CN105671492B - A kind of SERS substrates and preparation method based on REBCO masterplates - Google Patents
A kind of SERS substrates and preparation method based on REBCO masterplates Download PDFInfo
- Publication number
- CN105671492B CN105671492B CN201610031709.7A CN201610031709A CN105671492B CN 105671492 B CN105671492 B CN 105671492B CN 201610031709 A CN201610031709 A CN 201610031709A CN 105671492 B CN105671492 B CN 105671492B
- Authority
- CN
- China
- Prior art keywords
- rebco
- layer
- masterplates
- metal
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Physical Vapour Deposition (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
The invention discloses a kind of SERS substrates based on REBCO masterplates and preparation method thereof, the SERS substrates include the metal-modified layer of REBCO masterplates layer and the REBCO masterplates layer appearance plating；Wherein, the thickness of the REBCO masterplates layer is continuously adjusted in 10~2000nm, and structure is from amorphous to polycrystalline, and a, b axis are orientated and c-axis is orientated or hybrid orientation is arbitrarily adjustable；The metal-modified layer is metallic film or metal particle layer；The thickness of the metal-modified layer is 5~200nm.Compared with prior art, advantage is substrate of the present invention and preparation method thereof：The SERS substrates homogeneity prepared using the present invention is good, high sensitivity, and with metal flexible feature, can meet a variety of application demands；By numerous studies, the industrialization production under accurate control is easy to implement for REBCO growth mechanisms and growing method；The preparation method of the present invention is simple simultaneously, and the experiment parameter relative chemical method in growth course is more prone to control, and industrialization manufacturing cost can be less than 0.5 $/cm2。
Description
Technical field
The present invention relates to a kind of SERS substrates based on REBCO masterplates and preparation method thereof, i.e., a kind of to utilize rare-earth oxidation
SERS substrates that object coating conductor is prepared as template and preparation method thereof, more particularly to utilizing pulsed laser deposition technique
(later abbreviation PLD) and chemical method prepare rare earth oxide (later abbreviation REBCO, RE=with certain orientation and defect
Rare earth element) coating, then prepare that uniformity is good, enhancing effect is apparent, at low cost and can on a flexible substrate as template
The method of the strong SERS substrates of repeatability.
Background technology
Surface enhanced Raman spectroscopy (SERS) is a kind of very powerful High Sensitive Analysis technology, it can detect and analyze
All kinds of molecules that substance surface layer is adsorbed, for some systems, its sensitivity even up to detects single molecules level.By near
The development of decades, at present SERS fields still have some urgent problems to be solved, on the whole including following three aspect：
First, expand the range of SERS reinforcing materials；Second, prepare the Process Exploration of appropriate coarse SERS substrates；Third, it realizes
The theory and technology of SERS quantitative analyses.It obtains with hypersensitivity, high stability, the substrate of repeatability, and there is substrate
Selectivity well designs the critical issue with manufacturing for current Raman detection substrate.However, SERS substrates are really moved towards to apply
In addition to needing to meet a cassation other than requirement, being also largely dependent on the capability of industrialization of SERS substrates, production technology and being produced into
This.At present, the preparation method for commonly using SERS substrates is (Bottom-Up) and from top to bottom (Top-Down) two kinds of sides from bottom to top
Method.Generally, bottom-to-top method is the chemical synthesis process based on the nano particles such as gold and silver, although this method is simple
List is readily synthesized, but have the shortcomings that very big, is specifically included：1st, the SERS substrates prepared using the nano particle of solwution method synthesis,
In fact only a small part particle has SERS activity, and other nano particles are covered in substrate surface and SERS is inhibited to examine
Survey effect.2nd, nano particle prepared by solution is difficult to control their agglomerating effect, will necessarily influence the steady of SERS detection results
It is qualitative and repeated.3rd, it is of special importance that the method that stable nanometer SERS activity hot spots are synthesized for control is also immature,
That is also carry certain randomness about nanostructured of the control synthesis with specific morphology.Top-down methods are usually
Based on some conventional physical techniques, mainly include focused ion beam method, mould printing, CVD method, photoetching process etc., utilize them
Novel and macroscopic view SERS active-substrate can be built.The disadvantage of this kind of substrate is mainly：1st, the substrate of this high surface area is very
It is difficult technically to realize control completely, and then surface topography is not completely the same between being likely to result in different batches substrate.2、
Usual this substrate has poor mechanical performance, especially poor in flexibility, is easily broken off.In addition to this, life is also utilized
Object masterplate prepares the methods of three-dimensional active substrate, function of surface modification, laser corrosion.Although some of which method has been able to
In a small range property structure performance period and higher gain is obtained, but be provided simultaneously with the SERS bases that commercial application is required
Bottom not yet occurs.
