CN106501455A - A kind of preparation method of the highly sensitive stretchable biosensor in situ detection - Google Patents

A kind of preparation method of the highly sensitive stretchable biosensor in situ detection Download PDF

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CN106501455A
CN106501455A CN201610955194.XA CN201610955194A CN106501455A CN 106501455 A CN106501455 A CN 106501455A CN 201610955194 A CN201610955194 A CN 201610955194A CN 106501455 A CN106501455 A CN 106501455A
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molybdenum bisuphide
stretchable
substrate
foam
biosensor
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CN106501455B (en
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杨诚
刘子函
欧佳瑜
李天明
潘萧萧
徐媛媛
刘玫
姜守振
满宝元
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Shandong Normal University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/04—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by dissolving-out added substances
    • C04B38/045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by dissolving-out added substances the dissolved-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a prepreg obtained by bonding together dissolvable particles
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116—Ag or Au
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal

Abstract

The present invention relates to a kind of preparation method of the highly sensitive stretchable biosensor in situ detection, using chemical vapour deposition technique in 3 D stereo Grown molybdenum bisuphide；Then molybdenum bisuphide/the foam metal of preparation is immersed in etching solution; gone divided by going metal substrate by the concentration and temperature that control etching solution; obtain stretchable molybdenum bisuphide/metallic particles mixed structure; which is pulled out from etching solution; cleaning; molybdenum bisuphide/metallic particles mixed structure surface is covered in the stretchable adhesive tapes of 3M of pre-stretching to be pulled out and dried naturally; return to the original length or area; steeped in stannous chloride, silver nitrate, ascorbic acid and silver nitrate mixed solution so as to grow Argent grain.According to this preparing a kind of highly sensitive stretchable biosensor in situ detection.The stretchable excellent performance of this biosensor, good stability, sensitivity height, low cost and controllable, achievable large-scale production, have very big using value.

Description

A kind of preparation method of the highly sensitive stretchable biosensor in situ detection
Technical field
The invention belongs to Stretch material preparation field, more particularly to a kind of highly sensitive stretchable life in situ detection The preparation method of thing sensor.
Background technology
For current biosensor, high sensitivity, high stability, high efficiency are most important.High-sensitive original position SERS technology can in real time, quickly detect the canceration of environment, pollution of agricultural products and its initiation, to pollution control and medical consultations Deng with important effect.At present, related progress is more slow, and main cause is highly sensitive Stretch material Prepare relatively difficult.
The three-dimensional molybdenum bisuphide material prepared on 3 D stereo substrate has the excellent chemical property of two-dimentional molybdenum bisuphide, with The big specific surface areas of Shi Yougeng and more excellent pliability, the distortion of general level do not interfere with property and the spy of material Property, be conducive to the biosensor of stretchable, good stability.The elastic substrate that flexible 3 D molybdenum bisuphide is transferred to pre-stretching On, flexible self-assembled structures are formed, in stretching-contraction process, its basic structure will not be destroyed so as to draw with superelevation Performance is stretched, common molybdenum bisuphide is compared, which is flexible more preferably, and elasticity is bigger, its process based prediction model is rear basic before the stretching Keep constant, this is of great significance to preparing stretchable biosensor tool, and can be other stretchable devices Prepare and a kind of method is provided, be that the research and development of the new stretchable product of China contribute.
The research of stretchable biosensor for environmental monitoring, pollution control, medical consultations etc. are with important effect, Become the study hotspot of recent field of new.The three-dimensional method of a variety of two-dimentional molybdenum bisuphide or three-dimensional curing The direct preparation of molybdenum is widely studied in recent years.The molybdenum bisuphide of three-dimensional is further processed and prepares stretchable curing The research of molybdenum/metallic particles biosensor is at the early-stage, is the development trend of Related Research Domain.
The research of high performance stretchable molybdenum bisuphide biosensor also has the problem of two urgent need to resolve：1. stretchable The preparation process of molybdenum bisuphide biosensor is complicated, and preparation cost is also higher.Most of preparation method is required in higher temperatures Multi step strategy under the conditions of degree, higher vacuum etc., the preparation time of needs are longer, much also need to using complicated wet method or dry Method transfer process；2. independent molybdenum bisuphide Material Physics enhancement is not high, and individually three-dimensional molybdenum bisuphide is used as biosensor Sensitivity is not high.
