CN106979943A - High-sensitivity surface strengthens the preparation method of Raman scattering substrate - Google Patents
High-sensitivity surface strengthens the preparation method of Raman scattering substrate Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 32
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 40
- 239000004065 semiconductor Substances 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 9
- 230000002708 enhancing effect Effects 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims description 13
- 238000005468 ion implantation Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 5
- 229910003081 TiO2−x Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims 3
- 238000001514 detection method Methods 0.000 abstract description 19
- 230000035945 sensitivity Effects 0.000 abstract description 13
- 238000010884 ion-beam technique Methods 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000001965 increasing effect Effects 0.000 abstract description 3
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- 230000035800 maturation Effects 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
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- 238000011105 stabilization Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 49
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 20
- 238000001237 Raman spectrum Methods 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000006698 induction Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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Abstract
The invention discloses the preparation method that a kind of high-sensitivity surface strengthens Raman scattering substrate, belong to for spectroscopic molecular detection materials application field, this method introduces a series of Lacking oxygen energy levels using ion beam irradiation method in semiconductor forbidden band, so as to add the transfer efficiency of transmission of the photoexcited charge in semiconductor energy gap between energy level and the molecular entergy level matched, the Raman signal intensity of detectable substance molecule is drastically increased；Ion beam irradiation is combined with vacuum annealing process and further increases Molecular Raman signal intensity, obtains the maximum sensitivity in the current international all semi-conducting materials reported, it might even be possible to comparable with the precious metal material performance without focus.Sharpest edges of the inventive method compared with other preparation methods are technology maturation, it is adapted to industrialized production, prepared by the large area that can carry out high sensitivity nonmetallic surface enhancing Raman scattering substrate material, in addition, the product price prepared is cheap and detection signal stabilization is homogeneous.
Description
Technical field
The invention belongs to spectral detection Material Field, and in particular to combine the mode of heat treatment to prepare richness to ion implanting
The WO of oxygen-containing vacancy3-x、TiO2-xAnd ZnO1-xSurface enhanced Raman scattering substrate.
Background technology
SERS technology is as a kind of very quick and high spectrum detection technique of sensitivity, in analysisization
Learn, catalysis, the various fields such as biochemistry detection have very big application potential.Strong surface enhanced Raman scattering effect is high
The guarantee of detection sensitivity, and strong surface enhanced Raman scattering effect is produced, base material is crucial.
The base material of current main flow is noble metal, such as gold, silver, copper.However, noble metal base material is present
The shortcoming of its practical application is seriously restricted, such as cost is high, and stability is poor, and bio-compatibility is poor, not reproducible to utilize.Grind recently
Studying carefully discovery semi-conducting material also has surface enhanced Raman scattering effect, such as TiO2, WO3, ZnO, its surface-enhanced Raman dissipate
Penetrate effect and come from electric charge transfer between substrate and detection molecules.These semi-conducting materials are by inexpensively, and high stability is excellent
Bio-compatibility compensate for the defect of noble metal base material well.In addition, semiconductor base materials are also in semiconductor gold
Belong to Interface Study, have its unique advantage in terms of analyzing inorganic matter, metal ion.Therefore, semiconductor base materials are considered as
There is very much the surface enhanced Raman scattering substrate material of development potentiality.But the surface-enhanced Raman of semiconductor base materials dissipates at present
Penetrate effect still poor compared to noble metal, it is necessary to further improve.
The Lacking oxygen for regulating and controlling metal oxide semiconductor material is a kind of highly effective improvement means, and it can be in forbidden band
Middle introducing intermediate level, significantly improves semiconductor and detectable substance intermolecular charge transfer efficiency.The chemical preparation process reported
There is step complicated, concentration controls poor, the shortcomings of yielding poorly.Ion beam technology, can as a kind of ripe industrial doping techniques
To more precisely control vacancy concentration by regulating and controlling the parameters such as ion energy, dosage, base reservoir temperature, and meet large area production
Need.With reference to vacuum annealing technique, the unfavorable damage that injection is produced can be preferably eliminated, crystallinity is improved, and retain big
Partly favourable Lacking oxygen, so as to activate Lacking oxygen to a greater extent.In addition, ion beam technology can prepare and regulate and control nano surface
Structure, nanostructured can improve molecule load capacity, be conducive to strengthening Raman scattering intensities.