As a kind of high temperature superconducting materia of most application potential, the unique advantage that REBCO coating conductors have by it, quilt
Think to be likely to replace the 1st generation high-temperature superconductor band using bismuth system as representative, applied to numerous superconduction forceful electric power technologies.From its birth
Since, it gives pay high attention to both at home and abroad, countries in the world have put into numerous studies funds and its industrialization technology of preparing is carried out
Research has achieved a series of theoretical and Experiment Result.REBCO coating conductors are substantially a kind of granular pattern ceramic aluminas
Object, flexibility is poor, and has very strong anisotropy, therefore the universal technique of second-generation high-temperature superconductor, is using each
Kind plating membrane means plate one layer big in the conventional metals base band (alloys such as nickel-base alloy or stainless steel) of very thin (40~100 microns)
About 1 to several microns thickness and the REBCO films that should have biaxial texture simultaneously, this (its typical case's knot very harsh to technological requirement
Structure is shown in Figure of description 1).
The REBCO superconducting films being deposited directly on metal base band can be there are a large amount of defects, and superconductivity is very poor, therefore superconduction
The preparation of application must add a buffer layer on metal base band.On the one hand the effect of buffer layer is to induce taking for REBCO superconducting films
To growth, on the other hand can also be used as separation layer prevent REBCO and metallic substrates react and elements diffusion.It is led according to coating
The difference of body technique route, the selection of buffer layer would also vary from.Obviously, the selection of cushioning layer material, thickness, doping and life
Elongate member, it will largely influence the upgrowth situation of REBCO, and then influence its surface topography.For example, CeO2With superconduction
Layer, metallic substrates are respectively provided with smaller lattice mismatch, are used as the cushioning layer material of high-temperature superconductor all the time.But
When conductor of high-temperature superconductor coat is prepared, work as CeO2Thickness is more than certain value (about 50nm) to buffer layer on the metallic substrate
It just will appear micro-crack.The appearance and then the epitaxial growth of influence superconducting layer on the buffer layer of micro-crack.In addition to this, due to knot
Structure is complicated, and REBCO is extremely sensitive for growth conditions in itself.The key for preparing high performance superconductor band is through these factors
Regulation and control the defects of making generation specific, however for surface topography, REBCO surfaces can be made simultaneously to the regulation and control of these factors
Pattern generates a series of variation (see Figure of description 2).For stability, REBCO superconducting coatings can realize public affairs
In grade 300A/cm disposable preparation, it means that uniformity, the stability of prepared REBCO coatings can produce
It is guaranteed in journey.At the same time, as the stability of technique improves, the production cost of REBCO just reduces year by year, uses at present
The REBCO coatings average unit cost of PLD preparation methods production is less than 3$/cm2.This by the use of REBCO coating conductors as template just to repair
Shi Bi races metallic film and nano particle, preparing has uniform signal, the active height of SERS, process stabilizing, prepares speed soon and make
It makes SERS flexible substrates at low cost and provides possibility.
Invention content
For this problem, the application designer relies on the experiment experience of REBCO films growth, actively studies, it is proposed that
A kind of scheme that SERS substrates are prepared by the use of REBCO coatings as template, i.e., a kind of SERS substrates and system based on REBCO masterplates
Preparation Method.
An object of the present invention is to provide a kind of flexible SERS substrates with excellent specific property using REBCO as masterplate.
It is yet another object of the invention to provide a kind of using REBCO as the flexible SERS substrates with excellent specific property of masterplate
Preparation method.
The purpose of the present invention is what is be achieved through the following technical solutions：
In order to reach the first object of the present invention, the present invention provides a kind of SERS substrates based on REBCO masterplates, described
The metal-modified layer that SERS substrates include REBCO (R=Y) masterplate layers and the REBCO masterplates layer appearance coats.
Preferably, the thickness of the REBCO masterplates layer is continuously adjusted in 10-2000nm, and structure is from amorphous to polycrystalline, a, b
Axis is orientated and c-axis is orientated or hybrid orientation is arbitrarily adjustable.
Preferably, the metal-modified layer is metallic film or metal particle layer；The thickness of the metal-modified layer is 5
~200nm.
It is further preferred that superposition of the metal-modified layer for single metal layer or different metal layer.
It is further preferred that the metal-modified layer metal includes Au, Ag, Cu or Al.
In order to reach a further object of the present invention, the present invention provides a kind of SERS substrates based on REBCO masterplates
Preparation method includes the following steps：
REBCO targets are warming up to growth temperature, adjust laser energy and frequency, be passed through oxygen, coating system by step 1
Transmission device drives metal base band to pass through plated film area, you can forms REBCO masterplate layers in metal base band buffer-layer surface；
Step 2, REBCO targets are changed to modified metal target in situ, pass through pulsed deposition process, magnetically controlled sputter method
Or hot evaporation method plates metal decorative layer to get flexible SERS substrates in the REBCO masterplates layer surface.
