CN108330441A - A method of it improving film-substrate cohesion and prepares surface enhanced Raman substrate - Google Patents

A method of it improving film-substrate cohesion and prepares surface enhanced Raman substrate Download PDF

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CN108330441A
CN108330441A CN201810077316.9A CN201810077316A CN108330441A CN 108330441 A CN108330441 A CN 108330441A CN 201810077316 A CN201810077316 A CN 201810077316A CN 108330441 A CN108330441 A CN 108330441A
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substrate
film
enhanced raman
surface enhanced
cohesion
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CN108330441B (en
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张政军
马菱薇
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Guangxi Sanhuan hi tech Raman Chip Technology Co., Ltd
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Tsinghua University
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Abstract

A method of it improving film-substrate cohesion and prepares surface enhanced Raman substrate, this method grows smooth transition zone on substrate base first, Silver nanorod array film is grown on transition zone again, later in one layer of ultra-thin oxidation film of silver surface uniform fold, finally heated above-mentioned composite nanostructure obtains the surface enhanced Raman substrate with excellent film-substrate cohesion.Transition zone alleviates the mismatch factor between noble metal film and substrate, has adjusted stress distribution and atomistic binding within the scope of entire film base.The oxide layer of Silver nanorod very thin ensures that substrate has good SERS sensitivitys and thermal stability.Therefore substrate can be further heated, the diffusion of atom between film and substrate is promoted, reduces interface hole, improves adhesive force.Surface enhanced Raman substrate with excellent film-substrate cohesion is not easily to fall off, and stability is good, is readily transported, stores and uses, to make the practicability of surface enhanced Raman technique enhance.

Description

A method of it improving film-substrate cohesion and prepares surface enhanced Raman substrate
Technical field
The invention belongs to trace materials detection technique field, more particularly to a kind of raising film-substrate cohesion prepares surface enhanced The method of Raman substrate.
Background technology
Surface-enhanced Raman effects (surface-enhanced Raman scattering, SERS) can be by absorption point The Raman scattering signal of son amplifies several orders of magnitude, therefore can be used for the high sensitivity detection of trace materials, has identification of fingerprint Property, the advantages that detection is quick, simple and practicable, selectivity is good and non-destructive testing.
Surface-enhanced Raman effects need the enhancing substrate using the noble metal nanos such as gold, silver structure as high sensitivity, Preparation method includes electrochemical redox method, metal-sol method, masterplate method, self-assembly method, E-beam lithography, angle of inclination Sedimentation etc..When nanoparticle deposition is on surfaces such as silicon chip, glass substrate, organic matter substrates, noble metal film and substrate The binding force of material is often weaker, so that nano thin-film is fallen off from substrate during transporting, using and storing, affects SERS The practical application of substrate greatly limits the development of surface enhanced Raman technique.
Invention content
It is an object of the present invention to overcome above-mentioned the deficiencies in the prior art, a kind of raising film-substrate cohesion is provided and prepares table The method that face enhances Raman substrate.
In order to achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of method that above-mentioned raising film-substrate cohesion prepares surface enhanced Raman substrate, it is characterised in that the method Include the following steps：
1) angle of inclination deposition method is utilized, deposits one layer of smooth transition layer film first on substrate base, then One layer of Silver nanorod array film of regrowth on transition layer film；
2) utilize low temperature ald method in the one layer of ultra-thin oxidation of uniform fold of Silver nanorod array film surface Object film forms the composite nanostructure of oxide cladding；
3) composite nanostructure is heated under conditions of temperature is 150~300 DEG C, you can obtain that there is excellent film The surface enhanced Raman substrate of base junction resultant force.
Substrate base of the present invention uses silicon chip, glass substrate or organic matter substrate.