Chinese patent CN201510165967.X discloses a kind of system of the stretchable gas sensor of spongy graphene base Preparation Method, first prepares spongy graphene material with chemical gaseous phase depositing process in nickel foam, the Graphene/foam that will be prepared Nickel immersion is etched to make spongy graphene/nickel particle mixed structure, then using seal style drag for method pull out from etching solution, Clean, dry, pre-stretched elastic substrate slowly returns to the original length or area, in graphene/nickel granule mixed structure Two ends prepare electrode, obtain stretchable gas sensor.But the growth temperature of Graphene is higher, the application neck of gas sensor Domain is also narrower.
Content of the invention
Low for solving current biosensor sensitivity, it is more difficult to stretch, the shortcomings of drawing stability is inadequate, the present invention is proposed A kind of preparation method of the highly sensitive stretchable biosensor that can be used in situ detection；Using a kind of Ultra-Drawing performance The stretchable molybdenum bisuphide structure preparation of the material of (tensile elongation be more than 300%), and by itself and silver nanoparticle Granule is combined, and is strengthened sensitivity, is prepared stretchable mixed structure.The high-sensitive biosensor for preparing, to environmental monitoring, Crops participate in Pesticides Testing, high-acruracy survey of biomolecule etc. important meaning.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of highly sensitive Stretch material in situ detection, including：
Three-dimensional molybdenum bisuphide substrate；
The silver nano-grain being grown on the three-dimensional molybdenum bisuphide substrate；
The three-dimensional molybdenum bisuphide substrate is had the molybdenum bisuphide/etched removing of foam metal substrate of molybdenum bisuphide by deposition Foam metal, the seal style method of dragging for are pulled out, are shifted on pre-stretched elastic substrate, dried, are made pre-stretched elastic substrate restore to the original state And obtain.
In order to improve the sensitivity of three-dimensional molybdenum bisuphide, the present invention attempts molybdenum bisuphide area load nano-noble metal, but As the regulation and control of molybdenum bisuphide active sites are difficult, material conductivity is poor, after loading noble metal, the two adhesion is weak, sensitivity enhancement not Greatly.Chance in follow-up study：Using silver nano-grain as support materials, using its skin effect and superpower permeability Fully and closely combined with three-dimensional molybdenum bisuphide, highly active rim-site active sites in molybdenum bisuphide is fully exposed, greatly Width improves the integrity of material and stability in the sensitivity of composite and stretching-contraction process, overcome Argent grain without The problem that method is stretched or comes off with fold in drawing process.For this purpose, currently preferred nano-Ag particles particle diameter be 25～ 40nm.
When the particle diameter of silver nano-grain is less than 25nm, easily cluster in Argent grain, skewness on molybdenum bisuphide there is； When the particle diameter of silver nano-grain is more than 40nm, the specific surface area minimizing of Argent grain, absorbability decline, Argent grain and curing The bond strength of molybdenum reduces.
Present invention also offers a kind of manufacture method of the highly sensitive Stretch material in situ detection, including：
Molybdenum bisuphide material is deposited on foam metal, molybdenum bisuphide/foam metal is obtained；
The molybdenum bisuphide/foam metal etching removing foam metal, the seal style method of dragging for are pulled out, are shifted in pre-stretching bullet Property substrate on, dry, make pre-stretched elastic substrate restore to the original state, obtain stretchable molybdenum bisuphide structure；
Silver nano-grain is grown on the stretchable three-dimensional molybdenum bisuphide structure, obtain final product.
In the preparation process of stretchable molybdenum bisuphide/silver nano-grain mixing material, stretchable substrate and flexible two sulfur Change effective combination technology of molybdenum/silver nano-grain mixed structure：The quality of tensility energy is depended primarily in drawing process and is passed Whether sensor is easily damaged, and flexible molybdenum bisuphide/silver nano-grain mixed structure material and stretchable substrate are effectively combined, Preparation process forms periodic folded structure, in stretching-contraction process, only allows the gauffer of flexibility to be taken exercises, could preferably Guarantee flexible material integrity, it is ensured that the good process based prediction model of sensor.
Preferably, the foam metal is nickel foam, foam palladium, foam ruthenium, foam iridium, at least one in foam copper.
The present invention selects nickel foam as base material, but finds in actual vapor phase chemical vapor deposition：Nickel substrate Weaker with the attachment force of the molybdenum bisuphide/nickel composite substrate for being formed, and there is molybdenum bisuphide enrichment phenomenon, subsequently performing etching During, the lack of homogeneity of the flexible material of formation, stretch resistance are poor.
In order to improve the uniformity of molybdenum bisuphide Elemental redistribution in the molybdenum bisuphide/nickel composite substrate of deposition, the present invention is right Chemical vapor deposition process technique is improved, and finds：Under inertia protection, the stopping temperature of CVD method is arranged on 500 DEG C When can be effectively facilitated the phase counterdiffusion of molybdenum bisuphide and nickel, improve foam metal matrix and molybdenum bisuphide material cohesive force, Ensure that the molybdenum bisuphide/nickel particle after etching processing has uniform pliability and stretch resistance.
Preferably, the deposition process is chemical vapour deposition technique.
Preferably, the pre-stretched elastic substrate is be stretched to original length in one direction 1.5 to 4 times, Huo Zheyan Two orthogonal directions are stretched to the elastic substrate of 2 to 10 times of original area.
Preferably, in the etching, etching solution is iron chloride or iron nitrate solution, and concentration is 0.5-5mol/L.Will system Standby molybdenum bisuphide/foam metal is immersed in etching solution, is controlled the concentration and temperature of etching solution, is made foam metal complete Replaced, while not destroying molybdenum bisuphide structure.If the concentration of etching solution is more than 5mol/L, corrosion rate is too fast, can not The structure of molybdenum bisuphide is effectively maintained；If the concentration of etching solution is less than 0.5mol/L, corrosion rate is excessively slow, molybdenum bisuphide Pliability is not good, it is impossible to be fabricated to stretchable material.
In three-dimensional molybdenum bisuphide material preparation process, base material is performed etching frequently with etching method, but etching process In be also easy to produce pore space structure, destroy the structure of molybdenum bisuphide；Although and can be better controled over using inactive metal material The generation of hole, but the inertness due to metal, often result in residual of the metal in substrate material surface that be etched again.For Solve the above problems, the present invention to foam metal material during subsequent etching remove and reaction rate control condition It is optimized, finds：Compared with palladium, ruthenium, iridium, preferably molybdenum bisuphide/carbon/carbon-copper composite material is performed etching and can prepare knot Structure is continuous, size is controllable, the three-dimensional molybdenum bisuphide material that pliability is good, stretch resistance is excellent.
Preferably, the growth silver nano-grain is concretely comprised the following steps：Stretchable molybdenum bisuphide is steeped molten into stannous chloride In liquid, rear deionized water cleaning is dried naturally；Then steeped in silver nitrate solution, rear deionized water cleaning is natural Dry；Repeat above step three times；Then steeped in the mixed solution of ascorbic acid and silver nitrate, rear deionized water is clear Wash, dry naturally, obtain final product.
The biosensor of the new three-dimensional molybdenum bisuphide/silver nano-grain mixed structure of present invention research, new material Cladding can achieve stretchable biosensor preparation, so as to realize in situ detection；Molybdenum bisuphide is mutually tied with silver nano-grain Close and can make full use of the chemisorbed of molybdenum bisuphide and the physics mechanism and enhancement mechanism of silver nano-grain, improve the spirit of biosensor Sensitivity, and a kind of method can be provided for the preparation of other biological sensor, it is the research and development of the biosensor product of China Contribute.
Present invention also offers a kind of preparation method for being preferably used for the highly sensitive Stretch material of in situ detection, including Step is as follows：
(1) chemical gaseous phase depositing process prepares three-dimensional molybdenum bisuphide material on 3 D stereo substrate nickel
Foam metal is immersed in (NH4)2MoS4(NH is formed in solution4)2MoS4Thin film, after put it into vacuum response stove and add In warm area, evacuation, while heating, argon is injected in vacuum response stove, after by hydrogen injection vacuum response stove, question response After furnace temperature is warmed up to 500 DEG C, constant temperature is annealed for 60 minutes, closes gas and is down to room temperature two sulfur of Direct precipitation is obtained Change the substrate of molybdenum, i.e. molybdenum bisuphide/foam metal；
(2) preparation and its transfer of stretchable molybdenum bisuphide/metallic particles mixed structure
Molybdenum bisuphide/the foam metal of preparation is immersed in etching solution, slow reaction makes foam metal be put by chemistry Change, then flexible molybdenum bisuphide pulled out with the seal style method of dragging for from etching solution, in deionized water clean three times, after will Pre-stretched elastic substrate is sticked on hollow stent, is dragged for method with same seal style and is shifted on pre-stretched elastic substrate, dries in the air naturally Dry, the substrate pre-stretching is be stretched to original length in one direction 1.5 to 4 times, or along two orthogonal direction stretchings 2 to 10 times to original area；Then the pre-stretched elastic substrate for covering flexible molybdenum bisuphide is allowed slowly to return to original length Degree or area, according to this preparing a kind of stretchable molybdenum bisuphide structure；
(3) long silver nano-grain in the elastic substrate of attachment molybdenum bisuphide
Stretchable molybdenum bisuphide is steeped in stannous chloride solution, rear deionized water cleaning is dried naturally；Then by which Steep in silver nitrate solution, rear deionized water cleaning is dried naturally；Repeat above step three times.Then steeped into anti-bad In the mixed solution of hematic acid and silver nitrate, rear deionized water cleaning is dried naturally, carrys out the elasticity in attachment molybdenum bisuphide with this Long silver nano-grain on substrate.
In above-mentioned preparation method,
Foam metal described in step () is nickel foam, foam palladium, foam ruthenium, foam iridium, the one kind in foam copper Or multiple foamed alloys, preferably nickel, copper.The size of the foam metal is 1cm × 1cm-20cm × 20cm.The argon In 1-80sccm, purity is higher than 99.99% for flow-control；In 1-20sccm, purity is higher than 99.99% for the flow-control of hydrogen. The vacuum response stove evacuation degree is 3 × 10-3-3×10-6Torr, to remove the active gasess in furnace chamber, keeps cleaning Growing environment.Described annealing refers to the process for dispelling the impurity such as oxide to substrate surface.Obtain Direct precipitation curing After the substrate of molybdenum, gas valve is closed, the molybdenum bisuphide of deposition is taken out after lowering the temperature.
The method for taking out backing material is to wait after vacuum response furnace temperature drops to room temperature, closes hydrogen gas valve, true Empty pump, is filled to an atmospheric pressure state with air by furnace cavity is reacted, then takes out backing material.The curing of preparation In molybdenum/foam metal, the number of plies of molybdenum bisuphide is 1-10 layers.
Etching solution described in step (two) is iron chloride or iron nitrate solution, and the solution concentration is 0.5-5mol/ L；The elastic substrate is the elastic substrates such as PMMA, PDFS；The chemical replacement response time is 10-1000 minutes, reacts temperature Spend for 10-55 degree Celsius；
Stannous chloride solution concentration described in step (three) is 0.02mol/L, and soak time is 2 minutes；Silver nitrate is molten Liquid concentration is 0.02mol/L, and soak time is 2 minutes；In mixed solution ascorbic acid solution concentration be 0.1mol/L, silver nitrate Solution concentration is 0.01mol/L, and soak time is 2-10 minutes；Deionized water scavenging period is 2 minutes；
The seal style method of dragging for is specially：It is covered in molybdenum bisuphide structure with flexible substrate, the light pressure 10-30 seconds, so Slowly gently lift from a side of substrate afterwards, using the little contact force between molybdenum bisuphide and substrate, by molybdenum bisuphide Substrate is pulled out.
Present invention also offers Stretch material prepared by the above-mentioned method of any one.
Present invention also offers a kind of highly sensitive stretchable biosensor in situ detection, including arbitrary above-mentioned Stretch material.
Present invention also offers arbitrary above-mentioned Stretch material prepare human body implanting device, intelligent flexible equipment, can Application in wearable device, unlimited induction installation.
Beneficial effects of the present invention
(1) present invention achieves molybdenum bisuphide growth temperature precise control；The molybdenum bisuphide defect peak of growth is low, with pole High crystal mass；The molybdenum bisuphide size of growth is only limited by CVD cavitys, can achieve the large area deposition of molybdenum bisuphide；
(2) PMMA glue need not be used in wet method transfer process of the present invention, time saving and energy saving；Transfer process is turned using seal style Move, molybdenum bisuphide will not arbitrarily drift in the solution, it is to avoid the damage of molybdenum bisuphide in transfer process, process are simple；
(3) metallic particles is coated in flexible molybdenum bisuphide, mixed structure is not damaged by during stretching, protected Hold original physics and chemical property；Molybdenum bisuphide after the metallic particles of growth/metallic particles mixed structure has high Chemisorbed and physics mechanism and enhancement mechanism；
(4) the inventive method is simply controllable, with low cost, and using value is high, and detection efficiency is high, practical.
Description of the drawings
Fig. 1 is the syntheti c route figure of stretchable molybdenum bisuphide/silver nano-metal granular materialss；
Fig. 2 is the device of self-control energy restrained stretching-contraction speed and number of times.
Fig. 3 is the SEM figures of stretchable molybdenum bisuphide/silver nano-metal granule mixed structure.
Specific embodiment
By the following examples feature of present invention and other correlated characteristics are described in further detail, in order to the same industry The understanding of technical staff：
Embodiment 1
In 3 D stereo substrate nickel foam, growth molybdenum bisuphide obtains three-dimensional molybdenum bisuphide, and finally gives curing Molybdenum/silver nano-grain mixed structure, syntheti c route figure as described in Figure 1, including following preparation process：
1. by 0.25g (NH4)2MoS4It is added to the concentration of formation 1.25wt% in the dimethylformamide (DMF) of 20ml simultaneously Ultrasonic 20min.
2. take size cleaning in acetone is placed in for 8cm × 8cm nickel foam.
3. temperature is placed in for drying 10min at 80 DEG C.
4. by drying after nickel foam be immersed in (NH4)2MoS4(NH is formed in solution4)2MoS4Thin film.
5. temperature is placed in for drying 30min at 120 DEG C.
6. it is placed in tube furnace.
7. open vacuum pump and the air pressure of tube furnace is evacuated to end vacuum state 3 × 10-6Support (Torr)；
8. vacuum state 3 × 10 is kept-6Torr after 15 minutes, (dispel inside quartz ampoule by the vacuum effect of 15 minutes Impurity, air etc., it is ensured that reaction chamber is clean), the air pressure of quartz ampoule 3 is raised to 3 × 10-3Torr；
9. argon flow amount meter is set as 80sccm, and argon is injected in vacuum chamber；
10. hydrogen flowmeter is set as 20sccm, by hydrogen injection vacuum chamber；
After 11. tubular type furnace temperatures are warmed up to 500 DEG C, constant temperature is annealed for 60 minutes；
Tubular type furnace temperature is simultaneously quickly down to room temperature with the speed of 10 DEG C/min by 12. cut out hydrogen gas effusion meters；
13. close argon flow amount meter and vacuum pump；
14. open valve, and quartz ampoule air pressure is filled to an atmospheric pressure state with air；
15. open quartz ampoule vacuum interface, take out the nickel foam for having deposited molybdenum bisuphide；
16. by FeCl3Add in deionized water according to certain mass and dissolve, prepare certain density etching solution FeCl3 (5mol/L)；
17. molybdenum bisuphide/the nickel foam for preparing are immersed in 20 DEG C of FeCl3(5mol/L) 140 minutes in solution；
The pattern of 18. observation molybdenum bisuphide/nickel foam, until its structure becomes flexible molybdenum bisuphide structure；
Flexible molybdenum bisuphide structure is cleaned 3 times, every time 10 minutes by 19. in deionized water；
Flexible substrate is pressed on flexible molybdenum bisuphide body structure surface by 20., light pressure 20 seconds；
21. slowly gently lift from substrate side, using the little contact force between molybdenum bisuphide and substrate, will Molybdenum bisuphide mixed structure is pulled out；
22. 1.5 to 4 times that PDFS elastic substrates are stretched to original length in one direction, or orthogonal along two Direction is stretched to 2 to 10 times of original area；
23. by stretching after elastic substrate on paste on empty support in a circle；
Elastic substrate one side on support is pressed on flexible molybdenum bisuphide body structure surface by 24., light pressure 20 seconds；
25. slowly gently lift from substrate side, using little between molybdenum bisuphide mixed structure and substrate Contact force, molybdenum bisuphide structure is pulled out；
26. dry in the air in vacuum drying oven 3 hours；
27. elastic substrates that will be covered with molybdenum bisuphide structure from hollow circular or square set are removed, and side is glued On support；
28. in vacuum drying oven clear-cutting forestland 5 hours so as to return to original size；
29. steep 2 minutes in 0.02mol/L stannous chloride solutions, and rear deionized water is cleaned 2 minutes, is pulled out, is dried in the air naturally Dry；
30. steep 2 minutes in 0.02mol/L silver nitrate solutions, and rear deionized water is cleaned 2 minutes, is pulled out, is dried in the air naturally Dry；
31. repeat steps 29,30 3 times；
32. steep 10 minutes in 0.1mol/L ascorbic acid and 0.01mol/L silver nitrate mixed solutions, rear deionized water Cleaning 2 minutes, pulls out, dries naturally, obtain final product the molybdenum bisuphide elastomer of loading nano silvery, wherein, the particle diameter of nano-Ag particles For 25～40nm.
Embodiment 2
On 3 D stereo substrate foam copper, growth molybdenum bisuphide obtains three-dimensional molybdenum bisuphide, and finally gives curing Molybdenum/silver nano-grain mixed structure, including following preparation process：
1. by 0.25g (NH4)2MoS4It is added to the concentration of formation 1.25wt% in the dimethylformamide (DMF) of 20ml simultaneously Ultrasonic 20min.
2. take size cleaning in acetone is placed in for 7cm × 8cm foam coppers.
3. temperature is placed in for drying 10min at 80 DEG C.
4. by drying after foam copper be immersed in (NH4)2MoS4(NH is formed in solution4)2MoS4Thin film.
5. temperature is placed in for drying 30min at 120 DEG C.
6. it is placed in tube furnace.
7. open vacuum pump and the air pressure of tube furnace is evacuated to end vacuum state 3 × 10-6Support (Torr)；
8. vacuum state 3 × 10 is kept-6Torr after 15 minutes, (dispel inside quartz ampoule by the vacuum effect of 15 minutes Impurity, air etc., it is ensured that reaction chamber is clean), the air pressure of quartz ampoule 3 is raised to 3 × 10-3Torr；
9. argon flow amount meter is set as 80sccm, and argon is injected in vacuum chamber；
10. hydrogen flowmeter is set as 20sccm, by hydrogen injection vacuum chamber；
After 11. tubular type furnace temperatures are warmed up to 500 DEG C, constant temperature is annealed for 60 minutes；
Tubular type furnace temperature is simultaneously quickly down to room temperature with the speed of 10 DEG C/min by 12. cut out hydrogen gas effusion meters；
13. close argon flow amount meter and vacuum pump；
14. open valve, and quartz ampoule air pressure is filled to an atmospheric pressure state with air；
15. open quartz ampoule vacuum interface, take out the foam copper for having deposited molybdenum bisuphide；
16. by FeCl3Add in deionized water according to certain mass and dissolve, prepare certain density etching solution FeCl3 (0.5mol/L)；
17. molybdenum bisuphide/the foam coppers for preparing are immersed in 40 DEG C of FeCl3(0.5mol/L) 140 minutes in solution；
The pattern of 18. observation molybdenum bisuphide/foam coppers, until its structure becomes flexible molybdenum bisuphide structure；
Flexible molybdenum bisuphide structure is cleaned 3 times, every time 10 minutes by 19. in deionized water；
Flexible substrate is pressed on flexible molybdenum bisuphide mixed structure surface by 20., light pressure 15 seconds；
21. slowly gently lift from substrate side, using the little contact force between molybdenum bisuphide and substrate, will Molybdenum bisuphide copper granule mixed structure is pulled out；
22. 1.5 to 4 times that PDFS elastic substrates are stretched to original length in one direction, or orthogonal along two Direction is stretched to 2 to 10 times of original area；
23. by stretching after elastic substrate on paste on empty support in a circle；
Elastic substrate one side on support is pressed on flexible molybdenum bisuphide body structure surface by 24., light pressure 30 seconds；
25. slowly gently lift from substrate side, using the little contact between molybdenum bisuphide structure and substrate Power, molybdenum bisuphide structure is pulled out；
26. dry in the air in vacuum drying oven 3 hours；
27. elastic substrates that will be covered with molybdenum bisuphide structure from hollow circular or square set are removed, and side is glued On support；
28. in vacuum drying oven clear-cutting forestland 5 hours so as to return to original size；
29. steep 2 minutes in 0.02mol/L stannous chloride solutions, and rear deionized water is cleaned 2 minutes, is pulled out, is dried in the air naturally Dry；
30. steep 2 minutes in 0.02mol/L silver nitrate solutions, and rear deionized water is cleaned 2 minutes, is pulled out, is dried in the air naturally Dry；
31. repeat steps 29,30 3 times；
32. steep 10 minutes in 0.1mol/L ascorbic acid and 0.01mol/L silver nitrate mixed solutions, rear deionized water Cleaning 2 minutes, pulls out, dries naturally, obtain final product the molybdenum bisuphide elastomer of loading nano silvery, wherein, the particle diameter of nano-Ag particles For 25～40nm.
