CN109648096A - A kind of any nano-cone array converted in-situ is the method for the micro/nano structure array that Nano silver piece is constructed - Google Patents
A kind of any nano-cone array converted in-situ is the method for the micro/nano structure array that Nano silver piece is constructed Download PDFInfo
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Abstract
The invention discloses a kind of methods that any nano-cone array converted in-situ is the micro/nano structure array that Nano silver piece is constructed, and sputter one layer of copper film on any nano-cone array surface, obtain copper array；Using the comproportionation reaction between copper and copper salt solution, copper array is immersed in copper salt solution, cuprous oxide array is obtained after reaction；Cuprous oxide array is immersed in the solution containing silver nitrate, the micro/nano structure array that Nano silver piece is constructed is obtained after reaction.Not only array structure can be obtained, but also can not be limited by substrate.The structure has the high-specific surface area of nanometer sheet, provides more active sites, while array structure can guarantee the uniformity and stability of sample.
Description
Technical field
The present invention relates to a kind of method that micro/nano structure array is converted in situ more particularly to a kind of any nanocone battle arrays
Column converted in-situ is the method for the micro/nano structure array that Nano silver piece is constructed.
Background technique
Noble metal nano particles or micro/nano structure particle have stronger SERS activity and higher structural stability.
In addition, needing micro/nano structure particle carrying out ordered arrangement in order to ensure the good reproduction of SERS measurement.Nanometer sheet structure
The micro/nano structure array built will generate more hot spots, because there are many sharp edges.The system of plasma nano piece
Preparation Method has very much, such as electrochemical deposition method, galvanic couple displacement method and Cu2O template etc..
The problem of research encounters at present mainly has following two:
(1) Cu can readily be utilized2O prepares the micro-nano structure of Ag nanometer sheet assembling, but is difficult this method system
For at array；
(2) method for being prepared into array structure has certain limitation, is only capable of the side using electrochemical deposition at present
Method prepares the micro/nano structure array that Nano silver piece is constructed on conductive substrates, this is just restricted it.
Summary of the invention
It is the micro-/ nano knot that Nano silver piece is constructed the object of the present invention is to provide a kind of any nano-cone array converted in-situ
The method of structure array.
The purpose of the present invention is what is be achieved through the following technical solutions:
Any nano-cone array converted in-situ of the invention is the method for the micro/nano structure array that Nano silver piece is constructed,
The following steps are included:
(1) method for utilizing gas-liquid interface self assembly prepares compact arranged PS ball self assembly in clean substrate surface
Monofilm；
(2) method for utilizing reactive ion etching, utilizes SF6Gas performs etching the substrate that surface is PS ball array,
Obtain any nano-cone array structure；
(3) method for utilizing magnetron sputtering sputters one layer of copper film on any nano-cone array surface, obtains copper array；
(4) using the comproportionation reaction between copper and copper salt solution, copper array is immersed in copper salt solution, is obtained after reaction
Cuprous oxide array；
(5) cuprous oxide array is immersed in the solution containing silver nitrate, after reaction obtain Nano silver piece construct it is micro-/
Micro-nano structure array.
As seen from the above technical solution provided by the invention, any nano-cone array provided in an embodiment of the present invention is former
The method that position is converted into the micro/nano structure array that Nano silver piece is constructed is based on Cu2The method of the converted in-situ of O is arbitrarily being received
Rice cone array surface converted in-situ, obtains the particle assembled by nanometer sheet, further assembles obtained array, can be not
Micro-/micro-nano structure array that the assembling of Ag nanometer sheet can also be prepared on conductive substrate, can not only obtain array structure, but also can not
It is limited by substrate.The structure has the high-specific surface area of nanometer sheet, provides more active sites, while array structure energy
Enough guarantee the uniformity and stability of sample.
Detailed description of the invention
Fig. 1 is the 1000nm PS ball obtained using gas-liquid interface self-assembly method in surface of silicon in the embodiment of the present invention
The scanning electricity of array is by photo；
Fig. 2 is the stereoscan photograph that etching 1000nm PS array obtains silicon array in the embodiment of the present invention；
Fig. 3 is to obtain the stereoscan photograph of copper film on silicon array surface using magnetron sputtering in the embodiment of the present invention；
Fig. 4 is that comproportionation reaction is utilized in the embodiment of the present invention, by the array switching scanning electron microscope for cuprous oxide array of copper
Photo (amplification that illustration is individual particle)；
Fig. 5 is the micro/nano structure array that cuprous oxide array is converted into that Nano silver piece is constructed in the embodiment of the present invention
Stereoscan photograph.
