CN113363140A - Biological mask and method for patterning on substrate - Google Patents
Biological mask and method for patterning on substrate Download PDFInfo
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- CN113363140A CN113363140A CN202110616453.7A CN202110616453A CN113363140A CN 113363140 A CN113363140 A CN 113363140A CN 202110616453 A CN202110616453 A CN 202110616453A CN 113363140 A CN113363140 A CN 113363140A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/76—Patterning of masks by imaging
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Abstract
The application relates to a biological mask and a patterning method on a substrate, belonging to the technical field of integrated circuit preparation. A method of patterning a substrate, comprising the steps of: a photoresist layer is formed on a substrate. And forming a biological mask on the surface of the photoresist layer, which is far away from the substrate. And exposing and developing the biological mask, removing the biological mask, etching and removing the photoresist to obtain the patterned substrate. Wherein, the biological mask comprises a phospholipid double-layer membrane and a porin embedded in the phospholipid double-layer membrane. In the application, the mask used in patterning on the substrate is a biological mask, and the pattern is formed by the pore protein, so that the process cost can be effectively reduced.
Description
Technical Field
The present application relates to the field of integrated circuit fabrication technologies, and more particularly, to a biological mask and a method for patterning on a substrate.
Background
With the continuous breakthrough of the integrated semiconductor manufacturing process technology, the performance of the integrated circuit device is rapidly developed, and the corresponding microelectronic packaging technology gradually becomes an important factor restricting the development of the semiconductor technology. To achieve smaller size, faster processing speed, and lower manufacturing cost of semiconductor devices. More and more advanced packaging techniques are being proposed beyond the traditional packaging concept. The three-dimensional packaging technology realizes interconnection communication through interlayer interconnection, effectively shortens interconnection length, reduces interconnection parasitic parameters and reduces power consumption; the three-dimensional packaging technology reduces the packaging size and improves the packaging density through system integration; the three-dimensional packaging technology improves the functionality of the system by integrating more different functional modules, so that the three-dimensional packaging technology is widely applied to various multifunctional high-speed circuits and miniaturized systems.
The TSV (Through Silicon Via) technology is a main technology for realizing three-dimensional packaging of an integrated circuit, and the functions of the TSV structure prepared at present are limited to interconnection among different layers of chip modules. Meanwhile, the TSV technology occupies a large area of the silicon substrate, so that the packaging density and the chip layout of the system are influenced, and the parasitic parameters of the system and the difficulty of interlayer wiring are increased.
The Monolithic Inter-Tier Vias (MIVs) process is a new type of integrated circuit fabrication process that not only can achieve interconnection between different levels of chip modules. Meanwhile, the integration of logic gates at a gate level can be realized, so that the PMOS and the NMOS at a transistor level are connected in a splitting mode. The design layout of the integrated circuit is more flexible, and the packaging density of the system is improved.
Compared with the etching diameter of 5-100 μm in the traditional TSV technology, the etching diameter of 0.05-5 μm in the MIVs technology. However, mask plates of TSV technology and MIVs technology are mainly classified into chrome plate (chrome), dry plate, liquid relief plate and film, and their prices are high.
Disclosure of Invention
The embodiment of the application provides a biological mask and a patterning method on a substrate, and the biological mask is used for patterning, so that the process cost can be effectively reduced.
In a first aspect, embodiments of the present application provide a biological mask comprising a phospholipid bilayer membrane and a porin embedded in the phospholipid bilayer membrane.
The biological mask forms patterns through the pore proteins, so that the cost of the biological mask is low, and the manufacturing cost can be effectively saved.
In a second aspect, the present application provides a method of patterning a substrate, comprising the steps of: a photoresist layer is formed on a substrate. And forming a biological mask on the surface of the photoresist layer, which is far away from the substrate. And exposing and developing the biological mask, removing the biological mask, etching and removing the photoresist to obtain the patterned substrate. Wherein, the biological mask comprises a phospholipid double-layer membrane and a porin embedded in the phospholipid double-layer membrane.