Finally it should be noted that the foregoing is only the preferred embodiments of the present invention, this is not limited to Bright, although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, which is still Technical scheme described in previous embodiment can be modified, or equivalent is carried out to which part.All at this Within bright spirit and principle, any modification, equivalent substitution and improvements that is made etc. should be included in protection scope of the present invention Within.Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to the scope of the present invention Restriction, one of ordinary skill in the art should be understood that, on the basis of technical scheme, those skilled in the art are not required to The various modifications that make by creative work to be paid or deformation are still within protection scope of the present invention.

Claims (10)

1. a kind of highly sensitive Stretch material in situ detection, it is characterised in that include：
Three-dimensional molybdenum bisuphide substrate；
The silver nano-grain being grown on the three-dimensional molybdenum bisuphide substrate；
The three-dimensional molybdenum bisuphide substrate has the etched removing foam of the molybdenum bisuphide/foam metal substrate of molybdenum bisuphide by deposition Metal, the seal style method of dragging for are pulled out, are shifted on pre-stretched elastic substrate, dried, pre-stretched elastic substrate is restored to the original state and is obtained.
2. a kind of manufacture method of the highly sensitive Stretch material in situ detection, it is characterised in that include：
Molybdenum bisuphide material is deposited on foam metal, molybdenum bisuphide/foam metal is obtained；
The molybdenum bisuphide/foam metal etching removing foam metal, the seal style method of dragging for are pulled out, are shifted in pre-stretched elastic lining On bottom, dry, make pre-stretched elastic substrate restore to the original state, obtain stretchable molybdenum bisuphide structure；
Silver nano-grain is grown on the stretchable three-dimensional molybdenum bisuphide structure, obtain final product.
3. method as claimed in claim 2, it is characterised in that the foam metal be nickel foam, palladium, ruthenium, iridium, in copper extremely Few one kind.
4. method as claimed in claim 2, it is characterised in that the deposition process is electrochemical deposition.
5. method as claimed in claim 2, it is characterised in that the pre-stretched elastic substrate is for being stretched to original in one direction Carry out length 1.5 to 4 times, or 2 to 10 times of original area of elastic substrate is stretched to along two orthogonal directions.
6. method as claimed in claim 2, it is characterised in that in the etching, etching solution are that iron chloride or ferric nitrate are molten Liquid, concentration are 0.5-5mol/L.
7. method as claimed in claim 2, it is characterised in that the growth silver nano-grain is concretely comprised the following steps：Can draw Stretch molybdenum bisuphide to steep in stannous chloride solution, rear deionized water cleaning is dried naturally；Then steeped into silver nitrate solution In, rear deionized water cleaning is dried naturally；Repeat above step three times；Then steeped into ascorbic acid and silver nitrate In mixed solution, rear deionized water cleaning is dried naturally, is obtained final product.
8. the Stretch material that prepared by the method described in any one of claim 2-7.
9. a kind of highly sensitive stretchable biosensor in situ detection, it is characterised in that including 1 or 8 institute of claim The Stretch material that states.
10. the Stretch material of claim 1 or 9 is preparing human body implanting device, intelligent flexible equipment, wearable device, nothing Application in limit induction installation.
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CN113026350A (en) * 2021-02-23 2021-06-25 辽宁石油化工大学 Preparation method and application of information modulation type anti-counterfeiting fiber
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