CN106680252A - Nanotube-based fluorescence marked carrier and preparation method thereof - Google Patents
Nanotube-based fluorescence marked carrier and preparation method thereof Download PDFInfo
- Publication number
- CN106680252A CN106680252A CN201611055447.4A CN201611055447A CN106680252A CN 106680252 A CN106680252 A CN 106680252A CN 201611055447 A CN201611055447 A CN 201611055447A CN 106680252 A CN106680252 A CN 106680252A
- Authority
- CN
- China
- Prior art keywords
- wall
- nanometer
- growth
- quantum
- nanotube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The invention discloses a nanotube-based fluorescence marked carrier and a preparation method thereof. The fluorescence marked carrier comprises a nanotube inner wall, a quantum structure and a nanotube outer wall. The size of the nanotube structure is designed according to the characteristics of a simulated carrying object, and the size of the nanotube structure is regulated and controlled accurately by controlling the growth condition; in the fixed-temperature annealing process, a nanowire in a core-shell structure is guaranteed to be decomposed completely and the quantum structure limited between the nanotube inner wall and the nanotube outer wall is not damaged; the fluorescence marked part of the nanotube adopts a semiconductor quantum structure, has high fluorescence intensity, long duration time and stable photochemical property, is insusceptible to photobleaching and realizes high-efficiency radiative recombination; furthermore, continuous broad spectrum excitation can be adopted, the absorption coefficient is big, fluorescence emission peak is narrow, wavelength trailing is avoided, and the distinguishing degree is high; the nanotube structure can realize fluorescence marked carrying of the carrying object in the tube and also can perform the traditional wrapping or combined type fluorescence marked carrying.
Description
Technical field
The present invention relates to the preparation method of fluorescent mark carrier, more particularly to a kind of fluorescent mark carrier based on nanotube
Preparation method.
Background technology
Fluorescent labelling techniques originate from the forties in 20th century, and labelled antibody is used for earliest to detect corresponding antigen.With
The development in the field such as the progress of science and technology and biomedicine, material science, Cell-oriented yardstick or molecule, the target of atomic scale
Become one of the goal in research in multiple subjects such as medical science, biology, chemistry and materialogy and field to detection and targeted therapy,
The marking of medicine, reagent etc., lossless delivery are accurate medical treatment, the critical problem that precisely detection etc. is achieved.Tradition is glimmering
The method that signal is adopted is mainly used to be entered with the chemical reagent that fluorescent characteristic can be produced after fluorescent characteristic or combination
Line flag, such as fluoresceins dyestuff, dye stuff of rhodamine kinds, cyanine dyes, green fluorescent protein.With sending out for semiconductor technology
Exhibition, the quantum dot with nano-grade size is gradually applied to fluorescence labeling.Chan and Nie and Bruchez in 1998 etc. is first
Success quantum dot marked HeLa cells and 3T3 fibroblasts, indicate that quantum dot starts in the application of field of biology
Starting.But traditional Quantum Dot Labeling method cannot be avoided damage of the labeled thing in transport process, residual or spread,
Other non-detections or treatment target is caused to be affected, so as to bring interference to detection and analysis.Conventional tag thing is different from (as measured
Sub- point) be wrapped in interior mode, the structure (such as nanotube) that a kind of labeled thing is placed in label, can effectively overcome on
Problem is stated, targeting detection or treatment for target is realized.The hollow structure of semiconducting nanotubes can be bioprotein, medicine
Molecule or other inorganic material provide it is good transport carrier, meanwhile, the stable physics of semiconducting nanotubes and chemical property can
The lossless transport of carrying material to guarantee, and high efficiency can be realized by the coupling quantum spot in nanotube or SQW
Fluorescent emission.Realize having the controllable standby of the fluorescent mark carrier of mark and transportation function, energy concurrently using semiconducting nanotubes
The development of enough effectively promotion Related Research Domains.
Existing nanotube is mainly obtained by chemical synthesis process, the size (diameter, length and pipe thickness) of nanotube
It is difficult to accuracy controlling.Further, since the restriction of material and structure, existing nano-tube material exist do not light, luminous efficiency it is low or
The technical bottleneck such as person's emission wavelength is non-adjustable.Above technological difficulties cause to be prepared for the nanotube of specific wavelength and specific dimensions
It is difficult to.