Preferably, in step 1, the metal base band needs to clean it with organic solvent before use, and purpose exists
The buffer layer for having on metal base band and being centainly orientated is grown in cleaning, to remove surface impurity.
Preferably, in step 1, the REBCO is prepared by high temperature sintering；The organic solvent refers to such as acetone
Nonpolarity organic solvent.
Preferably, in step 1, the growth temperature is 650~850 DEG C.
Preferably, in step 1, the laser energy and frequency are specially：E=50~300mJ, f=1~200Hz.
Preferably, in step 1, the oxygen refers specifically to pure oxygen, purity 99.99%.
Further, before being passed through oxygen, plated film area is vacuum state, be passed through after oxygen the air pressure of plated film area for 5~
200mTorr；Further, the specific air pressure of the vacuum state is 1 × 10-4~1 × 10-7Torr。
Preferably, in step 1, it is described pass through be with the speed of 5~10m/h once by plated film area or with 30~
The speed of 50m/h passes through multichannel plated film area.
Preferably, in step 1, the distance of the REBCO targets to plated film area is 5~25cm；
Preferably, in step 1,10~2000nm of the REBCO masterplates layer.
Preferably, in step 2, in situ replace is specifically to be reduced for heating the heter temperature of REBCO targets
Vacuum degree to 50 DEG C, plated film area is less than 1 × 10-7It is carried out under conditions of Torr.
Preferably, it is described to be repaiied by pulse laser sediment method in REBCO masterplates layer surface plating metal in step 2
Decorations layer specifically includes：It adjusts laser energy and frequency, the metal base band for being coated with REBCO masterplate floor passes through plated film area, you can
The surface of REBCO masterplate layers plates metal decorative layer.
It is further preferred that the laser energy and frequency refer specifically to：E=50~300mJ, f=1~200Hz.
It is further preferred that the metal base band that REBCO masterplate layers are coated with by referring to once is passed through with the speed of 30m/h
Plated film area passes through multichannel plated film area with the speed of 150m/h.
Preferably, it is described that metal decorative layer is plated in the REBCO masterplates layer surface by magnetically controlled sputter method in step 2
It specifically includes：The metal base band for being coated with REBCO masterplate layers winding is arranged in magnetron sputtering coating system, is passed through argon gas, is controlled
Sputtering power processed, the metal base band for being coated with REBCO masterplate floor pass through multiple tracks plated film area, you can are plated on the surface of REBCO masterplate layers
Upper metal-modified layer.
It is further preferred that build-up of luminance condition should be reached by being passed through the air pressure in plated film area after argon gas.
It is further preferred that the sputtering power is specially 10~1000W.
It is it is further preferred that described by referring specifically to the metal base band by REBCO masterplate layers are coated with the speed of 1~50m/h
Degree once passes through multichannel plated film area by plated film area or with the speed of 7~200m/h.
Preferably, it is described that metal decorative layer tool is plated in the REBCO masterplates layer surface by hot evaporation method in step 2
Body includes：The metal base band for being coated with REBCO masterplate layers is cut, is fixed, adjusts vacuum degree, melts modified metal target
Material is opened MASK and is deposited to modified metal layer, you can.
It is further preferred that the vacuum degree refers specifically to vacuum degree less than 3 × 10-6Torr。
Above-mentioned technical proposal provides a kind of thin using REBCO as flexible noble metal of the masterplate preparation with optical application potentiality
Film method.REBCO template layers are prepared by pulsed laser deposition (PLD) system in common metal base band, and metal thereon is repaiied
Decorations layer can be realized (such as magnetron sputtering, hot evaporation) by physical vapour deposition (PVD).The surface topography diversity of RBCO can pass through
Change the sedimentary conditions Effective Regulations such as growth temperature, film thickness, have benefited from superconducting thin film growth control technology, in the process film
With very high stable appearance and repeatability.Meanwhile the metal-modified layer of RBCO can also be by changing the side such as sedimentation time
Method is regulated and controled, to obtaining best SERS gain effects.The sample of optimization is to 10-11The R6G of M still has apparent inspection
Signal (close to unimolecule rank) is surveyed, and gain effect is uniformly distributed in sample surfaces.For speed of production and cost performance, this
Present invention is more simple with respect to for superconducting wire, therefore with faster speed of production and lower cost.Also,
Have benefited from function film to be grown in flexible metal substrate, this also allows the SERS substrates of the present invention according in actual use
It needs to be processed into required shape.