Specific embodiment
The embodiment of the present invention will be described in further detail below.What is be not described in detail in the embodiment of the present invention is interior
Appearance belongs to the prior art well known to professional and technical personnel in the field.
Any nano-cone array converted in-situ of the invention is the method for the micro/nano structure array that Nano silver piece is constructed,
Its preferable specific embodiment is:
The following steps are included:
(1) method for utilizing gas-liquid interface self assembly prepares compact arranged PS ball self assembly in clean substrate surface
Monofilm；
(2) method for utilizing reactive ion etching, utilizes SF6Gas performs etching the substrate that surface is PS ball array,
Obtain any nano-cone array structure；
(3) method for utilizing magnetron sputtering sputters one layer of copper film on any nano-cone array surface, obtains copper array；
(4) using the comproportionation reaction between copper and copper salt solution, copper array is immersed in copper salt solution, is obtained after reaction
Cuprous oxide array；
(5) cuprous oxide array is immersed in the solution containing silver nitrate, after reaction obtain Nano silver piece construct it is micro-/
Micro-nano structure array.
The step (1) includes:
The PS ball for selecting 120~1000nm of diameter first, ultrasound after being dispersed in deionized water and ethyl alcohol, it is equal to be allowed to dispersion
It is even.PS globule is then added in the clean slide surface that surface adds water, is allowed to form monofilm.After dry a period of time,
Coverslip is transferred in the beaker for filling with water, at this point, PS ball monofilm will swim in the surface of water.Utilize the clean of 1cm × 1cm
Net substrate gets the PS ball array at water and air interface, that is, is transferred to substrate surface, obtains compact arranged PS ball single layer
Membrane array, the clean substrates are silicon, glass, polytetrafluoroethylene (PTFE) or PE film；
The step (2) includes:
It is arranged with PS spherical array as exposure mask, substrate is performed etching, specific experiment parameter are as follows: size of current is 0.5~5A, pressure
It is powerful it is small be 0.05~0.50Pa, 10~50sccm of flow velocity of sulfur hexafluoride gas, power is 100~500w, and etch period is
30s~9min；
In the step (3), specific experiment parameter are as follows:
Vacuum degree is 10~70mTorr, and sputtering current size is 15~90mA, and sputtering time is 2min~30min；
In the step (4), the mantoquita includes copper nitrate, copper sulphate and/or copper acetate, is specifically included:
Configuration copper salt solution: 0.0200~1.0000g mantoquita is dissolved into 10~100mL deionized water, copper is obtained
Precursor solution；
Then, by surface covering copper film nano-cone array be immersed in the precursor solution of copper, set soaking time as
10~30min；
After reaction, substrate is taken out, alternately cleaning for several times, obtains cuprous oxide battle array with deionized water and dehydrated alcohol
Column；
Use N2After drying, cuprous oxide array is obtained, for reacting in next step；
The step (5) includes:
Configure the reaction solution of silver nitrate: by 0.0100~0.3000g silver nitrate, the anhydrous lemon of 0.0100~1.0000g
Sour sodium and 5~50uL concentrated nitric acid are distributed in 5~50mL deionized water, are later placed in the cuprous oxide substrate of 1cm × 1cm
1~30min is impregnated in mixed solution；
After reaction, substrate is taken out, is alternately cleaned for several times with deionized water and dehydrated alcohol.
In the step (1), the size of PS ball is 1000nm, and substrate selects silicon wafer.
In the step (2), size of current 3A, pressure size be 0.1Pa, the flow velocity 36sccm of sulfur hexafluoride gas,
Power is 200w, etch period 7min.
In the step (3), vacuum degree 35mTorr, sputtering current size is 40mA, sputtering time 5min.
In the step (4), 0.4000g anhydrous cupric sulfate (CuSO4) be dissolved into 50mL deionized water, obtain copper sulphate
Solution sets soaking time as 30min.
In the step (5), 0.0306g silver nitrate, 0.0352g anhydrous citric acid sodium and 10uL concentrated nitric acid are dispersed
Into 20mL deionized water, the cuprous oxide substrate of 1cm × 1cm is placed in 30min in mixed solution later.