The content of the invention
For above problems of the prior art, the present invention proposes a kind of fluorescent mark carrier based on nanotube
And preparation method thereof, can prepare based on the fluorescent mark carrier of nanotube, by the diameter to nanotube, tube wall, length
The controllable of the fluorescent mark carrier based on nanotube with high-efficiency fluorescence emission function is realized with the regulation of coupling quantum structure
Prepare.Using biology, chemically or physically method will treat that load is inserted in nanotube, you can realize the delivery to predetermined substance.
It is an object of the present invention to provide a kind of fluorescent mark carrier based on nanotube.
The present invention's is included based on the fluorescent mark carrier of nanotube：Nanometer inside pipe wall, quantum structure and nanometer pipe outer wall；
Wherein, the vertical growth nano wire in growth substrates；In the outside growing nano-tube inwall of nano wire, nanometer inside pipe wall parcel is received
The side wall of rice noodles and top, in barrel-shaped；In the apical growth quantum structure of nanometer inside pipe wall；The luminescence band of quantum structure and inspection
Survey wave band consistent；In the side wall and the superficial growth nanometer pipe outer wall of quantum structure of nanometer inside pipe wall, nanometer pipe outer wall parcel
The side wall and quantum structure thereon of nanometer inside pipe wall, in barrel-shaped；Outside nano wire, nanometer inside pipe wall, quantum structure and nanotube
Wall forms nucleocapsid structure；Nucleocapsid structure is transferred on high temperature-resistant liner bottom from growth substrates, and high temperature is carried out under fixed temperature
Annealing, the nano wire inside nucleocapsid structure decomposes, and obtains including nanometer inside pipe wall, quantum structure and nanometer pipe outer wall
Nano tube structure；Quantum structure as fluorescent-labeled portions be located at barrel-shaped nanometer inside pipe wall and nanometer pipe outer wall top it
Between, form three-dimensional quantum and limit, realize that efficient radiation recombination lights in detection process.
The material of nano wire is the binary or ternary alloy three-partalloy of II-VI group or iii-v, nano wire a diameter of 10~
100nm, is highly 0.1~5 μm.
Nanometer pipe outer wall and nanometer inside pipe wall adopt identical material, and its decomposition temperature is higher than the decomposition temperature of nano wire,
Respective thickness is 0.2~10nm, and nanometer inside pipe wall and nanometer pipe outer wall collectively form nanotube walls.Decomposition temperature refers to material
In interatomic chemical bond start rupture when temperature.
Quantum structure is located between nanometer inside pipe wall and the top of nanometer pipe outer wall as fluorescent-labeled portions, forms good
Three-dimensional quantum limit so that quantum structure is not impacted in high-temperature annealing process, and quantum structure can be realized
Alloy ordered arrangement, can realize that efficient radiation recombination lights in detection process；The form of quantum structure is single quantum
Trap or MQW, or for single quantum dot or multi layered quantum dots；The emission wavelength of quantum structure can in the range of 200~2000nm
Adjust.
The fixed temperature of high annealing is less than the decomposition temperature of nanotube walls more than the decomposition temperature of nano wire simultaneously, it is ensured that
Nano wire is completely broken down, and nanotube walls are not destroyed；The decomposition temperature of quantum structure does not have with the fixed temperature of high annealing
There is direct relation, quantum structure will not be destroyed in annealing process.
Further object is that providing a kind of preparation method of the fluorescent mark carrier based on nanotube.
