CN106990266B - It is a kind of to prepare needle point, the method for probe and needle point, probe - Google Patents
It is a kind of to prepare needle point, the method for probe and needle point, probe Download PDFInfo
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- CN106990266B CN106990266B CN201710281379.1A CN201710281379A CN106990266B CN 106990266 B CN106990266 B CN 106990266B CN 201710281379 A CN201710281379 A CN 201710281379A CN 106990266 B CN106990266 B CN 106990266B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
- G01Q60/24—AFM [Atomic Force Microscopy] or apparatus therefor, e.g. AFM probes
- G01Q60/38—Probes, their manufacture, or their related instrumentation, e.g. holders
Abstract
Needle point, the method for probe and needle point, probe are prepared the present invention provides a kind of, which includes: to grow carbon nanotube by chemical vapor deposition manner；Control gaseous transition compound is contacted with the carbon nanotube, and the gaseous transition compound is deposited at least one crystal with certain structure on the carbon nanotubes；One section of carbon nanotube that each described crystal is connect with by Van der Waals force forms a needle point.Scheme provided by the invention can effectively improve the preparation efficiency of carbon nano-tube point.
Description
Technical field
The present invention relates to device fabrication arts, in particular to a kind of to prepare needle point, the method for probe and needle point, probe.
Background technique
Exploration with fields such as physics, chemistry, biology, materials to micro-structure is able to detect microstructure or even molecule
Or the scanning probe microscopy of atomic structure such as atomic force microscope
(AtomicForceMicroscope, AFM) application is more and more extensive.And influence scanning probe microscopy imaging
One of key factor of resolution ratio is shape, the tip radius etc. of the performance such as probe tip of probe.
Currently, the common needle point of scanning probe microscopy mainly uses silicon or silicon nitride material, pass through photoetching or etching
Etc. wieners processing technology be made.And 30 are generally by photoetching or etching silicon or the obtained needle point tip radius of silicon nitride material~
50nm greatly limits imaging resolution.
Carbon nanotube not only has very high aspect ratio as novel nano material, but also has very big Young mould
Amount, these properties make carbon nanotube become ideal tip point material.Current research it has also been shown that, with common silicon or silicon nitride
Needle point is compared, and single-root carbon nano-tube can effectively improve imaging resolution as needle point.Currently, the preparation of carbon nano-tube point
Method is mainly the in-situ growing carbon nano tube on existing silicon or nitride tips.And growth in situ mode is unable to control carbon
The position or orientation of nanotube growth, therefore, existing this growth in situ mode often results in the preparation of carbon nano-tube point
Efficiency is lower.
Summary of the invention
Needle point, the method for probe and needle point, probe are prepared the embodiment of the invention provides a kind of, can be effectively improved
Imaging resolution.
The present invention provides a kind of methods for preparing needle point, grow carbon nanotube by chemical vapor deposition manner；Also wrap
It includes:
Control gaseous transition compound is contacted with the carbon nanotube, and the gaseous transition compound is described
At least one crystal with certain structure is deposited into carbon nanotube；
One section of carbon nanotube that each described crystal is connect with by Van der Waals force forms a needle point.
In the above-mentioned method for preparing needle point, since the surface area of carbon nanotube is larger, it can pass through with the crystal of deposition
The more firm connection of Van der Waals force, so that crystal consolidates compared with the needle point that carbon nanotube forms, in addition, passing through research table
Bright, above-mentioned gaseous transition compound is deposited into the crystal of certain structure, and a carbon nanometer on single-root carbon nano-tube
Pipe can deposit the crystal of multiple certain structures, i.e., a carbon nanotube can produce multiple needle points by the above process, because
This, scheme provided by the invention can effectively improve the preparation efficiency of carbon nano-tube point.
Meanwhile compared with existing silicon or silicon nitride material needle point, the diameter of carbon nanotube is greatly reduced, generally 3~
5nm, therefore needle point provided in an embodiment of the present invention can identify the pattern etc. within the scope of 3~5nm, to effectively improve into
As resolution ratio.
It is optionally, described that carbon nanotube is grown by chemical vapor deposition manner, comprising:
Slit is set in substrate；
Make catalyst with metal nanoparticle, the substrate be heated to 800 DEG C~1100 DEG C, and control carbon-source gas,
The mixed gas of hydrogen and vapor composition flows through the substrate, to grow carbon on the substrate and among the slit
Nanotube.
Wherein, the process for slit being arranged in substrate may include: to stick muti-piece in the biggish substrate surface of a block size
The lesser substrate of size, wherein the gap between substrate that size reduces is slit.Alternatively, through photoetching process in substrate
Carve slit one by one.
Substrate is generally the substrate of silicon material.
In addition, metal nanoparticle can be any one nano particle in Fe, Mo, Cu and Cr.
The preparation process of above-mentioned metal nanoparticle can be with are as follows: by the metal chloride of any one in Fe, Mo, Cu and Cr
Ethanol solution or aqueous solution be applied in substrate, then substrate is placed in reactor and heat state reactor to 600 DEG C~
At 1000 DEG C, the mixed gas that hydrogen or hydrogen and inert gas are passed through in Xiang Suoshu reactor carries out reduction reaction, and gold is made
Metal nano-particle.
Optionally, the control gaseous transition compound is contacted with the carbon nanotube, comprising:
The substrate that growth has the carbon nanotube is inverted in transition metal on piece, heats the transition metal piece to 300
DEG C~500 DEG C, make the transition metal piece and is oxidized into transition metal oxide, the transition metal oxide in air
Distillation becomes gaseous transition oxide, so that the carbon nanotube is located in the gaseous transition oxide atmosphere,
Keep 5min~60min.
Optionally, the control gaseous transition compound is contacted with the carbon nanotube, comprising:
There are the substrate of the carbon nanotube and transition metal oxide powder to be placed in same reactor growth, is passed through
The gas for being not involved in reaction carries out atmosphere protection, and is heated to 500 DEG C~1000 DEG C, and the transition metal oxide distillation becomes
Gaseous transition oxide, so that the carbon nanotube is located at the gaseous transition oxide and is not involved in reaction
In gas atmosphere, 30min~60min is kept.
Optionally, the transistion metal compound, comprising: transition metal oxide, transient metal sulfide and transition
Any one in metal selenide, wherein
The transition metal oxide is preferably molybdenum oxide or tungstic acid；
The transient metal sulfide is preferably molybdenum disulfide or tungsten disulfide；
The transition metal selenides is preferably two selenizing molybdenums or two tungsten selenides.
Optionally, the crystal of certain structure, comprising: hexagonal crystal, the apex angle junction of the hexagon is described
In carbon nanotube.
Optionally, the crystalline size of certain structure is 100nm~10 μm.The size of the crystal is larger be conducive to it is subsequent
With the welding of probe cantilever.
The present invention provides the needle point using the preparation of any of the above-described needle point preparation method, comprising: the crystal of certain structure and
Carbon nanotube, wherein
The crystal of certain structure belongs to one end of needle point, and the carbon nanotube belongs to the other end of needle point；
The carbon nanotube portion is inlaid into the crystal of certain structure, so that the crystal of certain structure and institute
It states and forms Van der Waals force between carbon nanotube；
The crystal of certain structure includes transistion metal compound.
Optionally, the crystal of certain structure, comprising: hexagonal crystal, the apex angle junction of the hexagon is described
In carbon nanotube.
Optionally, the crystalline size of certain structure is 100nm~10 μm.
The present invention provides a kind of probe, comprising: any of the above-described needle point and silicon nitride cantilevers, wherein
One end of the silicon nitride cantilevers is connected with the crystal of certain structure in the needle point.
The present invention provides a kind of method for preparing above-mentioned probe, comprising:
Respectively in one end of silicon nitride cantilevers beam and the crystal terminal sprayed metal layer of needle point；
When the one end for the silicon nitride cantilevers beam for being coated with the metal layer connects with the crystal terminal for being coated with the metal layer
When touching, the metal layer is heated and melted using laser is focused, connect the silicon nitride cantilevers beam with the crystal terminal.
It is using bottom-up method, i.e., raw first with air-flow guiding and top in the above-mentioned method for preparing needle point
Then long mechanism, in-situ growing carbon nano tube in substrate and on the slit of substrate deposit one by one on the carbon nanotubes
Crystal, compared to the prior art in micro- sodium processing method of top-down for using, scheme provided by the invention is simpler,
It is easy to operate.Simultaneously as same root carbon nanotube has consistent mechanical property and chirality etc., then receiving for same root carbon
The needle point of mitron is by length having the same, diameter, chirality and mechanical constant etc..Simultaneously as crystalline size can reach it is micro-
Meter level, it is more preferably simple for nanoscale welding when crystal is connected to form probe by welding manner and cantilever
It is single, easy to operate.
The embodiment of the invention provides the method for preparing needle point, probe and needle points, probe, by studies have shown that above-mentioned
Gaseous transition compound is deposited into the crystal of certain structure on single-root carbon nano-tube, and a carbon nanotube can sink
Product goes out the crystal of multiple certain structures, i.e., a carbon nanotube can produce multiple needle points by the above process, therefore, the present invention
The scheme of offer can effectively improve the preparation efficiency of carbon nano-tube point.
In addition, the diameter of carbon nanotube greatly reduces compared with existing silicon or silicon nitride material needle point, generally 3~
5nm, therefore needle point provided in an embodiment of the present invention can identify the pattern etc. within the scope of 3~5nm, to effectively improve into
As resolution ratio.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the top view for the substrate that a kind of growth provided by one embodiment of the present invention has carbon nanotube；
Fig. 2 is a kind of structural schematic diagram for preparing needle point provided by one embodiment of the present invention；
Fig. 3 is a kind of structural schematic diagram for preparing needle point that another embodiment of the present invention provides；
Fig. 4 is the structural schematic diagram of needle point provided by one embodiment of the present invention；
Fig. 5 is the scanning electron microscope provided by one embodiment of the present invention for growing and having the carbon nanotube of multiple molybdenum oxide crystal
Figure；
Fig. 6 is the transmission electron microscope provided by one embodiment of the present invention for growing and having the carbon nanotube of multiple molybdenum oxide crystal
Figure；
Fig. 7 is the transmission electron microscope of molybdenum oxide crystal and carbon nanotube junction in needle point provided by one embodiment of the present invention
Figure；
Fig. 8 is molybdenum oxide crystal provided by one embodiment of the present invention and the needle point transmission electron microscope picture that carbon nanotube is formed.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments, based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.In following embodiments, institute
Various kinds of equipment, reagent and the material used is that conventional commercial can obtain unless otherwise noted.
Below by several specific embodiments, the present invention is further illustrated.
It is specifically included that by the process that chemical vapor deposition manner grows carbon nanotube
Multiple slits are carved in substrate by photoetching process；
The ethanol solution of the metal chloride of any one in Fe, Mo, Cu and Cr or aqueous solution are applied in substrate, so
Substrate is placed in reactor afterwards and is heated when stating reactor to 600 DEG C~1000 DEG C, be passed through in Xiang Suoshu reactor hydrogen or
The mixed gas of hydrogen and inert gas carries out reduction reaction, and metal nanoparticle is made；
Make catalyst with metal nanoparticle, substrate is heated to 800 DEG C~1100 DEG C by reactor, and control carbon source
The mixed gas of gas, hydrogen and vapor composition flows through substrate, to grow carbon nanotube in substrate and among slit.
Substrate top view after substrate grown carbon nanotube is as shown in Figure 1, it can be seen from the figure that single-root carbon nano-tube can be across
Each slit forms hanging carbon nanotube.The hanging carbon nanotube can be single-walled carbon nanotube, double-walled carbon nano-tube or more
Wall carbon nano tube etc..
The process for preparing needle point specifically includes that
Carbon nanotube is grown by above-mentioned chemical vapor deposition manner；
Control gaseous transition compound is contacted with the carbon nanotube, and the gaseous transition compound is described
At least one crystal with certain structure is deposited into carbon nanotube；
One section of carbon nanotube that each described crystal is connect with by Van der Waals force forms a needle point.
Wherein, the mode that is contacted with the carbon nanotube of control gaseous transition compound can there are two types of:
Mode one: it is contacted by sheet metal with the oxygen in air and generates progress for metal oxide layer contacts with carbon nanotube
Explanation.
As shown in Fig. 2, the substrate that growth has the carbon nanotube is inverted in transition metal on piece, the transition gold is heated
Belong to piece to 300 DEG C~500 DEG C, makes the transition metal piece and be oxidized into transition metal oxide, the transition in air
Metal oxide distillation becomes gaseous transition oxide, so that the carbon nanotube is located at gaseous transition oxidation
In object atmosphere, 5min~60min is kept.
Mode two: being to be unfolded to say for gaseous metal hydroxide is contacted with carbon nanotube by metal oxide powder distillation
It is bright.
As shown in figure 3, there have the substrate of the carbon nanotube and transition metal oxide powder to be placed in growth to be same anti-
It answers in device such as tube furnace, is passed through the gas progress atmosphere protection for being not involved in reaction, and be heated to 500 DEG C~1000 DEG C, the mistake
Crossing metal oxide distillation becomes gaseous transition oxide, so that the carbon nanotube is located at the gaseous transition oxygen
It compound and is not involved in the gas atmosphere of reaction, keeps 30min~60min.
Through the above way one or the needle point structure that is prepared of mode two as shown in figure 4, it can be seen from the figure that should
Needle point includes: the crystal such as hexagonal crystal and carbon nanotube of certain structure, wherein
The crystal of certain structure belongs to one end of needle point, and the carbon nanotube belongs to the other end of needle point；
The carbon nanotube portion is inlaid into the crystal of certain structure such as when crystal is hexagonal structure, six sides
The apex angle junction of shape on the carbon nanotubes so that forming Van der Waals between the crystal and the carbon nanotube of certain structure
Power；In addition, the preparation process of pass-through mode one or mode two was it is found that the crystal of certain structure included in the needle point being prepared
Cross metallic compound.
It prepares carbon nanotube used in the process of needle point it is to be appreciated that above-mentioned and can be received for single-walled carbon nanotube, double-walled carbon
The multi-walled carbon nanotubes such as mitron or three wall carbon nano tubes.
The process of preparation carbon nanotube is elaborated, the process of needle point is prepared and utilizes preparation with several embodiments below
Needle point out prepares the process of probe.
Embodiment 1 utilizes metal molybdenum to illustrate using metal iron nano-particle as catalyst preparation carbon nanotube
Piece and carbon nanotube obtained prepare needle point and prepare probe using obtained needle point.
Embodiment 1:
Step A1: grade slit being set in substrate using photoetching process, wherein substrate contains silica oxide layer,
The presence of the silica oxide layer can prevent the pasc reaction in metal particulate and substrate；
Step B1: the ethanol solution for the ferric trichloride that concentration is 0.0001mol/L is applied in substrate, and three will be coated with
The substrate of the ethanol solution of iron chloride is sent into quartz tube reactor, and the mixing of hydrogen and argon gas is passed through into quartz tube reactor
Gas and heated quartz pipe reactor, the flow velocity for controlling hydrogen is 100ml/min, and the flow velocity of argon gas is 200ml/min；Work as temperature
When rising to 900 DEG C, constant temperature carries out reduction reaction 20min, and obtaining partial size is metal iron nano-particle；
Step C1: rising to 1000 DEG C for the temperature of quartz tube reactor, closes argon gas at this time, and the flow velocity of hydrogen is changed
For 70ml/min, while it being passed through the methane of 20ml/min and the gaseous mixture of vapor, reacts 50min, obtain carbon nanotube,
In, the length of the carbon nanotube is up to 50cm；
Step D1: metal molybdenum sheet is put on warm table, and the substrate with carbon nanotube is inverted in metal molybdenum on piece,
Warm table is heated to 500 DEG C, make metal molybdenum sheet and is oxidized into molybdenum oxide in air, the molybdenum oxide of formation is in 500 DEG C of items
It under part, distils as gaseous oxidation molybdenum, keeps reaction 60min that can deposit after the gaseous oxidation molybdenum encounters the carbon nanotube in substrate
Crystallization becomes hexagonal crystal, and the apex angle of the hexagonal crystal intersects in carbon nanotube, in addition, can by above-mentioned preparation process
So as to deposit multiple crystal in a carbon nanotube as shown in figure 5, the Fig. 4 that can be further cut by micro-nano cutting mode
Shown in needle point, therefore, by the experimental results showed that, after a carbon nanotube deposited crystal, can be cut into 100~
1000 needle points, and the size of each hexagonal crystal is 10 μm；
Step E1: respectively in one end of silicon nitride cantilevers beam and the molybdenum oxide crystal terminal sprayed metal layer of needle point, work as spray
When the one end for being coated with the silicon nitride cantilevers beam of the metal layer is in contact with the molybdenum oxide crystal terminal for being coated with the metal layer, benefit
The metal layer is heated and melted with laser is focused, the silicon nitride cantilevers beam is connect with the molybdenum oxide crystal terminal, is formed
Probe.
In the preparation process of above-mentioned probe, focusing laser quickly can be such that metal layer melts, without destroying silicon nitride cantilevers
The structure of beam and molybdenum oxide crystal to ensure that the yield of probe, while in probe preparation process, significantly reducing
Waste to needle point.
Embodiment 2 still prepares carbon nanotube using the process of A1 to C1 in embodiment 1, and is prepared using molybdenum oxide powder
Then needle point prepares probe using needle point obtained.Embodiment 2 may include:
Step A2 to step C2 prepares the process of carbon nanotube, the process one with the step A1 to step C1 in embodiment 1
It causes, details are not described herein；
Step D2: the growth that step C2 is obtained has the substrate of carbon nanotube and molybdenum oxide powder to be placed in same reactor
It is interior, it is passed through argon gas and carries out atmosphere protection, and be heated to 1000 DEG C, molybdenum oxide distillation becomes gaseous oxidation molybdenum, so that carbon nanotube
In gaseous oxidation molybdenum and argon atmosphere, 60min is kept, molybdenum oxide is deposited into six sides one by one on the carbon nanotubes
Shape crystal, as shown in fig. 6, multiple molybdenum oxide crystal can be deposited in a carbon nanotube；And further by micro-nano
Cutting mode is cut into needle point one by one；Wherein, hexagonal crystal is having a size of 100nm；
Step E2: respectively in one end of rectangle silicon nitride cantilevers beam and the molybdenum oxide crystal terminal spray metal of needle point
Layer, when the one end for the rectangle silicon nitride cantilevers beam for being coated with the metal layer be coated with the molybdenum oxide crystal of the metal layer
When end is in contact, the metal layer is heated and melted using laser is focused, keeps the silicon nitride cantilevers beam and the molybdenum oxide brilliant
Body end connection, forms probe.
Embodiment 3:
Step A3: grade slit is set in the way of pasting in substrate, wherein substrate contains silica oxidation
Layer, the presence of the silica oxide layer can prevent the pasc reaction in metal particulate and substrate；
Step B3: the ethanol solution for the copper chloride that concentration is 0.5mol/L is applied in substrate, and copper chloride will be coated with
The substrate of ethanol solution be sent into quartz tube reactor, the mixed gas of hydrogen and argon gas is passed through into quartz tube reactor simultaneously
Heated quartz pipe reactor, the flow velocity for controlling hydrogen is 200ml/min, and the flow velocity of argon gas is 500ml/min；When temperature rises to
At 250 DEG C, constant temperature carries out reduction reaction 30min, and obtaining partial size is metal molybdenum nano particle；
Step C3: rising to 800 DEG C for the temperature of quartz tube reactor, closes argon gas at this time, and the flow velocity of hydrogen is changed
For 160ml/min, while it being passed through the methane of 80ml/min and the gaseous mixture of vapor, reacts 120min, obtain carbon nanotube,
In, the length of the carbon nanotube is up to 60cm；
Step D3: the growth that step C4 is obtained has the substrate of carbon nanotube and molybdenum oxide powder to be placed in same reactor
It is interior, it is passed through argon gas and carries out atmosphere protection, and be heated to 900 DEG C, molybdenum oxide distillation becomes gaseous oxidation molybdenum, so that carbon nanotube position
In in gaseous oxidation molybdenum and argon atmosphere, 50min is kept, molybdenum oxide is deposited into hexagon one by one on the carbon nanotubes
Crystal, as shown in fig. 7, the middle carbon nanotube for the needle point that molybdenum oxide crystal and carbon nanotube are formed and molybdenum oxide crystal junction
Transmission plot.Can significantly it find out from figure, carbon nanotube portion is located in molybdenum oxide crystal, and molybdenum oxide crystal is stretched out in part.
Reach firm by stronger Van der Waals force between molybdenum oxide crystal positioned at the brilliant intracorporal part carbon nanotube of molybdenum oxide
Purpose.In addition, the molybdenum oxide hexagonal crystal size obtained by above-mentioned preparation process can be 200nm；
Step E3: respectively in one end of silicon nitride cantilevers beam and the molybdenum oxide crystal terminal sprayed metal layer of needle point, work as spray
When the one end for being coated with the silicon nitride cantilevers beam of the metal layer is in contact with the molybdenum oxide crystal terminal for being coated with the metal layer, benefit
The metal layer is heated and melted with laser is focused, the silicon nitride cantilevers beam is connect with the molybdenum oxide crystal terminal, is formed
Probe.
Embodiment 4:
Step A4: grade slit is set in the way of pasting in substrate, wherein substrate contains silica oxidation
Layer, the presence of the silica oxide layer can prevent the pasc reaction in metal particulate and substrate；
Step B4: the ethanol solution for the molybdenum trichloride that concentration is 0.005mol/L is applied in substrate, and three will be coated with
The substrate of the ethanol solution of molybdenum chloride is sent into quartz tube reactor, and the mixing of hydrogen and argon gas is passed through into quartz tube reactor
Gas and heated quartz pipe reactor, the flow velocity for controlling hydrogen is 200ml/min, and the flow velocity of argon gas is 100ml/min；Work as temperature
When rising to 800 DEG C, constant temperature carries out reduction reaction 25min, and obtaining partial size is metal molybdenum nano particle；
Step C4: rising to 1100 DEG C for the temperature of quartz tube reactor, closes argon gas at this time, and the flow velocity of hydrogen is changed
For 80ml/min, while it being passed through the methane of 30ml/min and the gaseous mixture of vapor, reacts 30min, obtain carbon nanotube,
In, the length of the carbon nanotube is up to 30cm；
Step D4: the growth that step C3 is obtained has the substrate of carbon nanotube and molybdenum oxide powder to be placed in same reactor
It is interior, it is passed through argon gas and carries out atmosphere protection, and be heated to 800 DEG C, molybdenum oxide distillation becomes gaseous oxidation molybdenum, so that carbon nanotube position
In in gaseous oxidation molybdenum and argon atmosphere, 40min is kept, molybdenum oxide is deposited into hexagon one by one on the carbon nanotubes
Crystal, as shown in figure 8, the positive transmission plot for the needle point that molybdenum oxide crystal and carbon nanotube are formed, it can be significantly from figure
The hexagonal structure of molybdenum oxide Crystallization out, meanwhile, the molybdenum oxide crystal growth of the hexagonal structure is in carbon nanotube.Separately
Outside, the hexagonal crystal size obtained by the above process is about 500nm；
Step E4: respectively in one end of silicon nitride cantilevers beam and the molybdenum oxide crystal terminal sprayed metal layer of needle point, work as spray
When the one end for being coated with the silicon nitride cantilevers beam of the metal layer is in contact with the molybdenum oxide crystal terminal for being coated with the metal layer, benefit
The metal layer is heated and melted with laser is focused, the silicon nitride cantilevers beam is connect with the molybdenum oxide crystal terminal, is formed
Probe.
Embodiment 5:
Its reaction process is similar to Example 1, and metal molybdenum sheet is only replaced with metal leaf, by the heating temperature of warm table
Degree is adjusted to 300 DEG C, and is located at carbon nanotube in gaseous oxidation tungsten atmosphere, 30min is kept, to obtain needle point.
Embodiment 6:
Its reaction process is similar to Example 1, the heating temperature of warm table is adjusted to 500 DEG C, and make carbon nanotube position
In in gaseous oxidation tungsten atmosphere, 5min is kept, needle point is obtained.
Embodiment 7:
Its reaction process is similar to Example 1, the heating temperature of warm table is adjusted to 400 DEG C, and make carbon nanotube position
In in gaseous oxidation tungsten atmosphere, 40min is kept, needle point is obtained.
Embodiment 8:
Its reaction process is similar to Example 2, and molybdenum oxide powder is only replaced with molybdenum disulfide powder, by reactor
Heating temperature is adjusted to 500 DEG C, and is located at carbon nanotube in gaseous state molybdenum disulfide atmosphere, 30min is kept, so that two sulphur of gaseous state
Change molybdenum to deposit in carbon nanotube, obtains the needle point with crystal of molybdenum disulfide.
Embodiment 9:
Its reaction process is similar to Example 3, molybdenum oxide powder is only replaced with two selenizing molybdenum powders, by reactor
Heating temperature is adjusted to 800 DEG C, and is located at carbon nanotube in two selenizing molybdenum atmosphere of gaseous state, 50min is kept, so that two selenium of gaseous state
Change molybdenum to deposit in carbon nanotube, obtains the needle point with two selenizing molybdenum crystal.
Embodiment 10:
Its reaction process is similar to Example 2, and molybdenum oxide powder is only replaced with tungsten trioxide powder, by reactor
Heating temperature is adjusted to 600 DEG C, and is located at carbon nanotube in gaseous state tungstic acid atmosphere, 60min is kept, so that three oxygen of gaseous state
Change tungsten to deposit in carbon nanotube, obtains the needle point with tungstic acid crystal.
Embodiment 11:
Its reaction process is similar to Example 4, and molybdenum oxide powder is only replaced with tungsten disulphide powder, by reactor
Heating temperature is adjusted to 700 DEG C, and is located at carbon nanotube in gaseous state tungsten disulfide atmosphere, 30min is kept, so that two sulphur of gaseous state
Change tungsten to deposit in carbon nanotube, obtains the needle point with tungsten disulfide crystal.
Embodiment 12:
Its reaction process is similar to Example 3, molybdenum oxide powder is only replaced with two selenizing tungsten powders, by reactor
Heating temperature is adjusted to 500 DEG C, and is located at carbon nanotube in gaseous state tungsten disulfide atmosphere, 60min is kept, so that two selenium of gaseous state
Change tungsten to deposit in carbon nanotube, obtains the needle point with two tungsten selenide crystal.
Embodiment 13:
Its reaction process is similar to Example 3, only replaces with the solution for the molybdenum trichloride that concentration is 0.005mol/L
Concentration is the chromium trichloride solution of 0.01mol/L, to prepare carbon nanotube, and it is subsequent anti-using carbon nanotube obtained progress
It answers, to prepare needle point and probe.
In addition, the temperature that above-mentioned each embodiment in probe preparation process, focuses laser can be according to the metal of spraying
The fusing point of layer carrys out modulation.
According to above scheme, various embodiments of the present invention are at least had the following beneficial effects:
1, the carbon nanotube in needle point provided in an embodiment of the present invention, by studies have shown that above-mentioned gaseous transition
The crystal that object is deposited into certain structure on single-root carbon nano-tube is closed, and a carbon nanotube can deposit multiple certain knots
The crystal of structure, i.e., a carbon nanotube can produce multiple needle points by the above process, and therefore, scheme provided by the invention can
Effectively improve the preparation efficiency of carbon nano-tube point.
2, compared with existing silicon or silicon nitride material needle point, the diameter of carbon nanotube is greatly reduced, generally 3~5nm,
Therefore needle point provided in an embodiment of the present invention can identify the pattern etc. within the scope of 3~5nm, to effectively improve imaging point
Resolution.
3, in needle point preparation method provided in an embodiment of the present invention, carbon nanotube can with the multiple crystal of deposition growing,
Therefore each needle point mechanical constant having the same and chirality that same root cutting carbon nanotube goes out, can form probe array to come
It realizes synchronous scanning, improves scanning speed with whole.
4, the embodiment of the present invention is during preparing needle point, the carbon nanotube, transition metal piece or the transition metal that use
The raw materials such as oxide, transient metal sulfide and reactor have generality, simple process, and raw material is easy to get, and are conducive to needle point
Production and popularization and application.
5, the embodiment of the present invention is during preparing probe, be by cantilever beam together with micron-sized crystal welding,
Rather than directly connect with carbon nanotube, reduce technical difficulty of operation and instrument requirements, may be implemented to produce in batches on a large scale,
Potential route is provided for carbon nano-tube point commercialization.
6, the needle point of preparation of the embodiment of the present invention is the scanning realized by carbon nanotube to sample, due to carbon nanotube sheet
Body has certain elasticity, reduces the damage in scanning process to sample, while also avoiding the damage of needle point to a certain extent
Wound, to effectively raise the service life of needle point.
It should be noted that, in this document, such as first and second etc relational terms are used merely to an entity
Or operation is distinguished with another entity or operation, is existed without necessarily requiring or implying between these entities or operation
Any actual relationship or order.Moreover, the terms "include", "comprise" or its any other variant be intended to it is non-
It is exclusive to include, so that the process, method, article or equipment for including a series of elements not only includes those elements,
It but also including other elements that are not explicitly listed, or further include solid by this process, method, article or equipment
Some elements.In the absence of more restrictions, the element limited by sentence " including one ", is not arranged
Except there is also other identical factors in the process, method, article or apparatus that includes the element.
Finally, it should be noted that the foregoing is merely presently preferred embodiments of the present invention, it is merely to illustrate skill of the invention
Art scheme, is not intended to limit the scope of the present invention.Any modification for being made all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., are included within the scope of protection of the present invention.
Claims (10)
1. a kind of method for preparing needle point, which is characterized in that grow carbon nanotube by chemical vapor deposition manner；Further include:
Control gaseous transition compound is contacted with the carbon nanotube, and the gaseous transition compound is received in the carbon
At least one crystal with certain structure is deposited on mitron；
One section of carbon nanotube that each described crystal is connect with by Van der Waals force forms a needle point.
2. the method according to claim 1, wherein described grow carbon nanometer by chemical vapor deposition manner
Pipe, comprising:
Slit is set in substrate；
Make catalyst with metal nanoparticle, the substrate is heated to 800 DEG C~1100 DEG C, and control carbon-source gas, hydrogen
The substrate is flowed through with the mixed gas of vapor composition, to grow carbon nanometer on the substrate and among the slit
Pipe.
3. according to the method described in claim 2, it is characterized in that, the control gaseous transition compound is received with the carbon
Mitron contact, comprising:
Will growth have the carbon nanotube substrate be inverted in transition metal on piece, heat the transition metal piece to 300 DEG C~
500 DEG C, the transition metal piece is made to be oxidized into transition metal oxide in air, the transition metal oxide is sublimed into
It is kept for gaseous transition oxide so that the carbon nanotube is located in the gaseous transition oxide atmosphere
5min~60min；
Alternatively,
There are the substrate of the carbon nanotube and transition metal oxide powder to be placed in same reactor growth, is passed through and does not join
Atmosphere protection is carried out with the gas reacted, and is heated to 500 DEG C~1000 DEG C, the transition metal oxide distillation becomes gaseous state
Transition metal oxide, so that the carbon nanotube is located at the gaseous transition oxide and is not involved in the gas of reaction
In atmosphere, 30min~60min is kept.
4. method according to claim 1 or 2, which is characterized in that
The transistion metal compound, comprising: in transition metal oxide, transient metal sulfide and transition metal selenides
Any one, wherein
The transition metal oxide is molybdenum oxide or tungstic acid；
The transient metal sulfide is molybdenum disulfide or tungsten disulfide；
The transition metal selenides is two selenizing molybdenums or two tungsten selenides.
5. method according to any one of claims 1 to 3, which is characterized in that
The crystal of certain structure, comprising: hexagonal crystal, the apex angle junction of the hexagon is on the carbon nanotubes；
And/or
The crystalline size of certain structure is 100nm~10 μm.
6. utilizing the needle point of claim 1 to 5 either method preparation characterized by comprising the crystal and carbon of certain structure
Nanotube, wherein
The crystal of certain structure belongs to one end of needle point, and the carbon nanotube belongs to the other end of needle point；
The carbon nanotube portion is inlaid into the crystal of certain structure, so that the crystal of certain structure and the carbon
Van der Waals force is formed between nanotube；
The crystal of certain structure includes transistion metal compound.
7. needle point according to claim 6, which is characterized in that
The crystal of certain structure, comprising: hexagonal crystal, the apex angle junction of the hexagon is on the carbon nanotubes.
8. needle point according to claim 6 or 7, which is characterized in that
The crystalline size of certain structure is 100nm~10 μm.
9. a kind of probe characterized by comprising claim 6 to the 8 any needle point and silicon nitride cantilevers beam,
In,
One end of the silicon nitride cantilevers beam is connected with the crystal of certain structure in the needle point.
10. a kind of method for preparing probe as claimed in claim 9 characterized by comprising
Respectively in one end of silicon nitride cantilevers beam and the crystal terminal sprayed metal layer of needle point；
When being coated with one end of silicon nitride cantilevers beam of the metal layer and being in contact with the crystal terminal for being coated with the metal layer,
The metal layer is heated and melted using laser is focused, connect the silicon nitride cantilevers beam with the crystal terminal.
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| CN107528001B (en) * | 2017-08-31 | 2019-10-11 | 清华大学 | A kind of preparation method and nanotube diode of nanotube diode |
| CN107352528B (en) * | 2017-08-31 | 2020-01-14 | 清华大学 | Preparation method of metal oxide nanochain and nanochain |
| CN107539972B (en) * | 2017-08-31 | 2020-05-05 | 清华大学 | Preparation method of metal oxide nanotube and metal oxide nanotube |
| CN109678138B (en) * | 2019-01-09 | 2022-04-26 | 温州大学 | Preparation method of single-chiral single-walled carbon nanotube |
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