The content of the invention
Dissipated it is an object of the invention to provide a kind of oxide semiconductor surface-enhanced Raman of large area high detection sensitivity
Penetrate the preparation method of substrate.
The technical scheme for realizing the object of the invention is to use ion irradiation and carry out the side of later stage vacuum environment heat treatment
Method is that abundant Lacking oxygen, included specific preparation process are formed close to material surface area is as follows：
1) using oxide semiconductor as raw material, using ion implantation apparatus by energy 10-200keV, dosage 1 × 1016-2×
1017ions/cm2Ion pair oxide semiconductor thin-film irradiated, make its material surface and it is internal in produce it is abundant
Lacking oxygen；
2) sample after irradiation is annealed 1-3 hours for 300-700 DEG C under vacuum, vacuum pressure is less than 2 × 10- 4Pa, repairs the damage that ion beam is caused, film is reached higher crystallinity.
Above-mentioned steps 1) in, it is WO as the oxide semiconductor of raw material3、TiO2, it is any in ZnO.
Above-mentioned steps 1) in, the ion irradiated to oxide semiconductor thin-film is Ar+Ion or N+Ion.
Preferably, high-crystallinity is prepared using the method that thermal anneal process under vacuum condition is carried out after ion irradiation
The WO rich in Lacking oxygen3-xSurface enhanced Raman scattering substrate, included specific preparation process is as follows：
1) with WO3Film is raw material, using ion implantation apparatus by energy 130-190keV, dosage 3 × 1016-1×
1017ions/cm2Ar+Ion or N+Ion irradiation is to WO3Film, makes it produce abundant Lacking oxygen in material surface；
2) by the WO after irradiation3Film is warming up to 400-600 DEG C, then under vacuum insulation annealing 1-3 hours, it
Temperature fall afterwards, vacuum pressure is less than 2 × 10-4Pa, makes film reach higher crystallinity, and the damage that ion beam is caused is eliminated as far as possible
Wound, such as amorphous area, metal gap atom etc..
Preferably, high-crystallinity is prepared using the method that thermal anneal process under vacuum condition is carried out after ion irradiation
The TiO rich in Lacking oxygen2-xSurface enhanced Raman scattering substrate, included specific preparation process is as follows：
1) with TiO2Film is raw material, using ion implantation apparatus by energy be 30-60keV, dosage be 5 × 1016-1.5
×1017ions/cm2Ar+Ion or N+Ion irradiation is to TiO2Monocrystalline；Using Ar+Ion irradiation, makes it in material surface
Produce abundant Lacking oxygen；Using N+Ion irradiation, except introducing Lacking oxygen energy level in material surface, also introduces azepine mass-energy
Level and nanostructured；
2) by the TiO after irradiation2Monocrystalline is warming up to 400-600 DEG C, then under vacuum insulation annealing 1-3 hours,
Temperature fall afterwards, vacuum pressure is less than 2 × 10-4Pa, makes film reach higher crystallinity, eliminates what ion beam was caused as far as possible
Damage, such as amorphous area, metal gap atom etc..
