CN107012684A - A kind of preparation method of plasma etching electrospun fiber membrane SERS substrates - Google Patents

A kind of preparation method of plasma etching electrospun fiber membrane SERS substrates Download PDF

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CN107012684A
CN107012684A CN201710169300.6A CN201710169300A CN107012684A CN 107012684 A CN107012684 A CN 107012684A CN 201710169300 A CN201710169300 A CN 201710169300A CN 107012684 A CN107012684 A CN 107012684A
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fiber membrane
preparation
sers
sers substrates
plasma etching
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CN107012684B (en
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刘志承
贾露
李洋
张涛
刘亚青
白露
颜照东
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North University of China
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Plasma & Fusion (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention belongs to Raman detection technical field, and in particular to a kind of preparation method of plasma etching electrospun fiber membrane SERS substrates.The substrate of the present invention is obtained by gas plasma process composite nano-fiber membrane.In the present invention, the metal Nano silver grain in composite cellulosic membrane, by in-situ reducing, has obtained polymer/metal Nano silver grain composite cellulosic membrane SERS substrates in gas plasma process.Can be by controlling the presoma content of plasma etch conditions and metal Nano silver grain to regulate and control SERS enhancing effect of the tunica fibrosa SERS substrates to probe molecule.Method therefor of the present invention is simple, and the cycle is short, and the SERS substrates of preparation have good enhancing effect and signal repeatability, significant in terms of the theoretical research of Raman detection and practical application.