The preparation method of the fluorescent mark carrier based on nanotube of the present invention, comprises the following steps：
1) growth substrates are provided, growth substrates have the crystal face for being adapted to nano wire vertical growth；
2) according to the property of load, the parameter of nano tube structure is set, the parameter of nano tube structure is tied including nanotube
The thickness of the internal diameter of structure, length, nanometer inside pipe wall and nanometer pipe outer wall；
3) the vertical growth nano wire in growth substrates, by the line ratio and growth time that control growth source, control is received
The diameter and height of rice noodles；
4) in nano wire outgrowth nanometer inside pipe wall, by the line ratio and growth time that control growth source, nanometer is controlled
The thickness of inside pipe wall, the side wall of nanometer inside pipe wall parcel nano wire and top；
5) according to detection wave band, the emission wavelength quantum structure consistent with detection wave band is designed, on the top of nanometer inside pipe wall
End grown quantum structure；
6) in the side wall and the superficial growth nanometer pipe outer wall of quantum structure of nanometer inside pipe wall, by controlling growth source
Line ratio and growth time, control the thickness of nanometer pipe outer wall, the side wall of nanometer pipe outer wall parcel nanometer inside pipe wall and thereon
Quantum structure, forms nucleocapsid structure；
7) nucleocapsid structure is transferred on high temperature-resistant liner bottom from growth substrates；
8) the high temperature anneal is carried out under fixed temperature, the nano wire inside nucleocapsid structure decomposes, and obtains including nanometer
The nano tube structure of inside pipe wall, nanometer pipe outer wall and quantum structure；
9) process is cleaned to nano tube structure, the nano tube structure of cleaning is obtained；
10) nano tube structure is dispersed in solution, using centrifugal process, extracts the nano tube structure of size uniform；
11) load is inserted in nano tube structure, realization can be fluorescently-labeled to load based on nano tube structure
Transport.
Wherein, in step 1) in, the surface of growth substrates can realize that II-VI group or the binary or ternary of iii-v are closed
The vertical growth of golden material, the direction of growth of nano wire is along growth substrates normal to a surface direction.
In step 2) in, the features such as load size, composition form, design the parameter of nano tube structure, bag
Include the thickness of internal diameter, length, nanometer inside pipe wall and the nanometer pipe outer wall of nano tube structure.
In step 3) in, the growth pattern of nano wire adopts selective area growth, or adopts self-organizing growth.Selective area growth is
Nano wire is grown in a part for growth substrates.Self-organizing growth is to start nano wire after self-organizing nucleation in growth substrates
Growth.The material of nano wire is using II-VI group or the binary or ternary alloy three-partalloy of iii-v.The mode of growth nano wire is adopted
Molecular beam epitaxy MBE, metal-organic chemical vapor deposition equipment MOCVD, chemical vapor deposition CVD or pulsed laser deposition PLD etc..
According to step 2) in design parameter, select the line of II races and VI races or III and V races growth source when growth time,
So as to control the diameter (10~100nm) and height (0.1~5 μm) of nano wire.
In step 4) in, the decomposition temperature of nanotube inner-wall material is more than the decomposition temperature of nano-material, using II-VI
Race or the ternary or bianry alloy of iii-v, according to step 2) in design nanometer inside pipe wall thickness, select II races and VI races
Or the line of III and V races growth source when growth time, so as to control the thickness (0.2~10nm) of nanometer inside pipe wall.
In step 5) in, according to the detection wave band for being adopted, design quantum structure so that the emission wavelength of quantum structure with
Detection wave band is consistent.The material that quantum structure is adopted belongs to same material body with nano wire, nanometer inside pipe wall and nanometer pipe outer wall
System.The form of quantum structure is single quantum well or MQW, or for single quantum dot or multi layered quantum dots.
In step 6) in, nanometer pipe outer wall and nanometer inside pipe wall adopt identical material, according to step 2) in design receive
Mitron outer wall thickness, select with step 4) in identical growth source line ratio, control growth time, so as to control outside nanotube
The thickness (0.2~10nm) of wall, nano wire, nanometer inside pipe wall, quantum structure and nanometer pipe outer wall form nucleocapsid structure.
In step 7) in, nucleocapsid structure is removed from growth substrates, it is dispersed in the surface at high temperature-resistant liner bottom.High temperature resistant
The surface of substrate needs cleaning, it is to avoid nucleocapsid structure is contaminated.The dispersing mode of nucleocapsid structure adopts solwution method, i.e., first will
Nucleocapsid structure ultrasonic disperse is then transferred on high temperature-resistant liner bottom into solution；Or adopt Physical, i.e., directly core-shell structure copolymer tied
Structure is dispersed directly on high temperature-resistant liner bottom by methods such as strippings.
In step 8) in, the fixed temperature of annealing requires the decomposition temperature higher than nano wire, while being less than nanometer inside pipe wall
With the decomposition temperature of nanometer pipe outer wall.Anneal environment, can according to material behavior using vacuum, air, nitrogen or inert gas etc.
To adjust.
In step 9) in, the impurity introduced in annealing process is removed using hydrogen gas plasma, obtain clean nanotube
Structure.