In above-mentioned technical proposal, transition zone is prepared on substrate base using angle of inclination deposition method in the step 1) The step of film is：At room temperature, the substrate cleaned is fixed on the sample stage of electron beam evaporation deposition machine, by coating machine It is 10 that chamber, which is evacuated to vacuum degree,- 5Pa or less；The angle for adjusting chip bench, it is 0 ° to make the incidence angle of evaporation line, and makes sample stage It is static；Use Ti, Cr, TiN or ZrN for target, deposition rate control existsPrepare smooth transition layer film；It crosses The thickness for crossing layer film is 5~50nm.
The step of preparing Silver nanorod array film using angle of inclination deposition method in step 1) of the present invention be：It adjusts The incidence angle of whole evaporation line is 85 °~88 °, and keeps sample stage static or at the uniform velocity rotate, and grows one on transition layer film surface Layer Silver nanorod array film.The Silver nanorod array film is that tiltedly rod array film or the straight stick array of cylinder are thin for silver Film.
Oxidation is covered on Silver nanorod array film using low temperature ald technology in step 2) of the present invention The step of object is：The Silver nanorod array film prepared is put into the middle part of atomic layer deposition reaction cavity, cavity temperature 50 ~70 DEG C, select Al2O3、TiO2Or HfO2As precursors, alternating is passed through in reaction cavity, by changing atomic layer deposition Product parameter carrys out the thickness of control oxide film；The thickness of sull is preferably 0.5~2nm.
The step of composite nanostructure of step 3) high temperature heated oxide object of the present invention cladding is：By what is prepared Composite nanostructure heats 10~20 minutes in thermal station or annealing furnace.
The present invention has the following advantages and the technique effect of high-lighting：By adding transition zone and high-temperature heating substrate, carry High adhesive force of the Silver nanorod substrate on substrate base, has obtained the surface-enhanced Raman base with excellent film-substrate cohesion Bottom.By selecting suitable buffer layer material and thickness, eliminate the lattice constant of film and substrate base, coefficient of thermal expansion, The difference of the properties such as chemical constitution helps to adjust stress distribution and atomistic binding situation within the scope of entire film base.In Yin Na Rice stick surface covers ultra-thin sull, under the premise of ensureing SERS sensitivity, improves the thermal stability of substrate；Tool There is the substrate of thermal stability through high-temperature heating, the diffusion and interaction of atom between film and substrate is promoted, to reduce boundary Face gap has achieved the purpose that improve substrate adhesion.SERS substrates stability with excellent film-substrate cohesion is good, is transporting It is not easily to fall off during defeated, storage and use, to make the practicability of surface enhanced Raman technique greatly enhance.
Description of the drawings
Fig. 1 a are the scanning electron microscope of the Ag nanometer rods substrate (Ti-AgNRs substrates) for having Ti transition zones prepared in embodiment 1 Photo；Fig. 1 b depict 1 × 10-6The Raman light that M methylene blues molecule measures in Ag nanometer rods substrate and Ti-AgNRs substrates Spectrum；Fig. 1 c are the cut pattern of AgNRs substrates and Ti-AgNRs substrates under an optical microscope.
Fig. 2 covers Al for what is prepared in embodiment 22O3Ag nanometer stick arrays substrate (AgNRs@Al2O3)、Ti- AgNRs@Al2O3And the Ti-AgNRs@Al after 200 DEG C of heating2O3The cut pattern of substrate under an optical microscope.
Fig. 3 a, Fig. 3 b are respectively the TiN-AgNRs@HfO after the Ag nanometer rods substrate prepared in embodiment 3 and heating2Base Macro morphology of the bottom after ultrasonic 3min；Fig. 3 c are the TiN-AgNRs@HfO after heating2Substrate is microcosmic after ultrasonic 15min Pattern；Fig. 3 d are the TiN-AgNRs@HfO after heating2SERS spectra of the substrate before and after ultrasound, probe molecule are 1 × 10-6M is sub- Methyl blue.
