CN103681970A - Method for manufacturing black silicon materials - Google Patents
Method for manufacturing black silicon materials Download PDFInfo
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- CN103681970A CN103681970A CN201310694318.XA CN201310694318A CN103681970A CN 103681970 A CN103681970 A CN 103681970A CN 201310694318 A CN201310694318 A CN 201310694318A CN 103681970 A CN103681970 A CN 103681970A
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- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 35
- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 68
- 239000010703 silicon Substances 0.000 claims abstract description 68
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 238000001259 photo etching Methods 0.000 claims abstract description 6
- 238000005530 etching Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 28
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003486 chemical etching Methods 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 3
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 241000931526 Acer campestre Species 0.000 claims description 2
- 229910018503 SF6 Inorganic materials 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 230000009977 dual effect Effects 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 3
- 230000005855 radiation Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001020 plasma etching Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000035800 maturation Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- -1 boron ion Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/26—Bombardment with radiation
- H01L21/263—Bombardment with radiation with high-energy radiation
- H01L21/268—Bombardment with radiation with high-energy radiation using electromagnetic radiation, e.g. laser radiation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The embodiment of the invention discloses a method for manufacturing black silicon materials. The method comprises the steps that a mask layer is formed on a silicon substrate; a preset graph through hole array is formed in the mask layer in a photoetching mode; the silicon substrate is etched, and a preset graph groove array is formed in the silicon substrate; the mask layer is removed from the silicon substrate; the silicon substrate is put into sulfurous gas, laser pulse radiates the silicon substrate, and the black silicon materials are obtained. According to the method for manufacturing the black silicon materials, high-energy laser is used for radiating a periodic array structure on the silicon substrate in a sulfurous gas environment, so that a micro-nano dual structure is formed, and sulfur doping is achieved at the same time in the radiation process. The absorption wave length of the obtained black silicon materials is expanded, the absorption rate is higher, the range of the absorption wave length is larger, and process steps are simple.
Description
Technical field
The present invention relates to Electrophotosensitivmaterial material technical field, especially relate to a kind of method of manufacturing black silicon material.
Background technology
Silicon materials are a kind of important semi-conducting materials.Because it has, be easy to purify, easily doping, the feature such as high temperature resistant, in a plurality of fields such as microelectronics, photovoltaic industry and communication industry, have a wide range of applications.But due to the restriction of itself energy gap, crystalline silicon material can not absorbing wavelength be greater than the light wave of 1100 nanometers (nm).When incident light wave length is greater than 1100nm, silicon-based detector can significantly reduce the absorptivity of light and responsiveness, so the photoelectric detector that operation wavelength is greater than 1100nm is generally manufactured with materials such as germanium, Gallium indium arsenides.But these material prices are relatively costly, thermodynamic property and crystal mass is poor and can not be compatible with at present comparatively ripe silicon technology.These characteristics have all limited its application on silicon-based devices basis.
Therefore, adopt silicon materials to prepare infrared band photoelectric device and can effectively reduce the application to this type of material, overcome that this class material manufacturing process is complicated, production cost high make and production process in contain the noxious substances such as lead, mercury shortcoming, can effectively reduce cost, reduce environmental pollution.
Black silicon material is as a kind of to the new function material obtaining after ordinary silicon micro-structural, and it is to can effectively absorbing from the light of near ultraviolet-near infrared band (250nm-2500nm).And owing to having the photoconductive gain of superelevation, the photoelectric current that black silicon material produces is the hundred times of traditional silicon material.Therefore, black silicon material can effectively reduce the use amount of the silicon materials of optical sensor, can effectively save cost, makes product more cheap, small and exquisite and light.
The photoelectric properties of black silicon material brilliance become the ideal material of making High sensitivity infrared detector, high-quantum efficiency avalanche diode, high-responsivity infrared diode and solar cell, in fields such as remote sensing, optical communication and microelectronics, all have important potential using value.
Summary of the invention
One of object of the present invention is to provide a kind of method of manufacturing the black silicon material that absorptivity is higher, absorbing wavelength scope is larger, and its step is simple, is easy to realize array, integrated.
One of object of the present invention is to provide and a kind ofly can when forming black silicon material, realizes the method for the manufacture black silicon material of silicon doping.
Technical scheme disclosed by the invention comprises:
A kind of method of manufacturing black silicon material is provided, has it is characterized in that, having comprised: on silicon substrate, formed mask layer; On described mask layer, photoetching forms predetermined pattern via-hole array, obtains graphic mask silicon substrate; Described graphic mask silicon substrate is carried out to etching, on described silicon substrate, form predetermined pattern groove array; From described silicon substrate, remove described mask layer; Described silicon substrate is placed in to sulfurous gas, and with silicon substrate described in laser pulse irradiation, obtains described black silicon material.