In step 10) in, solution is generally not acrid volatile liquid, such as alcohol, isopropanol.According to nanometer
The concrete size (length and external diameter) of tubular construction, selects centrifugation rate, removes nano tube structure damaged in above-mentioned processing procedure,
Obtain the nano tube structure of size uniform.
In step 11) in, load inserts the method for nano tube structure to be included：Solwution method, sedimentation, siphonage etc., tool
Body method need to be selected according to the characteristics of load, final to realize load being inserted in nano tube structure, and not destroy load
And nano tube structure.
Advantages of the present invention：
(1) present invention designs the size of nano tube structure, including diameter, the length of nanotube according to the characteristics of plan load
And pipe thickness, carry out the size of accuracy controlling nano tube structure by controlling growth conditions；
(2) fixed temperature annealing process, it is ensured that the nano wire in nucleocapsid structure decomposes completely, not destruction is limited to receive
Quantum structure between mitron inwall and nanometer pipe outer wall, meanwhile, it is capable to the alloy order in quantum structure is further improved,
Guarantee the high efficiency radiation recombination of quantum structure；
(3) fluorescent-labeled portions of nanotube adopt semiconductor quantum structure, high with fluorescence intensity, and the duration is long,
Spectrochemical property is stablized, and is not susceptible to photobleaching；And absorption coefficient is big, and fluorescence emission peak is narrow, without wavelength tail, can identification
It is high；
(4) nano tube structure had both been capable of achieving the fluorescence labeling delivery of the load in pipe, moreover it is possible to carry out traditional packaging type
Or the delivery of convolution fluorescence labeling.
Description of the drawings
Fig. 1 be according to the present invention based on the fluorescent mark carrier preparation method of nanotube obtain in growth substrates
The schematic diagram of nucleocapsid structure；
Fig. 2 is resistance to according to being transferred to nucleocapsid structure based on the fluorescent mark carrier preparation method of nanotube of the present invention
Schematic diagram in high temperature substrate, wherein, (a) be annealing before schematic diagram, (b) be annealing after schematic diagram；
Fig. 3 is the fluorescent mark carrier obtained based on the fluorescent mark carrier preparation method of nanotube according to the present invention
Experimental results figure, wherein, (a) be annealing before nucleocapsid structure scanning electron microscope diagram, (b) at for annealing
The scanning electron microscope diagram of the nano tube structure for obtaining after reason, (c) be annealing after obtain nano tube structure it is saturating
Penetrate electron microscope picture.
Specific embodiment
Below in conjunction with the accompanying drawings, by embodiment, the present invention will be further described.
Embodiment
As shown in figure 1, the present embodiment is included based on the fluorescent mark carrier of nanotube：Nanometer inside pipe wall 31, Quantum Junction
Structure 4 and nanometer pipe outer wall 32, nanometer inside pipe wall 31 and nanometer pipe outer wall 32 collectively form nanotube walls 3；Wherein, in growth substrates
Vertical growth nano wire 2 on 1；The side wall of nano wire 2 and top are wrapped up in nano wire outgrowth nanometer inside pipe wall 31；In nanotube
The apical growth quantum structure 4 of inwall 31；Outside the side wall of nanometer inside pipe wall 31 and the apical growth nanotube of quantum structure 4
Wall 32, the side wall of the parcel nanometer of nanometer pipe outer wall 32 inside pipe wall 31 and the top of quantum structure 4, form nucleocapsid structure.
As shown in Fig. 2 nucleocapsid structure is transferred on high temperature-resistant liner bottom 6 from growth substrates 1, through the high temperature anneal, make
Nano wire 2 inside nucleocapsid structure decomposes, and obtains the nano tube structure 5 collectively formed by nanotube walls 3 and quantum structure 4.
In the present embodiment, AlN based nanotube structures are prepared, growth substrates adopt Si (111) face；The material of nanometer pipe outer wall
Using AlN, quantum well structure is single quantum well GaN, and the material of nanometer inside pipe wall adopts the material of AlN, nano wire to adopt GaN；
Nucleocapsid structure is grown using molecular beam epitaxy MBE technologies on Si (111) face；Growth course is carried out in ultrahigh vacuum chamber,
High-purity (7N) source metal is produced by K-Cell sources stove；Nitrogen source adopts radio frequency plasma nitrogen source.
