CN107748159A - A kind of surface enhanced Raman substrate and preparation method thereof - Google Patents

A kind of surface enhanced Raman substrate and preparation method thereof Download PDF

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Publication number
CN107748159A
CN107748159A CN201711131759.3A CN201711131759A CN107748159A CN 107748159 A CN107748159 A CN 107748159A CN 201711131759 A CN201711131759 A CN 201711131759A CN 107748159 A CN107748159 A CN 107748159A
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substrate
gold nano
gap
enhanced raman
golden film
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李月娥
蔡可苏
王�忠
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Lanzhou University
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Lanzhou University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

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  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
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  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention provides a kind of surface enhanced Raman substrate and preparation method thereof, is related to goods and materials structure detection technical field.The surface enhanced Raman substrate is applied to detection fluid sample, and surface enhanced Raman substrate includes substrate, golden film and gold nano cube;Substrate is formed using silicon materials, and golden film is arranged on substrate, and gold nano cube is arranged in golden film, and gold nano cube is arranged in matrix, has gap between gold nano cube, and gap is used to inject fluid sample to be measured.Gold nano cube is arranged in matrix, the gap arranging rule of formation, size uniform, behind product injection gap to be measured, product uniformity to be measured is good, the solution Raman scattering signal inspired is strengthened, high sensitivity, favorable reproducibility, it can more accurate, clearly measure the horizontal structural information of products molecule to be measured.

