CN113299551A - Method for regulating and controlling semiconductor corrosion area - Google Patents
Method for regulating and controlling semiconductor corrosion area Download PDFInfo
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- CN113299551A CN113299551A CN202110457710.7A CN202110457710A CN113299551A CN 113299551 A CN113299551 A CN 113299551A CN 202110457710 A CN202110457710 A CN 202110457710A CN 113299551 A CN113299551 A CN 113299551A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 104
- 230000007797 corrosion Effects 0.000 title claims abstract description 58
- 238000005260 corrosion Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000001276 controlling effect Effects 0.000 title claims abstract description 17
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000000758 substrate Substances 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 72
- 230000008021 deposition Effects 0.000 claims abstract description 63
- 229910052751 metal Chemical class 0.000 claims abstract description 58
- 239000002184 metal Chemical class 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 42
- 239000012266 salt solution Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000009736 wetting Methods 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 13
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- -1 iron ions Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910002601 GaN Inorganic materials 0.000 claims description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims 2
- 238000001035 drying Methods 0.000 abstract description 12
- 239000002070 nanowire Substances 0.000 abstract description 11
- 238000005530 etching Methods 0.000 abstract description 9
- 230000008595 infiltration Effects 0.000 abstract description 2
- 238000001764 infiltration Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 10
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 3
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
- H01L21/30608—Anisotropic liquid etching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/00555—Achieving a desired geometry, i.e. controlling etch rates, anisotropy or selectivity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/00555—Achieving a desired geometry, i.e. controlling etch rates, anisotropy or selectivity
- B81C1/00595—Control etch selectivity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a method for regulating and controlling a semiconductor corrosion area, belonging to the technical field of nano semiconductor materials; the method comprises the following steps: mixing hydrofluoric acid and metal salt solution to obtain deposition solution; mixing hydrofluoric acid and an oxidant to obtain a corrosive liquid; immersing the semiconductor substrate into the deposition solution for deposition; treating the substrate obtained after deposition to enable the surface of the substrate to be different in wetting state; and then etching to obtain the nano semiconductor material. According to the invention, by regulating and controlling the surface infiltration state of the substrate after deposition, the corrosion region can be completely matched with the metal coverage region, and can also be larger than the metal coverage region, so that the nano semiconductor material has excellent photoelectric, thermoelectric and electrochemical properties according to different requirements. The results of the examples show that the corrosion area of the nano semiconductor material prepared after the drying treatment is completely matched with the coverage area of the metal, and the nano wire array is more compact and uniform.
Description
Technical Field
The invention relates to the technical field of nano semiconductor materials, in particular to a method for regulating and controlling a semiconductor corrosion region.
Background
Semiconductor materials represented by silicon have a wide development space in the future scientific and technological energy fields including chips, memory elements, solar cells, lithium ion batteries, thermoelectric materials, lasers, artificial photosynthesis and the like.
In the prior art, a metal-assisted chemical etching technology is adopted to prepare a semiconductor nanowire array, but the nanowire prepared by the method at present has strong randomness, and a series of problems exist in the application of the method in different application fields. For example, in solar cells, it is desirable for the material to have a higher light absorption rate, and in lithium ion batteries and thermoelectric materials, it is desirable for the material to exhibit a finer size. The current relatively easy way to implement is to control the morphology of the catalyst by changing the deposition process of the catalyst, thereby controlling the corrosion area. However, the catalyst is generally made of precious metal materials such as gold, silver, platinum and the like, so that more precious metal waste can be generated by enlarging a corrosion area, and meanwhile, the deposition process of the catalyst is repeatedly adjusted according to different application conditions, so that large-scale batch production is not facilitated. Therefore, how to regulate and control the corrosion area to obtain the nanowire structure with different morphological characteristics is the key of the current technology.