The preparation method of the fluorescent mark carrier based on nanotube of the present embodiment, comprises the following steps：
1) growth substrates are provided, growth substrates 1 have the crystal face for being adapted to nano wire vertical growth：
GaN can realize the vertical growth of nano wire, nano wire edge on Si (111) faceDirection grows, and selects Si
(111) as the growth substrates 1 of nano wire.
2) according to the property of load, the structural parameters of nanotube are set, including the internal diameter of nanotube, length, inwall and
Outer wall thickness：
In the present embodiment intend load be metal Al, arrange nanotube internal diameter be 50nm, length be 750nm, inwall and
Outer wall thickness is 1nm.
3) the vertical growth nano wire in growth substrates, by the line ratio and growth time that control growth source, control is received
The diameter and height of rice noodles：
Using the nanometer of molecular beam epitaxy MBE methods upright GaN of self-assembled growth in the growth substrates 1 of Si (111)
Line 2, growth source used is gallium (Ga) source and plasma nitrogen (N) source, and the line ratio for selecting Ga/N sources is 1/5, growth
Time is 100min, a diameter of 50nm of nano wire, is highly 700nm.
4) in nano wire outgrowth nanometer inside pipe wall, by the line ratio and growth time that control growth source, nanometer is controlled
The thickness of inside pipe wall, the side wall of nanometer inside pipe wall parcel nano wire and top：
The decomposition temperature of GaN is 850 DEG C under vacuum, and the decomposition temperature of AlN is 1040 DEG C, therefore, in the nano wire 2 of GaN
Outer wall and apical growth AlN nanometers inside pipe wall 31, growth source used is metallic aluminium (Al) source and plasma nitrogen (N) source,
The line ratio for selecting Al/N sources is 1/20, and growth time is 10min, and the thickness of AlN nanometers inside pipe wall 31 is 1nm.
5) according to detection wave band, design emission wavelength quantum structure consistent with detection wave band, on the top of nanometer inside pipe wall
Grown quantum structure：
The detection wave band that the present embodiment is adopted is ultraviolet band (200-400nm), and design quantum structure 4 is that GaN/AlN is mono-
SQW, its emission wavelength is in 280nm.
6) in the side wall and the superficial growth nanometer pipe outer wall of quantum structure of nanometer inside pipe wall, by controlling growth source
Line ratio and growth time, control the thickness of nanometer pipe outer wall, the side wall of nanometer pipe outer wall parcel nanometer inside pipe wall and thereon
Quantum structure, forms nucleocapsid structure：
In the nanometer pipe outer wall 32 of the superficial growth AlN of the side wall and quantum structure 4 of the nanometer inside pipe wall 31 of AlN, institute
Growth source is metallic aluminium (Al) source and plasma nitrogen (N) source, and the line ratio for selecting Al/N sources is 1/20, and growth time is
The thickness of nanometer pipe outer wall 32 of 10min, AlN is 1nm, the nanometer inside pipe wall 31 of GaN nano wire 2, AlN, quantum structure 4 and nanometer
Pipe outer wall 32 forms nucleocapsid structure.
7) nucleocapsid structure is removed from substrate 1, and is dispersed to the surface of high temperature-resistant liner bottom 6 of the Si (111) of cleaning, such as
Shown in Fig. 2 (a).
8) the high temperature anneal is carried out under fixed temperature, the nano wire inside nucleocapsid structure decomposes, and obtains including nanometer
The nano tube structure of inside pipe wall, nanometer pipe outer wall and quantum structure：
In vacuum environment, 900 DEG C (850 DEG C<900℃<1040 DEG C) annealing 30min is carried out, make in nucleocapsid structure
The nano wire 2 in portion decomposes, and acquisition includes the nano tube structure 5 of AlN/GaN/AlN single quantum wells on top, such as Fig. 2 (b) institutes
Show.Fig. 3 (a) and (b) are respectively the sem test result before nano tube structure 5 is annealed in the present embodiment and after annealing, Fig. 3
C () is the transmissioning electric mirror test result of the nano tube structure 5 obtained after annealing.
9) nano tube structure is processed using hydrogen gas plasma, obtains clean nano tube structure：
Using the hydrogen gas plasma of 1.2sccm/400W, surface cleaning is carried out to nano tube structure 5 and processes 5min, removed
Impurity etc. present in nano tube structure 5 in annealing process.
