CN112326598A - Surface plasma resonance sensor chip of two-dimensional material sensitization - Google Patents
Surface plasma resonance sensor chip of two-dimensional material sensitization Download PDFInfo
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Abstract
The invention relates to the technical field of optical sensor chips, in particular to a surface plasma resonance sensor chip with two-dimensional material sensitization, which comprises: high refractive index prism, nickel film, two-dimensional material BlueP/WS2An analyte; the high-refractive-index prism, the nickel film and the two-dimensional material BlueP/WS2And the analytes are sequentially arranged from bottom to top to form a composite structure, so that the sensitivity of the surface plasma sensor is greatly improved, and the surface plasma sensor is suitable for surface plasma sensors with various structures.
Description
Technical Field
The invention relates to the technical field of optical sensor chips, in particular to a surface plasma resonance sensor chip with two-dimensional material sensitization.
Background
The phenomenon of surface plasmon resonance is an electromagnetic wave propagating at a metal-dielectric interface and is very sensitive to changes in the refractive index of the sensing medium near the metal layer. The surface plasma resonance sensor has the advantages of high controllability, multiple channels and no mark, and is widely applied to bioscience, gas detection and environmental monitoring. In order to efficiently support excitation of surface plasmon, noble metals such as gold, silver, and copper are used as the plasma material. Gold is generally considered to be the most suitable plasma material because of its oxidation resistance and good chemical stability. Gold also has the disadvantage of a wider formant, which reduces the accuracy of analyte detection. In addition, silver and copper are easily oxidized and copper forms a thick brittle oxide layer. The ferromagnetic metal nickel is a widely distributed metal and is used in many forms in industry. In addition, the metal nickel can enhance the photocatalytic activity, and the nickel foam can also be directly used as a sensing platform for electrochemical sensing. Compared with other noble metals, nickel has some remarkable advantages as a plasmon material, such as excellent magneto-optical advantages, and greatly improves the performance of the sensor.
However, the application of the conventional surface plasmon wave resonance sensor to the detection of substances still faces many problems. The action is mainly applied to the field of biological macromolecules, and the biological macromolecules play an important role in detecting biological interactions such as protein binding and DNA hybridization. However, if a small molecule compound or an analyte with a too low concentration is detected, it is difficult to detect it by the surface plasmon resonance sensor. If the sensitivity of the surface plasmon resonance sensor can be improved, the surface plasmon resonance sensor technology can be widely applied to medicine and early disease diagnosis. Therefore, in order to improve the sensitivity of the sensor, researchers have introduced two-dimensional materials into the field of surface plasmon resonance sensors. The larger specific surface area and unique electrical and optical characteristics of the two-dimensional material are utilized to increase the adsorption quantity of target small molecules, so that the response signal of the surface plasmon resonance sensor is enhanced, and the sensitivity of the surface plasmon resonance sensor is improved.
Disclosure of Invention
The invention aims to provide a film structure which is good in stability and easy to prepare, and the purpose of improving sensitivity is achieved.
In order to achieve the technical problem, the invention provides the following technical scheme:
a two-dimensional material-sensitized surface plasmon resonance sensor chip comprises: high-refractive-index prism (1), nickel film (2) and two-dimensional material BlueP/WS2(3) An analyte (4); high-refractive-index prism (1), nickel film (2) and two-dimensional material BlueP/WS2(3) And the analytes (4) are sequentially arranged from bottom to top to form a composite structure.
Further, the two-dimensional material BlueP/WS2The thickness of the film layer (3) is 0 nm-3.75 nm.
Further, the thickness of the nickel film (2) is 70 nm.
Further, the high-refractive-index prism (1) is an SF10 prism, and the refractive index of the SF10 prism is larger than or equal to that of the object to be measured.