In the application, the mask used in patterning on the substrate is a biological mask, and the pattern is formed by the pore protein, so that the cost of the biological mask is low, and the manufacturing cost can be effectively saved.
In some embodiments of the present disclosure, a method for preparing a biological mask includes: and forming a phospholipid bilayer membrane on the surface of the photoresist layer, which is far away from the substrate, so as to obtain a supporting phospholipid bilayer membrane. And embedding hole protein in the phospholipid double-layer membrane to form a pattern on the phospholipid double-layer membrane so as to obtain the biological mask.
The biological mask can be formed in the process of patterning the substrate, the biological mask can be used in time after the substrate is completely manufactured, and the pattern formed by the porin is uniform so as to facilitate subsequent exposure, development and etching.
In some embodiments of the present application, an electrospinning machine is used to embed pore proteins within phospholipid bilayer membranes.
The porin can be embedded into the phospholipid double-layer membrane through electrostatic spinning equipment, so that the preparation of the biological mask is more convenient.
In some embodiments of the present application, a method of intercalating a pore protein in a phospholipid bilayer membrane using an electrospinning machine, comprises: the supported phospholipid bilayer membrane was immersed in a buffer solution in a conductive container. The conductive container was placed in an electrospinning machine and grounded. Adding the porin solution into an injection device, injecting the porin solution into a phospholipid double-layer membrane layer through an electrostatic spinning machine, taking out and drying at the temperature of below 70 ℃.
By the method, the biological mask with the pattern can be prepared.
In some embodiments of the present application, a nozzle of the electrospinning machine is in contact with the buffer solution in the conductive container, the flow rate of the nozzle is 1.5-2.5 μ l/min, and the voltage of the nozzle is 0.15-0.25 mv.
The hole protein solution is injected under the condition, so that a biological mask with finer patterns can be obtained, and the line width of a subsequent patterned product is smaller.
In some embodiments of the present application, after removing the biological mask and before etching, the method further includes a step of hardening, including: the treatment is carried out for 100-140s under the conditions of 160-200 ℃.
The influence on the firmness of the photoresist layer is avoided in the process of removing the biological mask, so that the subsequent etching effect is better, and patterns with smaller line width are formed on the substrate.
In some embodiments of the present application, methods are used for via-hole processing between monolithic layers; the substrate is a semiconductor substrate or an insulating substrate.
The etching diameter of the formed hole is small, the line width is low, the packaging size can be effectively reduced, the packaging density is improved, and the method makes outstanding contribution to the production of the microcircuit.
In some embodiments of the present application, the substrate is a silicon substrate, a gallium nitride substrate, a silicon nitride substrate, or a glass substrate.
In some embodiments of the present application, a method of preparing a supported phospholipid bilayer membrane comprises: the vesicle solution is suspended on the surface of the photoresist layer facing away from the substrate and then dried at a temperature below 70 ℃.
The vesicle solution is used for preparing the supported phospholipid double-layer membrane, and the preparation method is simple and easy to implement.
In some embodiments of the present application, the method further comprises the step of activating the photoresist layer to introduce hydroxyl groups before the coating of the vesicle solution.
The combination of the photoresist layer and the phospholipid double-layer film can be firmer, so that the substrate can be patterned later, the formed pattern is finer, the line width can be lower, the etching diameter is smaller, and the finer pattern with the smaller line width is formed while the cost of the biological mask is reduced.
In some embodiments of the present application, a method of making a porin protein, comprising: introducing the porin gene into a plasmid, then recombining to obtain a recombinant plasmid, and mutating the recombinant plasmid to obtain a mutated recombinant plasmid. The mutated recombinant plasmid is introduced into Escherichia coli in a medium containing antibiotics, and the cultured cells are collected after amplification culture. And (3) cracking the cells, and removing cell walls to obtain the monomeric porin. Polymerizing monomer porin and red blood cells, and carrying out electrophoretic separation, gel slicing, gel dissolving and repeated freeze thawing on the polymerized protein mixed solution to finally precipitate out the porin.