Specific implementation mode
It is provided by the invention it is a kind of improve the film-substrate cohesion method for preparing surface enhanced Raman substrate, it is specific it is awkward-sounding such as Lower step：
1) one layer of smooth transition layer film is deposited on substrate base using angle of inclination deposition method first, deposited Method is at room temperature, the substrate cleaned to be fixed on the sample stage of electron beam evaporation deposition machine, and coating machine chamber is taken out It is 10 to vacuum degree- 5Pa or less；The angle for adjusting chip bench, it is 0 ° to make the incidence angle of evaporation line, and keeps sample stage static； Use Ti, Cr, TiN or ZrN for target, deposition rate control existsPrepare smooth transition layer film；The transition zone The thickness of film is generally 5~50nm.Transition zone alleviates the lattice constants of Ag films and substrate, coefficient of thermal expansion, chemistry knot The difference of the properties such as structure, to adjust the stress distribution and atomistic binding situation within the scope of entire film base.
2) the good Silver nanorod array film of discreteness is grown on transition layer film, prepares Silver nanorod array film The step of be：The incidence angle of adjustment evaporation line is 85 °~88 °, and keeps sample stage static or at the uniform velocity rotate, in transition layer film Surface grows one layer of Silver nanorod array film.The Silver nanorod array film is that tiltedly rod array film or cylinder are straight for silver Rod array film.The oxidation film of Silver nanorod very thin ensure that substrate has good SERS sensitivitys and thermostabilization Property；
3) utilize low temperature ald technology in one layer of ultra-thin oxidation film of Silver nanorod surface uniform deposition, in silver The step of covering oxide, is on nano-stick array thin film：It is anti-that the Silver nanorod array film prepared is put into atomic layer deposition It answers in the middle part of cavity, cavity temperature is 50~70 DEG C, selects Al2O3、TiO2Or HfO2As precursors, alternating is passed through reaction In cavity, by changing atomic layer deposition parameter come the thickness of control oxide film, the composite Nano of oxide cladding is formed The thickness of structure, sull is preferably 0.5~2nm；
4) composite nanostructure prepared is heated 10~20 minutes in thermal station or annealing furnace, heating temperature is 150 Between~300 DEG C.By further heating substrate, promotes the diffusion and interaction of atom between film and substrate, reduce interface Hole achievees the purpose that improve substrate adhesion.SERS substrates with excellent film-substrate cohesion are not easily to fall off, and stability is good, It is readily transported, stores and uses, improve the practicability of surface enhanced Raman technique.
The present invention is illustrated with reference to the accompanying drawings and examples.Following embodiments are illustrative, are not limits Qualitatively, protection scope of the present invention cannot be limited with following embodiments.
Embodiment 1
1) substrates such as silicon chip, glass acetone, alcohol, deionized water sequence are cleaned by ultrasonic and are dried by；
2) clean substrate is fixed on the sample stage of electron beam evaporation deposition machine by, and the chamber of coating machine is evacuated to very Reciprocal of duty cycle is 10- 5Pa magnitudes；
3) uses metal Ti for target, and transition layer film is coated on substrate base, and the incident angle for adjusting electron beam is 0 °, the evaporation rate of Ti isDeposition thickness is 15nm；
4) uses metal Ag for target, and Ag nano-stick array thin films are coated on transition zone, adjusts the incidence angle of electron beam To 85 °, and keep sample stage static, tilts the oblique rod array film of silver nanoparticle that growing nano-rod length is 700nm；
5) evaluates the film-substrate cohesion of film using the method for nano impress, and a diamond pressure is used in measurement process Head is slided in film surface, and continues to increase vertical load；When load reaches critical value, film scratched completely and start from It is removed on substrate, which can reflect the film-substrate cohesion of structure.In conjunction with the breakage of optical microphotograph sem observation cut With the degree of peeling, comprehensive descision goes out the binding performance of film layer.What film-substrate cohesion measured is preloaded as 0.3mN, and Ending Load is 10mN, loading velocity 19.4mN/min, cut speed are 200 μm/min.