Preferably, high-crystallinity is prepared using the method that thermal anneal process under vacuum condition is carried out after ion irradiation
The ZnO rich in Lacking oxygen1-xSurface enhanced Raman scattering substrate, included specific preparation process is as follows：
1), will be by energy 130-190keV, dosage 5 × 10 using ion implantation apparatus using ZnO film as raw material16-1.5×
1017ions/cm2Ar+Ion or N+Ion irradiation makes it produce abundant Lacking oxygen in material surface to ZnO film；
2) ZnO film after irradiation is warming up to 400-600 DEG C, then under vacuum insulation annealing 1-3 hours, it
Temperature fall afterwards, vacuum pressure is less than 2 × 10-4Pa, makes film reach higher crystallinity, and the damage that ion beam is caused is eliminated as far as possible
Wound, such as amorphous area, metal gap atom etc..
The WO rich in Lacking oxygen that the present invention is prepared using the method for ion irradiation combination thermal annealing3-x、ZnO1-x、TiO2-x
Surface enhanced Raman scattering substrate material has several advantages, is mainly manifested in：First, the implanter for irradiation is industrial life
The implanter of production.It can realize prepared by the large area of nonmetallic surface enhancing Raman scattering substrate material.Second, to annealing furnace
Equipment requirement is simple, and common annealing furnace can.3rd, the preparation process of whole base material is simple, it is thus only necessary to ion spoke
According to just can be with two processes of thermal annealing.4th, it can produce high concentration room using ion irradiation.5th, the Lacking oxygen of preparation
Doping type WO3-x、ZnO1-x、TiO2-xBase material sensitivity is high, and minimal detectable concentration is 10-7~10-8Mol/L, reaches even
Surmount the maximum sensitivity for the semi-conducting material currently reported, and than the noble metal for intending no focus, in addition, signal
Stability is good, and uniformity is high.
Brief description of the drawings
Fig. 1 (a) is in original WO3Loading concentrations are 1 × 10 on film-1With 1 × 10-2After mol/L rhodamine 6G molecules
Raman spectrum.
It is being 50keV using energy that Fig. 1 (b), which is, and dosage is 1 × 1017ions/cm2Ar+After ion irradiation, in vacuum
The WO annealed 1 hour in annealing furnace under 500 DEG C of environment3Loading concentrations are 1 × 10 on film-6、1×10-7With 5 × 10-8mol/
Raman spectrum after L rhodamine 6G molecules.(correspondence embodiment 1)
Fig. 2 (a) is in original TiO2Loading concentrations are 1 × 10 on monocrystalline-2With 1 × 10-3After mol/L rhodamine 6G molecules
Raman spectrum.
It is being 50keV using energy that Fig. 2 (b), which is, and dosage is 1 × 1017ions/cm2Ar+After ion irradiation, in vacuum
The TiO annealed 1 hour in annealing furnace under 500 DEG C of environment2Loading concentrations are 1 × 10 on monocrystalline-6、1×10-7With 5 × 10- 8Raman spectrum after mol/L rhodamine 6G molecules.(correspondence embodiment 2)
It is being 45keV using energy that Fig. 2 (c), which is, and dosage is 1 × 1017ions/cm2N+After ion irradiation, in vacuum
The TiO annealed 1 hour in annealing furnace under 500 DEG C of environment2Loading concentrations are 1 × 10 on monocrystalline-6、1×10-7、5×10-8With 1
×10-8Raman spectrum after mol/L rhodamine 6G molecules.(correspondence embodiment 3)
It is being 190keV using energy that Fig. 3, which is, and dosage is 6 × 1016ions/cm2Ar+After ion irradiation, in vacuum 400
Loading concentrations are 1 × 10 on the ZnO film of annealing 1 hour in annealing furnace under DEG C environment-4、1×10-5、1×10-6With 1 × 10- 7Mol/L rhodamine 6G molecules, and loading concentrations are 1 × 10 on original ZnO film-4Drawing after mol/L rhodamine 6G molecules
Graceful spectrum.(correspondence embodiment 4)
It is being 130keV using energy that Fig. 4, which is, and dosage is 1 × 1017ions/cm2Ar+After ion irradiation, in vacuum 500
The WO of annealing 1 hour in annealing furnace under DEG C environment3Loading concentrations are 1 × 10 on film-6Drawing after mol/L rhodamine 6G molecules
Graceful spectrum.(correspondence embodiment 5)
It is being 190keV using energy that Fig. 5, which is, and dosage is 1 × 1016, 3 × 1016, 6 × 1017, 1 × 1017ions/cm2's
Ar+After ion irradiation, the WO annealed 1 hour in the annealing furnace under 500 DEG C of environment of vacuum3Loading concentrations are 1 × 10 on film- 6Raman spectrum after mol/L rhodamine 6G molecules.(correspondence embodiment 6)
Embodiment
The present invention is further illustrated with reference to embodiment.