In one embodiment of the invention, described sulfurous gas is sulfur hexafluoride gas or hydrogen sulfide gas.
In one embodiment of the invention, described optical maser wavelength is 400 nanometer to 1000 nanometers.
In one embodiment of the invention, described laser pulse is 500 to 2100.
In one embodiment of the invention, the width of described laser pulse is 100 femtosecond to 10 nanometers.
In one embodiment of the invention, the air pressure of described sulfurous gas is 60 to 70 kPas.
In one embodiment of the invention, described mask layer is silicon nitride layer, silicon oxide layer, aluminium lamination, titanium layer or nickel-cadmium layer.
In one embodiment of the invention, described predetermined pattern is circle, rectangle, square and/or oval.
In one embodiment of the invention, the step that described graphic mask silicon substrate is carried out to etching comprises: with reaction particle etching method, ion, select injection assisted electrochemical etching method or chemical etching method to carry out etching to described graphic mask silicon substrate.
In one embodiment of the invention, the cycle of described predetermined pattern via-hole array is that the diameter of the through hole in 1 to 2 micron and/or described predetermined pattern via-hole array is 1 to 2 micron.
In the method for embodiments of the invention, on silicon substrate, form cyclic array structure, and in sulfurous gas environment, use superlaser to silicon substrate on periodically array structure carry out irradiation, form micro-nano dual structure, and in irradiation process, realized element sulphur doping simultaneously, obtained so required black silicon material.Because surface has formed nanostructure, Periodic structure surface reflectivity is reduced, and element sulphur is introduced impurity energy level, the absorbing wavelength of the black silicon material of acquisition is expanded, therefore this micro-nano dual structure is higher than single micro-meter scale array structure absorptivity, and absorbing wavelength scope is larger; More regular than simple nanostructured surface.And processing step is simple, compatible good with the silicon materials process technology of existing maturation, be easy to realize array, integrated, at optical sensor, there is huge application potential in the field of High sensitivity infrared detector and solar cell.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of method of the manufacture black silicon material of one embodiment of the invention.
Embodiment
Below in conjunction with accompanying drawing, describe the concrete steps of method of the manufacture black silicon material of embodiments of the invention in detail.
As shown in Figure 1, in embodiments of the invention, a kind of method of manufacturing black silicon material comprises step 10, step 12, step 14, step 16 and step 18.Below in conjunction with specific embodiment, describe wherein each step in detail.
Step 10: form mask layer on silicon substrate.
In embodiments of the invention, first on silicon substrate, form mask layer.
In embodiments of the invention, the mask layer here can be silicon nitride mask layer or silicon oxide masking film layer, and its thickness can be 90 to 600 nanometers.Silicon nitride mask layer or silicon oxide masking film layer can be formed on silicon substrate by the method for deposition, for example plasma enhanced chemical vapor deposition (PECVD) or other applicable CVD (Chemical Vapor Deposition) method etc.
In embodiments of the invention, the mask layer here can be also metal mask layer, for example aluminium lamination, titanium layer or nickel-cadmium layer etc., and its thickness can be 1 to 2 micron.The methods such as metal mask layer can deposited by electron beam evaporation method, magnetron sputtering method, vacuum thermal evaporation method are formed on silicon substrate.
Step 12: photoetching forms predetermined pattern via-hole array on mask layer.
Formed mask layer on silicon substrate after, in step 12, can use photoetching process photoetching on mask layer to form predetermined pattern via-hole array, thereby obtain graphic mask silicon substrate.
In embodiments of the invention, the predetermined pattern via-hole array here refers to that cross section is that the through hole of predetermined pattern is arranged the array of formation in a certain order, and this array can be periodic.
In embodiments of the invention, the predetermined pattern here can be circle, rectangle, square and/or oval, can be also any other applicable shape.
In embodiments of the invention, the cycle of predetermined pattern via-hole array can be close with near-infrared light waves wavelength or proportional, for example, can be 1 to 2 micron.Here, " cycle " of said predetermined pattern via-hole array refer to the distance between adjacent through-holes in the predetermined pattern through hole of periodic arrangement.