6) utilizes 1 × 10-6M methylene blue characterization of molecules Ag nanometer rods substrates and the Ag nanometer rods substrates for having Ti transition zones The SERS performances of (Ti-AgNRs substrates), the soaking time of substrate in the solution are 30min.
The stereoscan photograph of prepared Ti-AgNRs substrates is as shown in Figure 1a, it is seen that ultra-thin and smooth Ti transition zones The pattern of Ag nanometer stick arrays is not influenced, and AgNRs discreteness is good, a diameter of 40-50nm.Fig. 1 b depict 1 × 10-6M methylenes The Raman spectrum that base cyan molecule measures in Ag nanometer rods substrate and Ti-AgNRs substrates, it is seen that MB molecules are in two kinds of substrates Signal strength differences are little, in addition in Ti-AgNRs substrates it is slightly good.This is because Ti transition zones do not influence Ag nanometer rods Pattern, while the reflection of light can be increased, help to improve the SERS sensitivity of substrate.
Fig. 1 c are the cut pattern of AgNRs substrates and Ti-AgNRs substrates under an optical microscope.Ag nano-rod films Cut is wider, apparent damaged and peeling phenomenon occurs.The critical load of substrate is 2.39mN, and binding force is very poor.If in life One layer of Ti transition zone is first deposited before long Ag nanometer rods on silicon chip, then the adhesive force of substrate makes moderate progress.Ti-AgNRs films Breakdown point delay, illustrate that critical load increases, be 2.85mN, and cut narrows, and peeling is alleviated.Result above is said Bright, increasing Ti transition zones helps to improve the mismatch factor between film and substrate, and film-substrate cohesion is made to enhance.
Embodiment 2
1) substrates such as silicon chip, glass acetone, alcohol, deionized water sequence are cleaned by ultrasonic and are dried by；
2) clean substrate is fixed on the sample stage of electron beam evaporation deposition machine by, and the chamber of coating machine is evacuated to very Reciprocal of duty cycle is 10- 5Pa magnitudes；
3) uses metal Ti for target, and transition layer film is coated on substrate base, and the incident angle for adjusting electron beam is 0 °, the evaporation rate of Ti isDeposition thickness is 25nm；
4) uses metal Ag for target, and Ag nano-stick array thin films are coated on transition zone, adjusts the incidence angle of electron beam To 86 °, and keep sample stage static, tilts the oblique rod array film of silver nanoparticle that growing nano-rod length is 800nm；
5) utilizes low temperature ald technology, and the reaction chamber temperature that atomic layer deposition is arranged is 50 DEG C, is there is Ti transition One layer of ultra-thin Al of Silver nanorod array substrate surface uniform deposition of layer2O3Film obtains Ti-AgNRs@Al2O3Structure, wherein Al2O3The thickness of film about 0.8nm；Simultaneously identical Al is deposited in the Silver nanorod array surface of no Ti transition zones2O3Film is made For comparison, it is denoted as AgNRs@Al2O3Substrate；
6) the Ti-AgNRs@Al for preparing step 52O3Substrate heats 10 minutes in thermal station, and heating temperature is 200 DEG C.
7) evaluates AgNRs@Al using the method for nano impress2O3、Ti-AgNRs@Al2O3And the Ti- after 200 DEG C of heating AgNRs@Al2O3The film-substrate cohesion of substrate.It is preloaded as 0.3mN, Ending Load 10mN, loading velocity 19.4mN/min, Cut speed is 200 μm/min.