Embodiment 1
WO is deposited on a quartz substrate first with superhigh vacuum magnetron sputtering instrument (ULVAC ACS-400)3Film, substrate
400 DEG C of heating, deposit thickness is 70nm, the 200kV ion implantings then produced with Zhongkexin Electronic Equipment Co., Ltd., Beijing
Machine is by Ar+Ion irradiation is on film, and ion energy is 190keV, and dosage is 1 × 1017ions/cm2。
Then irradiation sample is annealed in conventional tube annealing furnace under vacuum environment, vacuum pressure is<2×10-4Pa is right
In the WO of irradiation3, annealing temperature is 500 DEG C, holding 1 hour, afterwards Temperature fall.
Embodiment 2
Energy is 50keV, dosage 1 by the 200kV ion implantation apparatuses produced with Zhongkexin Electronic Equipment Co., Ltd., Beijing
×1017ions/cm2Ar+Ion irradiation is to TiO2Monocrystalline.
Then all irradiation samples are annealed in conventional tube annealing furnace under vacuum environment, vacuum pressure is<2×10- 4Pa, for the TiO of irradiation2, annealing temperature is 500 DEG C, holding 1 hour, afterwards Temperature fall.
Embodiment 3
Using Kaufman ion source implanter by 45keV, dosage 1 × 1017ions/cm2N+Ion irradiation is to TiO2It is single
It is brilliant.
Then all irradiation samples are annealed in conventional tube annealing furnace under vacuum environment, vacuum pressure is<2×10- 4Pa, for the TiO of irradiation2, annealing temperature is 500 DEG C, holding 1 hour, afterwards Temperature fall.
Embodiment 4
ZnO film, substrate heating are deposited on a quartz substrate using superhigh vacuum magnetron sputtering instrument (ULVAC ACS-400)
200 DEG C, deposit thickness is 90nm, and the 200kV ion implantation apparatuses then produced with Zhongkexin Electronic Equipment Co., Ltd., Beijing will
Ar+Ion irradiation is on film, and ion energy is 190keV, and dosage is 6 × 1016ions/cm2。
Then all irradiation samples are annealed in conventional tube annealing furnace under vacuum environment, vacuum pressure is<2×10- 4Pa, for the ZnO of irradiation, annealing temperature is 400 DEG C, holding 1 hour, afterwards Temperature fall.
Embodiment 5
WO is deposited on a quartz substrate first with superhigh vacuum magnetron sputtering instrument (ULVAC ACS-400)3Film, substrate
400 DEG C of heating, deposit thickness is 70nm, the 200kV ion implantings then produced with Zhongkexin Electronic Equipment Co., Ltd., Beijing
Machine is by Ar+Ion irradiation is on film, and ion energy is 130keV, and dosage is 1 × 1017ions/cm2。
Then irradiation sample is annealed in conventional tube annealing furnace under vacuum environment, vacuum pressure is<2×10-4Pa is right
In the WO of irradiation3, annealing temperature is 500 DEG C, holding 1 hour, afterwards Temperature fall.