Further, the reflectivity and the sensitivity of the sensor chip are calculated by the following formulas:
R＝|ri,N|2
k(i+1)x＝k1x＝k0n1sinθ
wherein R is the reflectivity of the whole structure of the sensor chip; r isi,NIs the total reflection response of the structure; rhoi,i+1Is the reflection of the ith layer and the (i + 1) th layer; epsiloniRepresents the dielectric constant of the ith layer; epsiloni+1Represents the dielectric constant of the (i + 1) th layer; di+1Represents the thickness of the (i + 1) th layer; theta is the incident angle of incident light on the interface of the transparent dielectric substrate and the multilayer dielectric layer of the sensor; k is a radical of1xAnd k1yIs the wave vector (k) of the incident light1) The transverse and longitudinal components of (a); k is a radical ofiyLongitudinal wave vector of the ith layerAnd (4) components. k is a radical of(i+1)xAnd k(i+1)yIs the wave vector component of the (i + 1) th layer; k is a radical of0Is the wave vector of free space; n is1Is the refractive index of the prism; thetaresIs the resonance angle; n issIs the sensing layer refractive index; s is the sensitivity of the sensor.
Compared with the prior art, the two-dimensional material sensitization surface plasma resonance sensor chip provided by the invention has the following beneficial effects:
1. the invention provides a surface plasma resonance sensor chip with two-dimensional material sensitization, which adopts the excellent magneto-optical advantage of metal nickel and takes a metal nickel film as a plasma material film; the sensitivity of the sensor is improved, and a two-dimensional material BlueP/WS is added on the surface of the metal nickel2Compared with the BlueP/WS without two-dimensional material2The sensitivity of the sensor chip is greatly improved, and the sensor chip is suitable for surface plasma sensors with various structures.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a block diagram of the present invention;
FIG. 2 is a schematic diagram of a sensing test of the present invention;
FIG. 3 shows a two-dimensional material BlueP/WS of the present invention2A sensitivity optimization map of (1);
FIG. 4 shows a two-dimensional material BlueP/WS of the present invention2The reflection curve of (2) varies with the number of layers;
FIG. 5 is a sensory test chart of the present invention;
FIG. 6 shows the invention with no two-dimensional material BlueP/WS2A graph comparing the sensitivity of the sensors (2).
Reference numerals: 1-high refractive index prism; 2-nickel film; 3-two-dimensional Material BlueP/WS2(ii) a 4-minuteAnd (4) separating out the substance.
Detailed Description
The technical solution of the present invention will be clearly and completely described by the following detailed description. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1 to 6, the two-dimensional material-sensitized surface plasmon resonance sensor chip includes: high-refractive-index prism (1), nickel film (2) and two-dimensional material BlueP/WS2(3) An analyte (4); high-refractive-index prism (1), nickel film (2) and two-dimensional material BlueP/WS2(3) And the analytes (4) are sequentially arranged from bottom to top to form a composite structure.
Preferably, the two-dimensional material is BlueP/WS2The thickness of the film layer (3) is 0 nm-3.75 nm.
Preferably, the thickness of the nickel film (2) is 70 nm.
Preferably, the high-refractive-index prism (1) is an SF10 prism, and the refractive index of the SF10 prism is greater than or equal to that of the object to be measured.
Preferably, the reflectivity and the sensitivity of the sensor chip are calculated by the following formulas:
R＝|ri,N|2
k(i+1)x＝k1x＝k0n1sinθ
wherein R is the reflectivity of the whole structure of the sensor chip; r isi,NIs the total reflection response of the structure; rhoi,i+1Is the reflection of the ith layer and the (i + 1) th layer; epsiloniRepresents the dielectric constant of the ith layer; epsiloni+1Represents the dielectric constant d of the (i + 1) th layeri+1Represents the thickness of the (i + 1) th layer; theta is the incident angle of incident light on the interface of the transparent dielectric substrate and the multilayer dielectric layer of the sensor; k is a radical of1xAnd k1yIs the wave vector (k) of the incident light1) The transverse and longitudinal components of (a); k is a radical ofiyIs the longitudinal wave vector component of the ith layer; k is a radical of(i+1)xAnd k(i+1)yThe (i + 1) th layer is a wave vector component; k is a radical of0Is the wave vector of free space; r is the reflectivity of the whole structure of the sensor chip; n is1Is the refractive index of the prism; thetaresIs the resonance angle; n issIs the sensing layer refractive index; s is the sensitivity of the sensor.