Fig. 2 is AgNRs@Al2O3、Ti-AgNRs@Al2O3And the Ti-AgNRs@Al after 200 DEG C of heating2O3Substrate is in optics Cut pattern under microscope.AgNRs@Al2O3The film-substrate cohesion of substrate is not obviously improved compared to Ag nanometer rods substrate, The cut of substrate is wider and peels off serious, critical load 2.55mN.And Ti-AgNRs@Al2O3The binding force of structure has obviously It is promoted, obtained cut is regular, and film-substrate cohesion reaches 3.54mN.This is mainly due in atomic layer deposition process, reaction chamber Heating promote contacts and interaction of the Ti with substrate, Ti with Ag, and Al2O3There is certain protective effect to substrate, from And improve Ti-AgNRs@Al2O3The adhesive force of substrate.
In order to further increase film-substrate cohesion, by Ti-AgNRs@Al2O3Substrate is placed in thermal station and heats.It can be seen that after heating The cut of substrate shortens, narrows, and uniformity is good, shows excellent film-substrate cohesion, reaches 5.40mN, is received compared to pure Ag Rice stick substrate improves about 2.3 times.
Embodiment 3
1) substrates such as silicon chip, glass acetone, alcohol, deionized water sequence are cleaned by ultrasonic and are dried by；
2) clean substrate is fixed on the sample stage of electron beam evaporation deposition machine by, and the chamber of coating machine is evacuated to very Reciprocal of duty cycle is 10- 5Pa magnitudes；
3) uses metal TiN for target, and transition layer film is coated on substrate base, adjusts the incident angle of electron beam It it is 0 °, the evaporation rate of TiN isDeposition thickness is 40nm；
4) uses metal Ag for target, and Ag nano-stick array thin films are coated on transition zone, adjusts the incidence angle of electron beam To 87 °, and keep sample stage static, tilts the oblique rod array film of silver nanoparticle that growing nano-rod length is 900nm；
5) utilizes low temperature ald technology, and the reaction chamber temperature that atomic layer deposition is arranged is 70 DEG C, is there is TiN mistakes Cross one layer of ultra-thin HfO of Silver nanorod array substrate surface uniform deposition of layer2Film obtains TiN-AgNRs@HfO2Structure, wherein HfO2The thickness of film about 1.4nm；
6) the TiN-AgNRs@HfO for preparing step 52Substrate heats 20 minutes in thermal station, and heating temperature is 300 DEG C.
7) substrate is put into the beaker equipped with water by, is put into ultrasound in ultrasonic instrument, carrys out simulated substrate in transport, use Oscillation phenomenon in the process.
8) is with 1 × 10-6The aqueous solution characterization TiN-AgNRs@HfO of M methylene blue molecules2Substrate is before and after ultrasound SERS performances, the soaking time of substrate in the solution are 30min.
Fig. 3 a and 3b are the TiN-AgNRs@HfO after the Ag nanometer rods substrate grown on silicon chip and heating respectively2Substrate Macro morphology after ultrasonic 3min.Ag nanometer rods substrate is due to weaker film-substrate cohesion, and the Ag of ultrasonic rear surface is substantially completely It is detached from, exposes a large amount of surfaces Si；TiN-AgNRs@HfO after heating2Stability of the substrate under ultrasound environments significantly improves, There is no apparent Ag obscissions.Illustrate the film base junction of transition zone and high-temperature heating to raising Ag nanometer stick arrays and substrate base Resultant force has apparent facilitation.
From microscopic appearance and SERS performances (Fig. 3 c and 3d), the TiN-AgNRs@HfO after 300 DEG C of heating2Substrate exists Change without apparent pattern after ultrasonic 15min, the SERS property retentions before and after ultrasound are stablized.After ultrasonic 30min, have a small amount of Ag nanometer rods are collapsed, and SERS performances is caused slightly to decline.The above result shows that the TiN-AgNRs@HfO after high-temperature heating2Substrate With good film-substrate cohesion, the stability of substrate in actual use ensure that.