The advantages and positive effects of the present invention：
1st, the SERS substrates homogeneity prepared using the present invention is good, and surface topography and granular size, density are continuously adjusted；
2nd, higher using the SERS substrate sensitivity for preparing of the present invention, sample detection limit after optimization is close to unimolecule grade
Not；
3rd, the present invention has metal flexible feature, can meet a variety of application demands, and can be mechanically cut into sample
Required size reduces use cost；
4th, by numerous studies, the industrialization production under accurate control is held for REBCO growth mechanisms and industrialization growing method
Easily realize；
5 at the same the present invention preparation method it is simple, the experiment parameter relative chemical method in growth course is more prone to control
System, industrialization manufacturing cost can be less than 0.5 $/cm2。
Description of the drawings
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon：
The REBCO masterplate sectional views that Fig. 1 is prepared based on IBAD technologies；
Surface topography AFM pictures (10 μm * 10 μm) of Fig. 2 REBCO under condition of different temperatures；
Surface topography AFM pictures (20 μm 20 μm) during Fig. 3 REBCO different-thickness；
The XRD diffraction patterns of Fig. 4 REBCO；
Fig. 5 same samples are to the enhancing effect of various concentration R6G solution；
Fig. 6 different bases are to the enhancing effect of same concentration R6G solution；
Fig. 7 different-thickness substrate is to the enhancing effect of same concentration R6G solution；
The RAM mapping results of Fig. 8 200nm thickness masterplates；
Fig. 9 actual samples.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
It is to be cut in implementation process of the present invention using REBCO coating conductors prepared by IBAD technologies as shown in Figure of description 1
Face figure.It is characterized in that, REBCO is made to be grown on the substrate with certain texture.In the following, the present embodiment is with the technology of the present invention
Implemented under premised on scheme, give detailed embodiment and specific operating process, but protection scope of the present invention
It is not limited to following embodiments.
Embodiment 1
The present embodiment provides a kind of PLD preparation methods for preparing REBCO template layers and metal-modified layer on the metallic substrate,
Include the following steps：
Step 1, preparation of samples；
Step 1.1, by required length grow have orientation buffer layer metal base band take out and cleaned with organic solvent；
Step 1.2, by the cerium oxide substrate base band with biaxial texture, repeatedly winding is arranged on multi-channel laser plating membrane system
In system；
Step 2, Preparatory work of experiment；
Step 2.1 opens equipment, and the REBCO targets and noble metal target material that are prepared through high temperature sintering are attached separately to cavity
In target holder on；
Step 2.2, the distance for adjusting target to base band plated film area are 25cm；
Step 2.3, the Vacuum door for closing coating system, and it is evacuated to 1 × 10-7Torr；
Step 3 starts heater, while rotates REBCO targets, is warming up to required 850 DEG C of growth temperature；
Step 4 closes molecular pump, and oxygen is passed through coating system, and by total gas pressure control to required atmospheric pressure value, such as
200mTorr；
Step 5 starts excimer laser, and laser energy and frequency is raised to needed for REBCO template layer coating process
Value, E=300mJ, f=200Hz；
Step 6, etc. after air pressures, temperature, laser energy, laser frequency stabilization, open laser optical path switch, start laser target
Surface prevapourising process, this process last about greatly 5 minutes；
Step 7, etc. laser evaporations formed ellipsoid plasma stability after, start coating system transmission device, make pre-
First be fixed on the base band in coating system once passed through with the speed of 10m/h by plated film area or with the speed of 50m/h it is mostly logical
Road plated film area；
Step 8 after completing REBCO masterplate layer plated films, closes laser optical path switch, closes heater power source switch, closes
Oxygen gas flowmeter valve opens pumped vacuum systems, gradually reduces organ's device frequency and close excimer laser；
Step 9, device temperature to be heated are reduced to 50 DEG C hereinafter, vacuum degree is less than 1 × 10 simultaneously-7Torr is changed by situ
Target replaces REBCO targets as noble metal target material directly in vacuum chamber；
Step 10 starts excimer laser, and laser energy and frequency is raised to the value needed for metal layer coating process,
E=200mJ, f=50Hz；
Step 11, etc. after temperature, laser energy, laser frequency stabilization, open laser optical path switch, laser evaporations waited to be formed
Ellipsoid plasma stability after, start coating system transmission device, base band is made once to pass through plated film with the speed of 30m/h
Area passes through multichannel plated film area with the speed of 150m/h；
Step 12 after completing metal layer plated film, closes laser optical path switch and gradually reduces organ's device frequency and close accurate divide
Sub- laser；
Step 13 opens nitrogen charging valve, makes to fill air in vacuum chamber to 1 atmospheric pressure, takes out sample and cut into
Required size detects its SERS characteristic.