Description

A kind of surface enhanced Raman substrate and preparation method thereof
Technical field
The present invention relates to goods and materials structure detection technical field, in particular to a kind of surface enhanced Raman substrate and its Preparation method.
Background technology
SERS (Surface-Enhanced Raman Scattering, referred to as:SERS) refer to coarse Precious metal surface in the case where incident light excites, material molecule of the enhancing absorption on its surface sends Raman scattering signal A kind of phenomenon.
The enhancing of the Raman scattering signal of molecule produces the vibration of surface electronic under light illumination from rough surface, when entering When penetrating the frequency of the frequency of light and the plasma of metal itself and matching, electronic reaches maximum, then in metal surface Produce one and add local electromagnetic field with incident light frequency identical, the electromagnetic field of additional local electromagnetic field and incident light is superimposed upon Together.
The polarization of molecule itself and the interaction of external electrical field are come from due to the Raman scattering of molecule, so at this Molecule in individual superposition of electric field is also added local electromagnetic field by this and made in addition to the effect by the electromagnetic field of former incident light With, therefore the Raman scattering signal inspired is also strengthened accordingly.The Raman scattering signal of enhancing reflects tested The horizontal structural information of material molecule.
Current commonly used substrate is mostly noble metal colloidal sol prepared by chemical method, such as gold/silver nanoparticle ball, gold/Yin Na Rice rod etc..But existing colloidal sol substrate is a kind of metastable state system, the aggregation of free settling can be formed after addition analysis material, and And the granular size of colloid, shape, surface topography etc. are difficult consistent, thus the poor reproducibility of Raman signal, to a certain extent Application of this technology in multiple fields is hindered, and it is poor for the Detection results of material molecular structure, especially for The detection of fluid product is extremely difficult to ideal effect.
Therefore, a kind of substrate for being used to detect material molecular structure is designed, stronger Raman scattering signal, spirit can be excited Sensitivity is high, and has good signal reproducibility, and this is technical problem urgently to be resolved hurrily at present.
The content of the invention
The present invention provides a kind of surface enhanced Raman substrate and preparation method thereof, and it is intended at least partly solve existing base The technical problem for the Raman scattering signal poor reproducibility that bottom excites.
In a first aspect, the embodiment of the present invention, which provides a kind of surface enhanced Raman substrate, is applied to detection fluid sample, it is described Surface enhanced Raman substrate includes substrate, golden film and gold nano cube;The substrate is formed using silicon materials, and the golden film is set Put over the substrate, the gold nano cube is arranged in the golden film, and the gold nano cube is arranged in matrix, institute Stating between gold nano cube has gap, and the gap is used to inject fluid sample to be measured.
With reference in a first aspect, in the first way of first aspect of the embodiment of the present invention, the cubical side of gold nano A length of 50nm, the width in the gap between the two neighboring gold nano cube is 30nm.
With reference to the first way of first aspect, in the second way of first aspect of the embodiment of the present invention, the Jenner The one end of rice cube away from the golden film has fillet.
With reference to the second way of first aspect, in the third mode of first aspect of the embodiment of the present invention, the fillet Radius be 1nm.
With reference in a first aspect, in the 4th kind of mode of first aspect of the embodiment of the present invention, the substrate is rectangular parallelepiped structure, The long 2000nm of the substrate, a width of 2000nm of the substrate, a height of 110nm of the substrate.
With reference to the 4th kind of mode of first aspect, in the fifth procedure of first aspect of the embodiment of the present invention, the golden film Long 2000nm, a width of 2000nm of the golden film, the thickness of the golden film is 40nm.
Second aspect, the embodiment of the present invention provide a kind of surface enhanced Raman substrate preparation method, and methods described includes:
Substrate is formed using silicon materials;
Titanium layer, and the gold-plated film on the titanium layer are deposited in the substrate surface;
The gold nano cube that matrix is arranged, the gold nano are formed on the surface of the golden film by method for stripping metal There is gap, the gap is used to inject fluid sample to be measured between cube.
With reference to second aspect, in the first way of second aspect of the embodiment of the present invention, the cubical side of gold nano A length of 50nm, the width in the gap between the two neighboring gold nano cube is 30nm.
With reference to the first way of second aspect, in the second way of second aspect of the embodiment of the present invention, the Jenner The one end of rice cube away from the golden film has fillet.
With reference to the second way of second aspect, in the third mode of second aspect of the embodiment of the present invention, the fillet Radius be 1nm.
The beneficial effect of surface enhanced Raman substrate provided by the invention and preparation method thereof is:
The gap between gold nano cube can be prepared using the method for physics, the gold nano cube is in matrix Arrangement, the gap arranging rule of formation, size uniform, after product to be measured injects gap, product uniformity to be measured is good, by incidence Light excites, and can produce stronger additional local electromagnetic field (" focus " effect), the Raman scattering signal inspired is also corresponding Strengthened, high sensitivity, favorable reproducibility, can more accurate, clearly measure the horizontal structural information of products molecule to be measured. Moreover, the ability of multicomponent while detection can be realized.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below by embodiment it is required use it is attached Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the structural representation at the visual angle of surface enhanced Raman substrate first that first embodiment of the invention provides.
Fig. 2 is the structural representation at the visual angle of surface enhanced Raman substrate second that first embodiment of the invention provides.
Fig. 3 is Fig. 2 partial enlargement structural representation.
When Fig. 4 is d=30nm, under different wave length λ, electric field maximum Emax and w1 graph of a relation.
When Fig. 5 is λ=633nm, under different spacing d, electric field maximum Emax and w1 graph of a relation.
Icon:100- surface enhanced Raman substrates;110- substrates;120- golden films;130- gold nano cubes;Between 140- Gap.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is Part of the embodiment of the present invention, rather than whole embodiments.The present invention implementation being generally described and illustrated herein in the accompanying drawings The component of example can be configured to arrange and design with a variety of.
Therefore, below the detailed description of the embodiments of the invention to providing in the accompanying drawings be not intended to limit it is claimed The scope of the present invention, but be merely representative of the present invention selected embodiment.It is common based on the embodiment in the present invention, this area The every other embodiment that technical staff is obtained under the premise of creative work is not made, belong to the model that the present invention protects Enclose.
It should be noted that:Similar label and letter represents similar terms in following accompanying drawing, therefore, once a certain Xiang Yi It is defined, then it further need not be defined and explained in subsequent accompanying drawing in individual accompanying drawing.
In the description of the invention, it is to be understood that term " " center ", " on ", " under ", "left", "right", " vertical ", The orientation or position relationship of the instruction such as " level ", " interior ", " outer " be based on orientation shown in the drawings or position relationship, or should Invention product using when the orientation usually put or position relationship, or the orientation or position that those skilled in the art usually understand Relation is put, it is of the invention necessary with simplified description, rather than the equipment or element of instruction or hint meaning to be for only for ease of description With specific orientation, with specific azimuth configuration and operation, therefore be not considered as limiting the invention.
In addition, term " first ", " second ", " the 3rd " etc. are only used for distinguishing description, and it is not intended that instruction or hint Relative importance.
In the description of the invention, it is also necessary to explanation, unless otherwise clearly defined and limited, term " setting ", " installation ", " connected ", " connection " should be interpreted broadly, for example, it may be fixedly connected or be detachably connected, or one Connect body;Can be mechanical connection or electrical connection;Can be joined directly together, can also be indirect by intermediary It is connected, can is the connection of two element internals.For the ordinary skill in the art, on being understood with concrete condition State the concrete meaning of term in the present invention.
Embodiments of the invention are related to surface enhanced Raman substrate and preparation method thereof.SERS (SERS) Appearance for expand Raman scattering techniques research range and application field play an important role.The expensive gold of SERS Technology applications The surface phasmon (SPPs) of category and medium interface realizes the Electromagnetic enhancement near sample, so as to cause the drawing of binding molecule Graceful scattered signal is than the phenomenon that greatly enhances of normal Raman scattering (NRS) signal.
Currently used substrate is mostly noble metal colloidal sol prepared by chemical method, such as gold/silver nanoparticle ball, gold/silver nanoparticle Rod etc..Following defect at least be present in existing colloidal sol substrate:
First, existing colloidal sol substrate is a kind of metastable state system, adds the aggregation of formation free settling after analysis material, And the granular size of colloid, shape, surface topography etc. are difficult consistent, so as to cause the aggregation extent of colloidal sol to be difficult to control, because And the poor reproducibility of Raman scattering signal, testing result are poor.
Second, sample processing is relative complex, and sample is adsorbed onto sol surface, the drawing of many molecules or group Graceful scattered signal is difficult to obtain, and susceptibility is low.
With the continuous development of nano material, the presence of organic pollution in environment is detected with SERS It has been received significant attention that, it is the pass realized trace, quantitatively detected to prepare active substrate repeatable, homogeneous, that enhancing activity is splendid Key.Using the technology of preparing of increasingly mature nano material, the nano particle that grain shape and size can control very well is obtained, And SERS enhancing mechanism is studied as cast material, this is the design that the embodiment of the present invention mainly uses.
First embodiment