The method prepares the porin, and injects the porin into the phospholipid bilayer membrane so as to form the biological mask with the pattern.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a process flow diagram of a method of patterning a substrate.
Detailed Description
In the prior art, mask plates of the MIVs technology are generally four types, namely chrome plate (chrome), dry plate, liquid relief plate and film. The price of the chrome mask with different line widths is shown in table 1, and the price of the mask rises rapidly along with the reduction of the line width. This not only increases the cost of the MIVs technology, but also becomes a major factor limiting the development of the MIVs technology.
TABLE 1 line width and price relationship of chrome mask
| Line width/nm | 180 | 130 | 90 | 65 | 45 |
| Price per ten thousand dollars | 26 | 87 | 150 | 300 | 600 |
Therefore, in the present application, a new mask, a biological mask, is provided, which can reduce the line width and the cost. In order to make the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the present application are described below clearly and completely.
The embodiment of the application provides a biological mask, which comprises a phospholipid double-layer film and a porin embedded in the phospholipid double-layer film. The pattern is formed by the hole protein, the formed pattern is finer, the line width is lower, the etching diameter is smaller, the cost of the biological mask is low, and the manufacturing cost can be effectively saved.
In the present application, specific materials of the phospholipid bilayer membrane and the porin are not limited, and any biological mask that can form a pattern on the phospholipid bilayer membrane through the porin is within the scope of the present application as long as the biological mask is a general phospholipid bilayer membrane and a general porin.
In the application, after the biological mask is prepared, the mask is carried out through the biological mask, and then the substrate is patterned; the biological mask can also be manufactured in real time during the process of patterning the substrate, which is not limited in the present application.
The first mode is as follows: a biological reticle is fabricated in real time during the patterning of a substrate, and fig. 1 is a process flow diagram of a method of patterning a substrate. Referring to fig. 1, the method includes the following steps:
s10: preparing the porin:
s110: introducing the porin gene into a plasmid, then recombining to obtain a recombinant plasmid, and mutating the recombinant plasmid to obtain a mutated recombinant plasmid.
Alternatively, the α HL gene was first amplified using s. The amplified alpha HL gene is recombined to a Pt7 plasmid which is named pT 7-alpha HL.
And then using the mutant M113C gene and pT 7-alpha HL plasmid as a template, carrying out site-directed mutagenesis by using a specific primer according to the operation steps of a TMuta-direct gene site-directed mutagenesis kit, and obtaining a mutated recombinant plasmid pT 7-M113C.
S120: the mutated recombinant plasmid is introduced into Escherichia coli in a medium containing antibiotics, and the cultured cells are collected after amplification culture.
pT 7-alpha HL and the mutated pT7-M113C were transformed into BL21(DE3) pLys, respectively, and inoculated with a Koran strain in 5ml LB solid medium. Wherein, the LB solid medium contains 100 ug/ml ampicillin (ampicilin, Amp) and 34 ug/ml chloramphenicol (Cm), and is cultured at 37 ℃ for 12 h.
The culture was transferred to fresh LB liquid medium containing Amp and Cm at 1%, and amplification-cultured at 37 ℃ for 3 hours, followed by addition of IPTG (inducible hormone) at a concentration of 0.6 mmol/L. The induction is carried out for 8h at 30 ℃, protein expression is analyzed by 12 percent SDS-PAGE, and cultured cells are collected by centrifugation at 5500r/min at 4 ℃.
S130: and (3) cracking the cells, and removing cell walls to obtain the monomeric porin.