Claims (9)

1. a kind of method for improving film-substrate cohesion and preparing surface enhanced Raman substrate, it is characterised in that this method includes following step Suddenly：
1) angle of inclination deposition method is utilized, one layer of smooth transition layer film is deposited first on substrate base, then in mistake Cross one layer of Silver nanorod array film of regrowth on layer film；
2) utilize low temperature ald method thin in Silver nanorod array film surface one layer of ultra-thin oxide of uniform fold Film forms the composite nanostructure of oxide cladding；
3) composite nanostructure is heated under conditions of temperature is 150~300 DEG C, you can obtain that there is excellent film base junction The surface enhanced Raman substrate of resultant force.
2. a kind of method for improving film-substrate cohesion and preparing surface enhanced Raman substrate as described in claim 1, feature exist In：The substrate base uses silicon chip, glass substrate or organic matter substrate.
3. a kind of method for improving film-substrate cohesion and preparing surface enhanced Raman substrate as described in claim 1, feature exist In：It is the step of preparing transition layer film on substrate base using angle of inclination deposition method in step 1)：At room temperature, will The substrate cleaned is fixed on the sample stage of electron beam evaporation deposition machine, and it is 10 that coating machine chamber, which is evacuated to vacuum degree,- 5Pa with Under；The angle for adjusting chip bench, it is 0 ° to make the incidence angle of evaporation line, and keeps sample stage static；Using Ti, Cr, TiN or ZrN For target, deposition rate control existsPrepare smooth transition layer film.
4. a kind of method for improving film-substrate cohesion and preparing surface enhanced Raman substrate as claimed in claim 1,2 or 3, special Sign is：The thickness of the transition layer film is in 5~50nm.
5. a kind of preparation method of surface enhanced Raman substrate improving film-substrate cohesion as described in claim 1, feature It is：The step of preparing Silver nanorod array film using angle of inclination deposition method in step 1) be：Adjustment evaporation line Incidence angle is 85 °~88 °, and keeps sample stage static or at the uniform velocity rotate, and grows one layer of Silver nanorod battle array on transition layer film surface Row film.
6. the method that a kind of raising film-substrate cohesion as described in claim 1,2 or 5 prepares surface enhanced Raman substrate, special Sign is：The Silver nanorod array film is silver tiltedly rod array film or the straight rod array film of cylinder.
7. a kind of method for improving film-substrate cohesion and preparing surface enhanced Raman substrate as described in claim 1, feature exist In：It is the step of covering oxide on Silver nanorod array film using low temperature ald method in step 2)：It will system The Silver nanorod array film got ready is put into atomic layer deposition reaction cavity, and cavity temperature is 50~70 DEG C, selects Al2O3、 TiO2Or HfO2As precursors, alternating is passed through in reaction cavity, by changing atomic layer deposition parameter come control oxide The thickness of film.
8. a kind of method for improving film-substrate cohesion and preparing surface enhanced Raman substrate as claimed in claim 1 or 7, feature It is, the thickness of sull is 0.5~2nm.
9. a kind of method for improving film-substrate cohesion and preparing surface enhanced Raman substrate as described in claim 1, feature exist In：The composite nanostructure prepared is heated 10~20 minutes in thermal station or annealing furnace in step 3).
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110468376A (en) * 2019-08-27 2019-11-19 吉林大学 A kind of carbon-coated Silver nanorod array and its preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103439308A (en) * 2013-06-25 2013-12-11 复旦大学 Surface-enhanced Raman substrate and preparation method thereof
CN104789939A (en) * 2015-03-17 2015-07-22 清华大学 Surface enhanced Raman scattering substrate and production method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103439308A (en) * 2013-06-25 2013-12-11 复旦大学 Surface-enhanced Raman substrate and preparation method thereof
CN104789939A (en) * 2015-03-17 2015-07-22 清华大学 Surface enhanced Raman scattering substrate and production method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110468376A (en) * 2019-08-27 2019-11-19 吉林大学 A kind of carbon-coated Silver nanorod array and its preparation method and application

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