Description

A kind of preparation method of plasma etching electrospun fiber membrane SERS substrates
Technical field
The invention belongs to Raman detection technical field, and in particular to a kind of plasma etching electrospun fiber membrane SERS substrates Preparation method.
Background technology
SERS (SERS) is as a kind of strong chemistry and bioanalysis spectral technique, in analysisization There is very wide application prospect in terms of, biological medicine and environment measuring.Due to surface plasmon resonance effect, gold The noble metal nano particles such as silver are used frequently as SERS base materials.It is worth noting that, gold and silver nano-particle is easier group Poly-, its SERS substrates performance constituted is less stablized, for this reason, it may be necessary to by these nanometer particle loads in particular substrate.It is quiet Electricity spinning fibre film is due to turning into supported precious metal nano-particle with larger specific surface area and advantage simple and easy to get Preferable substrate.
Preparing the method for supported precious metal nano-particle electrospun fiber membrane in the past mainly has：1. the tunica fibrosa prepared is soaked Bubble is in metal nanoparticle colloidal sol well prepared in advance；2. polymer is combined with the presoma of metal nanoparticle, electrospinning Metal nanoparticle is prepared after into tunica fibrosa with chemistry or heat-treating methods again；3. by polymer and metal nanoparticle Electrostatic spinning is into tunica fibrosa after solution mixing.But because these metal nanoparticles are distributed in the inside of fiber mostly, they SERS performances tend to be affected.Therefore, in order to improve SERS performances, it is necessary to nano-particle is exposed to greatest extent Fiber surface.
The content of the invention
It is an object of the invention to provide a kind of preparation method of plasma etching electrospun fiber membrane SERS substrates, with logical The method for crossing simplicity prepares the SERS substrates of excellent performance.Composite fibre prepared by specifically a kind of use electrostatic spinning technique After film is by gas plasma process, obtained composite cellulosic membrane SERS substrates.The SERS substrates have good enhancing effect Fruit and signal repeatability.
The present invention is achieved by the following technical solutions：A kind of system of plasma etching electrospun fiber membrane SERS substrates Preparation Method, including polymer is combined with the presoma of metal Nano silver grain, compound receive is prepared by electrostatic spinning technique Rice tunica fibrosa, then passes through gaseous plasma etching processing composite nano-fiber membrane, the metal silver nanoparticle on tunica fibrosa surface again The presoma of particle is reduced into metal Nano silver grain, obtains polymer/metal Nano silver grain composite cellulosic membrane SERS bases Bottom.
Compared with prior art, the present invention has following advantage：
(1) the SERS substrate combination electrostatic spinning techniques and plasma etching technology prepared by the present invention are obtained. The SERS substrates not only remain the big advantage of specific surface area that electrospun fibers film has, but also by gas etc. from Daughter lithographic technique causes the metal Nano silver grain of in-situ reducing formation to be more exposed to fiber surface, so as to improve fibre Tie up the SERS enhancing effects of film.
(2) preparation method of the invention is very easy, and the cycle is short, and resulting SERS substrates have good enhancing effect It is repeated with signal, it is significant in terms of the theoretical research of Raman detection and practical application.
Brief description of the drawings
Fig. 1 is scanning electron microscope (SEM) photograph of the SERS substrates of the preparation of the embodiment of the present invention 14 under different amplification.
Fig. 2 is the Raman spectrogram of SERS basal signals repeatability test prepared by the embodiment of the present invention 14.With concentration For 10-4M R6G is probe molecule, randomly selects 20 points, carries out the signal repeatability detection of SERS substrates.Can be with by figure Find out：The Raman signal intensity of 20 random points is basically identical, and the substrate has good signal repeatability.
Fig. 3 is Raman test of the R6G probe molecules of various concentrations in SERS substrates prepared by the embodiment of the present invention 14 Spectrogram.It can be seen that the least concentration for the R6G molecules that the substrate can be detected is 10-12M。
Fig. 4 is the Raman spectrogram and 1641cm of the SERS substrates prepared under different etching power and etch period-1Raman Corresponding raman scattering intensity distribution map at displacement.A and c is Raman spectrogram in figure, and b and d are raman scattering intensity distribution map.
Fig. 5 be the Raman spectrogram of SERS substrates that is prepared under the content of the presoma of different metal Nano silver grain and 1641cm-1Corresponding raman scattering intensity distribution map at Raman shift.A is Raman spectrogram in figure, and b is raman scattering intensity distribution map.
Embodiment
The present invention passes through content, gaseous plasma etch period and the etching of the presoma for changing metal Nano silver grain The SERS performances of power adjusting tunica fibrosa SERS substrates.
To make the object, technical solutions and advantages of the present invention of greater clarity, below in conjunction with specific embodiment, and reference Accompanying drawing, the present invention will be described in further detail.
As a kind of embodiment of the present invention, composite nano-fiber membrane is put into preparation method of the present invention Etching processing is realized in plasma etching machine；Wherein, the technological parameter of etching processing is：Gas flow is in etching process 10cc/min, pressure is 100mTorr, and etching power is 25W~100W, and etch period is 1~8min.
Certainly, can be in advance by polymerization in order that polymer can be combined preferably with the presoma of metal Nano silver grain Thing is dissolved in solvent, and then presoma is dissolved in mixed solution and carries out electrostatic spinning again.Some of the present invention are provided below Embodiment, in these embodiments, the presoma of metal Nano silver grain is AgNO3, polymer is polyacrylonitrile (PAN).And And the preparation method of composite nano-fiber membrane is：