Alternatively, the cells were resuspended in cell lysate (50mmol/L Tris-HC1, 50mmol/L EDTA, 1% (V/V) Triton X-100,1mg/ml lysozyme, pH 8.0), placed in an ice bath and shaken intermittently using a vortex shaker until the cells were completely lysed. Centrifugation was carried out at 400g for 40min at 4 ℃ and cell lysis supernatant was collected.
Adding the cracking supernatant into an ultrafiltration tube with the molecular weight cutoff of 50kDa, and centrifuging for 10min at 5000 g; adding the lower layer liquid into an ultrafiltration tube with the molecular weight cutoff of 30kDa, centrifuging for 10min at 5000g, and taking the upper layer solution to obtain a relatively pure alpha HL monomer porin solution.
S140: polymerizing monomer porin and red blood cells, and carrying out electrophoretic separation, gel slicing, gel dissolving and repeated freeze thawing on the polymerized protein mixed solution to finally precipitate out the porin.
Alternatively, rabbit erythrocytes were lysed with pre-cooled 0.01mol/LTris-HCL (pH7.4), the pellet was collected by centrifugation, and the cell membrane mixture was prepared with 0.5% (m/V) MBSA solution.
Then, 1ml of rabbit blood erythrocyte membrane mixed solution is added into 200ul of alpha HL monomer porous protein solution, and the mixture is evenly mixed and is bathed in water at 37 ℃ for 3 h. At 4 deg.C, 400g was centrifuged for 15min, and the pellet was washed 3 times with MBSA. Adding loading buffer sample buffer solution, carrying out 8% SDS-PAGE electrophoresis, and slicing to obtain the purified alpha HL pore protein.
Cutting purified alpha HL porin by a disinfection blade, adding 1.5ml of sterile water, mashing, freezing and thawing repeatedly by a freeze drier at the temperature of 80-26 ℃ below zero to separate out protein, and centrifuging by 100g to collect alpha HL porin solution.
The alpha HL porin solution can be prepared by the method, and can also be prepared by other methods, as long as the prepared porin solution can be embedded into a phospholipid bilayer membrane, and the patterned porin is within the protection scope of the application.
S20: a photoresist layer is formed on a substrate.
Wherein, a silicon wafer is selected as a substrate, and the thickness of the silicon wafer is 40-60 μm.
Alternatively, a silicon wafer with a < 100 > crystal phase and a thickness of 50 μm was selected, the surface having a dense silicon dioxide layer 10nm thick. And cleaning the silicon wafer by RCA standard process flow.
Coating positive photoresist on the silicon wafer. Optionally, the coating speed range is 2000-4000rpm, the coating acceleration is 1000-3000rpm/s, and the coating time is 10-30 s. After the coating is finished, drying for 120-240s at the temperature of 80-120 ℃.
For example: and coating positive photoresist on the cleaned silicon wafer. Wherein, the coating conditions are as follows: the coating speed was 3000rpm, the coating acceleration was 2000rpm/s, and the coating time was 20 s. After the coating was completed, the coating was dried at 100 ℃ for 180 seconds.
S30: and forming a biological mask on the surface of the photoresist layer, which is far away from the substrate.
S310: and forming a phospholipid bilayer membrane on the surface of the photoresist layer, which is far away from the substrate, so as to obtain a supporting phospholipid bilayer membrane.
Alternatively, the photoresist layer is activated to introduce hydroxyl groups, and then the vesicle solution is suspended on the surface of the photoresist layer facing away from the substrate and then dried at less than 70 ℃.
Optionally, the silicon wafer coated with the photoresist layer is immersed in a mixed solution of NHS/EDC (1.5-2.5mmol/LNHS +0.5-1.5mmol/L EDC) for activation for 8-12 min. Then immersing the protein into 0.08-0.12mol/L antibiotic protein solution for protein fixation for 4-6 min. Spin coating 0.5-1.5ml of vesicle solution on the surface of the silicon chip fixed by protein at the spin coating speed of 150-250rmp/30s, and heating after the spin coating is finished, wherein the heating conditions are as follows: heating at 50-70 deg.C for 0.5-1.5h to obtain supported phospholipid bilayer membrane.