Embodiment 6
WO is deposited on a quartz substrate first with superhigh vacuum magnetron sputtering instrument (ULVAC ACS-400)3Film, substrate
400 DEG C of heating, deposit thickness is 70nm, the 200kV ion implantings then produced with Zhongkexin Electronic Equipment Co., Ltd., Beijing
Machine is by Ar+Ion irradiation is on film, and ion energy is 190keV, and dosage is respectively 1 × 1016, 3 × 1016, 6 × 1017, 1 ×
1017ions/cm2。
Then all irradiation samples are annealed in conventional tube annealing furnace under vacuum environment, vacuum pressure is<2×10- 4Pa, for the WO of irradiation3, annealing temperature is 500 DEG C, holding 1 hour, afterwards Temperature fall.
Sample prepared by embodiment 1,2,4 is analyzed, table 1 is referred to：
The resistivity contrasts of the primary sample of table 1 and sample after ion irradiation and vacuum annealing
For WO3、TiO2, ZnO, their resistivity have dropped 6 respectively, 7,5 orders of magnitude, and this is mainly attributed to ion
It is radiation-induced to generate Lacking oxygen donor level.
Fig. 1 is the Raman spectrum using rhodamine 6G molecule as probe test, appear in 612,713,1360,1650cm-1Deng
The Raman band of position belongs to rhodamine 6G molecule.Original WO3The detectable limit of film is~10-1Mol/L, after irradiation and vacuum
The WO of annealing3The thin film testing limit has reached~10-7Mol/L, its detection sensitivity improves 6 orders of magnitude, this main attribution
The Lacking oxygen donor level produced is induced to enrich energy level in forbidden band for ion irradiation, so as to improve electric between molecule and semiconductor
Lotus efficiency of transmission, enhances Raman scattering of molecule intensity.
Fig. 2 is the Raman spectrum using rhodamine 6G molecule as probe test.Original TiO2Monocrystalline is examined to rhodamine 6G molecule
It is~10 to survey the limit-2Mol/L, Ar+Irradiate and the TiO after vacuum annealing2Monocrystalline reaches to the rhodamine 6G Molecular Detection limit
~10-7Mol/L, N+Irradiate and the TiO after vacuum annealing2Monocrystalline has reached~10 to the rhodamine 6G Molecular Detection limit-8mol/
5 and 6 orders of magnitude have been respectively increased in the detection sensitivity of two kinds of substrates after L, radiation modification, and this is mainly attributed to ion irradiation
The Lacking oxygen donor level that induction is produced enriches energy level in forbidden band, so as to improve electric charge transmission effect between molecule and semiconductor
Rate, enhances Raman scattering of molecule intensity.For N+Irradiate and the TiO after vacuum annealing2Single crystal samples, its detection sensitivity is
Highest, this is probably due to N+Irradiation also achieves nitrogen-doping, further enriched in forbidden band except introducing Lacking oxygen
Energy level, so as to improve charge transfer efficiency between molecule and semiconductor, enhances Raman scattering of molecule intensity.
Fig. 3 is the Raman spectrum using rhodamine 6G molecule as probe test, Ar+After irradiation and vacuum annealing ZnO to sieve
The red bright 6G Molecular Detections limit has reached~10-7Mol/L, its detection sensitivity improves at least three order of magnitude, this main attribution
The Lacking oxygen donor level produced is induced to enrich energy level in forbidden band for ion irradiation, so as to improve electric between molecule and semiconductor
Lotus efficiency of transmission, enhances Raman scattering of molecule intensity.
Fig. 4 is the Raman spectrum using rhodamine 6G molecule as probe test, by energy be 130keV, dosage be 1 ×
1017ions/cm2Ar+After irradiation and vacuum annealing WO3~10 have been reached to the rhodamine 6G Molecular Detection limit-6Mol/L,
Its detection sensitivity improves at least five order of magnitude, and this is mainly attributed to the Lacking oxygen donor level that ion irradiation induction is produced
Energy level in forbidden band is enriched, so as to improve charge transfer efficiency between molecule and semiconductor, Raman scattering of molecule intensity is enhanced.
