KR20170008045A - metal nano islands forming method for surface enhanced Raman spectroscopy using repeated dewetting - Google Patents
metal nano islands forming method for surface enhanced Raman spectroscopy using repeated dewetting Download PDFInfo
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- KR20170008045A KR20170008045A KR1020150099279A KR20150099279A KR20170008045A KR 20170008045 A KR20170008045 A KR 20170008045A KR 1020150099279 A KR1020150099279 A KR 1020150099279A KR 20150099279 A KR20150099279 A KR 20150099279A KR 20170008045 A KR20170008045 A KR 20170008045A
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- G—PHYSICS
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- 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
Description
The present invention relates to a large area metal nano-island forming method for surface enhanced Raman spectroscopy using repetitive non-wetting phenomena.
There are a lot of free electrons inside the conductor metal, and free electrons are not bound to metal atoms, so they can easily respond to specific external stimuli. The phenomenon of the simultaneous oscillation of electrons in such a material is called a plasmon. Especially, when the metal becomes nano-sized, the surface plasmon resonance characteristic is exhibited by the behavior of such free electrons, so that it has a unique optical property. Surface plasmon resonance is the phenomenon that free electrons on a metal surface are collectively vibrated due to resonance with the electromagnetic field of a specific energy of light when light is incident between the surface of metal nanoparticles as a conductor and the dielectric such as air or water. More specifically, the local surface plasmon resonance phenomenon is induced by a conductive nanoparticle or metal nanostructure having a size smaller than the wavelength of incident light, and the frequency of surface plasmon resonance is determined by the size or shape of the metal nanoparticles, . This resonance phenomenon has the effect of amplifying the electromagnetic field of the surrounding region of the nanostructure.
Surface-Enhanced Raman Spectroscopy (SERS) is a measurement technique using the local surface plasmon resonance phenomenon as described above. That is, the surface enhancement Raman spectroscopic measurement is a measurement using a phenomenon in which a Raman scattering signal, which is a unique spectrum generated when light passes through a material, is amplified several billion times by the local surface plasmon resonance as described above on the surface on which the nanostructure is formed . More specifically, when a substance to be detected is embedded in a substrate on which a nanostructure is formed and light is incident, a Raman scattering signal is generated and amplified by a substance to be detected, and by detecting the Raman scattering signal, . Such surface enhanced Raman spectroscopy techniques are widely applied in a variety of fields such as pharmaceuticals, materials science, drug detection, and biomolecule detection.
The sensor using the surface enhanced Raman spectroscopic measurement technique basically has a substrate form in which metal nanostructures are formed. In order to improve the functionality as a sensor, researches for making a sensor of a large area efficient have been made steadily. Techniques for fabricating such a sensor for surface enhanced Raman spectroscopy are disclosed in Korean Patent Registration No. 1259267 ("Method for manufacturing color patterning and surface enhancement Raman scattering patterning using glazed gold nanoparticle agglomerates by mineral oil disassembly ", 2013.04.23 , Prior art 1), Korean Patent Registration No. 1448111 ("Surface Enhanced Raman Spectroscopic Substrate and Method for Manufacturing the Same ", 2014.09.30, hereinafter referred to as Prior Art 2). In the prior art document 1, gold nanoparticle agglomerates are irradiated with light to cause dissociation of light oil, thereby forming a surface enhanced Raman scattering pattern. In the prior art 2, the metal nanostructure is implemented by forming the metal-containing nanoparticles on the protruding structure based on the polymer substrate on which the protruding structure is formed.
On the other hand, in order to further enhance such Raman signals, it is necessary to enhance local electromagnetic field integration or to maximize scattering from metal nanostructures. In order to enhance the local electromagnetic field integration, it is considered to increase the number of local electromagnetic field integration areas (hot spots) by densifying the intervals of the metal nanostructures. In order to maximize scattering from the metal nanostructures, Is being considered.
However, in order to manufacture a substrate having a dense metal nano structure, a very expensive process such as an electron beam lithography has been required, which increases the production cost of the sensor, there was. In the case of the prior art document 1, gold nanoparticles, which are expensive materials, are used. However, the above-described problem of cost still occurs, and in the case of the prior art document 2, the spacing or size of the metal nanostructures is limited It is not easy to improve the structure for Raman signal enhancement.
Therefore, various methods have been sought for realizing efficient nanostructure formation at a lower cost, and one of them is a method using dewetting phenomenon. Non-wetting phenomenon refers to the phenomenon that nanoparticles spontaneously aggregate when given appropriate conditions. When metal nanoparticles are formed on a substrate and appropriate environmental conditions are applied to cause wetting, metal nanoparticles spontaneously gather As a result, metal nano islands are formed, which is suitable for use as a sensor for measuring surface enhanced Raman spectroscopy. In addition, since such non-wetting phenomenon occurs in various metal nanoparticles regardless of the material, it is possible to reduce the production cost by using a low-cost material when necessary.
However, when a substrate is manufactured using the above-described non-wetting phenomenon, it is possible to manufacture the substrate at a low cost and at a low cost, but it is difficult to ensure uniformity in a large area. Above all, when metal nano-islands are formed using non-wetting phenomena, as the size of the metal nanostructure increases (the scattering maximization effect increases: Raman signal enhancement), the intervals of the metal nanostructures increase together (local electromagnetic field integration weakens : Raman signal weakening), which limits the amplification of the Raman signal as much as desired.
DISCLOSURE Technical Problem Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a method of fabricating a metal nanostructure by forming a metal nanostructure using repetitive non- A method of forming a large area metal nano island for the surface enhancement Raman spectroscopy measurement using a repetitive non-wetting phenomenon capable of simultaneously realizing the increase of the size and ultimately the sensor for the surface enhancement Raman spectroscopy measurement maximizing the Raman signal amplification .
In order to accomplish the above object, the present invention provides a large area metal nano-island forming method for surface enhanced Raman spectroscopy using repetitive non-wetting phenomenon, comprising the steps of: forming a metal nano- A method of forming a semiconductor device, comprising: forming a nano-level primary metal thin film (111) on a substrate (100); A heat treatment process is performed on the primary metal
At this time, the metal nano-island forming process may be performed at least one time.
The metal nano-
In addition, the metal nano-island forming method may be configured to form the primary metal
In addition, the metal nano-island forming process may be performed such that the first metal nano-
The metal nano-island forming method may further include a step of forming the metal
The sensor for measuring the surface enhanced Raman spectroscopy according to the present invention is formed by the method of forming a metal nano-island as described above and includes a
According to the present invention, the metal nanostructure is formed on the substrate in the form of metal nano-islands using the phenomenon of non-wetting, thereby realizing economical and efficient production of the sensor for surface enhanced Raman spectroscopy. In addition, since the phenomenon of non-wetting occurs in various metal nanoparticles regardless of the material, it is also possible to further reduce the production cost by using a low-cost material when necessary. That is, according to the present invention, the sensor for surface enhanced Raman spectroscopy can be economically mass produced.
In particular, according to the present invention, when a single non-wetting phenomenon is used, the spacing becomes large as the size of the metal nanostructure increases. Thus, to overcome the problem of amplifying the Raman signal as a sensor, By forming the nanostructure, the size of the metal nanostructure can be increased and the interval of the metal nanostructure can be narrowed. As the size of the metal nanostructure increases, the effect of maximizing the scattering increases, and as the distance between the metal nanostructures becomes more dense, the local electromagnetic field integration is strengthened, and ultimately, a large effect of amplifying the Raman signal can be obtained more effectively .
In addition, by using the repetitive wetting phenomenon, it is possible to form the metal nano-islands in a uniform distribution over a large area, and as a result, it is possible to manufacture a sensor for surface enhanced Raman spectroscopy in a large area.
That is, according to the present invention, it is possible to realize a low cost and high efficiency production, maximization of Raman signal amplification, and manufacture of a large area sensor by fabricating a sensor for surface enhanced Raman spectroscopy by forming metal nano-islands using repetitive wetting phenomenon You can get a great effect.
FIG. 1 illustrates an embodiment of a metal nano-island forming process using the repetitive non-wetting phenomenon of the present invention.
Fig. 2 is a step diagram of the process of Fig. 1; Fig.
FIG. 3 shows another embodiment of the metal nano-island formation process using the repetitive non-wetting phenomenon of the present invention.
FIG. 4 is a step diagram of the process of FIG. 3; FIG.
Hereinafter, a method for forming a large area metal nano-scale for surface enhanced Raman spectroscopy using the repetitive non-wetting phenomenon according to the present invention will be described in detail with reference to the accompanying drawings.
The metal nano-island forming method of the present invention is a method of forming a metal nano-island on the
FIG. 1 shows an embodiment of a metal nano-island forming process using the repetitive non-wetting phenomenon of the present invention, and FIG. 2 shows a step diagram of the process of FIG. 1, respectively. 1 and 2, a method of forming a metal nano-island according to the present invention will be described in detail.
The primary metal nano-island forming step consists of the steps shown in Figs. 1 (A) and 1 (B). That is, a first metal
Here, as shown in FIG. 1 (B), the size (diameter) of each of the primary metal nano-
The step of forming the secondary metal nano-island includes the steps shown in Figs. 1 (C) and (D). That is, after a nano-level secondary metal
At this time, as shown in FIG. 1C, the size (diameter) of each of the secondary metal nano-
Naturally, the size d2 of the secondary metal nano-
As described above, since the intervals between the centers of the metal nano-islands are fixed in the step of forming the second metal nano-islands, the intervals are adjusted accordingly as the sizes of the metal nano-islands are controlled. The size d1 and the interval p1 of the primary metal nano-
In carrying out the above-described processes in detail, the process of forming a metal thin film may be appropriately selected as one of various methods known as methods of forming a metal thin film such as thermal deposition, electron beam deposition, sputtering deposition and the like. The heat treatment process for inducing the non-wetting phenomenon may be any process capable of melting the metal thin film so as to cause non-wetting phenomenon such as heating with a heater or scanning with a laser. In addition, the metal used in the metal nano-island forming method may be any of various metals such as gold, silver, platinum, aluminum, iron, zinc, copper, tin, bronze, brass and nickel. Of course, depending on the kind and properties of the metal, the kind of the metal thin film forming process and the type of the heat treatment process can be appropriately selected so that the process progress becomes more advantageous when the metal is used, and the heat treatment process conditions , Heating time, etc.) can be appropriately determined.
As described above, in the surface enhanced Raman spectroscopic measurement sensor formed in the form of a substrate on which metal nanostructures are formed, in order to further strengthen the Raman signal as the measurement signal, it is necessary to enhance the local electromagnetic field integration, . In order to enhance the local electromagnetic field integration, it is desirable to increase the number of local electromagnetic field integration areas (hot spots) by making the intervals of the metal nanostructures small. In order to maximize scattering from the metal nanostructures, .
On the other hand, when metal nano-islands are formed from a metal thin film using a non-wetting phenomenon, the size and spacing of the metal nano-islands are affected by the thickness of the metal thin film, and as the thickness of the metal thin film is increased, It is known that the size and spacing of the metal nano-islands increase. In this case, as described above, as the size of the metal nano-island becomes larger and the interval becomes smaller, it is advantageous to amplify the Raman signal. Since the size and the interval become larger or smaller together, will be.
However, according to the present invention, as described above, the primary metal nano-island is formed by using the non-wetting phenomenon, and then the secondary metal nano-island is formed by covering the secondary metal nano-island. The secondary metal nano-islands are formed at the positions where the primary metal nano-islands are located (ie, the centers of the primary and secondary metal nano-islands do not change) It is larger than the secondary metal nano-islands, so that the spacing is rather reduced. That is, by causing the non-wetting phenomenon repeatedly using the method of the present invention, it becomes possible to make the size of the metal nano-island large and the interval small.
FIG. 3 shows another embodiment of the metal nano-island forming process using the repetitive non-wetting phenomenon of the present invention, and FIG. 4 shows a step diagram of the process of FIG. 3, respectively. In the embodiments of FIGS. 3 and 4, the first metal nano-island forming step and the second metal nano-island forming step are performed in the same manner as in the embodiment of FIGS. 1 and 2, .
3 (A), 3 (B), 3 (C) and 3 (D) are the same as FIG. 1 (A), (B), (C) and (D), respectively. 3 (D), the formation of the secondary metal nano-
According to the metal nano-island forming method of the present invention as described above, finally, a structure composed of the
As described above, according to the method of the present invention, as the non-wetting phenomenon is repeatedly performed, the size of the metal nano-island becomes larger and the interval becomes smaller. Accordingly, the amplification of the Raman signal is further enhanced, The enhanced Raman spectroscopy sensor can have much higher sensitivity than the conventional one. In addition, since the method of the present invention can use any metal, there is no limitation on the material, and metal nano-islands can be formed on a large-sized substrate easily and inexpensively, which can save much production cost. That is, by using the method of the present invention, it is possible to mass-produce a sensor for surface enhanced Raman spectroscopy at a low cost and a high efficiency.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It goes without saying that various modifications can be made.
100: substrate
111: Primary metal thin film
112: Primary metal nano island
121: Secondary metal thin film
122: Secondary metal nano island
Claims (7)
Forming a nano-level primary metal thin film (111) on the substrate (100); A heat treatment process is performed on the primary metal thin film 111 to cause a non-wetting phenomenon; Metal nanoparticles forming the primary metal thin film 111 are aggregated by non-wetting phenomenon to form primary metal nano-sized islands 112; A first metal nano-island forming step comprising:
Forming a nano-level secondary metal thin film (121) on the substrate (100) on which the primary metal nano-islands (112) are formed; The second metal thin film 121 and the first metal nano-island 112 are subjected to a heat treatment process to cause a non-wetting phenomenon; The metal nanoparticles constituting the secondary metal thin film 121 and the primary metal nano-islands 112 are agglomerated by the non-wetting phenomenon, and the positions corresponding to the positions where the primary metal nano- Forming secondary metal nano-sized islands 122, which are larger in size and narrower than the primary metal nano-islands 112; And a second metal nano-island formation step
Wherein the Raman spectroscopic measurement is performed using a repetitive non-wetting phenomenon.
Wherein the step of forming the second metal nano-island is performed at least once. The method for forming a large-area metal nano-island for the surface enhanced Raman spectroscopy using the repetitive non-wetting phenomenon.
The thickness of the primary metal thin film 111 or the secondary metal thin film 121 is controlled to adjust the size and the spacing of the primary metal nano island 112 or the secondary metal nano island 122 A method for forming large area metal nano - islands for surface enhanced Raman spectroscopy using repetitive non - wetting phenomena.
Wherein the first metal thin film (111) or the second metal thin film (121) is formed by at least one of thermal deposition, electron beam deposition, and sputter deposition. METHOD OF FORMING METAL NANO ISLAND FOR SENSOR MEASUREMENT.
Characterized in that heat treatment is performed by applying heat to the heater or scanning with a laser to form the primary metal nano-island 112 or the secondary metal nano-island 122. The surface enhancement using the repetitive non- Method of forming large area metal nano - islands for Raman spectroscopy.
The metal constituting the primary metal thin film 111 or the secondary metal thin film 121 is at least one selected from gold, silver, platinum, aluminum, iron, zinc, copper, tin, bronze, brass and nickel A method for forming large area metal nano - islands for surface enhanced Raman spectroscopy using repetitive non - wetting phenomena.
Wherein the sensor comprises a substrate (100) and the secondary metal nano-islands (122) formed on the substrate (100).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107037027A (en) * | 2016-11-16 | 2017-08-11 | 贵州师范学院 | A kind of wide area surface strengthens the preparation method of Raman scattering substrate |
| CN110132936A (en) * | 2019-06-04 | 2019-08-16 | 聊城大学 | A kind of large area SERS substrate, the preparation method and application of Al/Ag layered nano-structure |
| CN110268250A (en) * | 2017-01-31 | 2019-09-20 | 惠普发展公司，有限责任合伙企业 | Surface enhanced infrared absorption platform |
| KR102048573B1 (en) * | 2018-06-04 | 2019-11-26 | 한국기계연구원 | Method for manufacturing a film having multi wavelength filter |
| CN112240877A (en) * | 2019-07-16 | 2021-01-19 | 香港城市大学 | Method for forming nano material with gap plasma on substrate and sensor |
| KR20220000700A (en) * | 2020-06-26 | 2022-01-04 | (주)광림정공 | A substrate of surface enhanced raman scattering of nanoporous-structure increasing number of nano gap |
| KR20220008241A (en) * | 2020-07-13 | 2022-01-20 | 경희대학교 산학협력단 | Organic light emitting device including nano-island structures based on dewetting and manufacturing method thereof |
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| KR101259267B1 (en) | 2010-12-24 | 2013-04-29 | 단국대학교 산학협력단 | A method for preparation of color patterning and surface-enhanced Raman scattering patterning using photoinduced disassembly of gelated gold nanoparticle aggregates |
| KR101448111B1 (en) | 2013-09-17 | 2014-10-13 | 한국기계연구원 | A substrate for surface-enhanced Raman scattering spectroscopy and a preparing method thereof |
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2015
- 2015-07-13 KR KR1020150099279A patent/KR20170008045A/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101259267B1 (en) | 2010-12-24 | 2013-04-29 | 단국대학교 산학협력단 | A method for preparation of color patterning and surface-enhanced Raman scattering patterning using photoinduced disassembly of gelated gold nanoparticle aggregates |
| KR101448111B1 (en) | 2013-09-17 | 2014-10-13 | 한국기계연구원 | A substrate for surface-enhanced Raman scattering spectroscopy and a preparing method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107037027A (en) * | 2016-11-16 | 2017-08-11 | 贵州师范学院 | A kind of wide area surface strengthens the preparation method of Raman scattering substrate |
| CN110268250A (en) * | 2017-01-31 | 2019-09-20 | 惠普发展公司，有限责任合伙企业 | Surface enhanced infrared absorption platform |
| US11125693B2 (en) | 2017-01-31 | 2021-09-21 | Hewlett-Packard Development Company, L.P. | Surface enhanced infrared absorption stage |
| CN110268250B (en) * | 2017-01-31 | 2022-03-04 | 惠普发展公司，有限责任合伙企业 | Surface enhanced infrared absorption table |
| KR102048573B1 (en) * | 2018-06-04 | 2019-11-26 | 한국기계연구원 | Method for manufacturing a film having multi wavelength filter |
| CN110132936A (en) * | 2019-06-04 | 2019-08-16 | 聊城大学 | A kind of large area SERS substrate, the preparation method and application of Al/Ag layered nano-structure |
| CN112240877A (en) * | 2019-07-16 | 2021-01-19 | 香港城市大学 | Method for forming nano material with gap plasma on substrate and sensor |
| KR20220000700A (en) * | 2020-06-26 | 2022-01-04 | (주)광림정공 | A substrate of surface enhanced raman scattering of nanoporous-structure increasing number of nano gap |
| KR20220008241A (en) * | 2020-07-13 | 2022-01-20 | 경희대학교 산학협력단 | Organic light emitting device including nano-island structures based on dewetting and manufacturing method thereof |
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