For example: the silicon wafer is immersed into a mixed solution of NHS/EDC (2.0mmol/LNHS +1.0mmol/L EDC) for activation for 10min to introduce hydroxyl groups on the surface of the photoresist layer for subsequent growth of the phospholipid bilayer membrane. Then the membrane is immersed into 0.1mol/L antibiotic protein solution for protein fixation for 5min, so as to sterilize and disinfect the activated silicon wafer, and facilitate the growth of the subsequent phospholipid double-layer membrane and the embedding of the porin. And (3) spin-coating 1ml of vesicle solution on the surface of the silicon wafer fixed by the protein at the spin-coating speed of 200rmp/30s, and heating for 1h at the temperature of 60 ℃ after the spin-coating is finished to obtain the supported phospholipid double-layer membrane. Then repeatedly rinsing the quartz crystal plate by using ultrapure water, putting the quartz crystal plate into the quartz crystal plate, and injecting the ultrapure water for protection.
S320: and embedding hole protein in the phospholipid double-layer membrane to form a pattern on the phospholipid double-layer membrane so as to obtain the biological mask. Alternatively, the pore proteins are embedded in the phospholipid bilayer membrane using an electrospinning machine.
Further, the supported phospholipid bilayer membrane was immersed in a buffer solution in a conductive container. The conductive container was placed in an electrospinning machine and grounded. Adding the porin solution into an injection device, injecting the porin solution into a phospholipid double-layer membrane layer through an electrostatic spinning machine, taking out and drying at the temperature of below 70 ℃. Wherein, a nozzle of the electrostatic spinning machine is contacted with the buffer solution in the conductive container, the flow rate of the nozzle is 1.5-2.5 mul/min, and the voltage of the nozzle is 0.15-0.25 mv.
In the present application, the above-mentioned buffer solution may be disposed in the following manner: 500ml of a potassium chloride solution having a mass fraction of 8% was prepared, and 0.06g of Tris (hydroxymethyl) aminomethane was added, followed by adjustment to pH7.4 using hydrochloric acid.
The method for inserting the pore protein into the phospholipid bilayer membrane may be: and taking the silicon wafer out of the quartz crystallizing dish, placing the silicon wafer in a conductive container, and injecting the buffer solution to ensure that the silicon wafer just submerges. And putting the conductive container into an electrostatic spinning machine with a positioning function. And (4) adding the alpha HL pore protein solution prepared in the step (S10) into a micro-injection pump in an electrostatic spinning machine, setting the distance between a spray head and a silicon wafer, and determining that the spray head is in contact with the buffer solution. Setting the flow of the spray head to be 2 mul/min, setting the voltage of the spray head to be 0.2mv, and executing a set stepping program to embed the alpha HL pore eggs into the support phospholipid double-layer membrane. Taking out, repeatedly washing with ultrapure water, drying at 60 deg.C for 1 hr, and oven drying to obtain biological mask.
S40: and exposing and developing the biological mask, removing the biological mask, etching and removing the photoresist to obtain the patterned substrate.
Optionally, the complex of the biological mask, the photoresist layer and the substrate obtained by drying is placed into a photoetching machine for exposure for 1-3s, then a developing solution is used for development, 100-140s of treatment is carried out at the temperature of 160-200 ℃ for hardening, then a deep reactive ion etching mode is used for etching, and then the photoresist layer is removed, so as to obtain the patterned substrate.