Fig. 1 and Fig. 2 are referred to, present embodiments provides a kind of surface enhanced Raman substrate 100, surface enhanced Raman substrate 100 are used to detect fluid sample, and surface enhanced Raman substrate 100 includes substrate 110, golden film 120 and gold nano cube 130.
Substrate 110 is formed using silicon materials, and golden film 120 is set on a substrate 110, formed on a substrate 110 golden film 120 it Before, titanium layer can be first formed on a substrate 110, then golden film 120 is formed on titanium layer.Gold nano cube 130 is arranged on golden film 120 On, gold nano cube 130 is arranged in matrix, has gap 140 between gold nano cube 130, gap 140 is treated for injection The fluid sample of survey.
Substrate 110 is rectangular parallelepiped structure, the long L=2000nm of substrate 110, the wide W=2000nm of substrate 110, substrate 110 High h2=110nm.The long 2000nm of golden film 120, a width of 2000nm of golden film 120, the thickness h 1=40nm of golden film 120.
Referring to Fig. 3, the length of side W1=50nm of gold nano cube 130, between two neighboring gold nano cube 130 The width d=30nm in gap 140.The one end of gold nano cube 130 away from golden film 120 has fillet, the radius r=of fillet 1nm。
As W1=50nm, d=30nm, Gaussian beam can excite in the gap 140 between gold nano cube 130 Extremely strong uniform electric field, the Raman scattering signal that product to be measured inspires is set farthest to strengthen as far as possible, can accurately, clearly The molecular structure of product to be measured is embodied to Chu, concrete analysis process is as follows:
Surface enhanced Raman substrate 100 is excited using the Gaussian beam of specific linear polarization, also, selected different Wavelength excited.Referring to Fig. 4, when wavelength is respectively 532nm, 633nm, 785nm, there is a peak under each wavelength Value, and correspond to various sizes of gold nano cube 130.When select excitation wavelength for 633nm when, gold nano cube 130 The length of side w1=50nm when, its field strength is maximum.
Referring to Fig. 5, selection wavelength 633nm makees further research, as the gap 140d for changing gold nano cube 130 When, with gap 140d increase, the size of gold nano cube 130 is changing corresponding to the maximum of points of field strength, also, works as When gap 140d=30nm, length of side w1=50nm, corresponding field strength is maximum.
Therefore, the length of side w1=50nm of gold nano cube 130 is designed, gap 140d=30nm, product to be measured can be made The Raman scattering signal inspired farthest strengthens as far as possible.
The beneficial effect for the surface enhanced Raman substrate 100 that the present embodiment provides:
1. the surface of surface enhanced Raman substrate 100, which spreads all over, focus, detected for fluid sample, in specific incident light Excite lower absorption to be strengthened in the Raman scattering signal of the material molecule on the surface of surface enhanced Raman substrate 100, drawn with common Graceful scattered signal is compared, 4 orders of magnitude of the intensity enhancing of the Raman scattering signal in the present embodiment, and because nanostructured The systematicness of itself, the reappearance of signal are fine.
2. gold nano cube 130 is arranged in matrix, the arranging rule of gap 140 of formation, size uniform, product note to be measured After entering gap 140, product uniformity to be measured is good, is excited by incident light, can produce stronger additional local electromagnetic field, excite The Raman scattering signal gone out is also strengthened accordingly, can more accurate, clearly measure the horizontal knot of products molecule to be measured Structure information.Moreover, the ability of multicomponent while detection can be realized.
Reusable after over cleaning after 3. surface enhanced Raman substrate 100 detects sample, utilization rate is high, using just It is prompt.
4. the size design of gold nano cube 130 is based on, electromagnetic mode is theoretical, and being designed in specific wavelength can be real Existing targetedly application scenario, such as biological detection, disease detection, environment measuring, chemical analysis, there is wide using to lead Domain.
Second embodiment
The present embodiment provides a kind of surface enhanced Raman substrate preparation method, and method includes:
S1:Substrate is formed using silicon materials.
Substrate 110 is rectangular parallelepiped structure, the long L=2000nm of substrate 110, the wide W=2000nm of substrate 110, substrate 110 High h2=110nm.
S2:Titanium layer, and the gold-plated film on titanium layer are deposited in substrate surface.
Golden film is formed by the way of vacuum evaporation.The long 2000nm of golden film 120, a width of 2000nm of golden film 120, golden film 120 are completely covered on the upper surface of substrate 110.The thickness of golden film 120 is h1+W1=90nm.
S3:The gold nano cube that matrix is arranged, gold nano cube are formed on the surface of golden film by method for stripping metal There is gap, gap is used to inject fluid sample to be measured between body.
The length of side W1=50nm of gold nano cube 130, gap 140 between two neighboring gold nano cube 130 Width d=30nm.The one end of gold nano cube 130 away from golden film 120 has fillet, the radius r=1nm of fillet.
That is analyzed in the determination of W1 and d value such as first embodiment is identical, repeats no more here.
The surface enhanced Raman substrate preparation method that the present embodiment provides, is plated on a substrate 110 by vacuum evaporation first Golden film 120, then by preparing gold nano cube on golden film surface, there is gap 140, material to be detected, which injects, to be received between it Rice gap 140, technique is simple.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies Change, equivalent substitution, improvement etc., should be included in the scope of the protection.

Claims (10)

  1. A kind of 1. surface enhanced Raman substrate, applied to detection fluid sample, it is characterised in that the surface enhanced Raman substrate Including substrate, golden film and gold nano cube;
    The substrate is formed using silicon materials, and the golden film is set over the substrate, and the gold nano cube is arranged on institute State in golden film, the gold nano cube is arranged in matrix, has gap between the gold nano cube, the gap is used for Inject fluid sample to be measured.
  2. 2. surface enhanced Raman substrate according to claim 1, it is characterised in that the cubical length of side of gold nano is 50nm, the width in the gap between the two neighboring gold nano cube is 30nm.
  3. 3. surface enhanced Raman substrate according to claim 2, it is characterised in that the gold nano cube is away from described One end of golden film has fillet.
  4. 4. surface enhanced Raman substrate according to claim 3, it is characterised in that the radius of the fillet is 1nm.
  5. 5. surface enhanced Raman substrate according to claim 1, it is characterised in that the substrate is rectangular parallelepiped structure, institute State the long 2000nm of substrate, a width of 2000nm of the substrate, a height of 110nm of the substrate.
  6. 6. surface enhanced Raman substrate according to claim 5, it is characterised in that the long 2000nm of the golden film, it is described A width of 2000nm of golden film, the thickness of the golden film is 40nm.
  7. 7. a kind of preparation method of surface enhanced Raman substrate, it is characterised in that methods described includes:
    Substrate is formed using silicon materials;
    Titanium layer, and the gold-plated film on the titanium layer are deposited in the substrate surface;
    The gold nano cube that matrix is arranged, the gold nano cube are formed on the surface of the golden film by method for stripping metal There is gap, the gap is used to inject fluid sample to be measured between body.
  8. 8. according to the method for claim 7, it is characterised in that the cubical length of side of gold nano is 50nm, adjacent two The width in the gap between the individual gold nano cube is 30nm.
  9. 9. according to the method for claim 8, it is characterised in that one end tool of the gold nano cube away from the golden film There is fillet.
  10. 10. according to the method for claim 9, it is characterised in that the radius of the fillet is 1nm.
CN201711131759.3A 2017-11-15 2017-11-15 A kind of surface enhanced Raman substrate and preparation method thereof Pending CN107748159A (en)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN108827935A (en) * 2018-06-08 2018-11-16 南京师范大学 It is a kind of based on the DNA methylation Surface Enhanced Raman Scattering Spectrum detection method of gold nano hole array and its application
CN108896530A (en) * 2018-06-29 2018-11-27 上海交通大学 A kind of preparation method of Raman spectrum detection substrate
CN109827942A (en) * 2018-12-29 2019-05-31 安徽中科赛飞尔科技有限公司 A kind of high density hot spot SERS chip and its preparation method and application
CN110579461A (en) * 2019-05-15 2019-12-17 上海交通大学 Preparation method and application of SERS performance detection biosensor
CN111693502A (en) * 2019-03-12 2020-09-22 武汉大学 Liquid-phase Raman enhanced spectrum substrate combining cavity enhancement and surface enhancement
CN118291941A (en) * 2024-06-05 2024-07-05 上海理工大学 Preparation method of surface-enhanced Raman scattering substrate based on step structure

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CN107119252A (en) * 2017-05-26 2017-09-01 云南师范大学 A kind of silicon substrate surface strengthens the preparation method of Raman substrate

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108827935A (en) * 2018-06-08 2018-11-16 南京师范大学 It is a kind of based on the DNA methylation Surface Enhanced Raman Scattering Spectrum detection method of gold nano hole array and its application
CN108896530A (en) * 2018-06-29 2018-11-27 上海交通大学 A kind of preparation method of Raman spectrum detection substrate
CN109827942A (en) * 2018-12-29 2019-05-31 安徽中科赛飞尔科技有限公司 A kind of high density hot spot SERS chip and its preparation method and application
CN109827942B (en) * 2018-12-29 2021-12-21 安徽中科赛飞尔科技有限公司 High-density hot spot SERS chip and preparation method and application thereof
CN111693502A (en) * 2019-03-12 2020-09-22 武汉大学 Liquid-phase Raman enhanced spectrum substrate combining cavity enhancement and surface enhancement
CN111693502B (en) * 2019-03-12 2024-05-07 武汉大学 Liquid-phase Raman enhancement spectrum substrate combining cavity enhancement and surface enhancement
CN110579461A (en) * 2019-05-15 2019-12-17 上海交通大学 Preparation method and application of SERS performance detection biosensor
CN118291941A (en) * 2024-06-05 2024-07-05 上海理工大学 Preparation method of surface-enhanced Raman scattering substrate based on step structure
CN118291941B (en) * 2024-06-05 2024-09-17 上海理工大学 Preparation method of surface-enhanced Raman scattering substrate based on step structure

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