CN101540348A - Preparation technology of multi-purpose silicon micro-nano structure - Google Patents
Preparation technology of multi-purpose silicon micro-nano structure Download PDFInfo
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Abstract
The invention relates to a preparation technology of a multi-purpose silicon micro-nano structure, and belongs to the preparation technology field of new materials. A preparation method of a large-area highly-orderly silicon micro-nano structure array is researched though the combination of the metal-catalyzed silicon corrosion technology and the photoetching technology. A micro structure image on a photoetching mask plate is accurately copied to the surface of a clean silicon chip coated with a photoresist by utilizing an electron beam or ultraviolet light and other exposure technologies so as to obtain the image required during the corrosion process and protected by etching resist. A metal silver film is deposited on the surface of the silicon chip after the surface of the silicon chip is processed by utilizing high-vacuum heat-evaporation and other technologies; after the etching resist coated on the surface of the silicon chip and the silver film coated on the resist are removed, the silicon chip is immerged into a closed container of hydrofluoric acid corrosion solution containing an oxidant and processed for 10 to 100 minutes so as to obtain the large-area highly-orderly silicon micro-nano structure array. The large-area highly-orderly silica micro-nano structure array has wide application prospect in the fields of solar batteries, lithium battery cathode materials, gas sensors, active surface reinforced Raman spectrometry substrate and the like.
Description
Technical field
The present invention relates to the orderly silicon micro-nano structure technology of preparing of a kind of multipurpose, belong to new material technology and field of nanometer material technology.
Background technology
The semiconductor microactuator nano structural material has broad application prospects in application such as nano photoelectric and novel solar battery device owing to its peculiar structure and physical property.Because silicon materials are in the critical role of traditional microelectronic industry, the research of one dimension silicon nanowires has received great concern.Present silicon nanowire preparation method mainly contains chemical vapour deposition (CVD) and oxide assisting growth technology etc.These methods need quite high temperature and some complex apparatus usually, thereby cause higher production cost owing to the restriction of growth mechanism.As silicon line growth temperature in the patent 00117242.5 up to 1600-2000 ℃ [referring to Chinese patent 00117242.5, publication number 1277152, open date 2000.12.20].The nearest a kind of chemical corrosion technology that proposes can be easily goes out large-area silicon nanowire array [referring to Chinese patent CN1382626 in room temperature preparation; Chinese patent application numbers 2005100117533], this technology does not need high temperature and complex device.Though this technology can be applied to the silicon base that difference is mixed type, concentration and orientation, can control the length and the crystalline orientation of nano wire, this method is difficult to obtain the diameter homogeneous orderly silicon nanowires of arranging.Our seminar adopts pipe/polyhenylethylene nano ball and silica nanosphere mould plate technique to prepare diameter homogeneous orderly silicon nanowires [the Kuiqing Peng that arranges recently, 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 utilize pipe/polyhenylethylene nano playing skill art to prepare silicon nanowires and need adopt reactive ion etching (RIE), thereby cause serious reduction of silicon nanostructure preparation efficiency and cost to increase substantially.Simultaneously, all difficult preparation that realizes the bulk silicon micro nano structure of these two kinds of technology.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of large-area ordered silicon micro-nano structure array of arranging, the area size of silicon micro-nano line has employed silicon substrate area decision, thereby can realize 4 inches even the more preparation of bulk silicon micro nano structure array.
The present invention combines metal catalytic silicon corrosion technology with photoetching technique, developed a kind of preparation method of large tracts of land high-sequential silicon micro-nano structure array; This large-area ordered silicon micro-nano structure is with a wide range of applications on solar cell, lithium cell cathode material and sensor construction.The technology of preparing of a kind of multi-purpose silicon micro-nano structure array that the present invention proposes, it is characterized in that: described method is carried out successively as follows:
(1) utilize photoetching technique the figure with micro nano structure on the photo mask board accurately to be replicated in the cleaning silicon wafer surface that scribbles photoresist.Slice, thin piece after the exposure is put into developer solution dissolve unwanted photoresist, the figure needed during with the acquisition corrosion, that the resist protection is arranged.
