CN109799205A - A kind of infrared molecular fingerprint sensor of flat film structure and preparation method thereof - Google Patents
A kind of infrared molecular fingerprint sensor of flat film structure and preparation method thereof Download PDFInfo
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- CN109799205A CN109799205A CN201910127577.1A CN201910127577A CN109799205A CN 109799205 A CN109799205 A CN 109799205A CN 201910127577 A CN201910127577 A CN 201910127577A CN 109799205 A CN109799205 A CN 109799205A
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Abstract
The invention discloses infrared molecular fingerprint sensors of a kind of flat film structure and preparation method thereof, the infrared molecular fingerprint sensor includes duplicature planar structure sensor and monofilm planar structure sensor, the duplicature planar structure sensor by silicon (Si) substrate copper (Cu) and zinc selenide (ZnSe) two membranes constitute；The monofilm planar structure sensor is made of the golden film on silicon (Si) substrate.The sensor is based on the resonance of film optical cavity and interface enhancing principle, is made of planar multilayer metal and deielectric-coating, is not necessarily to graphical processing technology, has many advantages, such as that the processing is simple, at low cost, high yield rate, useful detection area are big and monolayer detectivity.
Description
Technical field
The invention belongs to optical molecular sensor technical fields, and in particular to a kind of infrared molecule of flat film structure refers to
Line sensor and preparation method thereof.
Background technique
Optical molecular detection technique can carry out quantitative detection point to substances such as micro protein, ribose and nucleic acid
Analysis, it is most important for the mankind's understanding life quintessences such as gene structure and gene expression and regulation problem, in pharmacy exploitation, food
The fields such as safety, environmental project, pharmaceutical formulation and disease surveillance have broad application prospects.In view of organic molecule and biology point
Son is closely bound up with the life, environment and disease of the mankind, and the innovation of molecular detection technology and application progress are directly related to the mankind
Health and production method, the level of especially novel detection, diagnosis and therapeutic equipments.
Which can be roughly divided into two types according to the difference of operation principle for common optical molecular sensor, a kind of by target point
Son is adsorbed on sensor surface so that the variations in refractive index of sensor surface, so as to cause sensor absorbing wavelength movement and
Complete detection to target molecule, this kind of sensor can only variations in refractive index caused by molecular detection quality, and can not distinguish point
Chemical structure characteristic inside son, is restricted in many important applications；Another kind is that had according to molecule in middle infrared band
Its specific " absorbing fingerprint " this characteristic, is enhanced the light field near target molecule using the micro-structure of sensor surface, drawn
The vibration enhancing of chemical bond in target molecule is played, to complete the specificity identification and detection to target molecule, obtains intramolecular
Portion's chemical bond characteristic information.In this kind of sensor absorbed based on fingerprint, common technology is the method using microfabrication
It makes in sensor surface with micro-structure of different shapes, to obtain the light field of localization enhancing, to reinforce being adsorbed on spy
Survey the vibration of chemical bond in the target molecule on device surface.The representative work specifically having been reported includes: 2008
F.Neubrech et al. proposition is completed to detect the high sensitivity of 1- stearylmercaptan with rod-like nano antenna, [Resonant
plasmonic and vibrational coupling in a tailored nanoantenna for infrared
Detection, PHYSICAL REVIEW LETTERS 101 (15), 157403 (2008)], 2009 years E.Cubukcu et al. are used
The resonance loop antenna of fine process production also achieves effective detection to target molecule, [Split ring
Resonator sensors for infrared detection of single molecular monolayers,
APPLIED PHYSICS LETTERS 95(4),043113(2009)】。
In existing technical solution, molecular fingerprint sensor be typically all by with micro-nano structure patterned metal or
Person's dielectric structure composition, preparation process need to make using the Film patterning processing method such as photoetching or electron beam lithography
Journey is complicated, at high cost, while the repeatability and controllability of device limit practical large-scale application.
Summary of the invention
The purpose of the present invention is to provide a kind of molecular fingerprint sensor without graphical flat film structure and its preparations
Method, the sensor are based on the resonance of film optical cavity and interface enhancing principle, are made of, are not necessarily to planar multilayer metal and deielectric-coating
Graphical processing technology, with the processing is simple, at low cost, high yield rate, useful detection area are big and monolayer detection is sensitive
The advantages that spending.