10) nano tube structure is dispersed in solution, using centrifugal process, extracts the nano tube structure with uniform-dimension：
By through step 5) process after nano tube structure 5 be dispersed in aqueous isopropanol, processed using centrifuge,
Nano tube structure damaged during annealing and cleaning treatment is removed, a diameter of 50nm, length is finally obtained for 750nm, tube wall
Thickness is the nano tube structure 5 of 2nm, and luminescence generated by light test confirms top AlN/GaN/AlN single quantum well fluorescence labeling structures
Emission wavelength is 280nm, so as to prepare fluorescent mark carrier.
11) load is inserted in nano tube structure, you can realization can fluorescence mark to load based on nano tube structure
That what is remembered transports：
By step 6) in obtain nano tube structure 5 be dispersed on Si (111) substrate, using molecular beam epitaxy MBE technologies
Deposited metal Al drops, then Al metals are injected into the inside of nano tube structure 5 using siphonic effect；Metal will be marked with afterwards
The nano tube structure 5 of Al is dispersed to again in aqueous isopropanol, using the laser excitation of 266nm, it is found that 280nm's is luminous, and
Determine its position.Realize the fluorescence labeling to metal Al using nano tube structure 5 to deliver.
It is finally noted that, the purpose for publicizing and implementing mode is that help further understands the present invention, but ability
The technical staff in domain is appreciated that：Without departing from the spirit and scope of the invention and the appended claims, it is various replacement and
Modification is all possible.Therefore, the present invention should not be limited to embodiment disclosure of that, the scope of protection of present invention with
The scope that claims are defined is defined.
Claims (10)
1. a kind of preparation method of the fluorescent mark carrier based on nanotube, it is characterised in that the preparation method includes following
Step：
1) growth substrates are provided, growth substrates have the crystal face for being adapted to nano wire vertical growth；
2) according to the property of load, the parameter of nano tube structure is set, the parameter of nano tube structure includes nano tube structure
The thickness of internal diameter, length, nanometer inside pipe wall and nanometer pipe outer wall；
3) the vertical growth nano wire in growth substrates, by the line ratio and growth time that control growth source, controls nano wire
Diameter and height；
4) in nano wire outgrowth nanometer inside pipe wall, by the line ratio and growth time that control growth source, in control nanotube
The thickness of wall, the side wall of nanometer inside pipe wall parcel nano wire and top；
5) according to detection wave band, the emission wavelength quantum structure consistent with detection wave band is designed, is given birth on the top of nanometer inside pipe wall
Long quantum structure；
6) in the side wall and the superficial growth nanometer pipe outer wall of quantum structure of nanometer inside pipe wall, by the line for controlling growth source
Than and growth time, control nanometer pipe outer wall thickness, nanometer pipe outer wall parcel nanometer inside pipe wall side wall and quantum thereon
Structure, forms nucleocapsid structure；
7) nucleocapsid structure is transferred on high temperature-resistant liner bottom from growth substrates；
8) the high temperature anneal is carried out under fixed temperature, the nano wire inside nucleocapsid structure decomposes, and obtains including in nanotube
The nano tube structure of wall, nanometer pipe outer wall and quantum structure；
9) process is cleaned to nano tube structure, the nano tube structure of cleaning is obtained；
10) nano tube structure is dispersed in solution, using centrifugal process, extracts the nano tube structure of size uniform；
11) load is inserted in nano tube structure, realization is transported based on the fluorescently-labeled to load of nano tube structure.
2. preparation method as claimed in claim 1, it is characterised in that in step 3) in, the growth pattern of nano wire is using choosing
Area grows, or adopts self-organizing growth.
3. preparation method as claimed in claim 1, it is characterised in that in step 5) in, according to the detection wave band for being adopted, if
Metering minor structure so that the emission wavelength of quantum structure is consistent with detection wave band；Material and nano wire that quantum structure is adopted, receive
Mitron inwall and nanometer pipe outer wall belong to same material system；The form of quantum structure is single quantum well or MQW, or
For single quantum dot or multi layered quantum dots.
4. preparation method as claimed in claim 1, it is characterised in that in step 7) in, by nucleocapsid structure from growth substrates
Remove, be dispersed in the surface at high temperature-resistant liner bottom；The dispersing mode of nucleocapsid structure adopts solwution method, i.e., first by nucleocapsid structure ultrasound
It is dispersed in solution and is then transferred on high temperature-resistant liner bottom；Or adopt Physical, i.e., directly by nucleocapsid structure by the side peeled off
Method is dispersed directly on high temperature-resistant liner bottom.