For example: and (3) placing the dried composite of the biological mask, the photoresist layer and the substrate into a photoetching machine for exposure for 1s, placing the composite into a developing solution for development for 50s after exposure, removing a supporting phospholipid double-layer membrane and alpha HL porin on the surface of the silicon wafer, repeatedly cleaning the composite by using ultrapure water, and treating the composite for 120s at the temperature of 180 ℃ for hardening. The through holes of the silicon wafer are then etched using Deep Reactive Ion Etching (DRIE) to etch MIVs through holes. And after etching, ultrasonically cleaning the silicon wafer for 0.5-1h by using deionized water, and then ultrasonically cleaning the silicon wafer for 0.5-1h by using an acetone solution to remove the photoresist on the surface of the silicon wafer. And cleaning by using a BOE solution to remove the silicon dioxide layer on the surface of the silicon wafer, then performing ultrasonic cleaning on the silicon wafer for 0.5-1h by using deionized water, and cleaning the silicon wafer according to the RCA standard process flow to obtain the patterned silicon wafer.
In the present application, for the monolithic interlayer via technology, the substrate is not limited to a silicon wafer, but may be other semiconductor substrate, or an insulating substrate, for example: the substrate may be a silicon substrate, a gallium nitride substrate, a silicon nitride substrate, or a glass substrate.
It should be noted that the substrate patterning process is not limited to the monolithic interlayer via technology, and other patterning processes may be performed, which may require adjustment of the etching manner, but may still be performed through the biological mask provided in the present application. In the present application, the use of the photoresist is not limited, and any photoresist and a developing solution may be used together, and the use is within the scope of the present application.
In the application, the biological mask is used for carrying out the photoetching process, so that the manufacturing cost of the mask is greatly reduced on the premise of achieving a smaller line width (the minimum line width can reach 7 nm). The manufacturing cost of a mask in an MIVs process is reduced, the preparation of the through holes between single layers is realized at a lower price, and the vertical interconnection between chips and the inside of the chips is finally realized, so that the design layout of an integrated circuit is more flexible, and the packaging density of an integrated circuit system is improved.
The second mode is as follows: preparing a biological mask plate in advance, and patterning a substrate, wherein the method comprises the following steps:
(1) preparing a biological mask: the preparation method of the biological mask can be the same as that of the biological mask in the first mode, and details are not repeated here.
(2) And forming a photoresist layer on the substrate: this may correspond to the first mode which is not S20, and will not be described in detail here.
(3) And arranging the biological mask on the surface of the photoresist layer, which is far away from the substrate. Wherein, hydroxyl can also be introduced on the photoresist layer so as to be firmly connected with the biological mask.
(4) And exposing and developing the biological mask plate, removing the biological mask plate, etching and removing the photoresist to obtain the patterned substrate.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a preparation method of a monolithic interlayer through hole, which comprises the following steps:
(1) selecting a silicon wafer with a crystalline phase of < 100 > and a thickness of 50 mu m, wherein the surface of the silicon wafer is provided with a compact silicon dioxide layer with a thickness of 10nm, and cleaning the silicon wafer according to the RCA standard process flow.
The cleaned silicon wafer was coated with a positive photoresist at a coating speed of 3000rpm, a coating acceleration of 2000rpm/s and a coating time of 20 s. After the coating was completed, the coating was dried at 100 ℃ for 180 seconds.
(2) And immersing the silicon wafer with the photoresist layer into a mixed solution of NHS/EDC (2.0mmol/LNHS +1.0mmol/L EDC) for activation for 10min, and then immersing the silicon wafer into a 0.1mol/L solution of antibiotic protein for protein fixation for 5 min. And (3) spin-coating 1ml of DPPC vesicle solution on the surface of a silicon wafer fixed by protein at the spin-coating speed of 200rmp/30s, and heating at 60 ℃ for 1h after the spin-coating is finished to obtain the supporting phospholipid double-layer membrane. Then, the quartz crystal is repeatedly rinsed with ultrapure water, placed in a quartz crystallization dish, and injected with ultrapure water for protection.
