CN103103494A - Method for preparing oxide surface on surface enhanced raman scattering (SERS) substrate through atomic layer deposition technology - Google Patents
Method for preparing oxide surface on surface enhanced raman scattering (SERS) substrate through atomic layer deposition technology Download PDFInfo
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- CN103103494A CN103103494A CN2013100318490A CN201310031849A CN103103494A CN 103103494 A CN103103494 A CN 103103494A CN 2013100318490 A CN2013100318490 A CN 2013100318490A CN 201310031849 A CN201310031849 A CN 201310031849A CN 103103494 A CN103103494 A CN 103103494A
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Abstract
The invention discloses a method for preparing a preparing oxide surface on a surface enhanced raman scattering (SERS) substrate through an atomic layer deposition technology. A layer of oxide thin film is formed on the SERS surface through a chemical absorption reaction on the surface by alternately filling precursor pulses and oxygen source pulses. The method, which prepares a layer of dense and stable oxide surface which is thinner than 5nm on the SERS substrate through the ALD technology, overcomes the shortcomings of uneven surface, instable performance and poor reproducibility of the original SERS substrate.
Description
Technical field
The present invention relates to surface light spectral technology field, relate in particular to a kind of preparation method of oxide surface of surface enhanced Raman scattering substrate.
Background technology
Find first surface enhanced Raman scattering (Surface enhanced Raman scattering from 20 century 70 Fleischmann, SERS) since phenomenon, development through decades, the SERS detection technique has been widely used in the every field such as physics, chemistry, biology, medicine, material, becomes the important tool of material molecule trace detection.The preparation of active substrate is the prerequisite that obtains the SERS signal, for SERS as a kind of routine, online analysis tool, the characteristics such as prepared SERS substrate should have that the enhancing ability is strong and homogeneity good, be easy to preparation and storage, easy to use.SERS substrate commonly used at present mainly contains the metal electrode active substrate, the substrate of metal island film activity, the substrate of chemical etching and electroless plating, be rich in the fenestral fabric active substrate of node, ordered fabrication active substrate, but that these substrate ubiquities metal nanoparticle is inhomogeneous, structure, character are unstable, the shortcoming of poor repeatability has limited the application of SERS technology greatly.
In recent years, the investigator finds that metal oxide has stronger SERS effect equally, metal oxide is compared with metallics and is had stability and circulation ratio preferably simultaneously, if prepare the thin layer of metal oxide of one deck densification in metal SERS substrate, will help to improve stability and the circulation ratio defective of traditional SERS substrate.But technical difficulty is how to obtain the thinnest, fine and close thin oxide layer.
Summary of the invention
in order to overcome the above problems, the invention provides and utilize surface atom deposition (ALD) technology to prepare the method for oxide surface in surface enhanced Raman scattering (SERS) substrate, ald (Atomic Layer Deposition, ALD), by the pulse of gas phase presoma alternately being passed into reactor and the film forming method of Chemisorption occuring on deposition substrate surface, because its surface has from the characteristics that limit, therefore ALD has excellent three-dimensional binding property and large-area uniformity, can simply reach the method for accurate control surface film thickness by control number reaction time.
Technical scheme of the present invention is achieved in the following ways: utilize technique for atomic layer deposition to prepare the method for oxide surface in the SERS substrate, comprise the steps: it is characterized in that:
1), metal SERS substrate is placed on ALD indoor;
Described SERS substrate comprises the metal electrode active substrate, the substrate of metal island film activity, and the fenestral fabric active substrate of node is rich in the substrate of chemical etching and electroless plating, a kind of in the ordered fabrication active substrate.
2), according to the kind of deposition oxide, the working parameter of ALD deposition is set;
Described oxide surface is titanium oxide, zinc oxide, and silicon oxide, aluminum oxide, zirconium white, germanium oxide, oxidation is returned, yttrium oxide, lanthanum trioxide, a kind of in stannic oxide.
3), pass into the ALD precursor compound steam that comprises the oxide compound central element with impulse form in the ALD working spaces;
The ALD precursor compound steam of described oxycompound central element is volatile halogenide, organometallics, metal beta diketone salt, alkoxide, metal alkylamino salt, organo-metallic cyclopentadiene compound, one or more mixture in metal nitrate.