In order to achieve the above technical purposes, the present invention is realized especially by following technical scheme:
A kind of infrared molecular fingerprint sensor of flat film structure, the infrared molecular fingerprint sensor include bilayer
Membrane plane structure sensor and monofilm planar structure sensor, the duplicature planar structure sensor is by silicon (Si) substrate
On copper (Cu) and zinc selenide (ZnSe) two membranes constitute；The monofilm planar structure sensor is by silicon (Si) substrate
Golden film and constitute.
The duplicature planar structure sensor by by the thickness of ZnSe dielectric layer be set as quarter-wave with
The maximum value of Fabry Perot resonant fields caused by ensuring is located at the surface of ZnSe, to complete to the effective of target molecule
Detection.
The monofilm planar structure sensor based on light field gold surface discontinuity boundary condition, gold surface
The superposition of incident electric fields and reflected field makes electric-field enhancing, to realize effective detection to molecule to be checked.
In another aspect of this invention, the preparation method of above-mentioned molecular fingerprint sensor is provided, comprising the following steps:
1) it is prepared in silicon wafer (or any other materials substrate) greater than 100nm's with electron beam vacuum coating technology
Single layer golden film is greater than 100nm copper/quarter-wave thickness ZnSe two membranes；
2) film sample of preparation is placed in molecular solution soaking to be checked 24 hours；
3) ethyl alcohol and deionized water is used to rinse respectively the film sample after soaking, it is then to be checked to complete with being dried with nitrogen
Absorption self assembly of the molecule in sensor surface.
Further, for typical test object stearylmercaptan ODT organic molecule, solvent is ethyl alcohol, ODT concentration in solution
Proportion is 1mM/L.
Further, for bovine serum albumin(BSA) BSA molecule, solvent is phosphate buffered saline (PBS) in solution, and BSA concentration is matched
Than for 1mg/ml.
The invention has the benefit that
The infrared molecular fingerprint sensor molecule detection of the present invention is discontinuous based on membrane well resonance and film interface light field
New principle, different from the localization light field Resonance Mechanism of conventional micro-nano structure sensor, device is by non-patterned multilayer
Film composition, has the advantages that preparation process is simple, at low cost, is suitble to large-scale application, is not necessarily to microfabrication, therefore micro- compared to conventional
The advantages that molecule sensor of fining-off has difficulty of processing small, at low cost, high yield rate, while there is the effective area of detection
Bigger feature.
Detailed description of the invention
Fig. 1 is two membranes planar structure molecule sensor schematic diagram；
Fig. 2 is the field enhancement factor of two membranes planar structure molecule sensor with incidence angle variation diagram；
Fig. 3 is monofilm planar structure molecule sensor schematic diagram；
Fig. 4 is the field enhancement factor of monofilm planar structure molecule sensor with incidence angle variation diagram；
Fig. 5 is the ODT molecule sensor schematic diagram based on two-layer film configuration；
Reflectance spectrum when Fig. 6 is s polarization under different incidence angles；
Fig. 7 is the BSA molecule sensor schematic diagram based on single-layer membrane structure；
Reflectance spectrum when Fig. 8 is p-polarization under different incidence angles.
Specific embodiment
Below in conjunction with specific embodiment of the present invention, technical solution of the present invention is clearly and completely described, is shown
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Based on flat film structure, the present invention is designed without graphical, highly sensitive molecule sensor.Specific design scheme is as schemed
Shown in 1~4.Fig. 1 is two membranes planar structure sensor, and the structure is by the copper (Cu) and zinc selenide (ZnSe) on silicon (Si) substrate
Two membranes are constituted, by setting quarter-wave for the thickness of ZnSe dielectric layer to ensure generated Fabry Perot
The maximum value of resonant fields is located at the surface of ZnSe, to complete effective detection to target molecule.Fig. 2 is that the difference of theoretical calculation is inclined
The relationship that the electric field enhancement factor on the surface ZnSe changes with incidence angle under vibration direction (s polarization and p-polarization), it can be seen that when s is inclined
When vibration light incidence, light field is effectively enhanced, and field enhancement factor maintains 1.87, should be increased based on the field of film optical cavity resonance principle
The Physical Mechanism of molecule sensing of the present invention is constituted by force.
Based on the principle that similar field enhances, Fig. 3 is the simpler monofilm planar structure molecule sensor design of structure,
The structure is made of the golden film on silicon (Si) substrate, based on light field gold surface discontinuity boundary condition, gold surface
The superposition of incident electric fields and reflected field makes electric-field enhancing, to realize effective detection to molecule to be checked.Fig. 4 is that theoretical calculation goes out
When different polarization light (s polarization and p-polarization) is incident, the rule that the electric field enhancement factor of Au film surface changes with incidence angle is right
In p-polarization light, field enhancement factor becomes larger with the increase of incidence angle, and field enhancement factor maximum can reach 1.94, this shows base
In interface, discontinuous field enhancing is also applied for molecular detection.