(1)PAN/AgNO3The configuration of solution：By AgNO3Powder is dissolved in the PAN/DMF solution that concentration is 10wt%, is kept away Light stirs 24h；
(2)PAN/AgNO3The preparation of electrospun fiber membrane：Use the PAN/AgNO obtained by (1)3Solution carries out electrostatic spinning, Spinning technology parameter is：Voltage 15kV, syringe needle to collecting board is obtained apart from 15cm, feed rate 500 μ L/h, spinning time 1h To PAN/AgNO3Composite nano-fiber membrane.
It will be clear for those skilled in the art that polymer can also use polyvinylidene fluoride in addition to it can use PAN Alkene, polystyrene etc. any one can be used for the polymer of electrostatic spinning；And the presoma of metal Nano silver grain is except can Using AgNO3Outside, other presomas can also be used.In addition, gas is in addition to argon gas, the gases such as helium or oxygen can be also used, But it is due to that formed in the present invention is metal Nano silver grain, and metal Nano silver grain is easily oxidized, so employing gas Argon gas in body.In the lab, argon gas is safer relative to other gases, more conventional, therefore the present invention is in specific embodiment The gas of middle use is argon gas.
Below by specific embodiment, the present invention is expanded on further.
Feedstock treating
(1)PAN/AgNO3The preparation method of solution, specifically includes following steps：
By PAN：AgNO3Mass ratio be respectively 10:1,10:3,10:5,10:7 ratio, by AgNO3Powder is added to dense Spend in the PAN/DMF solution for 10wt%, lucifuge stirs 24h, stand-by.
(2)PAN/AgNO3The preparation method of electrospun fiber membrane, specifically includes following steps：
By above-mentioned PAN/AgNO3Solution takes out a part and is fitted into 10mL syringe, and syringe needle internal diameter is 0.7mm, is being applied Making alive is 15kV, and the distance of syringe needle to collecting board is 15cm, and feed rate is progress 1h Static Spinnings under conditions of 500 μ L/h Silk.
In Feedstock treating, high voltage power supply of the present invention is to originate from Tianjin Dongwen High Voltage Power Supply Factory's model DW-P503-1ACDF high voltage power supply, the syringe used is originates from KD Scientific companies of U.S. model Legato Miniature injection pump, perform etching processing use originate from Plasma Etch companies of U.S. model PE-25 grade from Daughter etching machine.
In addition, being carried out by following embodiment to the PAN/Ag composite cellulosic membranes with optimal SERS performances of acquisition The signal repeatability test of SERS substrates：Using concentration as 10-4M R6G is probe molecule, randomly selects 20 points, is carried out The signal repeatability detection of SERS substrates.And the R6G of various concentrations is used for probe molecule, and the PAN/Ag of acquisition is combined The SERS performances of tunica fibrosa are detected.
Each embodiment etching processing parameter of table 1
In table 1, embodiment 1 to 4 is that different etching power is contrasted to SERS substrates performance impact.As seen from Figure 4, with The increase of power, raman scattering intensity also increases, and is then basically unchanged, in 50W, SERS enhancing effects basically reach maximum.This Be probably that the size of nano-particle is uneven due to the continuation increase with power, the surface of composite nano-fiber membrane also by What destruction was caused, therefore when polymer uses the presoma of PAN, metal Nano silver grain for AgNO3When, etching power 50W is Optimal etching power, now SERS enhancing effects are preferable.
Embodiment 5 to 12 is the different etching time SERS substrates performance impact to be contrasted in table 1.As seen from Figure 4, with The increase of processing time, raman scattering intensity is also in increase, but after 3min, the increase of intensity is not too obvious.And during 4min, draw The deviation of graceful intensity is also larger, and this is probably the nano-particle resulted in because composite nano-fiber membrane surface is destroyed It is uneven to cause, with reference to SEM results, selection 3min as corona treatment Best Times.Therefore when polymer is used PAN, the presoma of metal Nano silver grain are AgNO3When, etch period 3min is optimal etch period, now SERS enhancings effect Fruit is preferably.
When studying influence of the different etching condition to SERS enhancing effects, we are except that will select larger raman scattering intensity Beyond normative reference, the integrality of composite nano-fiber membrane is also kept, obtained fibrous substrate tool is so just can guarantee that There are repeatability and value well.Therefore, in follow-up experiment, the plasma process conditions that we select are 50W Handle 3min.Embodiment 13 to 15 is the content of the presoma of different metal Nano silver grain to SERS substrate performance shadows in table 1 Ring contrast.As seen from Figure 5, with the increase of silver nitrate content, SERS intensity, which first increases, then to be reduced.Therefore, selection PAN with AgNO3Mass ratio be 10:5 are used as optimum experimental condition.
In table 1, the difference of embodiment 16 and other embodiment is：PAN/AgNO obtained by embodiment 163Electrospinning is fine Film is tieed up without etching processing, SERS substrates are directly used as, but its Raman signal intensity is not obvious.
Contrasted from above-described embodiment, content, the argon plasma of the presoma by changing metal Nano silver grain Body etch period and etching power realize the regulation of the SERS performances of tunica fibrosa SERS substrates.And fiber of the present invention Film SERS substrates have good enhancing effect and signal repeatability.Also, when polymer uses PAN, metal nano grain of silver The presoma of son is AgNO3When, etching condition preferably is 50W processing 3min, PAN and AgNO preferably3Mass ratio be 10: 5。
Above-described embodiment is the specific embodiment of the present invention, it is only for illustrates example of the present invention, is not Restriction to the embodiment of invention.It can be done for person skilled in art on the basis of the technology of the present invention principle is not departed from Go out other various forms of changes and variation, this has no effect on the substantive content of the present invention.