Embodiment 2
REBCO is prepared with PLD and prepare metal-modified using magnetron sputtering on the metallic substrate the present embodiment provides one kind
The method of layer, includes the following steps：
Step 1, preparation of samples；
Step 1.1, by required length grow have orientation buffer layer metal base band take out and cleaned with organic solvent；
Step 1.2, by the cerium oxide substrate base band with biaxial texture, repeatedly winding is arranged on multi-channel laser plating membrane system
In system；
Step 2, Preparatory work of experiment；
Step 2.1 opens equipment, and the REBCO targets and noble metal target material that are prepared through high temperature sintering are attached separately to cavity
In target holder on；
Step 2.2, the distance for adjusting target to base band plated film area are 5cm；
Step 2.3, the Vacuum door for closing coating system, and it is evacuated to 1 × 10-4Torr；
Step 3 starts heater, while rotates REBCO targets, is warming up to required 650 DEG C of growth temperature；
Step 4 closes molecular pump, and oxygen is passed through coating system, and by total gas pressure control to required atmospheric pressure value, such as
5mTorr；
Step 5 starts excimer laser, and laser energy and frequency is raised to needed for REBCO template layer coating process
Value, E=50mJ, f=1Hz；
Step 6, etc. after air pressures, temperature, laser energy, laser frequency stabilization, open laser optical path switch, start laser target
Surface prevapourising process, this process last about greatly 5 minutes；
Step 7, etc. laser evaporations formed ellipsoid plasma stability after, start coating system transmission device, make pre-
First be fixed on the base band in coating system once passed through with the speed of 5m/h by plated film area or with the speed of 30m/h it is mostly logical
Road plated film area；
Step 8 after completing REBCO masterplate layer plated films, closes laser optical path switch, closes heater power source switch, closes
Oxygen gas flowmeter valve gradually reduces organ's device frequency and closes excimer laser；
Step 9, when temperature is down to below 50 DEG C, open nitrogen charging valve, interior air in vacuum chamber is made to be depressed into one
Atmospheric pressure, takes out sample and repeatedly winding is arranged on multichannel magnetron sputtering coating system by the base band with REBCO template layers
Interior, control vacuum degree is less than 1 × 10-7Torr；
Step 10 is passed through argon gas to build-up of luminance condition is reached, and starting current to build-up of luminance, the power for controlling sputtering is 10W；
Step 11, etc. sputterings stablize after, start coating system transmission device, base band is made once to pass through plating with the speed of 1m/h
Film area passes through multichannel plated film area with the speed of 7m/h；
Step 13 opens nitrogen charging valve, makes to fill air in vacuum chamber to 1 atmospheric pressure, takes out sample and cut into
Required size detects its SERS characteristic；
Embodiment 3
PLD is utilized to prepare REBCO template layers on the metallic substrate and prepares gold with vacuum evaporation the present embodiment provides a kind of
Belong to the method for decorative layer, include the following steps：
Step 1, preparation of samples；
Step 1.1, by required length grow have orientation buffer layer metal base band take out and cleaned with organic solvent；
Step 1.2, by the cerium oxide substrate base band with biaxial texture, repeatedly winding is arranged on multi-channel laser plating membrane system
In system；
Step 2, Preparatory work of experiment；
Step 2.1 opens equipment, and the REBCO targets and noble metal target material that are prepared through high temperature sintering are attached separately to cavity
In target holder on；
Step 2.2, the distance for adjusting target to base band plated film area are 25mm；
Step 2.3, the Vacuum door for closing coating system, and it is evacuated to 1 × 10-6Torr；
Step 3 starts heater, while rotates REBCO targets, is warming up to required 700 DEG C of growth temperature；
Step 4 closes molecular pump, and oxygen is passed through coating system, and by total gas pressure control to required atmospheric pressure value, such as
100mTorr；
Step 5 starts excimer laser, and laser energy and frequency is raised to needed for REBCO template layer coating process
Value, E=200mJ, f=100Hz；
Step 6, etc. after air pressures, temperature, laser energy, laser frequency stabilization, open laser optical path switch, start laser target
Surface prevapourising process, this process last about greatly 5 minutes；
Step 7, etc. laser evaporations formed ellipsoid plasma stability after, start coating system transmission device, make pre-
First be fixed on the base band in coating system once passed through with the speed of 10m/h by plated film area or with the speed of 50m/h it is mostly logical
Road plated film area；
Step 8 after completing REBCO masterplate layer plated films, closes laser optical path switch, closes heater power source switch, closes
Oxygen gas flowmeter valve opens pumped vacuum systems, gradually reduces organ's device frequency and close excimer laser；
Step 9, when temperature is down to below 50 DEG C, open nitrogen charging valve, interior air in vacuum chamber is made to be depressed into one
Atmospheric pressure takes out sample and cuts into required size；
Sample is fixed on specimen holder by step 10, and control vacuum degree is less than 3 × 10-6Torr；Step 11, galvanization will be pre-
The titanium first placed melts, and opens after MASK starts vapor deposition to thickness about 10nm and closes MASK；
The financeization that step 12, galvanization will be pre-placed is opened after MASK starts vapor deposition to thickness about 30nm and is closed
MASK；
Step 13 opens nitrogen charging valve, makes to fill air in vacuum chamber to 1 atmospheric pressure, takes out sample and cut into
Required size detects its SERS characteristic.