Any nano-cone array converted in-situ of the invention is the method for the micro/nano structure array that Nano silver piece is constructed,
Products therefrom is the array structure that the particle that Nano silver piece is constructed further assembles.What traditional preparation nanometer sheet was constructed
The method of micro/nano structure array is the method for electrochemical deposition, is also only limitted to prepare this structure on conductive silicon substrate,
And method of the invention can prepare Nano silver piece on the substrate that can arbitrarily obtain cone array and construct micro/nano structure battle array
Column.The structure includes the double-deck advantage of laminated structure and array structure, on the one hand, and laminated structure has bigger specific surface area,
More active sites can be provided when contacting with test molecule；On the other hand, due to array structure, it is ensured that structure it is equal
The stability of even property and test result, thus the structure has more excellent performance.
The present invention is by the method for converted in-situ, using chemical reaction, in the substrate that can arbitrarily obtain nano-cone array
Surface can prepare the micro/nano structure array that Nano silver piece is constructed by converted in-situ.On the one hand the structure has sheet
Structure can have bigger specific surface area, provide more active sites, on the other hand, particle of the structure compared to dispersion
Structure, more stable, more evenly, performance is more excellent.
Specific embodiment:
Embodiment 1
A kind of any nano-cone array converted in-situ that the present embodiment 1 describes is the micro/nano structure that Nano silver piece is constructed
The method of array, comprising the following steps:
(1) method for utilizing gas-liquid interface self assembly prepares compact arranged PS ball from group in clean surface of silicon
The monofilm of dress.It selects diameter for the PS ball of 1000nm, obtains compact arranged PS on the clean silicon substrate surface of 1cm × 1cm
Ball single layer membrane array, as shown in Figure 1.
(2) method for utilizing reactive ion etching, utilizes SF6Gas carves the silicon substrate that surface is PS ball array
Erosion obtains silicon array.Specific experiment parameter are as follows: size of current 3A, pressure size be 0.1Pa, the flow velocity 36sccm of gas,
Power is 200w, etch period 7min, and silicon array pattern is as shown in Figure 2.
(3) method for utilizing magnetron sputtering sputters one layer of copper film on silicon array surface, obtains copper array.Specific experiment
Parameter are as follows: vacuum degree 35mTorr, sputtering current size are 40mA, sputtering time 5min, obtain the battle array of surface covering copper film
Column, as shown in Figure 3.
(4) copper array is immersed in copper salt solution, cuprous oxide array is obtained after reaction.First by 0.4000g nitric acid
Copper [Cu (NO3)2] be dissolved into 50mL deionized water, obtain copper nitrate solution.The array of surface covering copper film is immersed in configuration
In good copper nitrate solution, 30min is impregnated, after reaction, substrate is taken out, obtains cuprous oxide array, as shown in Figure 4.With
With deionized water and dehydrated alcohol, alternately cleaning for several times, uses N afterwards2Stand for standby use after drying.
(5) cuprous oxide array is immersed in the solution containing silver nitrate, after reaction obtain Nano silver piece construct it is micro-/
Nano-structure array.Configure silver nitrate reaction solution: by 0.0306g silver nitrate, 0.0352g anhydrous citric acid sodium and
10uL concentrated nitric acid is distributed in 20mL deionized water, and the cuprous oxide substrate of 1cm × 1cm is placed in mixed solution later
30min.After reaction, substrate is taken out, alternately cleaning for several times, uses N with deionized water and dehydrated alcohol2After drying, base is obtained
In the micro/nano structure array that the Nano silver piece of the conversion preparation in situ of silicon array is constructed, as shown in Figure 5.
Embodiment 2
A kind of any nano-cone array converted in-situ that the present embodiment 2 describes is the micro/nano structure that Nano silver piece is constructed
The method of array, comprising the following steps:
(1) method for utilizing gas-liquid interface self assembly is prepared compact arranged on clean polytetrafluoroethylsubstrate substrate surface
The monofilm of PS ball self assembly.Select diameter for the PS ball of 1000nm, on the clean polytetrafluoroethylsubstrate substrate surface of 1cm × 1cm
Obtain compact arranged PS ball single layer membrane array.