In embodiments of the invention, the diameter of the through hole in predetermined pattern via-hole array can be close with near-infrared light waves wavelength or proportional, for example, can be 1 to 2 micron.Here, " diameter " of through hole refers to the external diameter of a circle of the shape of cross section of through hole, and for example, the cross section of through hole is that circle is, the diameter is here the diameter of this cross section; When the cross section of through hole is rectangle or square, the diameter is here this rectangle or foursquare external diameter of a circle (being also cornerwise length); When the cross section of through hole is oval, the diameter is here the external diameter of a circle (being also oval major axis) of this ellipse; When the cross section of through hole is other shapes, its diameter defines similarly.
Step 14: silicon substrate is carried out to etching.
After having obtained graphic mask silicon substrate in step 12, in step 14, this graphic mask silicon substrate (silicon substrate with the mask layer that has formed predetermined pattern via-hole array) is carried out to etching, the part being exposed in the predetermined pattern via-hole array in mask layer in silicon substrate is etched, make each through hole in predetermined pattern via-hole array, silicon substrate is etched and forms the shape groove corresponding with this shape of through holes, thereby on silicon substrate, forms predetermined pattern groove array.
In embodiments of the invention, can use several different methods to carry out etching to graphic mask silicon substrate, for example, can use reaction particle etching method, ion to select injection assisted electrochemical etching method or chemical etching method to carry out etching to graphic mask silicon substrate.
1) reactive ion etching (RIE) method.
Reactive ion etching (RIE) method is to utilize under certain pressure intensity etching gas under the effect of high-frequency electric field, make gas glow discharge produce molecule free radical (free atom, molecule or atomic group), to there being the silicon substrate of sheltering to carry out a kind of lithographic method of Ions Bombardment and chemical reaction generation escaping gas formation etching.Wherein etching gas can be selected oxygen base (O
2), fluorine-based (SF
6, CF
4, CHF
3deng), chloro (Cl
2deng) and bromo (HBr etc.) gas.
For example, in an embodiment, graphic mask silicon substrate is put into vacuum chamber, be evacuated to required vacuum degree, pass into reacting gas.Conventionally reacting gas can be chosen as HBr/He, Cl
2/ O
2, CF
4/ O
2, SF
6/ Ar, Cl
2/ Ar, SiCl
4the multiple gases combinations such as/Ar.The selection of etching gas, proportioning and detail parameters setting can determining depending on adopted equipment and concrete adopted mask material.
2) ion selects to inject assisted electrochemical etching method.
Implantation Assisted Chemical Etching Process is to take N-type silicon substrate as example according to different doping contents and the etch rate difference of semiconductor type, utilize boron ion to select to inject, local film micro area on N type silicon chip, formation is easy to the P type silicon of corrosion, with electrochemical etching method, prepares patterned periodic slots shape structure.Generally, adulterate heavier, resistivity is lower, easier etching.Accordingly, take N-type silicon substrate as example: carry out boron Implantation having deposited on the N-type silicon substrate of silicon nitride or silicon oxide masking film, remove after mask annealed processing, the method by electrochemical etching obtains required figure.
3) chemical etching method.
The method that common employing is adopted in chemical corrosion is silicon nitride, and silica etc. are as mask, uses anisotropic etchant, for example EPW(ethylenediamine, adjacent benzene two sweet smell and water), diamine, KOH, NaOH, LiOH, CsOH and NH
4oH etc., carry out etching to silicon under certain condition.
Adopt chemical etching method generally not use metal material as mask, conventionally adopt silicon nitride material as mask.Therefore, specific implementation method can be: by putting into anisotropic etchant with the silicon chip of silicon nitride mask, react under certain condition.Corrosive liquid can adopt KOH, water, isopropyl alcohol to configure by a certain percentage, and the temperature heating in experiment is 50-95 ℃, temperature control error ± 1 ℃.
Step 16: remove mask layer.
After graphic mask silicon substrate is carried out to etching processing, in step 16, can remove mask layer from silicon substrate (having passed through this graphic mask silicon substrate of etching processing).
Can use multiple applicable method to remove mask layer from silicon substrate.
Step 18: use laser pulse irradiation silicon substrate in sulfurous gas.
After having removed mask layer, in step 18, silicon substrate (passed through etching processing and removed the silicon substrate of mask layer) is placed in to sulfurous gas, and with this silicon substrate of laser pulse irradiation, like this, periodic structure that can be on silicon substrate (for example, aforesaid predetermined pattern groove array) surface forms cone-shaped micro-structural, simultaneously owing to carrying out irradiation in sulfurous gas, sulphur (S) element doping is occurred in irradiation process, , when forming periodic structure, irradiation also carried out sulfur doping, like this, the needed black silicon material of final acquisition.
In embodiments of the invention, the sulfurous gas here can be sulphur hexafluoride (SF
6) gas or hydrogen sulfide (H
2s) gas, or be other applicable sulfurous gass.
In embodiments of the invention, the wavelength of laser pulse can be 400 nanometer-1000 nanometers (nm), the quantity of the laser pulse irradiating can be 500-2100, the width of laser pulse can be for 100 femtoseconds (fs) be to 10 nanoseconds (ns), and the air pressure of sulfurous gas (operating air pressure) can be 60-70 kPa (KPa).
In the method for embodiments of the invention, on silicon substrate, form cyclic array structure, and in sulfurous gas environment, use superlaser to silicon substrate on periodically array structure carry out irradiation, form micro-nano dual structure, and in irradiation process, realized element sulphur doping simultaneously, obtained so required black silicon material.Because surface has formed nanostructure, Periodic structure surface reflectivity is reduced, and element sulphur is introduced impurity energy level, the absorbing wavelength of the black silicon material of acquisition is expanded, therefore this micro-nano dual structure is higher than single micro-meter scale array structure absorptivity, and absorbing wavelength scope is larger; More regular than simple nanostructured surface.And processing step is simple, compatible good with the silicon materials process technology of existing maturation, be easy to realize array, integrated, at optical sensor, there is huge application potential in the field of High sensitivity infrared detector and solar cell.
The black silicon material of manufacturing according to the method providing in the embodiment of the present invention, in ultraviolet-visible light-near infrared wavelength region (250nm-2500nm) absorptivity up to 90%, overcome traditional silicon detector and at wavelength, be greater than scope absorptivity and the low problem of responsiveness of 1100nm, tentatively overcome the restriction of silicon materials to absorbing wavelength itself.Higher than simple micrometre array structure or nanostructure absorptivity, absorbing wavelength scope is larger.
By specific embodiment, describe the present invention above, but the present invention is not limited to these specific embodiments.It will be understood by those skilled in the art that and can also make various modifications to the present invention, be equal to replacement, change etc., these conversion, all should be within protection scope of the present invention as long as do not deviate from spirit of the present invention.In addition, " embodiment " described in above many places represents different embodiment, can certainly be by its all or part of combination in one embodiment.
Claims (10)
1. a method of manufacturing black silicon material, is characterized in that, comprising:
On silicon substrate, form mask layer;
On described mask layer, photoetching forms predetermined pattern via-hole array, obtains graphic mask silicon substrate;
Described graphic mask silicon substrate is carried out to etching, on described silicon substrate, form predetermined pattern groove array;
From described silicon substrate, remove described mask layer;
Described silicon substrate is placed in to sulfurous gas, and with silicon substrate described in laser pulse irradiation, obtains described black silicon material.
2. the method for claim 1, is characterized in that: described sulfurous gas is sulfur hexafluoride gas or hydrogen sulfide gas.
3. the method as described in claim 1 or 2, is characterized in that: described optical maser wavelength is 400 nanometer to 1000 nanometers.
4. the method as described in any one in claims 1 to 3, is characterized in that: described laser pulse is 500 to 2100.
5. the method as described in any one in claims 1 to 3, is characterized in that: the width of described laser pulse is 100 femtosecond to 10 nanometers.
6. the method as described in any one in claims 1 to 3, is characterized in that: the air pressure of described sulfurous gas is 60 to 70 kPas.
7. the method as described in any one in claim 1 to 6, is characterized in that: described mask layer is silicon nitride layer, silicon oxide layer, aluminium lamination, titanium layer or nickel-cadmium layer.
8. the method as described in any one in claim 1 to 6, is characterized in that: described predetermined pattern is circle, rectangle, square and/or oval.
9. the method as described in any one in claim 1 to 6, it is characterized in that, the step that described graphic mask silicon substrate is carried out to etching comprises: with reaction particle etching method, ion, select injection assisted electrochemical etching method or chemical etching method to carry out etching to described graphic mask silicon substrate.
10. the method as described in any one in claim 1 to 6, is characterized in that: the cycle of described predetermined pattern via-hole array is that the diameter of the through hole in 1 to 2 micron and/or described predetermined pattern via-hole array is 1 to 2 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310694318.XA CN103681970A (en) | 2013-12-18 | 2013-12-18 | Method for manufacturing black silicon materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310694318.XA CN103681970A (en) | 2013-12-18 | 2013-12-18 | Method for manufacturing black silicon materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103681970A true CN103681970A (en) | 2014-03-26 |
Family
ID=50318878
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|---|---|---|---|
| CN201310694318.XA Pending CN103681970A (en) | 2013-12-18 | 2013-12-18 | Method for manufacturing black silicon materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103681970A (en) |
Cited By (5)
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