Disclosure of Invention
The invention aims to provide a method for regulating and controlling a semiconductor corrosion region, which is used for regulating and controlling the corrosion region according to the application condition when a nano semiconductor material array is prepared. In addition, the deposition process of the catalyst does not need to be changed in the process, and in order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a method for regulating and controlling a semiconductor corrosion region, which is applied to the preparation process of a nano semiconductor material and comprises the following steps:
(1) mixing hydrofluoric acid and metal salt solution to obtain deposition solution;
(2) mixing hydrofluoric acid and an oxidant to obtain a corrosive liquid;
(3) immersing a semiconductor substrate into the deposition solution obtained in the step (1) for deposition, and then drying to obtain a dried substrate;
or, immersing the semiconductor substrate into the deposition solution obtained in the step (1) for deposition, wherein after the deposition is finished, the substrate does not leave the aqueous solution all the time, and a wet substrate is obtained;
(4) processing the substrate obtained after deposition in the step (3) to adjust the surface wettability of the substrate;
(5) respectively immersing the substrates in different wet states obtained in the step (3) into the corrosive liquid obtained in the step (2) for corrosion, and respectively realizing small-area corrosion and large-area corrosion processes;
the step (1) and the step (2) are not in sequence.
Preferably, the concentration of the hydrofluoric acid in the step (1) is 1-5 mol/L.
Preferably, the metal element in the metal salt solution of step (1) comprises one of gold, silver and platinum; the concentration of the metal salt solution is 0.005-0.2 mol/L.
Preferably, the ratio of the amount of hydrogen fluoride in the hydrofluoric acid and the amount of the metal salt in the metal salt solution in the step (1) is 225: (0.02-4).
Preferably, the oxidizing agent in step (2) includes one of a hydrogen peroxide solution, an iron salt solution and oxygen.
Preferably, the concentration of the hydrogen peroxide solution and the concentration of the iron ions in the iron salt solution are independently 5-10 mol/L.
Preferably, the concentration of the hydrofluoric acid in the step (2) is 0.25-5 mol/L.
Preferably, the semiconductor substrate in step (3) comprises one of silicon, germanium, silicon carbide, gallium arsenide, and gallium nitride.
Preferably, the deposition time in the step (3) is 1-30 min.
Preferably, the aqueous solution of step (3) is deionized water.
The invention also provides the nano semiconductor material prepared by the preparation method of the nano semiconductor material.
The invention provides a method for regulating and controlling a semiconductor corrosion region, which comprises the following steps: mixing hydrofluoric acid and metal salt solution to obtain deposition solution; mixing hydrofluoric acid and an oxidant to obtain a corrosive liquid; immersing the semiconductor substrate into the deposition solution for deposition, and then drying to obtain a dry substrate, or keeping the substrate in an aqueous solution all the time to obtain a completely-soaked sediment; different corrosion results can be obtained by immersing the dried or soaked substrate into corrosive liquid or corrosive gas for corrosion. According to the invention, a semiconductor substrate is immersed in a mixed solution of hydrofluoric acid and a metal salt solution, metal nanoparticles obtained by reaction of the semiconductor substrate and the metal salt are deposited on the semiconductor substrate as a catalyst, and a nanowire array can be obtained by catalytic corrosion reaction; if the drying treatment is carried out after the deposition, the surface tension of the liquid on the surface of the substrate can be effectively utilized to enable the surface of the substrate to be in a non-complete infiltration state, so that the corrosion reaction is only carried out on the area where the metal is deposited, and the corrosion area is completely matched with the metal coverage area; if the substrate does not leave the aqueous solution all the time after deposition, the surface of the substrate is kept in a completely soaked state, so that the reaction can be carried out in the area where no metal is deposited, and the regulation and control of the corrosion area are realized.
Drawings
FIG. 1 is an SEM photograph of a dried substrate in example 1 of the present invention;
FIG. 2 is a SEM image of the upper surface of the nano-semiconductor material prepared in example 1 of the present invention;
FIG. 3 is a SEM image of the cross section of the nano-semiconductor material prepared in example 1 of the present invention;
FIG. 4 is a SEM photograph of the upper surface of the nano-semiconductor material prepared in example 2 of the present invention;
fig. 5 is an SEM image of a cross-section of the nano-semiconductor material prepared in example 2 of the present invention.