(2) method for utilizing reactive ion etching, utilizes SF6Gas is the polytetrafluoroethylsubstrate substrate of PS ball array to surface
It performs etching, obtains polytetrafluoroethylene (PTFE) array.Specific experiment parameter are as follows: size of current 3.2A, pressure size are 0.15Pa,
The flow velocity 35sccm of sulfur hexafluoride gas, power 200w, etch period 7min.
(3) method for utilizing magnetron sputtering sputters one layer of copper film in polytetrafluoroethylene (PTFE) array surface, obtains copper array.Tool
The experiment parameter of body are as follows: vacuum degree 30mTorr, sputtering current size are 40mA, sputtering time 5min, obtain surface covering
The array of copper film.
(4) copper array is immersed in copper salt solution, cuprous oxide array is obtained after reaction.It is first that 0.2000g is anhydrous
Copper sulphate (CuSO4) be dissolved into 50mL deionized water, obtain copper-bath.The array of surface covering copper film is immersed in and is matched
In the copper-bath set, 15min is impregnated, after reaction, substrate is taken out, obtains cuprous oxide array, use deionized water
Alternately cleaning for several times, uses N with dehydrated alcohol2It is stood after drying.
(5) cuprous oxide array is immersed in the solution containing silver nitrate, after reaction obtain Nano silver piece construct it is micro-/
Nano-structure array.Configure silver nitrate reaction solution: by 0.0306g silver nitrate, 0.0352g anhydrous citric acid sodium and
10uL concentrated nitric acid is distributed in 20mL deionized water, and the cuprous oxide substrate of 1cm × 1cm is placed in mixed solution later
30min.After reaction, substrate is taken out, alternately cleaning for several times, uses N with deionized water and dehydrated alcohol2After drying, base is obtained
In the micro/nano structure array that the Nano silver piece of polytetrafluoroethylene (PTFE) array is constructed.
Embodiment 3
A kind of any nano-cone array converted in-situ that the present embodiment 3 describes is the micro/nano structure that Nano silver piece is constructed
The method of array, comprising the following steps:
(1) method for utilizing gas-liquid interface self assembly prepares compact arranged PS ball from group in clean surface of silicon
The monofilm of dress.It selects diameter for the PS ball of 500nm, obtains compact arranged PS ball on the clean silicon substrate surface of 1cm × 1cm
Single layer membrane array.
(2) method for utilizing reactive ion etching, utilizes SF6Gas carves the silicon substrate that surface is PS ball array
Erosion obtains silicon array.Specific experiment parameter are as follows: size of current 3A, pressure size are 0.1Pa, the stream of sulfur hexafluoride gas
Fast 35sccm, power 200w, etch period 3min.
(3) method for utilizing magnetron sputtering sputters one layer of copper film on silicon array surface, obtains copper array.Specific experiment
Parameter are as follows: vacuum degree 30mTorr, sputtering current size are 35mA, sputtering time 5min, obtain the battle array of surface covering copper film
Column.
(4) copper array is immersed in copper salt solution, cuprous oxide array is obtained after reaction.It is first that 0.2000g is anhydrous
Copper sulphate (CuSO4) be dissolved into 50mL deionized water, obtain copper-bath.The array of surface covering copper film is immersed in sulphur
In sour copper solution, after impregnating 15min, substrate is taken out, alternately cleaning for several times, uses N with deionized water and dehydrated alcohol2It is quiet after drying
It sets, obtains cuprous oxide array.
(5) cuprous oxide array is immersed in the solution containing silver nitrate, after reaction obtain Nano silver piece construct it is micro-/
Nano-structure array.Configure the reaction solution of silver nitrate: by 0.0153g silver nitrate, 0.0176g anhydrous citric acid sodium and 5uL
Concentrated nitric acid is distributed in 20mL deionized water, and the cuprous oxide substrate of 1cm × 1cm is placed in 15min in mixed solution later.Instead
After answering, substrate is taken out, alternately cleaning for several times, uses N with deionized water and dehydrated alcohol2Drying, obtains based on silicon array
The micro/nano structure array that Nano silver piece is constructed.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (7)
1. a kind of any nano-cone array converted in-situ is the method for the micro/nano structure array that Nano silver piece is constructed, feature
It is, comprising the following steps:
(1) method for utilizing gas-liquid interface self assembly prepares the list of compact arranged PS ball self assembly in clean substrate surface
Tunic；
(2) method for utilizing reactive ion etching, utilizes SF6Gas performs etching the substrate that surface is PS ball array, is appointed
Meaning nano-cone array structure；
(3) method for utilizing magnetron sputtering sputters one layer of copper film on any nano-cone array surface, obtains copper array；
(4) using the comproportionation reaction between copper and copper salt solution, copper array is immersed in copper salt solution, is aoxidized after reaction
Cuprous array；
(5) cuprous oxide array is immersed in the solution containing silver nitrate, the micro-/ nano that Nano silver piece is constructed is obtained after reaction
Array of structures.
2. any nano-cone array converted in-situ according to claim 1 is the micro/nano structure battle array that Nano silver piece is constructed
The method of column, it is characterised in that:
The step (1) includes:
The PS ball for selecting 120~1000nm of diameter first, ultrasound after being dispersed in deionized water and ethyl alcohol, is allowed to be uniformly dispersed.
PS globule is then added in the clean slide surface that surface adds water, is allowed to form monofilm.After dry a period of time, it will cover
Slide is transferred in the beaker for filling with water, at this point, PS ball monofilm will swim in the surface of water.Utilize the cleaning lining of 1cm × 1cm
Bottom gets the PS ball array of water surface, that is, is transferred to substrate surface, obtains compact arranged PS ball single layer membrane array, described
Clean substrates are silicon, glass, polytetrafluoroethylene (PTFE) or PE film；
The step (2) includes:
It is arranged with PS spherical array as exposure mask, substrate is performed etching, specific experiment parameter are as follows: size of current is 0.5~5A, and pressure is big
Small is 0.05~0.50Pa, 10~50sccm of flow velocity of sulfur hexafluoride gas, and power is 100~500w, etch period be 30s~
9min；
In the step (3), specific experiment parameter are as follows:
Vacuum degree is 10~70mTorr, and sputtering current size is 15~90mA, and sputtering time is 2min~30min；
In the step (4), the mantoquita includes copper nitrate, copper sulphate and/or copper acetate, is specifically included:
Configuration copper salt solution: 0.0200~1.000g mantoquita is dissolved into 10~100mL deionized water, the presoma of copper is obtained
Solution；
Then, the nano-cone array of surface covering copper film is immersed in the precursor solution of copper, set soaking time as 10~
30min；
After reaction, substrate is taken out, alternately cleaning for several times, obtains cuprous oxide array with deionized water and dehydrated alcohol；
Use N2After drying, cuprous oxide array is obtained, for reacting in next step；
The step (5) includes:
Configure the reaction solution of silver nitrate: by 0.010 0~0.3000g silver nitrate, 0.0100~1.000g anhydrous citric acid sodium
And 5~50uL concentrated nitric acid is distributed in 5~50mL deionized water, and the cuprous oxide substrate of 1cm × 1cm is placed in mixing later
1~30min is impregnated in solution；
After reaction, substrate is taken out, is alternately cleaned for several times with deionized water and dehydrated alcohol.
3. any nano-cone array converted in-situ according to claim 2 is the micro/nano structure battle array that Nano silver piece is constructed
The method of column, which is characterized in that in the step (1), the size of PS ball is 1000nm, and substrate selects silicon wafer.
4. any nano-cone array converted in-situ according to claim 2 is the micro/nano structure battle array that Nano silver piece is constructed
The method of column, which is characterized in that in the step (2), size of current 3A, pressure size is 0.1Pa, sulfur hexafluoride gas
Flow velocity 36sccm, power 200w, etch period 7min.
5. any nano-cone array converted in-situ according to claim 2 is the micro/nano structure battle array that Nano silver piece is constructed
The method of column, which is characterized in that in the step (3), vacuum degree 35mTorr, sputtering current size is 40mA, sputtering time
For 5min.
6. any nano-cone array converted in-situ according to claim 2 is the micro/nano structure battle array that Nano silver piece is constructed
The method of column, which is characterized in that in the step (4), 0.4000g anhydrous cupric sulfate (CuSO4) it is dissolved into 50mL deionized water
In, copper-bath is obtained, sets soaking time as 30min.