The silicon wafer was taken out of the quartz crystal vessel, placed in a conductive container, and injected with a buffer solution (500 ml of 8% by mass potassium chloride solution, and 0.06g of Tris (hydroxymethyl) aminomethane, followed by adjustment to pH7.4 with hydrochloric acid to obtain a buffer solution) so as to just submerge the silicon wafer. And putting the conductive container into an electrostatic spinning machine with a positioning function. Adding the alpha HL pore protein solution into a micro-injection pump in an electrostatic spinning machine, setting the distance between a spray head and a silicon wafer, and determining the contact of the spray head and a buffer solution. Setting the flow rate of the spray head to be 2 mul/min, setting the voltage of the spray head to be 0.2mv, and executing a set stepping program to embed the alpha HL porin into the support phospholipid double-layer membrane. Taking out, repeatedly washing with ultrapure water, drying at 60 deg.C for 1 hr, and oven drying to obtain biological mask.
(3) And placing the dried composite of the biological mask, the photoresist layer and the silicon wafer into a photoetching machine for exposure for 1s, placing the composite into a developing solution for development for 50s after exposure, removing a supporting phospholipid double-layer membrane and alpha HL porin on the surface of the silicon wafer, repeatedly cleaning the composite by using ultrapure water, and treating the composite for 120s at the temperature of 180 ℃ for hardening. The through holes of the silicon wafer are then etched using Deep Reactive Ion Etching (DRIE) to etch MIVs through holes. And after etching, carrying out ultrasonic cleaning on the silicon wafer for 1h by using deionized water, and then carrying out ultrasonic cleaning on the silicon wafer for 1h by using an acetone solution to remove the photoresist on the surface of the silicon wafer. And cleaning by using a BOE solution to remove the silicon dioxide layer on the surface of the silicon wafer, then performing ultrasonic cleaning on the silicon wafer for 1h by using deionized water, and cleaning the silicon wafer according to the RCA standard process flow to form a through hole on the silicon wafer.
The line width of the through holes on the silicon wafer can be as low as 7 nm. The mode provided by the application can achieve smaller line width.
Example 2
Example 2 differs from example 1 in that: the porin is pleurotu ostreatus perforin PlyAB.
In this embodiment, the line width of the through hole on the silicon wafer can be as low as 14 nm.
Example 3
Example 3 differs from example 1 in that: the vesicle solution is clathrin and enveloped vesicle solution.
In this embodiment, the line width of the through hole on the silicon wafer can be as low as 7 nm.
Example 4
Example 4 differs from example 1 in that: the wafer with the photoresist was not immersed in a NHS/EDC mixture (2.0mmol/LNHS +1.0mmol/L EDC) for activation for 10 min.
In this embodiment, the line width of the through hole on the silicon wafer can be as low as 70 nm.
Comparative example 1
The comparative example provides a method for preparing a monolithic interlayer via, comprising the steps of:
(1) selecting a silicon wafer with a crystalline phase of < 100 > and a thickness of 50 mu m, wherein the surface of the silicon wafer is provided with a compact silicon dioxide layer with a thickness of 10nm, and cleaning the silicon wafer according to the RCA standard process flow.
The cleaned silicon wafer was coated with a positive photoresist at a coating speed of 3000rpm, a coating acceleration of 2000rpm/s and a coating time of 20 s. After the coating was completed, the coating was dried at 100 ℃ for 180 seconds.
(2) Placing the chromium plate on the surface of the photoresist layer, which is far away from the silicon wafer, placing the chromium plate, the photoresist layer and the silicon wafer composite body into a photoetching machine for exposure for 1s, placing the exposed chromium plate, the exposed photoresist layer and the silicon wafer composite body into a developing solution for development for 50s, then removing the chromium plate on the surface of the silicon wafer, then repeatedly cleaning the chromium plate by using ultrapure water, and then treating the chromium plate for 120s at the temperature of 180 ℃ for hardening. The through holes of the silicon wafer are then etched using Deep Reactive Ion Etching (DRIE) to etch MIVs through holes. And after etching, carrying out ultrasonic cleaning on the silicon wafer for 1h by using deionized water, and then carrying out ultrasonic cleaning on the silicon wafer for 1h by using an acetone solution to remove the photoresist on the surface of the silicon wafer. And cleaning by using a BOE solution to remove the silicon dioxide layer on the surface of the silicon wafer, then performing ultrasonic cleaning on the silicon wafer for 1h by using deionized water, and cleaning the silicon wafer according to the RCA standard process flow to form a through hole on the silicon wafer.
