT is obtained after the electrodes are drawn out on both sides. Solar battery.

Example 25

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 400 nm. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25° C. for 10 minutes to obtain an ordered silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. After depositing the intrinsic amorphous silicon film on the surface of the p-type ordered silicon micro-nano structure material, and then depositing the n-type amorphous silicon film, a PIN structure is formed, and a monolithic silicon nanowire is obtained after the electrodes are drawn out on both sides. HIT solar cells.

Example 26

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 100 nanometers. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25° C. for 10 minutes to obtain an ordered silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. After depositing the intrinsic amorphous silicon film on the surface of the p-type ordered silicon micro-nano structure material, and then depositing the n-type amorphous silicon film, a PIN structure is formed, and a monolithic silicon nanowire is obtained after the electrodes are drawn out on both sides. HIT solar cells.

Example 27

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 100 nanometers. After using high vacuum thermal evaporation technology to deposit a layer of 50nm thick metal silver film on the surface of the treated silicon wafer, the silicon wafer is soaked in the photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain a silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. After depositing the intrinsic amorphous silicon film on the surface of the n-type ordered silicon micro-nano structure material, and then depositing the p-type amorphous silicon film, the NIP structure is formed, and a monolithic silicon nanowire is obtained after the electrodes are drawn out on both sides. HIT solar cells.

Example 28

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 1 micron. After depositing a 100nm-thick metal silver film on the surface of the treated silicon wafer using high vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 10 minutes to obtain an ordered silicon microstructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. After depositing the intrinsic amorphous silicon film on the surface of the n-type ordered silicon micro-nano structure material, and then depositing the p-type amorphous silicon film, the NIP structure is formed, and a monolithic silicon nanowire is obtained after the electrodes are drawn out on both sides. HIT solar cells.

Example 29

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 2 microns. After depositing a 100nm-thick metal silver film on the surface of the treated silicon wafer using high vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 15 minutes to obtain an ordered silicon microstructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. After depositing the intrinsic amorphous silicon film on the surface of the n-type ordered silicon micro-nano structure material, and then depositing the p-type amorphous silicon film, the NIP structure is formed, and a monolithic silicon nanowire is obtained after the electrodes are drawn out on both sides. HIT solar cells.

Example 30

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 200 nanometers. After depositing a metal silver film with a thickness of 80 nanometers on the surface of the treated silicon wafer by using high-vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 15 minutes to obtain an ordered silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. By depositing metal electrodes on the surface of the ordered silicon micro-nano structure material, it can become a simple gas sensor sensitive to nitrogen oxides and other gases.

Example 31

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 200 nanometers. After depositing a metal silver film with a thickness of 80 nanometers on the surface of the treated silicon wafer by using high-vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+H ₂ O ₂ +H ₂ O etching solution, and treated at 25 degrees Celsius for 15 minutes to obtain an ordered silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. By depositing metal electrodes on the surface and back surface of the ordered silicon micro-nano structure material, it can become a simple gas sensor sensitive to nitrogen oxides and other gases.

Example 32

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a pattern line width of 200 nanometers. After depositing a metal silver film with a thickness of 80 nanometers on the surface of the treated silicon wafer by using high-vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+Fe(NO ₃ ) ₃ +H ₂ O etching solution, and treated at 25° C. for 30 minutes to obtain an ordered silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. By depositing metal electrodes on the surface and back surface of the ordered silicon micro-nano structure material, it can become a simple gas sensor sensitive to nitrogen oxides and other gases.