(2) utilize silicon chip surface deposition one deck silver (or gold) film of vacuum thermal evaporation technology after step (1) is handled.Subsequently the silicon chip that obtains is immersed in the stripping solution, the resist of silicon chip surface and silverskin or the golden film that covers are in the above removed.
(3) silicon chip that step (3) is obtained immerses and contains HF+H
2O
2+ H
2O (also can utilize Fe (NO
3)
3Deng the H in the oxidizing substance replacement corrosive liquid
2O
2) in the closed container of etchant solution, handled 4-150 minute for 25-50 degree centigrade.Sample is soaked at least one hour in the concentrated nitric acid solution the inside remove the residual silver of silicon micro-nano structure sample surfaces.
(4) utilize the platinum or the gold nano grain film of the discontinuous distribution of n type silicon micro-nano structure surface deposition that chemical plating or vacuum thermal evaporation technology obtain in step (3).The n type silicon micro-nano structure that is coated with platinum or gold nano grain film can be used as the optoelectronic pole use of efficiency light electrochemistry solar cell.
(5) the orderly silicon micro-nano structure material that obtains of step (3) can be used as the high-performance lithium cell negative electrode material and uses.
(6) the orderly silicon micro-nano structure material that obtains of step (3) can be used as highly sensitive gas sensitive and uses.
(7) utilize Raman active metal nanometer particle films such as silicon micro-nano structure surface deposition silver that chemical plating or vacuum thermal evaporation technology obtain in step (3) or gold.The silicon micro-nano structure that is coated with Raman active metal nanometer particle film such as silver can be used as active surface to be strengthened the Raman spectroscopy substrate and uses.
(8) carry out phosphorus (or boron) by the orderly silicon micro-nano structure material surface of the p type (or n type) that obtains in step (3) and diffuse to form the pn knot, behind the extraction electrode of two sides, just obtain the silicon nanometer line solar battery of a monolithic.
(9) form the pn knot by orderly silicon micro-nano structure material surface deposition n type (or p type) semi-conducting material of the p type (or n type) that obtains in step (3) such as amorphous silicon etc., just behind the extraction electrode of two sides, obtain the silicon nanometer line solar battery of a monolithic.
(10) by behind the orderly silicon micro-nano structure material surface deposition intrinsic amorphous silicon membrane of the p type (or n type) that obtains in step (3), then deposit n type (or p type) amorphous silicon membrane again, thereby form PIN (or NIP) structure, behind the extraction electrode of two sides, just obtain the silicon nanowires HIT solar cell of a monolithic.
In the preparation method of above-mentioned silicon nanowire array, described step 4 hydrofluoric acid concentration scope is between the 0.2mol/l-10mol/l, and the concentration of hydrogen peroxide scope is 0.02-2mol/L, and the iron nitrate concentration scope is 0.01-0.50mol/L.
In the present invention, the silicon micro-nano structure pattern is determined by the micro nano structure figure on the photo mask board.By the silicon face plated metal silver of vacuum thermal evaporation technology after photoetching (or gold) film, utilize photoresist lift off solution, with the resist of silicon chip surface and cover and to form periodic silver (or gold) membrane structure after in the above silver (or gold) film is removed.Utilize this silver with periodic structure (or gold) film as silicon at HF+H
2O
2+ H
2Corrode catalyst in the O solution, the etching time through suitable just can form the silicon micro-nano structure array that large tracts of land is arranged orderly.This preparation method condition is simple, can successfully prepare large-area ordered silicon micro-nano structure array of arranging, as the silicon micro-nano linear array.
Description of drawings
Fig. 1 is the scanning electron microscopy pattern of the silicon nanowire array of preparation of the present invention.
Embodiment
The present invention combines metal catalytic silicon corrosion technology with photoetching technique, realize the preparation of large tracts of land high-sequential silicon micro-nano structure array at silicon chip surface; This large-area ordered silicon micro-nano structure has potential application prospect on applications such as solar cell, lithium cell cathode material and transducer.
The present invention will be further described below in conjunction with embodiment:
Embodiment 1
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 100nm.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes for 25 degrees centigrade.Just obtain the silicon nanostructure array.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.