Ion irradiation energy is illustrated in the range of 130-190keV with reference to Fig. 1 and 4 result, can be effectively improved semiconductor surface increasing
Hale graceful scattering property.
Fig. 5 is the Raman spectrum using rhodamine 6G molecule as probe test, is 190keV by energy, and dosage is 1 × 1016, 3
×1016, 6 × 1017, 1 × 1017ions/cm2Ar+After irradiation and vacuum annealing WO3It is~10 to realize to concentration-6mol/L
The detection of rhodamine 6G molecule, its detection sensitivity improves at least five order of magnitude, and this is mainly attributed to ion irradiation induction production
Raw Lacking oxygen donor level enriches energy level in forbidden band, so as to improve charge transfer efficiency between molecule and semiconductor, strengthens
Raman scattering of molecule intensity.This result illustrates ion irradiation dosage 3 × 1016-1×1017ions/cm2In the range of, can be with
It is effectively improved semiconductor surface enhancing Raman scattering performance.
Claims (6)
1. a kind of high-sensitivity surface strengthens the preparation method of Raman scattering substrate, it is characterised in that：
High-sensitivity surface enhancing Raman scattering is prepared using the method that thermal anneal process under vacuum condition is carried out after ion irradiation
Substrate, included specific preparation process is as follows：
1) using oxide semiconductor as raw material, using ion implantation apparatus by energy 10-200keV, dosage 1 × 1016-2×
1017ions/cm2Ion pair oxide semiconductor thin-film irradiated, make its material surface and it is internal in produce it is abundant
Lacking oxygen；
2) sample after irradiation is annealed 1-3 hours for 300-700 DEG C under vacuum, vacuum pressure is less than 2 × 10-4Pa, is repaiied
Complexion Shu Zaocheng damage, makes film reach higher crystallinity.
2. a kind of high-sensitivity surface according to claim 1 strengthens the preparation method of Raman scattering substrate, its feature exists
In：
Above-mentioned steps 1) in, it is WO as the oxide semiconductor of raw material3、TiO2, it is any in ZnO.
3. a kind of high-sensitivity surface according to claim 1 or 2 strengthens the preparation method of Raman scattering substrate, its feature
It is：
Above-mentioned steps 1) in, the ion irradiated to oxide semiconductor thin-film is Ar+Ion or N+Ion.
4. a kind of high-sensitivity surface according to claim 1 strengthens the preparation method of Raman scattering substrate, its feature exists
In：
Using method that thermal anneal process under vacuum condition is carried out after ion irradiation prepare high-crystallinity rich in Lacking oxygen
WO3-xSurface enhanced Raman scattering substrate, included specific preparation process is as follows：
1) with WO3Film is raw material, using ion implantation apparatus by energy 130-190keV, dosage 3 × 1016-1×1017ions/
cm2Ar+Ion or N+Ion irradiation is to WO3Film；
2) by the WO after irradiation3Film is warming up to 400-600 DEG C, then under vacuum insulation annealing 1-3 hours, afterwards from
So cooling, vacuum pressure is less than 2 × 10-4Pa。
5. a kind of high-sensitivity surface according to claim 1 strengthens the preparation method of Raman scattering substrate, its feature exists
In：
Using method that thermal anneal process under vacuum condition is carried out after ion irradiation prepare high-crystallinity rich in Lacking oxygen
TiO2-xSurface enhanced Raman scattering substrate, included specific preparation process is as follows：
1) with TiO2Film is raw material, using ion implantation apparatus by energy be 30-60keV, dosage be 5 × 1016-1.5×
1017ions/cm2Ar+Ion or N+Ion irradiation is to TiO2Monocrystalline；
2) by the TiO after irradiation2Monocrystalline is warming up to 400-600 DEG C, then under vacuum insulation annealing 1-3 hours, afterwards from
