CN208076440U - A kind of hanging molybdenum disulfide flexibility ion transducer - Google Patents

A kind of hanging molybdenum disulfide flexibility ion transducer Download PDF

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CN208076440U
CN208076440U CN201820495830.XU CN201820495830U CN208076440U CN 208076440 U CN208076440 U CN 208076440U CN 201820495830 U CN201820495830 U CN 201820495830U CN 208076440 U CN208076440 U CN 208076440U
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boron nitride
molybdenum
molybdenum disulfide
disulfide
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李鹏
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Tsinghua University
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Tsinghua University
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Abstract

A kind of hanging molybdenum disulfide flexibility ion transducer, including the boron nitride, molybdenum disulfide, the boron nitride that link together from top to bottom, metal electrode, flexible substrates;The molybdenum disulfide is located at below boron nitride, is located above boron nitride;The molybdenum disulfide and boron nitride, boron nitride form compound girder construction, and beam both ends are contacted with metal electrode respectively, and middle section is hanging;Flexible substrates are located at below the compound girder construction overhanging portion.Boron nitride is as protective layer; vapor effectively in isolation molybdenum disulfide upper and lower surface and air and air contacts, and prevents molybdenum disulfide from degenerating in air; hanging structure can prevent molybdenum disulfide to be in direct contact with flexible substrates, so as to avoid substrate from influencing the scattering of molybdenum disulfide;This structure can make molybdenum disulfide ion transducer obtain better Monitoring lower-cut, improve long-time stability, and reduce influence of the substrate deformation to device.