Detailed Description
The invention provides a method for regulating and controlling a semiconductor corrosion area, which is used in the preparation process of a nano semiconductor material and specifically comprises the following steps:
(1) mixing hydrofluoric acid and metal salt solution to obtain deposition solution;
(2) mixing hydrofluoric acid and an oxidant to obtain a corrosive liquid;
(3) immersing a semiconductor substrate into the deposition solution obtained in the step (1) for deposition, and then drying to obtain a dried substrate;
or, immersing the semiconductor substrate into the deposition solution obtained in the step (1) for deposition, wherein after the deposition is finished, the substrate does not leave the aqueous solution all the time, and a wet substrate is obtained;
(4) respectively immersing the substrates with different humidity degrees obtained in the step (3) into the corrosive liquid obtained in the step (2) for corrosion, and respectively realizing small-area corrosion and large-area corrosion processes;
(5) placing the substrate obtained in the step (3) in mixed gas of hydrofluoric acid and oxygen to realize a small-area corrosion process;
the step (1) and the step (2) are not in sequence.
The sources of the components are not particularly limited in the present invention unless otherwise specified, and may be those obtained by commercially available products or conventional production methods well known to those skilled in the art.
The method mixes hydrofluoric acid and metal salt solution to obtain the deposition solution.
In the invention, the concentration of the hydrofluoric acid is preferably 1-5 mol/L, more preferably 2-5 mol/L, more preferably 3-5 mol/L, and most preferably 4-5 mol/L. The preparation method of the hydrofluoric acid is not particularly limited, and the technical scheme for preparing the acid solution, which is well known to those skilled in the art, is adopted, and in the invention, the hydrofluoric acid is preferably prepared by mixing 40% by mass of hydrofluoric acid and water. In the present invention, the water is preferably deionized water. The invention limits the concentration of hydrofluoric acid in the range, can adjust the deposition speed and further improves the compactness and uniformity of the nano semiconductor material. In the present invention, the hydrofluoric acid is used to provide fluoride ions so that the deposition reaction proceeds.
In the present invention, the metal element in the metal salt solution preferably includes one of gold, silver and platinum, and more preferably silver. In the present invention, the concentration of the metal salt solution is preferably 0.005 to 0.2mol/L, more preferably 0.01 to 0.15mol/L, even more preferably 0.05 to 0.12mol/L, and most preferably 0.08 to 0.1 mol/L. The invention limits the concentration of the metal salt solution in the range, can adjust the deposition speed and further improves the compactness and uniformity of the nano semiconductor material. In the present invention, the metal salt solution is used to provide a metal deposit on a semiconductor substrate as a catalyst.
In the present invention, the metal salt in the metal salt solution preferably includes a metal nitrate or a metal sulfate, and more preferably a metal nitrate. In the present invention, the solvent in the metal salt solution is preferably water.
In the present invention, the ratio of the amounts of hydrogen fluoride in the hydrofluoric acid and the metal salt substance in the metal salt solution is preferably 225: (0.02 to 4), more preferably 225: (0.5 to 3.5), more preferably 225: (1-3), most preferably 225: (1.5-2). The present invention limits the ratio of the amounts of hydrogen fluoride in hydrofluoric acid and the metal salt in the metal salt solution within the above range, and enables a metal to be deposited in an appropriate amount.
The operation of mixing the hydrofluoric acid and the metal salt solution is not particularly limited in the present invention, and a technical scheme of mixing materials well known to those skilled in the art can be adopted. In the present invention, no chemical reaction occurs during the mixing of the hydrofluoric acid and the metal salt solution. In the invention, the mixing of the hydrofluoric acid and the metal salt solution is preferably carried out before the deposition reaction, so that the volatilization of the hydrogen fluoride can be avoided, and the uniformity and consistency of metal crystals in the deposition reaction can be further improved.
The method mixes hydrofluoric acid and an oxidant to obtain the corrosive liquid.