So cooling, vacuum pressure is less than 2 × 10-4Pa。
6. a kind of high-sensitivity surface according to claim 1 strengthens the preparation method of Raman scattering substrate, its feature exists
In：
Using method that thermal anneal process under vacuum condition is carried out after ion irradiation prepare high-crystallinity rich in Lacking oxygen
ZnO1-xSurface enhanced Raman scattering substrate, included specific preparation process is as follows：
1), will be by energy 130-190keV, dosage 5 × 10 using ion implantation apparatus using ZnO film as raw material16-1.5×
1017ions/cm2Ar+Ion or N+Ion irradiation is to ZnO film；
2) ZnO film after irradiation is warming up to 400-600 DEG C, then under vacuum insulation annealing 1-3 hours, afterwards from
So cooling, vacuum pressure is less than 2 × 10-4Pa。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359955A (en) * | 2018-01-23 | 2018-08-03 | 北京科技大学 | A method of improving nano porous metal Surface enhanced Raman scattering performance |
| CN109342400A (en) * | 2018-12-06 | 2019-02-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Application of the semiconducting compound in the identification and identification in grape wine source area |
| CN110961128A (en) * | 2019-10-24 | 2020-04-07 | 武汉大学苏州研究院 | Metal-carbon nitrogen composite electrocatalytic material and preparation method thereof |
| CN115259156A (en) * | 2022-07-18 | 2022-11-01 | 微集电科技(苏州)有限公司 | Capable of detecting low concentration NO at room temperature2Gas sensitive element and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978629A (en) * | 2012-12-03 | 2013-03-20 | 天津大学 | Preparation method and application of SERS (surface enhanced Raman scattering) substrate of Mo/Ag laminated metal-matrix composite material |
| CN103604796A (en) * | 2013-11-29 | 2014-02-26 | 苏州大学 | Preparation method for silicon-based surface-enhanced Raman scattering (SERS) substrate |
| CN105784667A (en) * | 2014-12-22 | 2016-07-20 | 深圳先进技术研究院 | Surface enhanced Raman scattering substrate, preparation method and applications thereof |
-
2017
- 2017-05-27 CN CN201710393238.9A patent/CN106979943B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978629A (en) * | 2012-12-03 | 2013-03-20 | 天津大学 | Preparation method and application of SERS (surface enhanced Raman scattering) substrate of Mo/Ag laminated metal-matrix composite material |
| CN103604796A (en) * | 2013-11-29 | 2014-02-26 | 苏州大学 | Preparation method for silicon-based surface-enhanced Raman scattering (SERS) substrate |
| CN105784667A (en) * | 2014-12-22 | 2016-07-20 | 深圳先进技术研究院 | Surface enhanced Raman scattering substrate, preparation method and applications thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHAN CONG 等: "Noble metal一comparable SERS enhancement from semiconducting metal oxides by making oxygen vacancies", 《NATURE COMMUNICATIONS》 * |
| 张晓东: "金属离子注入氧化物材料引起的结构和光学性质变化研究", 《中国万方数据库》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359955A (en) * | 2018-01-23 | 2018-08-03 | 北京科技大学 | A method of improving nano porous metal Surface enhanced Raman scattering performance |
| CN109342400A (en) * | 2018-12-06 | 2019-02-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Application of the semiconducting compound in the identification and identification in grape wine source area |
| CN109342400B (en) * | 2018-12-06 | 2021-06-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Application of semiconductor compound in identification and identification of origin of wine |
| CN110961128A (en) * | 2019-10-24 | 2020-04-07 | 武汉大学苏州研究院 | Metal-carbon nitrogen composite electrocatalytic material and preparation method thereof |
| CN115259156A (en) * | 2022-07-18 | 2022-11-01 | 微集电科技(苏州)有限公司 | Capable of detecting low concentration NO at room temperature2Gas sensitive element and preparation method thereof |
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