Embodiment 2
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 200nm.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.
Embodiment 3
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 800nm.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 100 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.
Embodiment 4
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 800nm.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 100 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 30 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.
Embodiment 5
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 1 micron.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 200 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained the silicon micro-nano structure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.
Embodiment 6
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 1 micron.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 200 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 20 minutes, and just obtained the silicon micro-nano structure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.
Embodiment 7
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 2 microns.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 200 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained silicon micrometer structure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.
Embodiment 8
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 2 microns.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 100 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained silicon micrometer structure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.Utilize the Pt nanoparticle film of chemical plating in the discontinuous distribution of n type silicon microstructure surface deposition.The n type silicon micro-nano structure that is coated with platinum can be used as the optoelectronic pole use of efficiency light electrochemistry solar cell.
Embodiment 9
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 1 micron.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 100 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 20 minutes, and just obtained the silicon micro-nano structure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.Utilize the Pt nanoparticle film of chemical plating in the discontinuous distribution of n type silicon microstructure surface deposition.The n type silicon microstructure that is coated with platinum can be used as the optoelectronic pole use of efficiency light electrochemistry solar cell.
Embodiment 10
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 200 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 20 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.Utilize the Pt nanoparticle film of chemical plating in the discontinuous distribution of n type silicon nanostructure surface deposition.The n type silicon nanostructure that is coated with platinum can be used as the optoelectronic pole use of efficiency light electrochemistry solar cell.
Embodiment 11
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 200 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 30 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.Prepared orderly silicon nanostructure material can be used as the high-performance lithium cell negative electrode material and uses.
Embodiment 12
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 100 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 20 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.Prepared orderly silicon nanostructure material can be used as the high-performance lithium cell negative electrode material and uses.
Embodiment 13
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 100 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 20 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.The silicon nanostructure surface deposition argent nanometer particle film that utilizes chemical plating to obtain.The silicon nanostructure that is coated with the silver nano-grain film can be used as active surface and strengthens the use of Raman spectroscopy substrate.
Embodiment 14
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 200 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 30 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.The silicon nanostructure surface deposition silver nano-grain film that utilizes chemical plating to obtain.The silicon nanostructure that is coated with the silver nano-grain film can be used as active surface and strengthens the use of Raman spectroscopy substrate.
Embodiment 15
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 600 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 100 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 30 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.The silicon nanostructure surface deposition silver nano-grain film that utilizes chemical plating to obtain.The silicon nanostructure that is coated with the silver nano-grain film can be used as active surface and strengthens the use of Raman spectroscopy substrate.
Embodiment 16
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 600 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 100 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 30 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.The silicon nanostructure surface deposition gold nano grain film that utilizes chemical plating to obtain.The silicon nanostructure that is coated with the gold nano grain film can be used as active surface and strengthens the use of Raman spectroscopy substrate.
Embodiment 17
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 600 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 100 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 30 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.Form the pn knot by carry out phosphorous diffusion at the orderly silicon nanostructure material surface of p type, behind the extraction electrode of two sides, just obtain the silicon nanometer line solar battery of a monolithic.
Embodiment 18
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 1 micron.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 200 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained the silicon micro-nano structure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.Form the pn knot by carry out phosphorous diffusion at the orderly silicon micro-nano structure material surface of p type, behind the extraction electrode of two sides, just obtain the silicon nanometer line solar battery of a monolithic.
Embodiment 19
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 1 micron.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 200 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained the silicon micro-nano structure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.Form the pn knot by carry out boron diffusion at the orderly silicon micro-nano structure material surface of n type, behind the extraction electrode of two sides, just obtain the silicon nanometer line solar battery of a monolithic.
Embodiment 20
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 2 microns.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 200 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained orderly silicon microstructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.Form the pn knot by carry out phosphorous diffusion on the orderly silicon microstructure of p type surface, behind the extraction electrode of two sides, just obtain the silicon nanometer line solar battery of a monolithic.