4), remove unnecessary ALD precursor compound steam to the indoor purging gas that passes into of ALD;
5), with impulse form to the indoor oxygen source steam that passes into of ALD;
6), remove unnecessary oxygen source steam to the indoor purging gas pulses that passes into of ALD;
The purging gas that passes in described step 4 or step 6 is high pure nitrogen or argon gas.
Described oxygen source is a kind of in water, ozone, alcohol, oxynitrides, atomic oxygen.
7), the step of repetition 3 to 6 is until the SERS substrate reaches required deposit thickness;
8), according to the deposition kind, adjust ALD working spaces temperature, take out the SERS substrate in the ALD working spaces, obtain the thickness of the suprabasil oxide surface of SERS less than 5 nm.
The present invention can prepare one deck less than 5 nm uniform surface in original SERS substrate, densification, and stable oxide surface, thus improve the surperficial heterogeneity of original SERS substrate, unstable properties, the shortcoming of poor reproducibility.
Embodiment
Utilize technique for atomic layer deposition to prepare the method for oxide surface in the SERS substrate, comprise the steps:
1, metal SERS substrate is placed on ALD indoor; The SERS substrate comprises the metal electrode active substrate, the substrate of metal island film activity, and the fenestral fabric active substrate of node is rich in the substrate of chemical etching and electroless plating, a kind of in the ordered fabrication active substrate.
2, according to the kind of deposition oxide, the working parameter of ALD deposition is set; Oxide surface is titanium oxide, zinc oxide, and silicon oxide, aluminum oxide, zirconium white, germanium oxide, oxidation is returned, yttrium oxide, lanthanum trioxide, a kind of in stannic oxide.
3), pass into the ALD precursor compound steam that comprises the oxide compound central element with impulse form in the ALD working spaces; The ALD precursor compound steam of oxycompound central element is volatile halogenide, organometallics, metal beta diketone salt, alkoxide, metal alkylamino salt, organo-metallic cyclopentadiene compound, one or more mixture in metal nitrate.
4, remove unnecessary ALD precursor compound steam to the indoor purging gas that passes into of ALD;
5, with impulse form to the indoor oxygen source steam that passes into of ALD;
6, remove unnecessary oxygen source steam to the indoor purging gas pulses that passes into of ALD;
The purging gas that passes in step 4 or step 6 is high pure nitrogen or argon gas.Oxygen source is a kind of in water, ozone, alcohol, oxynitrides, atomic oxygen.
7, the step of repetition 3 to 6 is until the SERS substrate reaches required deposit thickness;
8, according to the deposition kind, adjust ALD working spaces temperature, take out the SERS substrate in the ALD working spaces, obtain the thickness of the suprabasil oxide surface of SERS less than 5 nm.
Case study on implementation 1:
To put into the ALD working spaces at the bottom of the metal island film activity money base that has prepared, through vacuumizing, preserve after nitrogen purging three times the low vacuum state of inflated with nitrogen, be warming up to 300 ℃.According to the operational requirement of ALD, alternately passing into titanium tetrachloride (for titania precursor body) steam pulse, nitrogen purge pulse, water vapor is oxygen source pulse, nitrogen purge pulse, and this is an ALD deposition cycle.Titanium tetrachloride source and water source working temperature are room temperature, and the pulse length at titanium source and water source is 0.1 second, and purging and cleaning pulse length is 6 seconds.The ALD number of deposition cycles is 50 times, obtains aluminum oxide thickness and is about 3 nm, takes out the SERS substrate after cooling.
Case study on implementation 2:
Identical with case study on implementation one, but at the bottom of the SERS substrate was the money base that obtains with electroless plating, preparation target oxygen compound layer was silicon oxide.The presoma that uses is tetraethoxy-silicane, and oxygen source is water, and ALD system operation temperature is 350 ℃, through 30 times, is the thin layer of silicon oxide of 3 nm.