In this embodiment, as shown in fig. 1, a two-dimensional material sensitized surface plasmon resonance sensor chip is provided, which includes a high refractive index prism (1), metal nickel (2), and a two-dimensional material BlueP/WS2(3) (ii) a The coupling prism (1) and a two-dimensional material BlueP/WS2(3) Metal nickel (2) is arranged between the two layers; the two-dimensional material BlueP/WS2(3) Is positioned above the metal nickel (2) and is used as a biomolecule recognition layer to be contacted with an analyte (4).
Further, the thickness of the metallic nickel (2) is 70nm, and the dielectric function is-5.2169 +0.13825 i.
Further, the two-dimensional material BlueP/WS2(3) The thickness of the sensor is 0-3.75 nm, the refractive index is 2.48+0.17i, and the sensor is ensured to obtain high sensitivity while increasing the interaction with molecules of a sensing layer.
By adopting the sensor provided by the embodiment of the invention, the reflectivity of the structure at each angle is calculated by a Fresnel formula:
R＝|ri,N|2 (1)
in formula (1), R is the reflectivity of the whole structure of the sensor chip, and taking the structure including N layers as an example, the total reflection response of the structure can be given by the following formula:
in the formula (2), ri,NIs the total reflection response of the structure, pi,i+1Is the reflection of the ith and i +1 th layers, εiRepresents the dielectric constant, ε, of the i-th layeri+1Represents the dielectric constant d of the (i + 1) th layeri+1Represents the thickness of the (i + 1) th layer.
In addition to this, the present invention is,
in equation (3), θ is the incident angle of the incident light at the interface of the transparent dielectric substrate and the multilayer dielectric layer of the sensor. k is a radical of1xAnd k1yIs the wave vector (k) of the incident light1) The transverse and longitudinal components of (a). k is a radical ofiyIs the longitudinal wave vector component of the ith layer; k is a radical of(i+1)xAnd k(i+1)yIs the wave vector component of the (i + 1) th layer. k is a radical of0Is the wave vector of free space. n is1Is the refractive index of the prism. ThetaresIs the resonance angle. n issIs the sensing layer refractive index. Increase in refractive index (Δ n) near the sensing probes) Causes a shift in the surface plasmon resonance spectrum (Δ θ)res) The resonance parameters are changed by measuring the specific resonance angle through the reflection spectrum of the surface plasma resonance sensor. The sensitivity S is thus defined as:
the two-dimensional material-sensitized surface plasmon resonance sensor chip shown in fig. 1 is simulated by using the formula (1) and the formula (4), and the calculated reflectivity curve is shown in fig. 2.
As shown in fig. 2, a sharp surface plasmon resonance peak appears at the total reflection angle, and the points along the falling edge of the surface plasmon resonance peak are sensitive to the change of the refractive index of the measured sample. The shift of the surface plasmon resonance spectrum caused by the refractive index change was measured at a specific wavelength of 633nm to determine the magnitude of the sensitivity.
As shown in FIG. 3, the two-dimensional material BlueP/WS provided by the embodiment of the invention2(3) Sensitized surface plasma resonance sensor chip with two-dimensional material BlueP/WS2(3) The sensitivity changes with increasing number of layers.
As shown in FIG. 4, the two-dimensional material BlueP/WS provided by the embodiment of the invention2(3) Sensitized surface plasma resonance sensor chip with two-dimensional material BlueP/WS2(3) The resonance angle can be red shifted when the number of layers is increased, and the reflection curve becomes shallow and wide gradually. Wherein the increase of the resonance angle deviation is due to the two-dimensional material BlueP/WS2(3) Absorption due to a large real part of the dielectric constant; the reflection curve becomes shallow and wider due to the increase in surface plasmon damping.
As shown in fig. 5, when the refractive index of the sensing medium changes from 1.32 to 1.35, the curve of the reflectivity curve changing with the incident angle moves, and the resonance angle correspondingly shifts red, which indicates that the two-dimensional material-sensitized surface plasmon resonance sensor provided by the embodiment of the present invention is sensitive to the change of the refractive index of the analyte (4); the reason for the red shift of the resonance angle is the change of the resonance wave vector.
As shown in fig. 6, when the refractive index of the sensing medium changes from 1.32 to 1.35, the reflectivity curve shifts with the incident angle, and the resonance angle changes accordingly. As can be seen from the figure, the two-dimensional material BlueP/WS is not added2(3) Compared with the surface plasmon resonance sensor which is sensitized by adding the two-dimensional material BlueP/WS2(3), the surface plasmon resonance sensor is more sensitive to the change of the refractive index of the sensing layer.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (5)
1. A two-dimensional material sensitized surface plasma resonance sensor chip is characterized by comprising: high-refractive-index prism (1), nickel film (2) and two-dimensional material BlueP/WS2(3) An analyte (4); the high-refractive-index prism (1), the nickel film (2) and the two-dimensional material BlueP/WS2(3) And the analytes (4) are sequentially arranged from bottom to top to form a composite structure.
2. The two-dimensional material sensitized surface plasmon resonance sensor chip according to claim 1, wherein: the two-dimensional material BlueP/WS2The thickness of the film layer (3) is 0 nm-3.75 nm.
3. The two-dimensional material sensitized surface plasmon resonance sensor chip according to claim 1, characterized in that the thickness of the nickel film (2) is 70 nm.
4. The two-dimensional material sensitized surface plasmon resonance sensor chip according to claim 1, wherein: the high-refractive-index prism (1) is an SF10 prism, and the refractive index of the SF10 prism is larger than or equal to that of the object to be detected.
5. The two-dimensional material sensitized surface plasmon resonance sensor chip according to claim 1, wherein: the reflectivity and sensitivity of the sensor chip are calculated by the following formulas:
R＝|ri,N|2
k(i+1)x＝k1x＝k0n1sinθ
wherein R is the reflectivity of the sensor chip; r isi,NIs the total reflection response of the structure; rhoi,i+1Is the reflection of the ith layer and the (i + 1) th layer; epsiloniRepresents the dielectric constant of the ith layer; epsiloni+1Represents the dielectric constant d of the (i + 1) th layeri+1Represents the thickness of the (i + 1) th layer; theta is the incident angle of incident light on the interface of the transparent dielectric substrate and the multilayer dielectric layer of the sensor; k is a radical of1xAnd k1yIs the wave vector (k) of the incident light1) The transverse and longitudinal components of (a); k is a radical ofi,yIs the longitudinal wave vector component of the ith layer; k is a radical of(i+1)xAnd k(i+1)yIs the wave vector component of the (i + 1) th layer; k is a radical of0Is the wave vector of free space; n is1Is the refractive index of the prism; thetaresIs the resonance angle; n issIs the sensing layer refractive index; s is the sensitivity of the sensor.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101865841A (en) * | 2010-06-28 | 2010-10-20 | 北京航空航天大学 | High-sensitivity surface plasma resonance sensor |
| WO2015173580A1 (en) * | 2014-05-16 | 2015-11-19 | The University Of Manchester | Improved plasmonic structures and devices |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101865841A (en) * | 2010-06-28 | 2010-10-20 | 北京航空航天大学 | High-sensitivity surface plasma resonance sensor |
| WO2015173580A1 (en) * | 2014-05-16 | 2015-11-19 | The University Of Manchester | Improved plasmonic structures and devices |
Non-Patent Citations (2)
| Title |
|---|
| CHONG YUE ET.AL: "Sensitivity enhancement of an SPR biosensor with a graphene and blue phosphorene/transition metal dichalcogenides hybrid nanostructure", 《APPLIED OPTICS》 * |
| 张志伟: "《棱镜反射光技术与工程应用》", 31 March 2009, 国防工业出版社 * |
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Application publication date: 20210205 |