Embodiment 4
REBCO is prepared with PLD and prepare metal-modified using magnetron sputtering on the metallic substrate the present embodiment provides one kind
The method of layer, includes the following steps：
Step 1, preparation of samples；
Step 1.1, by required length grow have orientation buffer layer metal base band take out and cleaned with organic solvent；
Step 1.2, by the cerium oxide substrate base band with biaxial texture, repeatedly winding is arranged on multi-channel laser plating membrane system
In system；
Step 2, Preparatory work of experiment；
Step 2.1 opens equipment, and the REBCO targets and noble metal target material that are prepared through high temperature sintering are attached separately to cavity
In target holder on；
Step 2.2, the distance for adjusting target to base band plated film area are 5cm；
Step 2.3, the Vacuum door for closing coating system, and it is evacuated to 1 × 10-4Torr；
Step 3 starts heater, while rotates REBCO targets, is warming up to required 650 DEG C of growth temperature；
Step 4 closes molecular pump, and oxygen is passed through coating system, and by total gas pressure control to required atmospheric pressure value, such as
5mTorr；
Step 5 starts excimer laser, and laser energy and frequency is raised to needed for REBCO template layer coating process
Value, E=50mJ, f=1Hz；
Step 6, etc. after air pressures, temperature, laser energy, laser frequency stabilization, open laser optical path switch, start laser target
Surface prevapourising process, this process last about greatly 5 minutes；
Step 7, etc. laser evaporations formed ellipsoid plasma stability after, start coating system transmission device, make pre-
First be fixed on the base band in coating system once passed through with the speed of 5m/h by plated film area or with the speed of 30m/h it is mostly logical
Road plated film area；
Step 8 after completing REBCO masterplate layer plated films, closes laser optical path switch, closes heater power source switch, closes
Oxygen gas flowmeter valve gradually reduces organ's device frequency and closes excimer laser；
Step 9, when temperature is down to below 50 DEG C, open nitrogen charging valve, interior air in vacuum chamber is made to be depressed into one
Atmospheric pressure, takes out sample and repeatedly winding is arranged on multichannel magnetron sputtering coating system by the base band with REBCO template layers
Interior, control vacuum degree is less than 1 × 10-7Torr；
Step 10 is passed through argon gas to 5mTorr, and starting current to build-up of luminance, the power for controlling sputtering is 1000W；
Step 11, etc. sputterings stablize after, start coating system transmission device, base band is made once to pass through with the speed of 50m/h
Plated film area passes through multichannel plated film area with the speed of 200m/h；
Step 13 opens nitrogen charging valve, makes to fill air in vacuum chamber to 1 atmospheric pressure, takes out sample and cut into
Required size detects its SERS characteristic.
A kind of SERS substrates based on REBCO masterplates are obtained by above-mentioned preparation method, the SERS substrates include REBCO
(R=Y) masterplate layer and the metal-modified layer of REBCO masterplates layer appearance coating；The thickness of the REBCO masterplates layer is in 10-
2000nm is continuously adjusted, and structure is from amorphous to polycrystalline, and a, b axis are orientated and c-axis is orientated or hybrid orientation is arbitrarily adjustable；The metal
Decorative layer is metallic film or metal particle layer；The thickness of the metal-modified layer is 5~200nm.Attached drawing 2 is preparation process
Middle REBCO is in the AFM results of different growth temperature lower surfaces changing features；The XRD measurement results of attached drawing 4 show it with a, c
The characteristics of axis hypertrophy state, surface form the nano-cluster of cylindrical particle；Attached drawing 3 is REBCO moulds under 900 DEG C of set temperatures
Pattern feature of the plate layer in different-thickness, 4 XRD measurement results with reference to the accompanying drawings, with the increase of REBCO template layer thickness,
Its surface particles is gradually grown up, and quantity also gradually becomes more；Sample is immersed in corresponding dense before ram test in attached drawing 6, attached drawing 7
About 10 minutes are spent in solution, later natural air drying, measurement result shows enhancing effect, and it is closely related with REBCO configurations of surface,
And many experiments show it with excellent preparation stability and enhancing homogeneity (attached drawing 8)；Attached drawing 5 is laboratory sample (see figure
9) for 10-11The R6G solution of M still has apparent gain.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. a kind of SERS substrates based on REBCO masterplates, which is characterized in that the SERS substrates include REBCO masterplates layer and institute
State the metal-modified layer of REBCO masterplate layer appearance plating；
Wherein, the thickness of the REBCO masterplates layer is continuously adjusted in 10~2000nm, and structure is from amorphous to polycrystalline, a, b axis orientation
And c-axis is orientated or hybrid orientation is arbitrarily adjustable；
The metal-modified layer is metallic film or metal particle layer；The thickness of the metal-modified layer is 5~200nm.