Case study on implementation 3:
Identical with case study on implementation one, but the SERS substrate is the gold substrate with the metal electrode activity, and preparation target oxygen compound layer is zirconium white.The zirconium precursor body that uses is zirconium-n-butylate, and oxygen source is ozone, and ALD operating system is 250 ℃, and obtaining thickness through 10 deposition cycle is the zirconium white thin layer of 1 nm.
Case study on implementation 4:
Identical with case study on implementation one, but the SERS substrate is the copper substrate that obtains with nano-imprinting method, and preparation target oxygen compound layer is aluminum oxide.The aluminium presoma that uses is trimethyl aluminium, and oxygen source is water, and ALD operating system is 150 ℃, and obtaining thickness through 40 deposition cycle is the aluminum oxide thin layer of 4 nm.
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
Claims (6)
1. utilize technique for atomic layer deposition to prepare the method for oxide surface in the SERS substrate, comprise the steps: it is characterized in that:
1), metal SERS substrate is placed on ALD indoor;
2), according to the kind of deposition oxide, the working parameter of ALD deposition is set;
3), pass into the ALD precursor compound steam that comprises the oxide compound central element with impulse form in the ALD working spaces;
4), remove unnecessary ALD precursor compound steam to the indoor purging gas that passes into of ALD;
5), with impulse form to the indoor oxygen source steam that passes into of ALD;
6), remove unnecessary oxygen source steam to the indoor purging gas pulses that passes into of ALD;
7), the step of repetition 3 to 6 is until the SERS substrate reaches required deposit thickness;
8), according to the deposition kind, adjust ALD working spaces temperature, take out the SERS substrate in the ALD working spaces, obtain the thickness of the suprabasil oxide surface of SERS less than 5 nm.
2. prepare the method for oxide surface according to the technique for atomic layer deposition that utilizes as claimed in claim 1 in the SERS substrate, it is characterized in that: the SERS substrate in described step 1) comprises the metal electrode active substrate, the substrate of metal island film activity, the substrate of chemical etching and electroless plating, be rich in the fenestral fabric active substrate of node, a kind of in the ordered fabrication active substrate.
3. prepare the method for oxide surface according to the technique for atomic layer deposition that utilizes as claimed in claim 1 in the SERS substrate, it is characterized in that: the oxide surface described step 2) is titanium oxide, zinc oxide, silicon oxide, aluminum oxide, zirconium white, germanium oxide, oxidation is returned, yttrium oxide, lanthanum trioxide, a kind of in stannic oxide.
4. prepare the method for oxide surface according to the technique for atomic layer deposition that utilizes as claimed in claim 1 in the SERS substrate, it is characterized in that: the ALD precursor compound steam of the oxycompound central element in described step 3) is volatile halogenide, organometallics, metal beta diketone salt, alkoxide, metal alkylamino salt, organo-metallic cyclopentadiene compound, one or more mixture in metal nitrate.
5. prepare the method for oxide surface according to the technique for atomic layer deposition that utilizes as claimed in claim 1 in the SERS substrate, it is characterized in that: the purging gas that passes in described step 4) or step 6) is high pure nitrogen or argon gas.
6. prepare the method for oxide surface according to the technique for atomic layer deposition that utilizes as claimed in claim 1 in the SERS substrate, it is characterized in that: the oxygen source in described step 6) is a kind of in water, ozone, alcohol, oxynitrides, atomic oxygen.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102864417A (en) * | 2012-08-22 | 2013-01-09 | 吉林大学 | Method for encapsulating organic devices by passivation layer prepared by electron beam evaporation and atomic layer deposition |
| CN103866321A (en) * | 2014-03-14 | 2014-06-18 | 中国科学院合肥物质科学研究院 | Silver nanoparticle-zinc oxide porous nanosheet-carbon fiber cloth composite substrate as well as preparation method and use of substrate |
| TWI481858B (en) * | 2013-06-05 | 2015-04-21 | Ind Tech Res Inst | Surface-enhanced raman scattering substrate |
| CN104746049A (en) * | 2015-04-07 | 2015-07-01 | 南京大学 | Method for preparing surface-enhanced Raman scattering base with metal nanometer gaps by utilizing ALD (atomic layer deposition) |
| CN105944714A (en) * | 2016-05-24 | 2016-09-21 | 昆明理工大学 | Sulfur-resistant denitration catalyst preparation method |
| CN107516692A (en) * | 2016-06-15 | 2017-12-26 | 常州天合光能有限公司 | The method and solar cell of deposit dielectrics film on a silicon substrate |
| CN109470683A (en) * | 2018-10-23 | 2019-03-15 | 江苏大学 | A method of 2,4-D is carried out with SERS substrate combination multiple linear regression model and is quickly detected |
| CN112779520A (en) * | 2019-11-05 | 2021-05-11 | 有进科技材料股份有限公司 | Method for forming thin film using surface protective material |
| WO2024060806A1 (en) * | 2022-09-23 | 2024-03-28 | 隆基绿能科技股份有限公司 | Tin dioxide film, and preparation method therefor and use thereof |
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| US20050077184A1 (en) * | 2003-10-09 | 2005-04-14 | Organotek Defense System Corporation | Method for preparing surface for obtaining surface-enhanced Raman scattering spectra of organic compounds |
| CN101101263A (en) * | 2007-07-20 | 2008-01-09 | 苏州大学 | Core-shell nano granule with high activity surface intensified raman spectrum and preparation method thereof |
| CN102021534A (en) * | 2010-12-13 | 2011-04-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing substrate glass slide with effect of surface enhanced Raman scattering |
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| US20040165187A1 (en) * | 2003-02-24 | 2004-08-26 | Intel Corporation | Method, structure, and apparatus for Raman spectroscopy |
| US20050077184A1 (en) * | 2003-10-09 | 2005-04-14 | Organotek Defense System Corporation | Method for preparing surface for obtaining surface-enhanced Raman scattering spectra of organic compounds |
| CN101101263A (en) * | 2007-07-20 | 2008-01-09 | 苏州大学 | Core-shell nano granule with high activity surface intensified raman spectrum and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102864417A (en) * | 2012-08-22 | 2013-01-09 | 吉林大学 | Method for encapsulating organic devices by passivation layer prepared by electron beam evaporation and atomic layer deposition |
| TWI481858B (en) * | 2013-06-05 | 2015-04-21 | Ind Tech Res Inst | Surface-enhanced raman scattering substrate |
| US9500592B2 (en) | 2013-06-05 | 2016-11-22 | Industrial Technology Research Institute | Surface-enhanced Raman scattering substrate |
| CN103866321A (en) * | 2014-03-14 | 2014-06-18 | 中国科学院合肥物质科学研究院 | Silver nanoparticle-zinc oxide porous nanosheet-carbon fiber cloth composite substrate as well as preparation method and use of substrate |
| CN104746049A (en) * | 2015-04-07 | 2015-07-01 | 南京大学 | Method for preparing surface-enhanced Raman scattering base with metal nanometer gaps by utilizing ALD (atomic layer deposition) |
| CN105944714A (en) * | 2016-05-24 | 2016-09-21 | 昆明理工大学 | Sulfur-resistant denitration catalyst preparation method |
| CN107516692A (en) * | 2016-06-15 | 2017-12-26 | 常州天合光能有限公司 | The method and solar cell of deposit dielectrics film on a silicon substrate |
| CN109470683A (en) * | 2018-10-23 | 2019-03-15 | 江苏大学 | A method of 2,4-D is carried out with SERS substrate combination multiple linear regression model and is quickly detected |
| CN112779520A (en) * | 2019-11-05 | 2021-05-11 | 有进科技材料股份有限公司 | Method for forming thin film using surface protective material |
| TWI752516B (en) * | 2019-11-05 | 2022-01-11 | 南韓商優吉尼科技材料股份有限公司 | Methods of forming a thin film using a surface protection material |
| US11591691B2 (en) | 2019-11-05 | 2023-02-28 | Egtm Co., Ltd. | Method of forming a thin film using a surface protection material |
| WO2024060806A1 (en) * | 2022-09-23 | 2024-03-28 | 隆基绿能科技股份有限公司 | Tin dioxide film, and preparation method therefor and use thereof |
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