Claims (7)

1. a kind of preparation method of plasma etching electrospun fiber membrane SERS substrates, it is characterised in that including by polymer with The presoma of metal Nano silver grain is combined, and is prepared composite nano-fiber membrane by electrostatic spinning technique, is then passed through gas again Bulk plasmon etching processing composite nano-fiber membrane, the presoma of the metal Nano silver grain on tunica fibrosa surface is reduced into gold Belong to Nano silver grain, obtain polymer/metal Nano silver grain composite cellulosic membrane SERS substrates.
2. a kind of preparation method of plasma etching electrospun fiber membrane SERS substrates according to claim 1, its feature It is, tunica fibrosa SERS substrates can be adjusted by the content for the presoma for changing metal Nano silver grain in the preparation method SERS performances.
3. a kind of preparation method of plasma etching electrospun fiber membrane SERS substrates according to claim 1, its feature It is, tunica fibrosa SERS bases can be adjusted by changing gaseous plasma etch period and etching power in the preparation method The SERS performances at bottom.
4. a kind of preparation method of plasma etching electrospun fiber membrane SERS substrates according to claim 1 or 2 or 3, Characterized in that, composite nano-fiber membrane is put into plasma etching machine and realizes etching processing in the preparation method； Wherein, the technological parameter of etching processing is：Gas flow is 10 cc/min in etching process, and pressure is 100mTorr, etches work( Rate is 25W~100W, and etch period is 1~8min.
5. a kind of preparation method of plasma etching electrospun fiber membrane SERS substrates according to claim 1 or 2 or 3, Characterized in that, the polymer is Kynoar, polystyrene or polyacrylonitrile.
6. a kind of preparation method of plasma etching electrospun fiber membrane SERS substrates according to claim 5, its feature It is, it is preferred that the polymer is polyacrylonitrile.
7. a kind of preparation method of plasma etching electrospun fiber membrane SERS substrates according to claim 6, its feature It is, the preparation method of the composite nano-fiber membrane is：
（1）PAN/AgNO3The configuration of solution：By AgNO3Powder is dissolved in the PAN/DMF solution that concentration is 10wt%, and lucifuge is stirred Mix 24h；
（2）PAN/AgNO3The preparation of electrospun fiber membrane：Use（1）Resulting PAN/AgNO3Solution carries out electrostatic spinning, spinning Technological parameter is：Voltage 15kV, syringe needle to collecting board is obtained apart from 15cm, feed rate 500 μ L/h, spinning time 1h PAN/AgNO3Composite nano-fiber membrane.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103411946A (en) * 2013-06-24 2013-11-27 吉林大学 Method for preparing surface-enhanced Raman spectrum base by using electrospinning technique
CN104111246A (en) * 2014-07-29 2014-10-22 苏州大学 Sensing material for trace detection of heavy metal ions as well as preparation method and application of sensing material
CN104562223A (en) * 2014-12-29 2015-04-29 北京化工大学常州先进材料研究院 Preparation of supported sliver catalyst fibrous membrane and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103411946A (en) * 2013-06-24 2013-11-27 吉林大学 Method for preparing surface-enhanced Raman spectrum base by using electrospinning technique
CN104111246A (en) * 2014-07-29 2014-10-22 苏州大学 Sensing material for trace detection of heavy metal ions as well as preparation method and application of sensing material
CN104562223A (en) * 2014-12-29 2015-04-29 北京化工大学常州先进材料研究院 Preparation of supported sliver catalyst fibrous membrane and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
魏洤等: "《近代结构分析方法》", 30 November 1989 *

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