7. any nano-cone array converted in-situ according to claim 2 is the micro/nano structure battle array that Nano silver piece is constructed
The method of column, which is characterized in that in the step (5), by 0.0306g silver nitrate, 0.0352g anhydrous citric acid sodium and
10uL concentrated nitric acid is distributed in 20mL deionized water, and the cuprous oxide substrate of 1cm × 1cm is placed in mixed solution later
30min。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668397A (en) * | 2019-09-16 | 2020-01-10 | 吉林师范大学 | Preparation method of highly ordered inclined nano-column |
| CN111421133A (en) * | 2020-03-30 | 2020-07-17 | 扬州大学 | Silver nanosheet cluster array and preparation method thereof |
| CN114199854A (en) * | 2021-12-15 | 2022-03-18 | 曲阜师范大学 | Preparation method of SERS substrate constructed by flexible transparent cone ordered array |
| CN115863660A (en) * | 2022-12-09 | 2023-03-28 | 江苏正力新能电池技术有限公司 | Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464295A (en) * | 2010-10-30 | 2012-05-23 | 中国科学院合肥物质科学研究院 | Hollow ball micro/nano structure array with silver nano plates as basic elements and preparation method thereof |
| CN102633230A (en) * | 2012-04-26 | 2012-08-15 | 厦门大学 | Method for preparing silicon nano-pillar array based on nanosphere etching technology |
| CN102747320A (en) * | 2012-07-31 | 2012-10-24 | 武汉大学 | Preparation method of noble metal nano-particle array |
| US8455048B1 (en) * | 2010-03-18 | 2013-06-04 | Sandia Corporation | Method for making nanomaterials |
| CN103626119A (en) * | 2013-12-08 | 2014-03-12 | 中国科学院光电技术研究所 | Preparation method for nano metal ball bowl array structure |
| CN105197882A (en) * | 2015-08-13 | 2015-12-30 | 中国科学院合肥物质科学研究院 | Silicon nano cone array coated with gold film as well as preparation method and application thereof |
| CN108188386A (en) * | 2017-12-25 | 2018-06-22 | 西安交通大学 | A kind of ultra-thin Ag nanometer sheets of clean surface and preparation method thereof |
-
2019
- 2019-01-09 CN CN201910020496.1A patent/CN109648096B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8455048B1 (en) * | 2010-03-18 | 2013-06-04 | Sandia Corporation | Method for making nanomaterials |
| CN102464295A (en) * | 2010-10-30 | 2012-05-23 | 中国科学院合肥物质科学研究院 | Hollow ball micro/nano structure array with silver nano plates as basic elements and preparation method thereof |
| CN102633230A (en) * | 2012-04-26 | 2012-08-15 | 厦门大学 | Method for preparing silicon nano-pillar array based on nanosphere etching technology |
| CN102747320A (en) * | 2012-07-31 | 2012-10-24 | 武汉大学 | Preparation method of noble metal nano-particle array |
| CN103626119A (en) * | 2013-12-08 | 2014-03-12 | 中国科学院光电技术研究所 | Preparation method for nano metal ball bowl array structure |
| CN105197882A (en) * | 2015-08-13 | 2015-12-30 | 中国科学院合肥物质科学研究院 | Silicon nano cone array coated with gold film as well as preparation method and application thereof |
| CN108188386A (en) * | 2017-12-25 | 2018-06-22 | 西安交通大学 | A kind of ultra-thin Ag nanometer sheets of clean surface and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杭立峰: "模板法构筑微/纳复合材料及其性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668397A (en) * | 2019-09-16 | 2020-01-10 | 吉林师范大学 | Preparation method of highly ordered inclined nano-column |
| CN111421133A (en) * | 2020-03-30 | 2020-07-17 | 扬州大学 | Silver nanosheet cluster array and preparation method thereof |
| CN111421133B (en) * | 2020-03-30 | 2022-01-21 | 扬州大学 | Silver nanosheet cluster array and preparation method thereof |
| CN114199854A (en) * | 2021-12-15 | 2022-03-18 | 曲阜师范大学 | Preparation method of SERS substrate constructed by flexible transparent cone ordered array |
| CN114199854B (en) * | 2021-12-15 | 2024-01-12 | 曲阜师范大学 | Preparation method of SERS substrate constructed by flexible transparent cone ordered array |
| CN115863660A (en) * | 2022-12-09 | 2023-03-28 | 江苏正力新能电池技术有限公司 | Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof |
| CN115863660B (en) * | 2022-12-09 | 2024-05-17 | 江苏正力新能电池技术有限公司 | Negative electrode current collector of non-negative electrode lithium battery and preparation method and application thereof |
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