5. preparation method as claimed in claim 1, it is characterised in that in step 8) in, the fixed temperature of annealing require be higher than
The decomposition temperature of nano wire, while less than nanometer inside pipe wall and the decomposition temperature of nanometer pipe outer wall；Anneal environment adopts vacuum, sky
Gas, nitrogen or inert gas.
6. preparation method as claimed in claim 1, it is characterised in that in step 10) in, solution is easily waved for not acrid
Lotion body；According to the concrete size of nano tube structure, centrifugation rate is selected, remove damaged nano tube structure, obtain size equal
Even nano tube structure.
7. a kind of fluorescent mark carrier based on nanotube, it is characterised in that the fluorescent mark carrier includes：In nanotube
Wall, quantum structure and nanometer pipe outer wall；Wherein, the vertical growth nano wire in growth substrates；Receive in the outside growth of nano wire
Mitron inwall, the side wall of the nanometer inside pipe wall parcel nano wire and top, in barrel-shaped；In the apical growth amount of nanometer inside pipe wall
Minor structure；The luminescence band of the quantum structure is consistent with detection wave band；In the side wall and quantum structure of nanometer inside pipe wall
Superficial growth nanometer pipe outer wall, the side wall and quantum structure thereon of the nanometer pipe outer wall parcel nanometer inside pipe wall, in barrel-shaped；
The nano wire, nanometer inside pipe wall, quantum structure and nanometer pipe outer wall form nucleocapsid structure；The nucleocapsid structure is from growth lining
It is transferred on bottom on high temperature-resistant liner bottom, the high temperature anneal, the nano wire inside nucleocapsid structure point is carried out under fixed temperature
Solution, obtains including the nano tube structure of nanometer inside pipe wall, quantum structure and nanometer pipe outer wall；The quantum structure is used as fluorescence mark
Note part is located between the top of barrel-shaped nanometer inside pipe wall and nanometer pipe outer wall, is formed three-dimensional quantum and is limited, in detection process
In realize efficient radiation recombination light.
8. fluorescent mark carrier as claimed in claim 7, it is characterised in that the nanometer pipe outer wall and nanometer inside pipe wall are adopted
Identical material, decomposition temperature of its decomposition temperature higher than nano wire.
9. fluorescent mark carrier as claimed in claim 7, it is characterised in that the form of the quantum structure be single quantum well or
MQW, or for single quantum dot or multi layered quantum dots；The emission wavelength of the quantum structure can in the range of 200~2000nm
Adjust.
10. fluorescent mark carrier as claimed in claim 7, it is characterised in that the material of the nano wire be II-VI group or
The binary or ternary alloy three-partalloy of iii-v, a diameter of 10~100nm of the nano wire is highly 0.1~5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611055447.4A CN106680252B (en) | 2016-11-25 | 2016-11-25 | A kind of fluorescent mark carrier and preparation method thereof based on nanotube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611055447.4A CN106680252B (en) | 2016-11-25 | 2016-11-25 | A kind of fluorescent mark carrier and preparation method thereof based on nanotube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106680252A true CN106680252A (en) | 2017-05-17 |
| CN106680252B CN106680252B (en) | 2019-04-02 |
Family
ID=58865925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611055447.4A Active CN106680252B (en) | 2016-11-25 | 2016-11-25 | A kind of fluorescent mark carrier and preparation method thereof based on nanotube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106680252B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109524511A (en) * | 2018-10-25 | 2019-03-26 | 北京大学 | A kind of nano wire coupling quantum point structure and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1818650A (en) * | 2006-01-16 | 2006-08-16 | 南开大学 | Single-wall carbon nanometer tube tracer with fluorescent label DNA, its production and use |
| CN1884430A (en) * | 2006-06-30 | 2006-12-27 | 上海师范大学 | Fluorescent carbon nanometer tube and its preparation method and application |