A kind of 2. preparation method of the SERS substrates according to claim 1 based on REBCO masterplates, which is characterized in that packet
Include following steps：
REBCO targets are warming up to growth temperature, adjust laser energy and frequency by step 1, are passed through oxygen, coating system transmission
Device drives metal base band to pass through plated film area, you can forms REBCO masterplate layers in metal base band buffer-layer surface；
Step 2, REBCO targets are changed to modified metal target in situ, pass through pulsed deposition process, magnetically controlled sputter method or steaming
Electroplating method plates metal decorative layer to get flexible SERS substrates in the REBCO masterplates layer surface.
3. the preparation method of the SERS substrates according to claim 2 based on REBCO masterplates, which is characterized in that step 1
In, the growth temperature is 650~850 DEG C；
The laser energy and frequency are specially：E=50~300mJ, f=1~200Hz；
Before being passed through oxygen, plated film area is vacuum state, and the air pressure of plated film area is 5~200mTorr after being passed through oxygen.
4. the preparation method of the SERS substrates according to claim 2 based on REBCO masterplates, which is characterized in that step 1
In, it is described by once being plated by multichannel by plated film area or with the speed of 30~50m/h with the speed of 5~10m/h
Film area.
5. the preparation method of the SERS substrates according to claim 2 based on REBCO masterplates, which is characterized in that step 2
In, it is described to be specifically included by pulsed deposition process in REBCO masterplates layer surface plating metal decorative layer：Adjust laser energy
And frequency, the metal base band for being coated with REBCO masterplate floor pass through plated film area, you can plate metal on the surface of REBCO masterplate layers and repair
Adorn layer.
6. the preparation method of the SERS substrates according to claim 5 based on REBCO masterplates, which is characterized in that described to swash
Light energy and frequency refer specifically to：E=50~300mJ, f=1~200Hz；
It is described by refer to be coated with the metal base band of REBCO masterplate floor with the speed of 30m/h once by plated film area or with
The speed of 150m/h passes through multichannel plated film area.
7. the preparation method of the SERS substrates according to claim 2 based on REBCO masterplates, which is characterized in that step 2
In, it is described to be specifically included by magnetically controlled sputter method in REBCO masterplates layer surface plating metal decorative layer：REBCO will be coated with
The metal base band winding of masterplate layer is arranged in magnetron sputtering coating system, is passed through argon gas, is controlled sputtering power, be coated with REBCO
The metal base band of masterplate floor passes through multiple tracks plated film area, you can plates metal decorative layer on the surface of REBCO masterplate layers.
8. the preparation method of the SERS substrates according to claim 7 based on REBCO masterplates, which is characterized in that be passed through argon
The air pressure in Qi Hou plated films area should reach build-up of luminance condition；
The sputtering power is specially 10~1000W；
It is described by the metal base band that refers specifically to that REBCO masterplate floor will be coated with the speed of 1~50m/h once by plated film area,
Or multichannel plated film area is passed through with the speed of 7~200m/h.
9. the preparation method of the SERS substrates according to claim 2 based on REBCO masterplates, which is characterized in that step 2
In, it is described to be specifically included by evaporation coating method in REBCO masterplates layer surface plating metal decorative layer：To being coated with REBCO masterplates
The metal base band of layer is cut, is fixed, and adjusts vacuum degree, melts modified metal target, is opened MASK and is deposited to modified metal
Layer, you can.