Embodiment 21
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 2 microns.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 200 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained orderly silicon microstructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By form the pn knot at the orderly silicon microstructure surface deposition of p type n type amorphous silicon, behind the extraction electrode of two sides, just obtain the silicon nanometer line solar battery of a monolithic.
Embodiment 22
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 400 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By forming the pn knot, behind the extraction electrode of two sides, just obtain the silicon nanometer line solar battery of a monolithic at the orderly silicon nanostructure material surface deposition of p type n type amorphous silicon.
Embodiment 23
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 1 micron.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 200 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained orderly silicon micro-nano structure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By forming the pn knot, behind the extraction electrode of two sides, just obtain the silicon nanometer line solar battery of a monolithic at the orderly silicon micro-nano structure material surface deposition of p type n type amorphous silicon.
Embodiment 24
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 1 micron.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 200 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By behind the non-product silicon thin film of the orderly silicon microstructure array surface of p type deposition intrinsic, then deposit n type amorphous silicon membrane again, thereby form the PIN structure, behind the extraction electrode of two sides, just obtain the silicon nanowires HIT solar cell of a monolithic.
Embodiment 25
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 400 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained orderly silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By behind the orderly silicon micro-nano structure material surface of p type deposition intrinsic amorphous silicon membrane, then deposit n type amorphous silicon membrane again, thereby form the PIN structure, behind the extraction electrode of two sides, just obtain the silicon nanowires HIT solar cell of a monolithic.
Embodiment 26
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 100 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained orderly silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By behind the orderly silicon micro-nano structure material surface of p type deposition intrinsic amorphous silicon membrane, then deposit n type amorphous silicon membrane again, thereby form the PIN structure, behind the extraction electrode of two sides, just obtain the silicon nanowires HIT solar cell of a monolithic.
Embodiment 27
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 100 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 50 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained the silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By behind the orderly silicon micro-nano structure material surface of n type deposition intrinsic amorphous silicon membrane, then deposit p type amorphous silicon membrane again, thereby form the NIP structure, behind the extraction electrode of two sides, just obtain the silicon nanowires HIT solar cell of a monolithic.
Embodiment 28
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 1 micron.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 100 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 10 minutes, and just obtained orderly silicon microstructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By behind the orderly silicon micro-nano structure material surface of n type deposition intrinsic amorphous silicon membrane, then deposit p type amorphous silicon membrane again, thereby form the NIP structure, behind the extraction electrode of two sides, just obtain the silicon nanowires HIT solar cell of a monolithic.
Embodiment 29
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 2 microns.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 100 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 15 minutes, and just obtained orderly silicon microstructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By behind the orderly silicon micro-nano structure material surface of n type deposition intrinsic amorphous silicon membrane, then deposit p type amorphous silicon membrane again, thereby form the NIP structure, behind the extraction electrode of two sides, just obtain the silicon nanowires HIT solar cell of a monolithic.
Embodiment 30
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 200 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 80 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 15 minutes, and just obtained orderly silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By in orderly silicon micro-nano structure material surface deposit metal electrodes, can become a simple gas sensor to gas sensitizations such as oxynitrides.
Embodiment 31
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 200 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 80 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+H
2O
2+ H
2In the closed container of O etchant solution, handled 15 minutes, and just obtained orderly silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By at orderly silicon micro-nano structure material surface and back of the body surface deposition metal electrode, can become a simple gas sensor to gas sensitizations such as oxynitrides.
Embodiment 32
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 200 nanometers.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 80 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+Fe (NO
3)
3+ H
2In the closed container of O etchant solution, handled 30 minutes, and just obtained orderly silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By at orderly silicon micro-nano structure material surface and back of the body surface deposition metal electrode, can become a simple gas sensor to gas sensitizations such as oxynitrides.
Embodiment 33
Coat photoresist at clean silicon surface; electron beam exposure accurately is replicated in the nanostructure figure on the photo mask board cleaning silicon wafer surface that scribbles photoresist; with dissolving unwanted photoresist in the developer solution; the figure needed when obtaining corrosion, that the resist protection is arranged, the figure live width is 1 micron.Utilize the high vacuum thermal evaporation techniques behind the metal silverskin of the deposition of the silicon chip surface after processing one deck 100 nanometer thickness, silicon chip is immersed in the photoresist lift off solution, the resist of silicon chip surface and the silverskin that covers are in the above removed.Immediately silicon chip immerses and contains HF+Fe (NO
3)
3+ H
2In the closed container of O etchant solution, handled 30 minutes, and just obtained orderly silicon nanostructure array for 25 degrees centigrade.Subsequently sample is soaked at least one hour to remove the silverskin on surface in the concentrated nitric acid solution the inside.By at orderly silicon micro-nano structure material surface and back of the body surface deposition metal electrode, can become a simple gas sensor to gas sensitizations such as oxynitrides.
Claims (4)
1, a kind of preparation technology of multi-purpose silicon micro-nano structure is characterized in that: described method is carried out successively as follows:
(1) utilize photoetching technique the figure with micro nano structure on the photo mask board accurately to be replicated in the cleaning silicon wafer surface that scribbles photoresist.Slice, thin piece after the exposure is put into developer solution dissolve unwanted photoresist, the figure needed during with the acquisition corrosion, that the resist protection is arranged.
(2) utilize silicon chip surface deposition layer of metal silver (or gold) film of high vacuum thermal evaporation techniques after step (1) is handled.Subsequently the silicon chip that obtains is immersed in the stripping solution, the resist of silicon chip surface and silverskin or the golden film that covers are in the above removed.
(3) silicon chip that step (2) is obtained immerses and contains HF+H
2O
2+ H
2O (also can utilize Fe (NO
3)
3Deng the H in the oxidizing substance replacement corrosive liquid
2O
2) in the closed container of etchant solution, handled 4-150 minute for 25-50 degree centigrade; Then sample is soaked the silver that at least one hour remove the silicon micro-nano structure sample surfaces in concentrated nitric acid solution the inside.
(4) utilize the platinum or the gold nano grain film of the 5-10 nanometer of the discontinuous distribution of n type silicon micro-nano structure surface deposition that chemical plating or vacuum thermal evaporation technology obtain in step (3).
(5) utilize Raman active metal nanometer particle films such as silicon micro-nano structure surface deposition silver that chemical plating or vacuum thermal evaporation technology obtain in step (3) or gold.The silicon micro-nano structure that is coated with Raman active metal nanometer particle film such as silver can be used as active surface to be strengthened the Raman spectroscopy substrate and uses.
(6) carry out phosphorus (or boron) by the orderly silicon micro-nano structure material surface of the p type (or n type) that obtains in step (3) and diffuse to form the pn knot, behind the extraction electrode of two sides, just obtain the silicon nanometer line solar battery of a monolithic.
(7) form the pn knot by orderly silicon micro-nano structure material surface deposition n type (or p type) semi-conducting material of the p type (or n type) that obtains in step (3) such as amorphous silicon etc., just behind the extraction electrode of two sides, obtain the silicon nanometer line solar battery of a monolithic.
(8) by behind the orderly silicon micro-nano structure material surface deposition intrinsic amorphous silicon membrane of the p type (or n type) that obtains in step (3), then deposit n type (or p type) amorphous silicon membrane again, thereby form PIN (or NIP) structure, behind the extraction electrode of two sides, just obtain the silicon nanometer line solar battery of a monolithic.
2, preparation technology of multi-purpose silicon micro-nano structure according to claim 1, described step 3 hydrofluoric acid concentration scope is 1-10mol/L, and the concentration of hydrogen peroxide scope is 0.02-2mol/L, and the iron nitrate concentration scope is 0.05-0.20mol/L.
3, the orderly silicon micro-nano structure material that preparation technology of multi-purpose silicon micro-nano structure according to claim 1, described step 3 obtain is a kind of high-performance lithium cell negative electrode material, also is a kind of highly sensitive gas sensitive simultaneously.
4, the orderly silicon micro-nano structure material that preparation technology of multi-purpose silicon micro-nano structure according to claim 1, described step 4 obtain is a kind of high-performance optical electrochemistry solar cell photoelectric pole material.
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