Description

A kind of hanging molybdenum disulfide flexibility ion transducer
Technical field
The utility model is related to MEMS technology field, more particularly to a kind of hanging molybdenum disulfide flexibility ion transducer is A kind of hanging molybdenum disulfide sensor structure with nitridation boron protective layer, the structure can be such that molybdenum disulfide ion transducer obtains Better Monitoring lower-cut improves long-time stability, reduces influence of the deformation to device.
Background technology
Currently, the bottleneck of wearable flexible sensor development is that the performance of sensitive material cannot be satisfied demand.Two-dimentional material The appearance of material molybdenum disulfide brings hope in order to solve the above problem.There is molybdenum disulfide great specific surface area (can be promoted sensitive Degree;Extremely low noise (can get better Monitoring lower-cut;High breaking strain (bend resistance;Potentiality easy to process and integrated, because This is ideal sensitive material.
The molybdenum disulfide sensor performance of document report is restricted by device architecture at present, in the prior art molybdenum disulfide Ion transducer common structure refers to Fig. 1, in figure, 1-1-molybdenum disulfide, 1-2-metal electrode, 1-3-substrate;Curing Molybdenum 1-1 is in direct contact with substrate 1-3, and substrate surface dangling bonds form strong scattering to molybdenum disulfide inside carrier, and increase is made an uproar Sound floods useful signal, and device is made to be unable to reach due ultralow Monitoring lower-cut.Molybdenum disulfide upper surface is chronically exposed to air In, oxygen, vapor etc. can make its electrology characteristic gradually degenerate, and so that device performance is generated apparent drift, influence long-time stability (Selective gas sensing with h-BN capped MoS2heterostructrue thin-film transistors,G. Liu,IEEE Electron Device Letters,2015,36,1202-1204.Molybdenum disulfide has There are piezoresistive effect, resistance value to generate significant change (Peizoresistivity and strin-induced band with stress gap tuning in atomically thin MoS2,S.Manzeli,et al,Nano Letters,2015,15,5330- 5335, with reference to Fig. 2.Wearable flexible device needs often to generate compared with large deformation, and piezoresistive effect reduces molybdenum disulfide sensor Stability during dynamic use.The above non-ideal factor makes MoS2Excellent material property is unable to give full play, and is reduced Sensor performance.
Therefore a kind of MEMS new constructions easy to process are needed, can effectively promotes the property of molybdenum disulfide ion transducer Energy.
Invention content
In order to overcome the defect of the above-mentioned prior art, the purpose of this utility model is to provide a kind of hanging molybdenum disulfide is soft Property ion transducer, using boron nitride wrap up molybdenum disulfide upper and lower surface, prevent its electrology characteristic from gradually degenerating in air;It adopts Molybdenum disulfide is isolated with substrate with hanging structure, substrate scattering is avoided to influence;Hanging molybdenum disulfide composite beam is set to form relaxation Structure reduces influence of the stress to sensor in substrate deformation process.
In order to achieve the above object, the utility model is realized by following methods:
A kind of hanging molybdenum disulfide flexibility ion transducer, which is characterized in that including the nitrogen to link together from top to bottom Change boron layer, layer of molybdenum-disulfide, boron nitride layer, metal electrode and flexible substrates;The layer of molybdenum-disulfide is located at below boron nitride layer, Above boron nitride layer, and layer of molybdenum-disulfide and boron nitride layer, boron nitride layer form compound girder construction, composite beam both ends difference It is connect with metal electrode, composite beam middle section is hanging;The flexible substrates are located at below the compound girder construction overhanging portion.
The layer of molybdenum-disulfide be single-layer or multi-layer, generally 1-10 layers.
The boron nitride layer, boron nitride layer be single-layer or multi-layer, generally 1-10 layers.
The layer of molybdenum-disulfide, boron nitride layer and boron nitride layer form in the intermediate overhanging portion of compound girder construction, two sulphur It is identical with the shape of boron nitride layer, area to change molybdenum layer, boron nitride layer;It is covered completely by boron nitride layer the upper surface of layer of molybdenum-disulfide Lid, layer of molybdenum-disulfide lower surface, which is removed, to be completely covered with metal electrode contact portion, rest part by boron nitride layer.
The composite beam overhanging portion length is more than two metal electrode spacing, is in relaxed state.
The metal electrode is formed in flexible substrates upper surface, wherein metal material by sputtering or vapor deposition or other methods Material selects any one in Au, Ag, Cu, Al, Pt.
Region entirety of the flexible substrates surface in addition to metal electrode is to 1-10 microns of lower recess.
The utility model has the beneficial effects that:
(1 avoids substrate scattering from influencing, and reduces Monitoring lower-cut.The dangling bonds of substrate surface can generate molybdenum disulfide strong Scattering, and generate apparent low-frequency noise.Hanging structure can prevent molybdenum disulfide to be in direct contact with substrate, so as to keep away Exempting from substrate, (boron nitride does not hang and is good for, and can ignore to the scattering of molybdenum disulfide on the scattering of molybdenum disulfide influence.Sensor Monitoring lower-cut ultimately depends on signal-to-noise ratio, therefore reducing noise by hanging structure can be such that sensor reaches under lower detection Limit.
(2 avoid environment from influencing, and improve long-time stability.Boron nitride can effectively completely cut off on molybdenum disulfide as protective layer Vapor contact in lower surface and air and air, prevents molybdenum disulfide from degenerating in air, and then promote long term device Stability.
(3 reduce substrate influence of crust deformation.Wearable flexible device needs often to generate compared with large deformation, it is generally the case that two sulphur Changing molybdenum with substrate deformation together, can make the performance of sensor that respective change occur.In the technical program, the compressive deformation of substrate is only Composite beam can be made more to relax, not will produce apparent stress, the stretching of substrate in a certain range will not make composite beam complete It stretches, it is ensured that composite beam remains relaxed state in deformation process, avoids the internal apparent tensile stress of generation, reduces shape Become the adverse effect generated to sensor performance, more stable can be measured into Mobile state.
Description of the drawings
Fig. 1 is molybdenum disulfide ion transducer common structure in the prior art.
Fig. 2 is the measurement result figure of molybdenum disulfide piezoresistive effect, and molybdenum disulfide resistance value becomes with the shape generates significant change.
Fig. 3 is the hanging molybdenum disulfide sensor structure side view with nitridation boron protective layer of the utility model, in figure, 2-1-boron nitride, 2-2-molybdenum disulfide, 2-3-boron nitride, 2-4-metal electrode, 2-5-flexible substrates.
Fig. 4 is the hanging molybdenum disulfide sensor structure vertical view with nitridation boron protective layer of the utility model, in figure, 2-1-boron nitride, 2-4-metal electrode, 2-5 flexible substrates.
Fig. 5 is the molybdenum disulfide sensor flow process chart of the utility model.
Fig. 6 be with nitridation boron protective layer molybdenum disulfide ion transducer to different hydrogen ion concentrations (different pH value Response results figure.
Specific implementation mode
The technical solution of the utility model is described further with reference to the accompanying drawings and embodiments.
With reference to Fig. 3, Fig. 4, a kind of hanging molybdenum disulfide flexibility ion transducer, which is characterized in that including connecting from top to bottom Boron nitride layer 2-1, layer of molybdenum-disulfide 2-2, the boron nitride layer 2-3 being connected together, metal electrode 2-4 and flexible substrates 2-5;It is described Layer of molybdenum-disulfide 2-2 is located at below boron nitride layer 2-1, is located above boron nitride layer 2-3, and layer of molybdenum-disulfide 2-2 and boron nitride Layer 2-1, boron nitride layer 2-3 form compound girder construction, and composite beam both ends are connect with metal electrode 2-4 respectively, composite beam middle part Divide hanging;The flexible substrates 2-5 is located at below the compound girder construction overhanging portion.
The layer of molybdenum-disulfide 2-2 be single-layer or multi-layer, generally 1-10 layers.
The boron nitride layer 2-1, boron nitride layer 2-3 be single-layer or multi-layer, generally 1-10 layers.
The layer of molybdenum-disulfide 2-2, boron nitride layer 2-1 and boron nitride layer 2-3 form the intermediate suspending part of compound girder construction In point, layer of molybdenum-disulfide 2-2, boron nitride layer 2-1 are identical with the shape of boron nitride layer 2-3, area;Layer of molybdenum-disulfide 2-2's is upper Surface is completely covered by boron nitride layer 2-1, and the lower surfaces layer of molybdenum-disulfide 2-2 remove and metal electrode contact portion, rest part It is completely covered by boron nitride layer 2-3.
The composite beam overhanging portion length is more than two metal electrode spacing, is in relaxed state.
The metal electrode 2-4 is formed in the upper surfaces flexible substrates 2-5 by sputtering or vapor deposition or other methods, wherein Metal material selects any one in Au, Ag, Cu, Al, Pt.
Region entirety of the surfaces the flexible substrates 2-5 in addition to metal electrode is to 1-10 microns of lower recess.
The operation principle of the utility model is:Be adsorbed on composite beam surface is led to layer of molybdenum-disulfide 2-2's by measured ion Carrier concentration changes, and then leads to the change in resistance of layer of molybdenum-disulfide 2-2.Boron nitride 2-1 effectively completely cuts off as protective layer Vapor contact in molybdenum disulfide 2-2 upper and lower surfaces and air and air, prevents molybdenum disulfide from degenerating in air, hangs Hollow structure can prevent molybdenum disulfide 2-2 to be in direct contact with flexible substrates 2-5, so as to avoid substrate to molybdenum disulfide Scattering influences.
With reference to Fig. 5, the sensing implement body processing flow of the utility model is as follows:
(1) substrate is processed with metal electrode
In the one layer of negative photoresist (spin coating of spin coating of flexible polymer PET (polyethylene terephthalate) substrate surfaces Machine rotating speed 1000-4000RPM, time 30-90 second), it is heated 1-2 minutes for 90-120 DEG C on hot plate.Pass through (1-2 points of exposure Clock), it is rear to dry (90-120 DEG C, 2-3 minutes), keep it graphical with development (being impregnated 1-2 minutes in RD6 developer solutions).Using sputtering Technique grows the gold of 10 nano-titaniums and 50-100 nano thickness.Sample is impregnated in acetone, and is assisted with sonic oscillation, purpose It is the metal (stripping technology) for removing photoresist and the attachment of photoresist surface.Metal layer image is realized by stripping technology Change, forms metal electrode.Using dry etching, flexible polymer substrate surface is not etched downwards by the region that metal layer is protected 1-10 microns.Ensure that composite beam can not be contacted with substrate by etching depth.
(2) prepared by layer of molybdenum-disulfide/boron nitride layer
Layer of molybdenum-disulfide and boron nitride layer are prepared using chemical vapour deposition technique respectively.Pass through PDMS (polydimethylsiloxanes Alkane) layer of molybdenum-disulfide is transferred on first layer boron nitride layer, second layer boron nitride is transferred on layer of molybdenum-disulfide.It is logical Dry etch process is crossed by boron nitride layer/layer of molybdenum-disulfide/boron nitride layer/graphical.
(3) composite beam hanging structure is processed
Under an optical microscope, by microoperation technology will it is graphical after boron nitride layer/layer of molybdenum-disulfide/nitridation Right over boron layer/alignment base metal electrode.By adjustable range, make boron nitride layer/layer of molybdenum-disulfide/boron nitride layer/and base Electrode on bottom is longitudinal slowly close, and constantly accurately adjusts its laterally opposed position, finally makes layer of molybdenum-disulfide/boron nitride Layer/layer of molybdenum-disulfide is contacted with the electrode on both sides.Sample after fitting is heated 5-10 minutes on 90-120 DEG C of hot plate, is made Established between boron nitride and metal it is stronger contact, formed two fixed ends hanging structure.
(4) molybdenum disulfide transducer calibration and test
It uses the standard ionomer solution of various concentration to submerge molybdenum disulfide sensor respectively first, waits for 1-5 minutes sensors The resistance value of molybdenum disulfide between two metal electrodes is obtained using multimeter or semiconductor parametric tester measurement after stabilization, Changing rule of the sensor with ion concentration can be specified by calibration process.Detected solution immersion sensor portion is used later Point, wait for measuring its resistance value after sensor stabilization, and compare with calibration result, and then can obtain in detected solution it is to be measured from Sub- concentration value, with reference to Fig. 6.
Test result molybdenum disulfide ion transducer of the proof based on the utility model more preferable, substrate with long-time stability The small feature of influence of the deformation to device.

Claims (8)

1. a kind of hanging molybdenum disulfide flexibility ion transducer, which is characterized in that including the nitridation to link together from top to bottom Boron layer (2-1), layer of molybdenum-disulfide (2-2), boron nitride layer (2-3), metal electrode (2-4) and flexible substrates (2-5);Two sulphur Change molybdenum layer (2-2) to be located at below boron nitride layer (2-1), be located above boron nitride layer (2-3), and layer of molybdenum-disulfide (2-2) and nitrogen Change boron layer (2-1), the compound girder construction of boron nitride layer (2-3) composition, composite beam both ends are connect with metal electrode (2-4) respectively, multiple The middle sections He Liang are hanging;The flexible substrates (2-5) are located at below the compound girder construction overhanging portion.
2. a kind of hanging molybdenum disulfide flexibility ion transducer according to claim 1, which is characterized in that the curing Molybdenum layer (2-2) be single-layer or multi-layer, generally 1-10 layers.
3. a kind of hanging molybdenum disulfide flexibility ion transducer according to claim 1, which is characterized in that the boron nitride Layer (2-1), boron nitride layer (2-3) be single-layer or multi-layer, generally 1-10 layers.
4. a kind of hanging molybdenum disulfide flexibility ion transducer according to claim 1, which is characterized in that the curing Molybdenum layer (2-2), boron nitride layer (2-1) and boron nitride layer (2-3) form in the intermediate overhanging portion of compound girder construction, molybdenum disulfide Layer (2-2), boron nitride layer (2-1) are identical with the shape of boron nitride layer (2-3), area;The upper surface quilt of layer of molybdenum-disulfide (2-2) Boron nitride layer (2-1) is completely covered, and the lower surface layer of molybdenum-disulfide (2-2) removes and metal electrode contact portion, rest part quilt Boron nitride layer (2-3) is completely covered.
5. a kind of hanging molybdenum disulfide flexibility ion transducer according to claim 1, which is characterized in that the composite beam Overhanging portion length is more than two metal electrode spacing, is in relaxed state.
6. a kind of hanging molybdenum disulfide flexibility ion transducer according to claim 1, which is characterized in that the metal electricity Pole (2-4) by sputtering or vapor deposition or other methods are formed in the upper surface flexible substrates (2-5), wherein metal material select Au, Any one in Ag, Cu, Al, Pt.
7. a kind of hanging molybdenum disulfide flexibility ion transducer according to claim 1, which is characterized in that the curing Molybdenum layer (2-2) is 1-10 layers.
8. a kind of hanging molybdenum disulfide flexibility ion transducer according to claim 1, which is characterized in that the boron nitride Layer (2-1), boron nitride layer (2-3) are 1-10 layers.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108279260A (en) * 2018-04-09 2018-07-13 清华大学 A kind of molybdenum disulfide flexibility ion transducer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108279260A (en) * 2018-04-09 2018-07-13 清华大学 A kind of molybdenum disulfide flexibility ion transducer
CN108279260B (en) * 2018-04-09 2023-11-14 清华大学 Molybdenum disulfide flexible ion sensor

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