CN105355702B - Graphene plasmon device used for enhancing infrared spectrum detection and preparation method thereof - Google Patents
Graphene plasmon device used for enhancing infrared spectrum detection and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
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- 238000002329 infrared spectrum Methods 0.000 title claims abstract description 13
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
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- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
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Abstract
The invention provides a graphene plasmon device used for enhancing infrared spectrum detection. The graphene plasmon device comprises a substrate, a dielectric layer, a graphene layer, a source electrode, a drain electrode metal layer and material to be detected which are arranged from the bottom to the top in turn. The substrate also acts as a gate electrode. The dielectric layer is deposited on the substrate. The graphene layer covers the dielectric layer. The source electrode and the drain electrode metal layer are deposited on the graphene layer. The source electrode and the drain electrode metal layer are conducted by graphene. The dielectric layer is clamped between the substrate and the graphene layer. The partial region of the graphene layer between the source electrode and the drain electrode metal layer has a periodic micro-nano structure which includes multiple continuous structures with step-shaped longitudinal sections. A material layer to be detected is arranged to cover the step-shaped structures. The material of the dielectric layer is selected from NaCl, KBr, CsI, CsBr, MgF2, CaF2, BaF2, LiF, AgBr, AgCl, ZnS, ZnSe, KRS-5, AMTIR1-6, Diamond and SiO2.
Description
Technical field
The present invention relates to infrared light detecting technical field, more particularly to a kind of Graphene for strengthening infrared spectrum detection
Phasmon device and preparation method thereof.
Background technology
Infrared spectrum technology is that a kind of direct detection molecular vibrational mode is realized carrying out material feature recognition and quantitative point
The technology and method of analysis.The technology has " fingerprint " characteristic of height, without the need for sample mark, fast response time, instrument popularization
Rate highest, the advantages of spectrum picture library is most complete, is to determine molecular composition, powerful tools of conformation and structure change information and can not
Or scarce means, it is widely used to environmental monitoring, food safety detection, chemical composition analysis, explosive detection and biological doctor
Treat etc. involve the interests of the state and the people and lifelines of the national economy key areas.
Infra-red radiation includes abundant objective information, and its detection receives much attention.Infrared Detectors covered shortwave, medium wave with
Long wave limit, is widely applied in military and civilian field.Its detection principle is the opto-electronic conversion performance for utilizing material, will
The photon signal of infra-red radiation is converted to electronic signal, and the target of detection infrared signal is reached in combination with external circuit.
Graphene is the two dimensional crystal of monolayer carbon atomic building, the thickness about 0.35nm of mono-layer graphite.Currently, less than ten layers
Graphite be looked at as Graphene.With excellent mechanics, calorifics, electrical and optical properties, in electronic device and phototube
Part field has huge applications potentiality.Existing graphene-based photoelectric sensor not only have detecting light spectrum wide ranges, responsiveness it is high,
The advantage that speed is fast and noise is low, and it is easily mutually compatible with existing silicon base CMOS integrated circuit technology, realize that extensive, low cost is passed
The production of sensor array.Up to the present, the research of graphene-based photodetector is mainly concentrated in improving Graphene
Absorptivity.For example, using pyroelectric effect, metal exciton structure, Graphene exciton or for micro-cavity structure etc..
Surface-enhanced infrared spectroscopy technology (Surface-Enhanced Infrared Absorption) can show
Writing strengthens the Infrared spectra adsorption feature of tested molecule, and the sensitivity and accuracy for making molecular spectrum is increased substantially, gradually
Become micro detection and monomolecular feature, characterize the effective test analysis instrument of fine molecular structure.But the current technology
Presence enhancing wave band is very narrow, detectivity is extremely restricted, the defect that repeatability has much room for improvement, and does not possess trace molecule
The universal significance of detection.
The content of the invention
The invention provides a kind of Graphene phasmon device for strengthening infrared spectrum detection, including：From lower and
On the substrate, dielectric layer, graphene layer, source electrode and the drain metal layer that set gradually, and material to be detected；Wherein, it is described
Simultaneously as grid, over the substrate, graphene layer is covered on dielectric layer the dielectric deposition substrate, source electrode
It is deposited upon on graphene layer with drain metal, source electrode is turned on drain metal layer by Graphene, between substrate and graphene layer
Dielectric layer is clipped, similar plate capacitor structure is constituted；The office of the graphene layer between the source electrode and drain metal layer
Portion region has periodicity micro nano structure；The periodicity micro nano structure is step-like knot comprising multiple continuous vertical sections
Structure, the edge of the step-like structure in infrared ray excited lower generation local phasmon, the detected materials layer arrange with
Cover the step-like structure；The material of the dielectric layer is selected from：NaCl, KBr, CsI, CsBr, MgF2, CaF2, BaF2,
LiF, AgBr, AgCl, ZnS, ZnSe, KRS-5, AMTIR1-6, Diamond, SiO2。
Preferably, the step-like structure is the structure of blind hole or through hole.
Preferably, the horizontal tangent plane of the through hole or blind hole be annular, circle, ellipse, triangle, regular hexagon,
Rectangle, pentagon structure.
Preferably, the annular, circle, ellipse, triangle, regular hexagon, rectangle, the aperture of pentagon structure
For 10-1000nm.
Preferably, the thickness range of the dielectric layer is：10-1000nm.
Preferably, the preparation method of described Graphene phasmon device, in accordance with the following steps：
(1) dielectric layer is prepared：Using the method for electron beam evaporation plating, atomic deposition or molecular beam epitaxial growth on substrate
Dielectric layer film is prepared as without infrared-active dielectric substrate；
(2) graphene film is prepared：Graphene is obtained by standard mechanical stripping technology or chemical vapour deposition technique thin
Film；
(3) graphene film is shifted：The graphene film of stripping is transferred in the dielectric substrate of above-mentioned preparation；
(4) plasma etching is combined using ultraviolet photolithographic, electron beam exposure, nano impression, prepares the micro-nano knot of Graphene
Structure；
(5) source electrode and drain metal layer are made：Using the method system of ultraviolet photolithographic, atomic deposition or molecular beam epitaxial growth
Standby electrode；
(6) test substance is uniformly prepared to the surface of Graphene micro nano structure.
Preferably, the step-like structure is the structure of through hole or blind hole.
Preferably, the horizontal tangent plane of through hole or blind hole is annular, circle, ellipse, triangle, regular hexagon, rectangular
Shape, pentagon structure.
Preferably, wherein annular, circle, ellipse, triangle, regular hexagon, rectangle, the aperture of pentagon structure
For 10-1000nm.
It should be appreciated that aforementioned description substantially and follow-up description in detail are exemplary illustration and explanation, should not
As the restriction to claimed content of the invention.
Description of the drawings
With reference to the accompanying drawing enclosed, the present invention more purpose, function and advantages are by by the as follows of embodiment of the present invention
Description is illustrated, wherein：
Fig. 1 is that the longitudinal profile for strengthening the Graphene phasmon device of infrared spectrum detection of the present invention is illustrated
Figure.
Fig. 2 a-2g are that the Graphene phasmon device for strengthening infrared spectrum detection of the present invention is periodically micro-nano
Structural representation.
Fig. 3 a-3b are the longitudinal profile enlarged drawing of the Graphene micro nano structure of the present invention.
Fig. 4 is the preparation method flow process for strengthening the Graphene phasmon device of infrared spectrum detection of the present invention
Figure.
The accompanying drawing is only schematically and draws not in scale.Although entering to the present invention already in connection with preferred embodiment
Description is gone, it is to be understood that protection scope of the present invention is not limited to embodiment as described herein.
Specific embodiment
By reference to one exemplary embodiment, the purpose of the present invention and function and the side for realizing these purposes and function
Method will be illustrated.However, the present invention is not limited to one exemplary embodiment disclosed below；Can by multi-form come
It is realized.The essence of specification is only to aid in the detail of the various equivalent modifications Integrated Understanding present invention.
Hereinafter, embodiments of the invention will be described with reference to the drawings.In the accompanying drawings, identical reference represents identical
Or similar part, or same or like step.
A kind of longitudinal profile schematic diagram for strengthening the Graphene phasmon device of infrared spectrum detection of the present invention
As shown in Figure 1.
The Graphene phasmon device 100 includes substrate 101, the dielectric layer 102, stone for setting gradually from bottom to top
Black alkene layer 103, source electrode 104 and drain metal layer 105.The substrate 101 is silicon substrate, and substrate is simultaneously as grid, dielectric
On the substrate 101, graphene layer 103 is covered on dielectric layer 102 deposition of layer 102, and source electrode is deposited upon with drain metal
On graphene layer, source electrode is turned on drain metal layer by Graphene, and between substrate 101 and graphene layer 105 dielectric layer is clipped
102, similar plate capacitor structure is constituted, source electrode 104, drain electrode 105 also constitute similar plane-parallel capacitor knot with substrate 101
Structure, can be doped to graphene layer.Regional area on the graphene layer 103 at least between source electrode 104 and drain electrode 105
Graphene layer on have periodicity micro nano structure.As shown in Fig. 2 a-2g, the Graphene micro nano structure is step-like knot
Structure, the step-like structure is in the transverse direction of Graphene phasmon device in annulus, circle, ellipse, triangle, just
Hexagon, rectangle, pentagonal structure, the diameter range of these structures is in 10-1000nm.By taking Fig. 2 a as an example, in graphite
Circular through hole 202 is etched on alkene layer 201, to form Graphene micro nano structure.Can produce at the edge of these structures
From excimer, the molecular vibration of detected materials is strengthened under the strong local electromagnetic field effect of phasmon, and then is strengthened to be measured
The INFRARED ABSORPTION of material.The enlarged drawing of step-like structure longitudinal profile is as shown in Figure 3 a-3b.Step-like structure in Fig. 3 a is blind
Hole 301, and this kind of step-like structure can produce the structure (302) of square edge on graphene layer, when test substance 306 is applied
On Graphene micro nano structure, by increasing capacitance it is possible to increase the contact area with graphene-structured edge, and the phasmon energy of edge
Enough ratio of infrared absorption intensity for effectively strengthening test substance.Likewise, the step-like structure in Fig. 3 b is through hole 303, it is equally
The structure of square edge can be produced.The edge of these step-like structures can be in infrared ray excited lower generation local phasmon.
Aforesaid substrate can select but be not limited to the hard such as silicon chip, glass, plastics, stainless steel or flexible substrate, for supporting Graphene micro-
Nanostructured.
Dielectric layer 102 is deposited on substrate 101, and the material of dielectric layer 102 is selected from NaCl, KBr, CsI, CsBr,
MgF2, CaF2, BaF2, LiF, AgBr, AgCl, ZnS, ZnSe, KRS-5, AMTIR1-6, Diamond, SiO2.Preferably, this
On the one hand the dielectric layer material (calcirm-fluoride or magnesium fluoride) used in bright specific embodiment has dielectric properties, on the other hand several
Without infrared-active vibration mode, the interference of detection can be reduced, improve sensitivity.Micro-structural on graphene layer can be with
Strengthen the INFRARED ABSORPTION with detectable substance near it, fingerprint region (675-1500cm can be realized-1) detection, using different Jie
During electric layer even can be realized, far infrared (400-4000cm-1) detection.
Graphene layer 103 is covered on the dielectric layer 102 as the channel layer of the phasmon device 100,
The graphene layer 103 includes Graphene more than individual layer, two-layer or two-layer, it is preferable that can adopt the Graphene of 1-3 layers, its
It is covered on dielectric layer 102, and contacts with source electrode 104 and 105 lower surfaces of drain electrode, forms source electrode with drain metal interlayer
Conducting channel.
Source electrode 104 forms respectively the two ends of channel layer with 105 metal levels of drain electrode, and it is electrically connected with raceway groove.Institute
It is not determinate that source electrode is stated with the material of drain metal layer, may be selected from and be not limited to the single gold such as gold, silver, copper, aluminium, platinum, titanium
The overlaying structure of category layer, alloy-layer or various single metal levels or alloy-layer, its thickness is preferably 10-1000nm.According to this
Bright one embodiment, source electrode is gold with the material of drain metal layer.
In one embodiment of the invention, dielectric layer 102 selects MgF2, this is due to MgF2Itself chemistry, physics and
Thermal stability is good.And, it has good saturating infrared optical property (91000-1100nm).In addition, its dielectric constant
Higher (5.45), be it is a kind of can be used as the material of dielectric layer.
CaF2, BaF2With MgF2Similar, itself chemistry, physically and thermally stability are well and with good saturating infrared light
Performance (91000-1100nm).
ZnS, ZnSe belong to the semiconductor of broad stopband, and dielectric properties do not have calcirm-fluoride good.But thoroughly infrared performance all compares
It is advantageous.
NaCl, KBr, CaF2, BaF2, with CaF2, BaF2With MgF2Similar, itself chemistry, physically and thermally stability are good.
And, it has good saturating infrared optical property (91000-1100nm).In addition, they are all can be used as the material of dielectric layer
Material.Simply property soluble in water can limit its application.
Fig. 4 is the preparation method flow process for strengthening the Graphene phasmon device of infrared spectrum detection of the present invention
Figure.
First, step 401, makes substrate.The material that substrate 101 can be penetrated by middle infrared (Mid-IR) and far infrared, such as silicon
Piece, quartz etc., the infrared detection for graphene channel layers provides condition；
Then, step 402, prepares dielectric layer, using the side of electron beam evaporation plating, atomic deposition or molecular beam epitaxial growth
Method prepares dielectric layer film (10-1000nm) as without infrared-active dielectric substrate on substrate；
Step 403, prepares graphene film：Graphite is obtained by standard mechanical stripping technology or chemical vapour deposition technique
Alkene film；
Step 404, shifts graphene film：The graphene film of stripping is transferred in the dielectric substrate of above-mentioned preparation；
Step 405, using ultraviolet photolithographic, electron beam exposure, nano impression plasma etching is combined, and prepares Graphene micro-nano
Rice structure, the Graphene micro nano structure be annulus, circular hole, elliptical aperture, tri-angle-holed, regular hexagon hole, slot, five
The structure in angle star hole；
Step 406, makes source electrode and drain metal layer：Using electron beam evaporation plating, atomic deposition or molecular beam epitaxial growth
Method prepare electrode.As shown in figure 1, in this step, the drain electrode of source electrode 104 105 is formed by composition simultaneously, and source electrode 104 drains
105 can form Ohmic contact with Graphene.
Step 407, test substance is uniformly prepared to the surface of Graphene micro nano structure：Test substance film is by rotation
Apply or the tape casting is covered on Graphene micro nano structure.For example, it is with 1g PEO powder if test substance is PEO films
Last (molecular weight 100000) is dissolved in 60mL methanol solutions, and then 2000 (revs/min) are spun on Graphene micro nano structure
Surface.
So far, the Graphene phasmon device shown in Fig. 4 prepares to be formed substantially.
The Graphene phasmon device of the present invention has following advantage for infrared detection field：(1) Graphene is micro-
Structure is subject to infrared ray excited phasmon, and the local electromagnetic field formed around Graphene micro-structural can strengthen thing to be detected
The INFRARED ABSORPTION (experiment measures 5 times or so) of matter；(2) unique adjustability of Graphene phasmon, can be in infrared detection
The middle voltage modulated for realizing physical dimension regulation and control, dielectric substrate regulation and control and uniqueness, can realize near with reference to this several modulation
It is infrared in, the region (400-4000cm of far infrared band-1) detection；(3) dielectric substrate that this experiment is used has extremely low
Infrared active, can reduce the interference of detection, improve sensitivity.And fingerprint region (675-1500cm can be realized-1) inspection
Survey.
With reference to the explanation of the invention and practice that disclose here, the other embodiment of the present invention is for those skilled in the art
All will be readily apparent and understand.Illustrate and embodiment be to be considered only as it is exemplary, the present invention true scope and purport it is equal
It is defined in the claims.
Claims (9)
1. a kind of Graphene phasmon device for strengthening infrared spectrum detection, including：The lining for setting gradually from bottom to top
Bottom, dielectric layer, graphene layer, source electrode and drain metal layer, and material to be detected；
Wherein, simultaneously as grid, over the substrate, graphene layer is covered in electric Jie to the dielectric deposition to the substrate
On matter layer, source electrode and drain metal are deposited upon on graphene layer, and source electrode is turned on drain metal layer by Graphene, substrate with
Dielectric layer is clipped between graphene layer, similar plate capacitor structure is constituted；
The regional area of the graphene layer between the source electrode and drain metal layer has periodicity micro nano structure；
The periodicity micro nano structure is step-like structure comprising multiple continuous vertical sections, the side of the step-like structure
Edge is arranged to cover the step-like structure in infrared ray excited lower generation local phasmon, the material layer to be detected,
The step-like structure has square edge；
The material of the dielectric layer is selected from：NaCl, KBr, CsI, CsBr, MgF2, CaF2, BaF2, LiF, AgBr, AgCl, ZnS,
ZnSe, KRS-5, AMTIR1-6, Diamond, SiO2。
2. phasmon device according to claim 1, the step-like structure is the structure of blind hole or through hole.
3. the horizontal tangent plane of phasmon device according to claim 2, the through hole or blind hole be annular, circle,
Ellipse, triangle, regular hexagon, rectangle, pentagon structure.
4. phasmon device according to claim 3, the annular, circle, ellipse, triangle, regular hexagon,
Rectangle, the aperture of pentagon structure are 10-1000nm.
5. phasmon device according to claim 1, the thickness range of the dielectric layer is：10-1000nm.
6. the preparation method of Graphene phasmon device as claimed in claim 1, wherein, in accordance with the following steps：
(1) dielectric layer is prepared：Prepared on substrate using the method for electron beam evaporation plating, atomic deposition or molecular beam epitaxial growth
Dielectric layer film is used as without infrared-active dielectric substrate；
(2) graphene film is prepared：Graphene film is obtained by standard mechanical stripping technology or chemical vapour deposition technique；
(3) graphene film is shifted：The graphene film of stripping is transferred in the dielectric substrate of above-mentioned preparation；
(4) plasma etching is combined using ultraviolet photolithographic, electron beam exposure, nano impression, prepares Graphene micro nano structure, institute
Micro nano structure is stated including multiple step-like structures with square edge；
(5) source electrode and drain metal layer are made：Electricity is prepared using the method for ultraviolet photolithographic, atomic deposition or molecular beam epitaxial growth
Pole；
(6) material to be detected is uniformly prepared to the surface of Graphene micro nano structure.
7. the preparation method of Graphene phasmon device as claimed in claim 6, wherein the step-like structure is logical
Hole or the structure of blind hole.
8. the preparation method of Graphene phasmon device as claimed in claim 7, the wherein horizontal tangent plane of through hole or blind hole
For annular, circle, ellipse, triangle, regular hexagon, rectangle, pentagon structure.
9. the preparation method of Graphene phasmon device as claimed in claim 8, wherein annular, circle, ellipse, three
Angular, regular hexagon, rectangle, the aperture of pentagon structure are 10-1000nm.
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| CN104022186A (en) * | 2014-06-19 | 2014-09-03 | 电子科技大学 | Method for manufacturing black silicon material for enhancing infrared absorption |
| CN104993056A (en) * | 2015-06-11 | 2015-10-21 | 上海电力学院 | Wide-spectrum flexible photoelectric detector and making method thereof |
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