| US20080296538A1 (en) * | 2007-05-30 | 2008-12-04 | Ning-Yu Wu | Carbon nanotube and method of visualizing carbon nanotube |
| CN101974326A (en) * | 2010-09-21 | 2011-02-16 | 上海大学 | Method for preparing novel fluorescent silica nanospheres |
| CN102416180A (en) * | 2011-12-14 | 2012-04-18 | 浙江理工大学 | Functional integrated medicament carrier and preparation method thereof |
-
2016
- 2016-11-25 CN CN201611055447.4A patent/CN106680252B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1818650A (en) * | 2006-01-16 | 2006-08-16 | 南开大学 | Single-wall carbon nanometer tube tracer with fluorescent label DNA, its production and use |
| CN1884430A (en) * | 2006-06-30 | 2006-12-27 | 上海师范大学 | Fluorescent carbon nanometer tube and its preparation method and application |
| US20080296538A1 (en) * | 2007-05-30 | 2008-12-04 | Ning-Yu Wu | Carbon nanotube and method of visualizing carbon nanotube |
| CN101974326A (en) * | 2010-09-21 | 2011-02-16 | 上海大学 | Method for preparing novel fluorescent silica nanospheres |
| CN102416180A (en) * | 2011-12-14 | 2012-04-18 | 浙江理工大学 | Functional integrated medicament carrier and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 唐超越: ""碳纳米管的功能修饰及作为载体材料的初步应用"", 《复旦大学硕士学位论文》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109524511A (en) * | 2018-10-25 | 2019-03-26 | 北京大学 | A kind of nano wire coupling quantum point structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106680252B (en) | 2019-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Straight and smooth GaN nanowires | |
| Panev et al. | Sharp exciton emission from single InAs quantum dots in GaAs nanowires | |
| Banin et al. | Tunneling and optical spectroscopy of semiconductor nanocrystals | |
| Zheng et al. | Synthesis of Ultra‐Long and Highly Oriented Silicon Oxide Nanowires from Liquid Alloys | |
| Fontcuberta i Morral et al. | Prismatic quantum heterostructures synthesized on molecular-beam epitaxy GaAs nanowires | |
| Suárez et al. | Laser devices with stacked layers of InGaAs/GaAs quantum rings | |
| US7972694B2 (en) | Triple-layer semiconductor nanoparticle and triple-layer semiconductor nanorod | |
| US8569736B2 (en) | Light emitting diode | |
| Kats et al. | Optical study of GaAs quantum dots embedded into AlGaAs nanowires | |
| Chang et al. | Synergistic effects of SPR and FRET on the photoluminescence of ZnO nanorod heterostructures | |
| Tang et al. | SiGe quantum dots prepared on an ordered mesoporous silica coated Si substrate | |
| CN106680252B (en) | A kind of fluorescent mark carrier and preparation method thereof based on nanotube | |
| Prete et al. | Luminescence of GaAs/AlGaAs core–shell nanowires grown by MOVPE using tertiarybutylarsine | |
| Pan et al. | Liquid gallium ball/crystalline silicon polyhedrons/aligned silicon oxide nanowires sandwich structure: An interesting nanowire growth route | |
| Lorcy et al. | Coaxial nickel/poly (p-phenylene vinylene) nanowires as luminescent building blocks manipulated magnetically | |
| Novák et al. | Nanorods and nanocones for advanced sensor applications | |
| US7422632B2 (en) | Epitaxial growth of structures with nano-dimensional features from liquid phase by pulse cooling of substrate | |
| Wong et al. | Improved photoluminescence efficiency of patterned quantum dots incorporating a dots-in-the-well structure | |
| Jin et al. | Growth of low-density InAs/GaAs quantum dots on a substrate with an intentional temperature gradient by molecular beam epitaxy | |
| Lipsanen et al. | Fabrication and photoluminescence of quantum dots induced by strain of self-organized stressors | |
| Hanna et al. | GaInP 2 overgrowth and passivation of colloidal InP nanocrystals using metalorganic chemical vapor deposition | |
| Ishikawa et al. | (Al, Ga) Ox Microwire Ensembles on Si Exhibiting Luminescence over the Entire Visible Wavelength Range | |
| Zhao et al. | Cost-effective selective-area growth of GaN-based nanocolumns on silicon substrates by molecular-beam epitaxy | |
| Finnie et al. | Cold wall chemical vapor deposition of single walled carbon nanotubes | |
| Zha et al. | Self-assembly of single “square” quantum rings in gold-free GaAs nanowires |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |