CN113548641B - Preparation method of confined dielectric breakdown solid-state nano-pore device, product and application thereof - Google Patents

Preparation method of confined dielectric breakdown solid-state nano-pore device, product and application thereof Download PDF

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CN113548641B
CN113548641B CN202110850805.5A CN202110850805A CN113548641B CN 113548641 B CN113548641 B CN 113548641B CN 202110850805 A CN202110850805 A CN 202110850805A CN 113548641 B CN113548641 B CN 113548641B
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dielectric breakdown
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thin film
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CN113548641A (en
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王德强
刘业香
何石轩
谢婉谊
方绍熙
周大明
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Chongqing Institute of Green and Intelligent Technology of CAS
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00015Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00023Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
    • B81C1/00087Holes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81BMICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B1/00Devices without movable or flexible elements, e.g. microcapillary devices
    • B81B1/002Holes characterised by their shape, in either longitudinal or sectional plane
    • B81B1/004Through-holes, i.e. extending from one face to the other face of the wafer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00436Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
    • B81C1/00444Surface micromachining, i.e. structuring layers on the substrate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00436Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
    • B81C1/005Bulk micromachining
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00841Cleaning during or after manufacture
    • B81C1/00849Cleaning during or after manufacture during manufacture
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81BMICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B2201/00Specific applications of microelectromechanical systems
    • B81B2201/02Sensors
    • B81B2201/0214Biosensors; Chemical sensors

Abstract

The invention relates to a preparation method of a finite field dielectric breakdown solid-state nanopore device, a product and application thereof, and belongs to the technical field of nanopore device preparation. The invention discloses a preparation method of a finite field dielectric breakdown solid state nano-pore device, which is a method for double-sided etching of a channel thinning film based on a focused ion beam and a manufacturing method of the finite field dielectric breakdown solid state nano-pore device, and can effectively limit the positions and the number of nano-pores prepared by a dielectric breakdown method; meanwhile, compared with the common thin film thinning technology, the method has less damage to the material and higher material stability, and can be used for researching the extremely thin nanopore sensing performance formed by various bulk materials; in addition, the sensing performance of the ultrathin stable nano-pore prepared by superposing different compound materials can be known, and the method has great application development potential.

Description

Preparation method of confined dielectric breakdown solid-state nano-pore device, product and application thereof
Technical Field
The invention belongs to the technical field of nanopore preparation, and relates to a preparation method of a finite field dielectric breakdown solid-state nanopore device, a product and application thereof.
Background
Nanopore sensing technology has become a promising biosensing technology at present due to its advantages of high throughput, low cost, long reading, etc. In the aspect of nano-pore preparation, the existing solid nano-pore preparation methods mainly comprise ion beam etching, electron beam sputtering etching, electrochemical corrosion, an emerging dielectric breakdown method and the like, wherein the diameter of a pore generated by the dielectric breakdown punching method can be as small as 1nm, and the precision is 0.5nm (the precision is in the angstrom level). Since the dielectric breakdown perforation method does not require a beam line of sight to fabricate the nanopore, it allows for fabricating planar nanopores in existing nanostructures; since the dielectric breakdown punch-through method is cost effective and can be easily handled with minimal training using inexpensive hardware, the dielectric breakdown punch-through method is one of the punch-through techniques currently used in many laboratories.
Dielectric breakdown perforation, however, does not control the exact location of the holes on the film, which is critical for some electro-optic nanopore-based platforms. Many specific applications (including nanofluidic transistors, electrode-embedded devices, and plasma nanopores) require the formation of pores within a short distance of existing structures on the membrane. This is an electro-machining process that is not visible to the naked eye and therefore may sometimes create unwanted extra holes. Furthermore, the method of preparing nanopores by dielectric breakdown is suitable for making small holes (+.30nm and below thickness and diameter) in thin films, which may prevent their use in cell or molecular macrostructure detection. The TEM and FIB hole can be positioned at a certain position, but the structure is in the vacuum cavity at the moment, so that the in-situ nano hole preparation cannot be carried out in the electrolyte solution; second, dielectric breakdown to produce nanopores is not suitable for thin films with film thickness greater than 30 nm. For the nano-pore device structure, the thicker the film thickness is, the better the device stability is, which limits the application of dielectric breakdown technology to thick film samples.
There is therefore a need to develop a new method to prepare a confined dielectric breakdown solid state nanopore device that can solve both the pore size and thickness problems described above.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a solid state nanopore device with limited dielectric breakdown; the second object of the present invention is to provide a finite field dielectric breakdown solid state nanopore device; the invention further aims to provide an application of the finite field dielectric breakdown solid-state nanopore device in single molecule detection and current modulation analysis.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. a method of fabricating a confined dielectric breakdown solid state nanopore device, the method comprising the steps of:
(1) Preparing a limited-area ultrathin film by double-sided etching of a nano channel: placing the pretreated and blow-dried film substrate in a vacuum cavity for processing by a focused ion beam, processing by adopting a gallium ion beam, and processing the front surface and the back surface of the film substrate to form spatially intersected nanoscale channels, so as to realize thinning of the film material and form a nanoscale domain-limiting ultrathin film;
(2) Preparing a solid state nanopore device by confined dielectric breakdown: loading the limited-area nanoscale film window with the surface organic pollution and impurities removed through plasma cleaning into a flow cell chamber, filling electrolyte at two sides of the chamber respectively, and preparing a nanopore by using a customized Labview program by using a voltage source meter and adopting a dielectric breakdown technology to obtain the limited-area dielectric breakdown solid-state nanopore device;
the electrolyte is KCl solution and MgCl with the concentration of 0.1-3M 2 Solutions or CaCl 2 Any one or more of the solutions.
Preferably, in the step (1), the film substrate is any one or a superposition of any two of a silicon nitride film, a silicon dioxide film and an aluminum oxide film, and the thickness of the film substrate is 30-1000 nm.
Preferably, in step (1), the pretreatment specifically includes: and respectively soaking the film substrate for 1-2 h by adopting ethanol and deionized water, and then performing plasma treatment for 5-10 min to remove organic pollution and impurities on the surface of the sample.
Preferably, in the step (1), the drying is performed by using nitrogen.
Preferably, in the step (1), the parameters of the gallium ion beam processing in the processing procedure of the gallium ion beam are: ion beam 2.7E per dose volume -1 μm 2 and/nC for a duration of 1 to 100ms.
Preferably, in the step (1), the width of the nanoscale channel is 30-500 nm, the length is 0.1-5 μm, and the depth is 10-500 nm;
the thickness of the thin film substrate at the intersection of the nanoscale channels on the thin film substrate is 2-5 nm.
Preferably, in the step (2), the specific method for removing the organic pollution on the surface by plasma cleaning is as follows: sequentially placing the double-sided etched nano-channel ultrathin film into ethanol and deionized water, standing for 1h, performing plasma cleaning for 10-40 s with power of 10-30W, removing pollutants and impurities on the surface of the window of the limited nano-scale film, and reducing the sample capacitance.
Preferably, in the step (2), the preparing the nanopore specifically includes: preparation of nanopores using a current mode of dielectric breakdown method in which the initial current value is 1E -9 ~1E -7 A. Step size of 1E -9 ~1E -8 A。
2. The finite field dielectric breakdown solid-state nano-pore device prepared by the preparation method is provided.
3. The application of the finite field dielectric breakdown solid-state nano-pore device in single molecule detection and current modulation analysis.
The invention has the beneficial effects that:
1. the invention discloses a preparation method of a finite field dielectric breakdown solid-state nano-pore device, which is a mode of firstly using an ion beam to thin a film and then carrying out dielectric breakdown punching. The preparation method of the invention can also be carried out on thicker bulk materials; the structure is not directly thinned in a large area, so that the stability of the whole structure is ensured; the used front and back nanoscale rectangular strip-shaped structure can well ensure the integral mechanical stability of the structure, and overcomes the defect of a thin large-area film. In addition, compared with the traditional large-area square thinning area structure used for subsequent nano-hole preparation, the single-shot preparation method provided by the invention has the advantage that the range of the positioning holes is more accurate.
2. The invention prepares a finite field dielectric breakdown solid-state nano-pore device with extremely high mechanical stability. The bulk materials commonly used for nanopore detection have many material advantages not possessed by two-dimensional materials, for example, silicon nitride materials inherently have extremely high signal-to-noise ratios in terms of DNA detection, which are not possessed by other two-dimensional materials; second, since the breakdown principle of dielectric breakdown is accumulation of defects, although the formation of defects is random, the location of defect formation is closely related to the film thickness. The thickness of the intersection of the front and back channels in ion beam processing is far smaller than that of other positions on the film, so that the specific position of the formation of the nano holes is well limited, and according to known researches, the ion beam processing can damage the material, and the damage can certainly accumulate defects for subsequent dielectric breakdown, so that the processing time is greatly shortened, and the time economic cost is greatly improved; finally, as the highest output voltage set by dielectric breakdown is 30V, according to the relation between breakdown voltage and film thickness of different materials, the maximum thickness of the silicon nitride and silicon dioxide materials which can be broken down at the moment is about 29.4 nm and 20.0nm respectively, and the film thickness of other positions can not reach the condition of being smaller than the maximum thickness except the intersection of channels for ion beam processing, so that the limiting effect of the finite field dielectric breakdown solid state nano-pore device on the nano-pore processing position is further proved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is a flow chart of the process of the finite field dielectric breakdown solid state nanopore device of example 1;
FIG. 2 is a STEM characterization of the device after nanochannel etching of the finite field dielectric breakdown solid state nanopore device prepared in example 1 (a) and example 3 (b);
FIG. 3 is a graph of noise performance analysis of the finite field dielectric breakdown solid state nanopore device prepared in example 1, wherein (a) the noise power spectrum of the solid state nanopore device at 100mV in 1M KCl, pH=8 electrolyte, (b) the noise performance of the device prepared in example 1 at 100mV in 1M KCl, pH=8 electrolyte is compared to that of a conventional nanopore (a nanopore of similar pore size prepared from 15nm thick silicon nitride) at low frequency band;
FIG. 4 is a G4 conjunct molecular assay for a finite dielectric breakdown solid state nanopore device prepared in example 1, wherein (a) the solid state nanopore background current trace (above) and the current trace at the time of G4 conjunct solid state nanopore translocation, the current trace details at the time of G4 conjunct solid state nanopore translocation are magnified, (b) the corresponding scatter plot of current amplitude versus translocation residence time at 100mV, (c) a schematic of the G4 structure and typical events for G4 translocation in the solid state nanopore device, (d) some representative events for G4 molecular translocation;
FIG. 5 is a graph of the time stability test of a finite field dielectric breakdown solid state nanopore conjunct prepared in example 1, the relationship between conductance and G4 translocation events and nanopore device test time;
FIG. 6 is a plot of current amplitude versus translocation dwell time for a lambda DNA molecule test using the finite dielectric breakdown solid state nanopore device prepared in example 1 at 100 mV;
FIG. 7 is a graph of (a) IV and a straight line fit of the graph for rectifying effect of the finite field dielectric breakdown solid state nanopore device prepared in example 1; (b) the rectification ratio at different pH.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
Preparing a finite dielectric breakdown solid-state nano-pore device with a silicon dioxide film substrate as a film base, wherein a preparation flow chart is shown in fig. 1, and a specific method is as follows:
1. pretreatment of a film substrate is carried out:
the method selects a silicon dioxide film substrate with the thickness of 130nm as a film base, and pre-treatment is needed before film processing, wherein the specific pre-treatment steps comprise: and respectively soaking the silicon dioxide film substrate in ethanol and deionized water for 1h, then treating the silicon dioxide film substrate with plasma for 10min to remove organic pollution and impurities on the surface of the silicon dioxide film substrate, drying the silicon dioxide film substrate with nitrogen to keep the surface dry, and putting the silicon dioxide film substrate into a drying cabinet for standby.
2. Preparing a nano-channel double-sided etching ultrathin film: the pretreated silica film substrate prepared above was placed in a vacuum chamber for focused ion beam processing using a gallium ion beam (2.7E per dose volume -1 μm 2 nC for a duration of 8 ms), processing on the front and back sides of the film base (silicon dioxide film substrate), forming vertical nanochannels of width 50nm, depth 60nm and length 500nm on the back side, forming a lateral nanochannel of width 50nm, depth 60nm and length 500nm orthogonal to the vertical nanochannels processed on the front side, resulting in a square intersection region of about 50nm×50nm on the film base (silicon dioxide film substrate) (STEM diagram thereof is shown in fig. a).
3. Preparing a confined dielectric breakdown solid state nanopore device: plasma cleaning the ultra-thin film with the square intersection region formed by double-sided etching of the nano-channel (placing the ultra-thin film with double-sided etching of the nano-channel into ethanol and deionized water in sequence for standing for 1h, performing plasma cleaning with power of 30W for 10s, removing pollutants and impurities on the surface of the ultra-thin film with double-sided etching of the nano-channel and reducing sample capacitance), loading the ultra-thin film into a flow cell chamber (the volume of the chamber is 200 mu l), respectively injecting 200 mu l electrolyte (the electrolyte is KCl solution with the concentration of 1M) at two sides of the chamber, preparing a nanopore by using a customized Labview program by using a voltage source meter (preparing the nanopore by using a current mode of a dielectric breakdown method, wherein the initial current value of the current mode is 1E) -9 A. Step size of 1E -9 A) When fittingAnd stopping punching when the aperture is 3nm, and placing the nano-holes in clear water for standing for 1h to obtain the finite field dielectric breakdown solid nano-hole device.
Example 2
Test example 1 performance test of a confined dielectric breakdown solid state nanopore device with a silicon dioxide thin film substrate as a thin film base:
1. characterization of electrical properties:
loading the finite dielectric breakdown solid-state nanopore device prepared in the embodiment 1 and taking the silicon dioxide film substrate as a film substrate into a flow cell chamber, and respectively injecting electrolyte with the volume of 200 mu l at two sides of the chamber; the noise power spectrum of the nanopore at 100mV was recorded using a patch clamp amplifier using 1M KCl as electrolyte (ph=8) (as shown in fig. 3 a). Comparison of low frequency band noise performance with a similar pore size nanopore prepared from conventional 15nm thick silicon nitride, results are shown in fig. 3 b, illustrating that the period prepared in example 1 exhibits lower low frequency noise according to the results of the noise power spectrum reaction.
2. Nanopore biomolecular sensing experiments with biological samples G4 quadruplets:
the solid-state nanopore device with limited dielectric breakdown and the silicon dioxide film substrate as the film base prepared in the embodiment 1 is loaded into a flow cell chamber, electrolyte with the volume of 200 μl and biological samples with the concentration of 90nM prepared in the electrolyte are respectively injected at two sides of the chamber, a patch clamp amplifier is used for recording current blocking signals (shown in a of fig. 4) generated when biological molecules pass through the nanopore, wherein the biological samples are G4 conjuncts, and the detection sensitivity of the nanopore is detected by utilizing the tiny secondary structural difference of the biological samples. In the assay, a corresponding scatter plot of current amplitude versus translocation dwell time at 100mV is shown in fig. 4 b, a schematic diagram of G4 structure and typical events of G4 translocation in a solid state nanopore device are shown in fig. 4 c, and some representative events of G4 molecular translocation are shown in fig. 4 d. The device prepared in example 1 was demonstrated to have high enough sensitivity that the G4 conjunct formed many conformally different structures in 1M KCl electrolyte, and various secondary signals demonstrated the resolution of the prepared nanopore for different conformations, demonstrating the high sensitivity of the nanopore device.
3. Nanopore biomolecular long-time sensing experiments:
the solid state nanopore device of finite dielectric breakdown prepared in example 1 and using the silica thin film substrate as the thin film substrate was loaded into a flow cell chamber, 200 μl of electrolyte and a biological sample with a concentration of 90nM prepared in the electrolyte were injected into both sides of the chamber, and a patch clamp amplifier was used to record the current blocking signal generated when the biological molecule passed through the nanopore. The G4 conjunct is used as a biological sample to be detected for detecting the biological via hole events of the nanopores with the total event quantity exceeding 60000 for 1h, the conductance of the nanopores is basically unchanged in the long-time detection process, and meanwhile, the baseline is continuously kept stable, so that the time stability of the prepared structure is verified (as shown in figure 5).
4. The biological sample in the nano-pore biological molecule sensing experiment with the biological sample being the G4 tetrad is replaced by lambda DNA, the nanometer Kong Jixian is stable in detection, and the biological molecule detection capability of the finite field dielectric breakdown solid-state nano-pore device prepared in the embodiment 1 is verified by detecting the through hole signals (shown in fig. 6) with different blocking amplitudes and blocking times, which are generated by the lambda DNA due to different structures formed in the electrolyte.
Example 3
The method for preparing the finite field dielectric breakdown solid-state nano-pore device with the silicon nitride film substrate as the film base comprises the following steps:
1. pretreatment of a film substrate is carried out:
the method selects a silicon nitride film substrate with the thickness of 30nm as a film base, and pre-treatment is needed before film processing, wherein the specific pre-treatment steps comprise: and respectively soaking the silicon nitride film substrate in ethanol and deionized water for 2 hours, then treating the silicon nitride film substrate with plasma for 5 minutes to remove organic pollution and impurities on the surface of the silicon nitride film substrate, drying the silicon nitride film substrate with nitrogen to keep the surface dry, and putting the silicon nitride film substrate into a drying cabinet for standby.
2. Preparing a nano-channel double-sided etching ultrathin film: placing the pretreated silicon nitride film substrate prepared by the method in a poly-reactorJiao Lizi beam processing was performed in a vacuum chamber using a gallium ion beam (2.7E per dose volume -1 μm 2 nC for 4 ms), processing is performed on the front and back sides of the film base (silicon nitride film substrate), vertical nanochannels having a width of 50nm, a depth of 20nm and a length of 1000nm are formed on the back side, and a lateral nanochannel having a width of 50nm, a depth of 23nm and a length of 1000nm (STEM diagram thereof is shown in fig. 2 b) orthogonal to the vertical nanochannel processed on the back side is formed on the front side, resulting in formation of a square intersection region of about 50nm×50nm on the film base (silicon nitride film substrate).
3. Preparing a confined dielectric breakdown solid state nanopore device: plasma cleaning the ultra-thin film with the square intersection area formed by double-sided etching of the nano-channel (placing the ultra-thin film with double-sided etching of the nano-channel into ethanol and deionized water in sequence for standing for 1h, performing plasma cleaning with 10W power for 40s, removing pollutants and impurities on the surface of the ultra-thin film with double-sided etching of the nano-channel and reducing sample capacitance), loading the ultra-thin film into a flow cell chamber (the volume of the chamber is 200 mu l), respectively injecting 200 mu l of electrolyte (the electrolyte is KCl solution with the concentration of 1M) at two sides of the chamber (the electrolyte is filled into the flow cell chamber), preparing a nano-hole by using a customized Labview program by using a voltage source meter (the manufacturing of dielectric breakdown nano-hole is perforated by using a current mode, and the initial current value is 1E) -9 A. Step size of 1E -8 A) And stopping punching when the fitting aperture is 3nm, and placing the nano-holes in clear water and standing for 1h to obtain the finite field dielectric breakdown solid nano-hole device.
Example 4
Nanopore rectifying effect sensing experiments were performed on the finite field dielectric breakdown solid state nanopore device prepared in example 3:
loading the finite dielectric breakdown solid-state nanopore device prepared in example 3 into a flow cell chamber, injecting 200 μl of electrolyte (1M KCl solution, pH 4, 6 and 8 respectively) at two sides of the chamber, and recording IV current tracks under different pH electrolytes by using a patch clamp amplifier; the rectification effect of the KCl solution with the concentration of 1M is detected by using the KCl solution as an electrolyte, and a remarkable asymmetric IV curve is observed; further, 1M KCl solutions with different pH values are used as electrolyte to detect the change of the rectification ratio, and as the isoelectric point of the silicon nitride surface is about 6-7, the rectification ratio reaches the minimum value at pH 6 according to the experimental result (as shown in figure 7, wherein a is an IV curve and a straight line fitting graph thereof; and b is the rectification ratio at different pH values), the intrinsic cause of the asymmetry of the IV curve is further verified to be caused by the existence of the surface charge of the finite field dielectric breakdown solid state nanopore device prepared in the embodiment 3 and the asymmetry of the structure per se.