Example 33

Coat photoresist on the clean silicon surface, and electron beam exposure will accurately copy the nanostructure pattern on the photolithographic mask on the clean silicon wafer surface coated with photoresist, and dissolve the unnecessary photoresist in the developing solution to obtain The resist-protected pattern required for etching has a line width of 1 micron. After depositing a 100nm-thick metal silver film on the surface of the treated silicon wafer using high vacuum thermal evaporation technology, the silicon wafer is soaked in a photoresist stripping solution, and the resist on the surface of the silicon wafer is covered on it. silver film removal. Immediately afterward, the silicon wafer was immersed in a closed container containing HF+Fe(NO ₃ ) ₃ +H ₂ O etching solution, and treated at 25° C. for 30 minutes to obtain an ordered silicon nanostructure array. The samples were then soaked in concentrated nitric acid solution for at least one hour to remove the silver film on the surface. By depositing metal electrodes on the surface and back surface of the ordered silicon micro-nano structure material, it can become a simple gas sensor sensitive to nitrogen oxides and other gases.

Claims (4)

1. A method for preparing a multipurpose silicon micro-nanostructure, characterized in that: the method is carried out as follows: (1) Using photolithography technology to accurately copy the pattern with micro-nano structure on the photolithography mask on the surface of the clean silicon wafer coated with photoresist. Put the exposed silicon wafer into the developing solution to dissolve the unnecessary photoresist, so as to obtain the photoresist-protected pattern required for etching. (2) Depositing a metal silver or gold film on the surface of the silicon wafer treated in step (1) by using high vacuum thermal evaporation technology. Then the obtained silicon wafer is immersed in a stripping solution to remove the resist on the surface of the silicon wafer and the silver or gold film covering it. (3) Immerse the silicon wafer obtained in step (2) in an airtight container containing HF+H ₂ O ₂ +H ₂ etching solution, and treat it at 25-50 degrees Celsius for 4-150 minutes; the H ₂ O in the etching solution can also be ₂ Replace with ferric nitrate solution; then soak the silicon wafer in concentrated nitric acid solution for at least one hour to remove the silver or gold on the surface of the silicon micro-nanostructure sample. (4) Depositing a discontinuously distributed 5-10 nanometer platinum or gold nanoparticle film on the surface of the n-type silicon micro-nano structure obtained in step (3) by using electroless plating or vacuum thermal evaporation technology. (5) Depositing a thin film of Raman active metal nanoparticles such as silver or gold on the surface of the silicon micro-nano structure obtained in step (3) by using electroless plating or vacuum thermal evaporation technology. Silicon micro-nanostructures coated with thin films of silver or gold Raman-active metal nanoparticles can be used as substrates for active surface-enhanced Raman spectroscopy. (6) Phosphorus or boron is diffused on the surface of the p-type or n-type ordered silicon micro-nanostructure material obtained in step (3) to form a pn junction, and a monolithic silicon nanowire solar cell is obtained after electrodes are drawn on both sides. (7) Deposit n-type or p-type semiconductor amorphous silicon on the surface of the p-type or n-type ordered silicon micro-nanostructure material obtained in step (3) to form a pn junction, and a monolithic silicon is obtained after the electrodes are drawn out on both sides Nanowire solar cells. (8) After depositing an intrinsic amorphous silicon film on the surface of the p-type or n-type ordered silicon micro-nanostructure material obtained in step (3), then depositing an n-type or p-type amorphous silicon film to form a PIN or With the NIP structure, a monolithic silicon nanowire solar cell is obtained after the electrodes are drawn out on both sides. 2. a kind of multipurpose silicon micro-nano structure preparation method according to claim 1, described step (3) hydrofluoric acid concentration scope is 1-10mol/L, and hydrogen peroxide concentration scope is 0.02-2mol/L, The concentration range of ferric nitrate is 0.05-0.20mol/L. 3. a kind of multipurpose silicon micro-nano structure preparation method according to claim 1, the ordered silicon micro-nano structure material that described step (3) obtains is a kind of high-performance lithium battery negative electrode material, is also a kind of high-performance simultaneously Sensitive gas-sensitive materials. 4. a kind of multipurpose silicon micro-nano structure preparation method according to claim 1, the ordered silicon micro-nano structure material that described step (4) obtains is a kind of high-performance photoelectrochemical solar cell photoelectrode material.

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