In the invention, the concentration of the hydrofluoric acid is preferably 0.25-5 mol/L, more preferably 0.5-4 mol/L, more preferably 1-3 mol/L, and most preferably 1.5-2 mol/L. The preparation method of the hydrofluoric acid is not particularly limited, and the technical scheme for preparing the acid solution, which is well known to those skilled in the art, is adopted, and in the invention, the hydrofluoric acid is preferably prepared by mixing 40% by mass of hydrofluoric acid and water. In the present invention, the water is preferably deionized water. The concentration of the hydrofluoric acid is limited within the range, the corrosion rate can be adjusted, and the compactness and uniformity of the nano semiconductor material are further improved. In the present invention, the hydrofluoric acid is used to provide fluorine ions and hydrogen ions so that the etching reaction proceeds.
In the present invention, the oxidizing agent preferably includes one of a hydrogen peroxide solution, an iron salt solution, and oxygen, and more preferably a hydrogen peroxide solution. In a preferable embodiment of the present invention, the concentration of the hydrogen peroxide solution is preferably 5 to 10mol/L, and more preferably a hydrogen peroxide solution with a mass fraction of 30%. The invention limits the concentration of the hydrogen peroxide solution in the range, can adjust the corrosion rate and further improves the compactness and uniformity of the nano semiconductor material. In the invention, the oxidant oxidizes the semiconductor substrate, and under the action of the metal catalyst, the oxidation product reacts with hydrofluoric acid to form the nano semiconductor material.
In a preferred embodiment of the present invention, the ratio of the amounts of the hydrogen fluoride in the hydrofluoric acid and the hydrogen peroxide in the hydrogen peroxide solution is preferably 225: (0.05 to 10), more preferably 225: (0.1 to 8), more preferably 225: (0.5 to 5), most preferably 225: (1-3). The invention limits the quantity ratio of the hydrogen fluoride in the hydrofluoric acid to the hydrogen peroxide in the hydrogen peroxide solution within the range, can continuously carry out the corrosion reaction, improve the length of the nanowire array, adjust the corrosion rate, uniformly carry out the corrosion process and further improve the compactness and the uniformity of the nano semiconductor material.
The present invention is not limited to the mixing of the hydrofluoric acid and the oxidizing agent, and the mixing operation of the materials known to those skilled in the art may be employed. In the present invention, no chemical reaction occurs during the mixing of the hydrofluoric acid and the oxidizing agent. In the invention, the mixing of the hydrofluoric acid and the oxidizing agent is preferably carried out before the etching reaction, so that the volatilization of the hydrogen fluoride can be avoided, and the uniformity and consistency of the etching process can be further improved.
After the deposition solution is obtained, the semiconductor substrate is immersed into the deposition solution for deposition, and then the subsequent corrosion area is regulated and controlled by controlling the drying and wetting states of the substrate surface.
In the present invention, the semiconductor substrate preferably includes one of silicon, germanium, silicon carbide, gallium arsenide, and gallium nitride, more preferably silicon, and most preferably single crystal silicon. In an embodiment of the present invention, the single crystal silicon is preferably (100) -type single crystal silicon.
In the present invention, when the semiconductor substrate is silicon and the metal element in the metal salt solution is silver, the deposition reaction equation is shown in formula i:
Si+4Ag++6F-＝4Ag+SiF6 2-formula I.
In the present invention, when the volume of the semiconductor substrate is 2cm × 2cm, the amount of the deposition solution is preferably not less than 10mL, and more preferably 30 to 50 mL.
In the invention, the time of the deposition reaction is preferably not less than 1min, and more preferably 15-25 min. In the invention, the temperature of the deposition reaction is preferably 20-30 ℃, and more preferably 25 ℃.
The invention limits the dosage of the deposition solution, the time and the temperature of the deposition reaction within the above range, can enable the metal to have more proper deposition amount, and further improves the compactness of the nano semiconductor material.
The invention preferably washes the substrate after deposition reaction is finished, and then dries.
The drying operation is not particularly limited in the present invention, and a drying operation known to those skilled in the art may be used. In the present invention, the drying preferably includes one of natural drying, air drying, blow drying, oven drying, vacuum drying, and freeze drying. The drying time is not specially limited, and the substrate can be completely dried.
The operation of keeping the substrate in a wet state can be directly transferred into the corrosive liquid after the catalyst is deposited, and the substrate can also be stored in the deionized water after the catalyst is deposited.
In the present invention, when the semiconductor substrate is silicon and the oxidizing agent is hydrogen peroxide solution, the formula of the etching reaction is shown as formula ii:
4H++6F-+H2O2+Si＝SiF6 2-+2H2O+H2×) formula ii.
In the present invention, when the volume of the semiconductor substrate is 2cm × 2cm, the amount of the etching solution is preferably not less than 10mL, and more preferably 30 to 50 mL.
In the invention, the time of the corrosion reaction is preferably not less than 1min, and more preferably 15-25 min. In the invention, the temperature of the corrosion reaction is preferably 20-30 ℃, and more preferably 25 ℃.
The invention limits the dosage of the corrosive liquid, the time of the corrosion reaction and the temperature within the above range, can enable the nanowire array to have longer length, and further improves various performances of the nano semiconductor material.
The invention also provides the nano semiconductor material prepared by the preparation method of the technical scheme.
The invention makes the prepared nano semiconductor material respectively suitable for different applications such as photoelectricity, thermoelectricity, energy storage and the like by regulating and controlling the corrosion area.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In the embodiment, the deposited substrate is dried in the preparation process of the nano semiconductor material, so that the adjustment and control of the semiconductor corrosion area are realized.
The method comprises the following specific steps:
(1) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing the hydrofluoric acid with 1.5mL of 0.2mol/L silver nitrate solution (the ratio of the amount of hydrogen fluoride in the hydrofluoric acid to the amount of silver nitrate in the silver nitrate solution is 225:0.3) to obtain a deposition solution;
(2) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1mL of hydrogen peroxide solution with the mass fraction of 30% (the concentration of hydrogen peroxide is 10mol/L) (the ratio of the hydrogen fluoride in the hydrofluoric acid to the hydrogen peroxide in the hydrogen peroxide solution is 225:10) to obtain an etching solution;
(3) immersing a (100) type monocrystalline silicon substrate of 2cm multiplied by 2cm into the deposition solution, depositing for 20min at 25 ℃, then taking out and washing for 5s with deionized water, and naturally airing the deposited substrate in a room temperature environment for 15 min;
(4) and immersing the dried substrate into a corrosive liquid, and corroding for 10min at 25 ℃ to obtain the nano semiconductor material.
The SEM image of the dried substrate of example 1 was tested, and the results are shown in fig. 1. As can be seen from fig. 1, the metallic silver is deposited on the surface of the substrate, and the silver particles do not agglomerate significantly, so that the deposition is uniform.
SEM images of the nano-semiconductor material prepared in example 1 were tested, and the results are shown in fig. 2 to 3. Fig. 2 is an SEM image of the upper surface of the nano-semiconductor material prepared in example 1, and fig. 3 is an SEM image of a cross-section of the nano-semiconductor material prepared in example 1. As can be seen from fig. 2 to 3, the corroded area of the nano semiconductor material prepared in example 1 is completely matched with the area covered by the metal, and the nano semiconductor material is compact, uniform and small in size; the drying treatment is performed after the deposition, so that the surface tension of the liquid on the surface of the substrate can be effectively utilized, the corrosion reaction is only performed in the area where the metal is deposited, the corrosion area is completely matched with the metal covering area, the black area is formed under the naked eye, the light absorption is high, the solar cell is suitable for the field of solar cells, the solar cell is microscopically strip-shaped, and the nanowire array is compact.
Example 2
In the embodiment, the substrate after deposition is kept in a wet state in the preparation process of the nano semiconductor material, so that the adjustment and control of the semiconductor corrosion area are realized.
The method comprises the following specific steps:
(1) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1.5mL of 0.2mol/L silver nitrate solution to obtain a deposition solution;
(2) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1mL of hydrogen peroxide solution with the mass fraction of 30% to obtain corrosive liquid;
(3) immersing a (100) type monocrystalline silicon substrate of 2cm multiplied by 2cm into the deposition solution, depositing for 20min at 25 ℃, and then taking out and washing for 5s by using deionized water;
(4) and immersing the rinsed substrate into an etching solution, and etching for 10min at 25 ℃ to obtain the nano semiconductor material.
SEM images of the nano-semiconductor material prepared in example 2 were tested, and the results are shown in fig. 4 to 5, fig. 4 is an SEM image of the upper surface of the nano-semiconductor material prepared in example 2, and fig. 5 is an SEM image of a cross-section of the nano-semiconductor material prepared in example 2.
As can be seen from fig. 4 to 5, the corrosion area of the nano semiconductor material prepared in example 2 is significantly larger than the area covered by the metal, the surface of the nano semiconductor material is loose, and the pores are large; the substrate is not dried after deposition, and the surface of the substrate has liquid residue, so that the corrosion area is obviously larger than the metal coverage area, the surface of the nano semiconductor material is loose, the whole size is smaller, and the nano semiconductor material is more suitable for being applied to the fields of lithium ion batteries and thermoelectric materials.
Example 3
In the embodiment, the deposited substrate is dried in the preparation process of the nano semiconductor material, so that the adjustment and control of the semiconductor corrosion area are realized.
The method comprises the following specific steps:
(1) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1.5mL of 0.2mol/L silver nitrate solution to obtain a deposition solution;
(2) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1mL of hydrogen peroxide solution with the mass fraction of 30% to obtain corrosive liquid;
(3) immersing a (100) type monocrystalline silicon substrate of 2cm multiplied by 2cm into the deposition solution, depositing for 20min at 25 ℃, then taking out and washing for 5s with deionized water, blowing off the liquid on the surface of the substrate by an ear washing ball, and then naturally airing at room temperature for 10 min;
(4) and immersing the dried substrate into a corrosive liquid, and corroding for 10min at 25 ℃ to obtain the nano semiconductor material.
The nano semiconductor material is tested, the corrosion area of the nano semiconductor material is completely matched with the area covered by the metal, the nano semiconductor material is black under naked eyes, has higher light absorption, is suitable for the field of solar cells, is in a strip shape under the microcosmic condition, and has a compact nano wire array.
Example 4
In the embodiment, the deposited substrate is dried in the preparation process of the nano semiconductor material, so that the adjustment and control of the semiconductor corrosion area are realized.
The method comprises the following specific steps:
(1) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1.5mL of 0.2mol/L silver nitrate solution to obtain a deposition solution;
(2) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1mL of hydrogen peroxide solution with the mass fraction of 30% to obtain corrosive liquid;
(3) soaking a (100) type monocrystalline silicon substrate of 2cm × 2cm in the deposition solution, depositing at 25 deg.C for 20min, taking out, washing with deionized water for 5s, and drying at 50 deg.C for 5 min;
(4) and immersing the dried substrate into a corrosive liquid, and corroding for 10min at 25 ℃ to obtain the nano semiconductor material.
The nano semiconductor material is tested, the corrosion area of the nano semiconductor material is completely matched with the area covered by the metal, the nano semiconductor material is black under naked eyes, has higher light absorption, is suitable for the field of solar cells, is in a strip shape under the microcosmic condition, and has a compact nano wire array.
Example 5
In the embodiment, the deposited substrate is dried in the preparation process of the nano semiconductor material, so that the adjustment and control of the semiconductor corrosion area are realized.
The method comprises the following specific steps:
(1) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1.5mL of 0.2mol/L silver nitrate solution to obtain a deposition solution;
(2) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1mL of hydrogen peroxide solution with the mass fraction of 30% to obtain corrosive liquid;
(3) soaking a (100) type monocrystalline silicon substrate of 2cm × 2cm in the deposition solution, depositing at 25 deg.C for 20min, taking out, washing with deionized water for 5s, and drying at 50 deg.C for 5 min;
(4) and transferring the dried substrate to an environment with hydrogen fluoride gas, and keeping the air smooth for 1h to obtain the semiconductor nano material.
The nano semiconductor material is tested, the corrosion area of the nano semiconductor material is completely matched with the area covered by the metal, the nano semiconductor material is black under naked eyes, has higher light absorption, is suitable for the field of solar cells, is in a strip shape under the microcosmic condition, and has a compact nano wire array.
Example 6
In the embodiment, the substrate after deposition is kept in a wet state in the preparation process of the nano semiconductor material, so that the adjustment and control of the semiconductor corrosion area are realized.
The method comprises the following specific steps:
(1) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1.5mL of 0.2mol/L silver nitrate solution to obtain a deposition solution;
(2) mixing 35mL of deionized water and 10mL of hydrofluoric acid with the mass fraction of 40% to obtain 5mol/L hydrofluoric acid, and mixing with 1mL of hydrogen peroxide solution with the mass fraction of 30% to obtain corrosive liquid;
(3) immersing a (100) type monocrystalline silicon substrate of 2cm multiplied by 2cm into the deposition solution, and depositing for 20min at 25 ℃;
(4) and immersing the deposited substrate into a corrosive liquid, and corroding for 10min at 25 ℃ to obtain the nano semiconductor material.
The nano semiconductor material is tested, the corrosion area of the nano semiconductor material is obviously larger than the area covered by metal, the surface of the nano semiconductor material is loose, the whole size is smaller, and the nano semiconductor material is more suitable for being applied to the fields of lithium ion batteries and thermoelectric materials.
In conclusion, by controlling the surface wetting state of the deposited substrate, the surface tension of the liquid on the surface of the substrate can be effectively utilized to regulate and control the corrosion area, so that the corrosion area is larger than or equal to the coverage area of the metal catalyst, and the catalyst with the same morphology can corrode a strip-shaped structure with larger light absorption and a linear structure with smaller size.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A method for regulating and controlling a semiconductor corrosion area is applied to a nano semiconductor material preparation process and comprises the following steps:
(1) mixing hydrofluoric acid and metal salt solution to obtain deposition solution;
(2) mixing hydrofluoric acid and an oxidant to obtain a corrosive liquid;
(3) immersing a semiconductor substrate into the deposition solution obtained in the step (1) for deposition;
(4) processing the substrate obtained after deposition in the step (3) to obtain substrates with different surface wetting states;
(5) immersing the substrate obtained in the step (4) into the corrosive liquid obtained in the step (2) for corrosion to obtain a nano semiconductor material;
the step (1) and the step (2) are not in sequence.
2. The method for controlling the area of the semiconductor corrosion according to claim 1, wherein the concentration of the hydrofluoric acid in the step (1) is 1-5 mol/L.
3. The method for conditioning the corroded area of the semiconductor as recited in claim 1, wherein the metal element in the metal salt solution of step (1) comprises one of gold, silver and platinum; the concentration of the metal salt solution is 0.005-0.2 mol/L.
4. The method for conditioning the semiconductor corrosion region according to claim 1, wherein the ratio of the hydrogen fluoride in the hydrofluoric acid and the amount of the metal salt in the metal salt solution in the step (1) is 225: (0.02-4).
5. The method of claim 1, wherein the oxidizing agent in step (2) comprises one of a hydrogen peroxide solution, an iron salt solution, and oxygen.
6. The method of claim 5, wherein the concentration of the hydrogen peroxide solution and the concentration of the iron ions in the iron salt solution are independently 5-10 mol/L.
7. The method according to claim 1, wherein the concentration of hydrofluoric acid in step (2) is 0.25-5 mol/L.
8. The method of claim 1, wherein the semiconductor substrate in step (3) comprises one of silicon, germanium, silicon carbide, gallium arsenide, and gallium nitride.
9. The method for controlling the corrosion area of the semiconductor as claimed in claim 1, wherein the deposition time in the step (3) is 1-30 min.
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