In the preparation method of the present invention, the electrolyte used may be not only KCl solution having a concentration of 1M used in the examples, but also MgCl 2 Solutions or CaCl 2 The concentration of the solution can be between 0.1 and 3M, and the preparation effect is not affected; in addition, the duration of the gallium ion beam processing adopted in the preparation method of the invention can be between 1 and 100ms, and the initial current value in the current mode can be 1E -9 ~1E -7 Between A, the step length can be 1E -9 ~1E -8 Between A; the channels formed by the front and back surfaces can be orthogonally distributed and can be intersected at any other angle; the prepared nanoscale channel has the width of 30-500 nm, the length of 0.1-5 mu m and the depth of 10-500 nm, and the thickness of the finally formed film substrate is 30-1000 nm.
In summary, the invention discloses a method for preparing a finite field dielectric breakdown solid state nanopore device, which is a method for double-sided etching of a channel thinning film based on a focused ion beam and a method for manufacturing the finite field dielectric breakdown solid state nanopore device, and can effectively limit the positions and the number of nanopores prepared by a dielectric breakdown method; meanwhile, compared with the common thin film thinning technology, the method has less damage to the material and higher material stability, and can be used for researching the extremely thin nanopore sensing performance formed by various bulk materials; in addition, the sensing performance of the ultrathin stable nano-pore prepared by superposing different compound materials can be known, and the method has great application development potential.
The application of controlled dielectric breakdown (CBD) methods to prepare nanopores in situ in a water environment facilitates the integration of solid nanopores in microfluidic networks, which is not possible with other techniques such as FIB, TEM-prepared nanopores; meanwhile, as a traditional solid pore material, the bulk material has unique advantages in material property compared with a two-dimensional ultrathin material, such as high signal to noise ratio of silicon nitride in DNA detection. However, for bulk materials, how to make a thinned material with minimal damage has been a hotspot problem. Traditional thinning technology is based on large-area milling, and the mode can lead to fragile processing structure and deteriorate mechanical stability of the structure; meanwhile, large-area milling is inconvenient for more accurate specific positioning of the preparation position of the nano hole. The preparation method disclosed by the invention solves the defects of unstable structure caused by insufficient spatial resolution and over-thin spatial resolution of the bulk material, enables the thickness and mechanical stability of the structure to reach required states, has the potential of mass production in combination with low-cost dielectric breakdown, has the technical potential of preparing ultrathin nanopores on the bulk material in the future, overcomes the defects that the dielectric breakdown technology is difficult to realize nanopore positioning and is not suitable for preparing thick film materials, greatly shortens the processing time, saves the time and economic cost, and ensures that the technology for preparing nanopores by dielectric breakdown is more practical.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.

Claims (6)

1. A method for preparing a finite field dielectric breakdown solid state nanopore device, the method comprising the steps of:
(1) Preparing a limited-area ultrathin film by double-sided etching of a nano channel: placing the pretreated and blow-dried film substrate in a vacuum cavity for processing by a focused ion beam, processing by adopting a gallium ion beam, and processing the front surface and the back surface of the film substrate to form spatially intersected nanoscale channels, so as to realize thinning of the film material and form a nanoscale domain-limiting ultrathin film;
(2) Preparing a solid state nanopore device by confined dielectric breakdown: loading the nanoscale limited-area ultrathin film window with the surface organic pollution and impurities removed through plasma cleaning into a flow cell chamber, filling electrolyte at two sides of the chamber respectively, and preparing a nanopore by using a customized Labview program based on a dielectric breakdown technology by using a voltage source meter to obtain the limited-area dielectric breakdown solid-state nanopore device;
the electrolyte is KCl solution and MgCl with the concentration of 0.1-3M 2 Solutions or CaCl 2 Any one or more of the solutions;
in the step (1), the pretreatment specifically includes: respectively soaking the film substrate for 1-2 h by adopting ethanol and deionized water, and then performing plasma treatment for 5-10 min to remove organic pollution and impurities on the surface of a sample; the parameters of gallium ion beam processing in the gallium ion beam processing process are as follows: ion beam 2.7E per dose volume -1 μm 2 and/nC, the duration is 1-100 ms; the width of the nanoscale channel is 30-500 nm, the length is 0.1-5 mu m, and the depth is 10-500 nm; the thickness of the thin film substrate at the intersection of the nanoscale channels on the thin film substrate is 2-5 nm;
in the step (2), the specific method for removing the organic pollution on the surface by plasma cleaning comprises the following steps: sequentially placing the nano-channel double-sided etched ultrathin film into ethanol and deionized water, standing for 1h, performing plasma cleaning for 10-40 s with power of 10-30W, removing pollutants and impurities on the surface of the window of the limited nano-scale film, and reducing the sample capacitance.
2. The method according to claim 1, wherein in the step (1), the thin film substrate is any one or a superposition of any two of a silicon nitride thin film, a silicon dioxide thin film and an aluminum oxide thin film, and the thickness of the thin film substrate is 30-1000 nm.
3. The method of claim 1, wherein in step (1), the drying is performed with nitrogen.
4. The method according to claim 1, wherein in the step (2), the preparation of the nanopore is specifically: preparation of nanopores using a current mode of dielectric breakdown method in which the initial current value is 1E -9 ~1E -7 A. Step size of 1E -9 ~1E -8 A。
5. The finite field dielectric breakdown solid-state nanopore device prepared by the preparation method according to any one of claims 1 to 4.
6. The use of the finite field dielectric breakdown solid state nanopore device of claim 5 in single molecule detection and current modulation analysis.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102369059A (en) * 2008-06-06 2012-03-07 博纳基因技术有限公司 Integrated analysis devices and related fabrication methods and analysis techniques
CA2829833A1 (en) * 2011-03-15 2012-09-20 President And Fellows Of Harvard College Controlled fabrication of nanopores in nanometric solid state materials
CN103512869A (en) * 2013-10-11 2014-01-15 华东理工大学 Preparation method of nanopore chip with plasmon resonance scattering response function
CN105344387A (en) * 2015-09-11 2016-02-24 北京大学 Nano mesh thin film microfluidic device design based on focused ion beam and MEMS machining method
CN108279312A (en) * 2018-03-08 2018-07-13 冯建东 The analytical equipment and Virus monitory method of a kind of proteomics based on nano-pore and application
CN108706543A (en) * 2018-06-05 2018-10-26 广东工业大学 A kind of nano-pore manufacturing method accurately controlled
CN109580718A (en) * 2018-12-28 2019-04-05 瑞芯智造(深圳)科技有限公司 A kind of preparation method of nano thickness thin film
CN112198194A (en) * 2020-10-15 2021-01-08 中国科学院重庆绿色智能技术研究院 Method for preparing near-zero thickness nanopore by double-sided helium ion beam etching, product and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8206568B2 (en) * 1999-06-22 2012-06-26 President And Fellows Of Harvard College Material deposition techniques for control of solid state aperture surface properties

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102369059A (en) * 2008-06-06 2012-03-07 博纳基因技术有限公司 Integrated analysis devices and related fabrication methods and analysis techniques
CA2829833A1 (en) * 2011-03-15 2012-09-20 President And Fellows Of Harvard College Controlled fabrication of nanopores in nanometric solid state materials
CN103512869A (en) * 2013-10-11 2014-01-15 华东理工大学 Preparation method of nanopore chip with plasmon resonance scattering response function
CN105344387A (en) * 2015-09-11 2016-02-24 北京大学 Nano mesh thin film microfluidic device design based on focused ion beam and MEMS machining method
CN108279312A (en) * 2018-03-08 2018-07-13 冯建东 The analytical equipment and Virus monitory method of a kind of proteomics based on nano-pore and application
CN108706543A (en) * 2018-06-05 2018-10-26 广东工业大学 A kind of nano-pore manufacturing method accurately controlled
CN109580718A (en) * 2018-12-28 2019-04-05 瑞芯智造(深圳)科技有限公司 A kind of preparation method of nano thickness thin film
CN112198194A (en) * 2020-10-15 2021-01-08 中国科学院重庆绿色智能技术研究院 Method for preparing near-zero thickness nanopore by double-sided helium ion beam etching, product and application thereof

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