The line width of the through holes on the silicon wafer can be as low as 45 nm. The chromium plate is used as a mask plate, so that the obtained silicon wafer has high line width and high preparation cost.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (10)
1. A biological mask is characterized by comprising a phospholipid double-layer membrane and a porin embedded in the phospholipid double-layer membrane.
2. A method of patterning a substrate, comprising the steps of:
forming a photoresist layer on a substrate;
forming a biological mask on the surface of the photoresist layer, which is far away from the substrate;
exposing and developing the biological mask, removing the biological mask, etching and removing photoresist to obtain a patterned substrate;
wherein, the biological mask comprises a phospholipid double-layer membrane and a porin embedded in the phospholipid double-layer membrane.
3. The method of claim 2, wherein the method of making the biological mask comprises:
forming a phospholipid double-layer membrane on the surface of the photoresist layer, which is far away from the substrate, so as to obtain a supporting phospholipid double-layer membrane;
and embedding hole protein into the phospholipid double-layer membrane to form a pattern on the phospholipid double-layer membrane so as to obtain the biological mask.
4. The method according to claim 3, wherein a pore protein is embedded in the phospholipid bilayer membrane using an electrospinning machine.
5. The method of claim 4, wherein the method of inserting the pore protein into the phospholipid bilayer membrane layer using an electrospinning machine comprises:
immersing the supported phospholipid bilayer membrane in a buffer solution in a conductive container;
placing the conductive container in an electrostatic spinning machine and grounding;
adding a porin solution into an injection device, then injecting the porin solution into the phospholipid bilayer membrane layer through an electrostatic spinning machine, and then taking out and drying at the temperature lower than 70 ℃.
6. The method of claim 5, wherein a spray head of the electrospinning machine is in contact with the buffer solution in the conductive container, the flow rate of the spray head is 1.5 to 2.5 μ l/min, and the voltage of the spray head is 0.15 to 0.25 mv.
7. The method of claim 3, further comprising the step of hardening after removing the bio-mask and before etching, comprising: the treatment is carried out for 100-140s under the conditions of 160-200 ℃.
8. The method of any of claims 2-7, wherein the method is used for via-hole processing between monolithic layers; the substrate is a semiconductor substrate or an insulating substrate;
or/and the substrate is a silicon substrate, a gallium nitride substrate, a silicon nitride substrate or a glass substrate.
9. The method according to any one of claims 3 to 7, wherein the supported phospholipid bilayer membrane is prepared by a method comprising: coating a vesicle solution on the surface of the photoresist layer, which is far away from the substrate, and then drying the photoresist layer at the temperature of lower than 70 ℃;
or/and before the vesicle solution coating, the step of activating the photoresist layer to introduce hydroxyl is further included.
10. The method of any one of claims 2 to 7, wherein the method of preparing the porin comprises:
introducing a porin gene into a plasmid, then recombining to obtain a recombinant plasmid, and mutating the recombinant plasmid to obtain a mutated recombinant plasmid;
introducing the mutated recombinant plasmid into escherichia coli in a culture medium containing antibiotics, performing amplification culture, and collecting cultured cells;
lysing the cells, removing cell walls, and obtaining monomeric porin;
polymerizing the monomer porin and the red blood cells, and finally separating out the polymerized protein mixed solution to obtain the porin through electrophoretic separation, gel slicing, gel dissolution and repeated freeze thawing.
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