A representative instance of the invention is as shown in Fig. 5, and target acquisition molecule is stearylmercaptan (ODT).The molecule passes
Sensor greater than 100nm copper and 362nm ZnSe two membranes by forming on silicon substrate, and wherein the thickness of ZnSe meets a quarter
Wavelength condition, it is ensured that fingerprint absorbing wavelength (2850cm-1 and the 2918cm-1 of the resonant fields frequency of film and molecule ODT to be checked
Place) it is overlapped.The sensor is prepared by conventional electron beam evaporation film coating technique.Single layer ODT molecule to be checked passes through
The method of self assembly is adsorbed on the surface ZnSe.The reflectance spectrum that Fig. 6 is the sensor under s polarization when different incidence angles, can be with
Being clearly seen has obvious absorption peaks in 2850cm-1 and 2918cm-1, corresponds respectively to the symmetric and anti-symmetric of ODT intramolecular CH2
Resonance mode realizes the detection of single layer ODT molecule.The absorption peak of ODT molecule increases as incidence angle increases, at 75 degree of angles
When, the depth of absorption peak is up to 5.07% and 8.54% at two, believes with the molecule sensor detection based on micro-nano structure has been reported
Number quite.
Another representative instance of the invention is as shown in Fig. 7, and target acquisition molecule is bovine serum albumin(BSA) (BSA).It should
Molecule sensor is made of the 180nm gold monolayers film on silicon substrate.Equally, the sensor is by conventional electron beam coating technique system
It is standby to form.Single layer bovine serum albumin(BSA) (BSA) molecule is adsorbed on golden film surface by self assembling process in solution.Fig. 8 is the device
The Infrared Reflective Spectra of part.It can be clearly seen in 1546cm-1 and 1664cm-1 there are two absorption peak, correspond respectively to BSA egg
The characteristic absorption of Amide II and Amide the I functional group of white molecule, realizes the fingerprint detection of BSA molecule.When angle increases
When, this absorption peak at two becomes larger, and at 80 degree of angles, the depth of absorption peak reaches 1.14% and 0.5% at two, realizes single point
Effective detection of sublayer BSA.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understand without departing from the principles and spirit of the present invention can to these examples carry out it is a variety of variation, modification, replacement and
Modification, the scope of the present invention is defined by the appended.
Claims (6)
1. a kind of infrared molecular fingerprint sensor of flat film structure, which is characterized in that the infrared molecular fingerprint sensing
Device includes duplicature planar structure sensor and monofilm planar structure sensor, the duplicature planar structure sensor by
Copper and zinc selenide two membranes on silicon substrate are constituted；Monofilm planar structure sensor structure by the golden film on silicon substrate
At.
2. a kind of infrared molecular fingerprint sensor of flat film structure according to claim 1, which is characterized in that described
Duplicature planar structure sensor by setting quarter-wave for the thickness of ZnSe dielectric layer.
3. a kind of infrared molecular fingerprint sensor of flat film structure according to claim 1, which is characterized in that described
Discontinuity boundary condition of the monofilm planar structure sensor based on light field in gold surface, incident electric fields of gold surface and anti-
The superposition of radio field makes electric-field enhancing, to realize effective detection to molecule to be checked.
4. the preparation method of molecular fingerprint sensor described in claim 1, which comprises the following steps:
1) the single layer golden film greater than 100nm is prepared on silicon wafer with electron beam vacuum coating technology or be greater than 100nm copper/tetra-
/ mono- wavelength thickness ZnSe two membranes；
2) film sample of preparation is placed in molecular solution soaking to be checked 24 hours；
3) ethyl alcohol and deionized water is used to rinse respectively the film sample after soaking, then with being dried with nitrogen to complete molecule to be checked
In the absorption self assembly of sensor surface.
5. the preparation method according to claim 4, which is characterized in that organic for typical test object stearylmercaptan ODT
Molecule, solvent is ethyl alcohol in solution, and ODT concentration proportioning is 1mM/L.
6. the preparation method according to claim 4, which is characterized in that molten in solution for bovine serum albumin(BSA) BSA molecule
Agent is phosphate buffered saline (PBS), and BSA concentration proportioning is 1mg/ml.
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