10. the preparation method of the SERS substrates according to claim 9 based on REBCO masterplates, which is characterized in that described true
Reciprocal of duty cycle refers specifically to vacuum degree less than 3 × 10-6Torr。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610031709.7A CN105671492B (en) | 2016-01-18 | 2016-01-18 | A kind of SERS substrates and preparation method based on REBCO masterplates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610031709.7A CN105671492B (en) | 2016-01-18 | 2016-01-18 | A kind of SERS substrates and preparation method based on REBCO masterplates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105671492A CN105671492A (en) | 2016-06-15 |
| CN105671492B true CN105671492B (en) | 2018-07-03 |
Family
ID=56301304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610031709.7A Active CN105671492B (en) | 2016-01-18 | 2016-01-18 | A kind of SERS substrates and preparation method based on REBCO masterplates |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105671492B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108565067B (en) * | 2018-01-19 | 2019-07-30 | 清华大学深圳研究生院 | Multi-layer compound structure rare earth barium copper oxide superconducting film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101566570A (en) * | 2009-05-27 | 2009-10-28 | 东南大学 | Orderly controllable surface-reinforced Raman scattering active substrate and preparation method thereof |
| CN103033496A (en) * | 2012-12-17 | 2013-04-10 | 南开大学 | Preparation method of large-area surface enhancement raman scattering substrate |
| CN103091983A (en) * | 2013-01-29 | 2013-05-08 | 南京丰强纳米科技有限公司 | Preparation method of surface-enhanced Raman scattering substrate |
-
2016
- 2016-01-18 CN CN201610031709.7A patent/CN105671492B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101566570A (en) * | 2009-05-27 | 2009-10-28 | 东南大学 | Orderly controllable surface-reinforced Raman scattering active substrate and preparation method thereof |
| CN103033496A (en) * | 2012-12-17 | 2013-04-10 | 南开大学 | Preparation method of large-area surface enhancement raman scattering substrate |
| CN103091983A (en) * | 2013-01-29 | 2013-05-08 | 南京丰强纳米科技有限公司 | Preparation method of surface-enhanced Raman scattering substrate |
Non-Patent Citations (1)
| Title |
|---|
| YBCO涂层导体长带与厚膜制备技术及钉扎机制研究;杨坚;《中国博士学位论文全文数据库 工程科技II辑》;20131015;第C042-10页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105671492A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Anthony et al. | Tuning optical band gap of vertically aligned ZnO nanowire arrays grown by homoepitaxial electrodeposition | |
| Manikandan et al. | Zinc oxide epitaxial thin film deposited over carbon on various substrate by pulsed laser deposition technique | |
| Zhuo et al. | Morphology-controlled synthesis, growth mechanism, optical and microwave absorption properties of ZnO nanocombs | |
| Hidalgo et al. | Yttria-stabilized zirconia thin films deposited by pulsed-laser deposition and magnetron sputtering | |
| KR101467118B1 (en) | METHOD OF SYNTHESIZING β??Ga2O3 NANOWIRES USING SPUTTERING TECHNIQUE | |
| Dellasega et al. | Tungsten oxide nanowires grown on amorphous-like tungsten films | |
| Krunks et al. | Zinc oxide thin films by spray pyrolysis method | |
| CN108411267A (en) | A method of preparing free state polyhedron Ag nano particles | |
| Chi et al. | An approach for synthesizing various types of tungsten oxide nanostructure | |
| CN108611613A (en) | A kind of preparation method of nano-multilayered structures carbon-base film | |
| Jiang et al. | Influence of oxygen plasma treatment on the microstructure of SnOx thin films | |
| Goto et al. | Morphology and preferred orientation of Y2O3 film prepared by high-speed laser CVD | |
| CN105671492B (en) | A kind of SERS substrates and preparation method based on REBCO masterplates | |
| Götsch et al. | Preparation and characterization of epitaxially grown unsupported yttria-stabilized zirconia (YSZ) thin films | |
| Kar et al. | Fabrication of ZnO nanostructures of various dimensions using patterned substrates | |
| Iwaya et al. | Atomically resolved surface structure of SrTiO3 (001) thin films grown in step-flow mode by pulsed laser deposition | |
| He et al. | XPS analysis of ZnO thin films obtained by pulsed laser deposition | |
| Wang et al. | Ir coating prepared on Nb substrate by double glow plasma | |
| CN105671485A (en) | CeO2-x nano film based on flexible metal base band and preparation method of CeO2-x nano film based on flexible metal base band | |
| CN108950500A (en) | A kind of preparation method of the nano-pore structure gold electrode based on magnetron sputtering | |
| Ali et al. | Influence of Co loading on structural and morphological properties of Co-doped ZnO thin films grown by pulsed electron beam ablation | |
| Nishimura et al. | Catalyst-free growth of high-quality ZnO nanorods on Si (100) substrate by two-step, off-axis pulsed-laser deposition | |
| KR101413230B1 (en) | Sn-embedded MgO nanorods and method for preparing the same | |
| Abdolrezapour et al. | High optical quality long ultrafine ZnO nanowires by low-temperature oxidation of sputtered nanostructured Zn templates | |
| Parkansky et al. | Growth of ZnO nanorods by air annealing of ZnO films with an applied electric field |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |