CN113399233A - Silicon wafer substrate hard film with humidity response and self-assembly-based preparation method and application thereof - Google Patents
Silicon wafer substrate hard film with humidity response and self-assembly-based preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/062—Pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/104—Pretreatment of other substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
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- Testing Or Measuring Of Semiconductors Or The Like (AREA)
Abstract
The invention belongs to the technical field of film manufacturing, and particularly relates to a silicon wafer substrate hard film with humidity response, a preparation method based on self-assembly and application thereof. The method comprises the following steps: 1) preparing a deionized water solution of chitosan; preparing a deionized water solution of carboxymethyl cellulose; preparing a plurality of parts of hydrochloric acid solution for cleaning; 2) obtaining a clean silicon wafer substrate; 3) activating the surface of the substrate; 4) and (3) carrying out self-assembly at room temperature to obtain the silicon wafer substrate hard film with humidity response. The silicon wafer substrate LBL film prepared by the invention can quickly respond to humidity and is highly reversible.
Description
Technical Field
The invention belongs to the technical field of film manufacturing, and particularly relates to a silicon wafer substrate hard film with humidity response, a preparation method based on self-assembly and application thereof.
Background
The layer-by-layer self-assembly (LBL) technology is a film manufacturing technology, is simple to operate, can flexibly select a substrate material, and can accurately control the structure and the thickness of a nano-scale film. There are three reasons that LBL technology is considered to be an effective method for producing nanomembranes: i) the thickness of the film (hundreds of nanometers) can be accurately controlled by gradual deposition; ii) the modified LBL film chemistry provides the possibility of patterning the film surface; iii) the dynamic response of the silicon wafer substrate LBL film offers the potential to achieve real-time and durable observations. The most common method of performing LBL assembly is to deposit different solutions of positively and negatively charged groups alternately onto a substrate by electrostatic pairing, the LBL technique produces a multilayer polyelectrolyte membrane with inherent humidity response capability due to its hydrophilic nature. The solutions selected by the invention are chitosan solution with amido positrons and carboxymethyl cellulose solution with carboxyl negative electrons, and the chitosan and carboxymethyl cellulose are obtained in a simpler manner and are selected from common film-forming raw materials. The layer-by-layer self-assembly technology has the advantages of high product orderliness, controllable film generation, no need of complex and expensive instruments and the like, and films based on functional materials such as proteins, DNA, nano particles, complex polymers and the like are reported by utilizing the layer-by-layer self-assembly technology.
Zhao Xia et al have invented a method for preparing the protective film of hole sealing of self-assembly, deposit and form the protective film of anticorrosion (CN103003374A) on the surface of base plate through sol-gel way and layer-by-layer self-assembly of metal surface that is treated by anodic oxidation; wan Jiangling et al have invented a kind of chitosan-sodium carboxymethylcellulose layer upon layer self-assembly probiotics microcapsule and its preparation, utilize polyelectrolyte layer upon layer self-assembly of chitosan and sodium carboxymethylcellulose component to form the capsule wall, the chitosan-sodium carboxymethylcellulose layer upon layer self-assembly probiotics microcapsule obtained is acid-resistant, resistant to bile salt, resistant to digestive enzyme, improve the stability of the probiotics (CN 110025638A). The inventor of the patent application proves a preparation method of a phosphoric acid doped layer-by-layer self-assembled polymer composite membrane, and the high-temperature proton exchange membrane (CN106356546A) with high proton conductivity, good mechanical property and stability of a layer-by-layer self-assembled structure is prepared. The method aims at the blank existing in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a silicon wafer substrate hard film with humidity response, a preparation method based on self-assembly and application thereof. The preparation method is simple, the cost is low, industrial batch production can be realized, the prepared silicon wafer substrate LBL film can quickly respond to humidity and is highly reversible, the formed film is stable, and long-time observation can be realized. The substrate has a large selectable range, the preparation process is pollution-free and non-toxic, the humidity response of the membrane can be triggered by human breath, and the method has wide application prospects in the fields of humidity detection, response and the like.
The technical scheme provided by the invention is as follows:
a preparation method based on self-assembly of a silicon wafer substrate hard film with humidity response comprises the following specific steps:
1) preparing a deionized water solution of chitosan with the concentration of 0.5-1 mg/ml, and adjusting the pH value of the deionized water solution to 3.5-4.5 by using a hydrochloric acid solution; preparing a deionized water solution of carboxymethyl cellulose with the concentration of 0.5-1 mg/ml, and adjusting the pH of the deionized water solution to 3.5-4.5 by using a hydrochloric acid solution; preparing a plurality of washing hydrochloric acid solutions with the pH value of 3.5-4.5;
2) obtaining a clean silicon wafer substrate;
3) activating the surface of the substrate obtained in step 2);
4) rapidly dipping the activated substrate obtained in the step 3) in the deionized water solution of the chitosan obtained in the step 1) for 5-10 min at room temperature, so that a layer of thin film is formed by adsorbing positive charge amino groups on the surface of the substrate through electrostatic adsorption;
then placing the substrate in a part of the washing hydrochloric acid solution obtained in the step 1) for 4-5 min so as to remove redundant positive groups;
then placing the substrate in another part of the hydrochloric acid solution for cleaning obtained in the step 1) for 4-5 min so as to remove redundant positive charge groups;
taking out the substrate, soaking the substrate in the deionized water solution of the carboxymethyl cellulose obtained in the step 1) for 4-5 min, and constructing another negative electricity group film layer with carboxyl on the basis of the previous positive electricity film layer by utilizing electrostatic adsorption;
then placing the mixture in another part of the washing hydrochloric acid solution obtained in the step 1) for 4-5 min, so as to remove redundant electronegative groups;
then placing the membrane in another part of the hydrochloric acid solution obtained in the step 1) for 4-5 min to remove redundant negative charge groups and complete self-assembly of one layer;
5) and (5) repeating the step 4) for 20-30 times to obtain the silicon wafer substrate hard film with humidity response.
Based on the technical scheme, the silicon wafer substrate hard film with humidity response can be obtained by adopting chitosan and carboxymethyl cellulose and controlling self-assembly conditions.
Specifically, in step 1): the viscosity of the chitosan is 100-200 mu m, and the deacetylation degree is more than or equal to 95%.
Chitosan at this parameter favors adsorption of positive charges at this viscosity for the self-assembly method of the invention.
Specifically, in step 1): the viscosity of the carboxymethyl cellulose is 1500-;
carboxymethyl cellulose at this parameter favors the adsorption of negative charges at this viscosity for the self-assembly process of the present invention.
Specifically, in step 1): the concentration of the deionized water solution of the chitosan is the same as that of the deionized water solution of the carboxymethyl cellulose.
The uniformity of electrostatic adsorption is facilitated under the same concentration, and the uniformity of film formation is ensured.
Specifically, in the step 2): the silicon chip is firstly used with the composition ratio of H2SO4:H2O24:1, decomposing and removing organic matters by strong oxidizing property of the cleaning solution; by using deionizationWashed by water and then the component ratio is H2O:H2O2:NH4Cleaning with an alkaline cleaning solution with OH being 5:2:1, due to H2O2Oxidation and NH of4The complexation of OH, metal ions form stable soluble complex and are dissolved in water; then using the composition ratio of H2O:H2O2HCl 7:2:1, due to H2O2The oxidation of the silicon wafer, the dissolution of hydrochloric acid and the complexation of chloride ions, metal impurities on the surface of the silicon wafer become complex ions dissolved in water, finally the silicon wafer is put into deionized water for cleaning, the aim of cleaning is achieved, and the cleaned silicon wafer is put into a vacuum oven for standby.
Specifically, in step 3): placing the clean silicon wafer substrate obtained in the step 2) in a glass vessel, and activating the surface of the substrate in an ultraviolet curing box with the wavelength of 365nm for 5-10 min.
Specifically, in the step 4): the time for each impregnation was the same.
The same immersion time will ensure consistent film thickness for each self-assembly.
Specifically, in the step 4): in each dipping process, the substrate is placed perpendicular to the liquid level, so that the adsorption is more uniform, and the formed film is smoother.
The invention also provides the silicon wafer substrate hard film with humidity response prepared by the preparation method.
The invention also provides application of the silicon wafer substrate hard film with humidity response, which is used for anti-counterfeiting, humidity detection and the like. .
The invention has the following benefits:
1) the selected film forming raw materials are easy to obtain, stable in chemical properties, green and non-toxic, the prepared silicon wafer substrate LBL film can quickly respond to humidity and is highly reversible, the formed film is stable, and long-time observation can be achieved.
2) The selection range of the substrate is wide, and the substrate is convenient to obtain.
3) The preparation method has simple process, is beneficial to reducing the cost and can realize industrialized mass production.
Drawings
FIG. 1 is an infrared spectroscopic analysis chart of a silicon wafer without a film formed thereon.
FIG. 2 is an infrared spectroscopic analysis chart of a film-forming silicon wafer.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Taking a silicon wafer as a substrate, taking deionized water as a solvent, preparing 250mg of chitosan (a product purchased from Jinhu Chiba products Co., Ltd. in Hengtai county, the viscosity of the chitosan is 100-200 mu M, the deacetylation degree is more than or equal to 95%) into a chitosan solution (CHI) with the concentration of 1mg/ml, adjusting the pH of the solution to 3.5 by using a 0.1M hydrochloric acid solution, preparing a certain amount of carboxymethyl cellulose (a product purchased from Shanghai Aladdin Biotechnology Co., Ltd., the number average molecular weight of the carboxymethyl cellulose is 25000, the viscosity of the carboxymethyl cellulose is 1500-3100mPa.s) into a carboxymethyl cellulose solution (CMC) with the concentration of 1mg/ml, and adjusting the pH of the solution to 3.5 by using a 0.1M hydrochloric acid solution; hydrochloric acid solutions with pH 3.5 were prepared and labeled as solution 1, solution 2, solution 3, and solution 4. Placing the cleaned silicon wafer in an ultraviolet curing box for surface activation for 10min, quickly placing in CHI solution for 5min after activation, then placing in solution 1 for 5min, taking out and placing in solution 2 for 5 min; then placing in CMC solution for 5min, then placing in solution 3 for 5min, taking out and placing in solution 4 for 5 min; the method is a cycle, and a silicon wafer substrate LBL film is obtained after 20 cycles.
And (3) carrying out a humidity response test on the obtained silicon wafer substrate hard film with humidity response:
the test method is as follows: and (3) placing the substrate after film formation in an atomization box, changing the humidity environment on the surface of the film through an atomization nozzle, and photographing by using a camera every 1 second to record and observe the response condition of the film to the humidity. Due to the film thickness dependent interference in the optical reflection, the films produced exhibit a unique structural color, which can be directly observed with the naked eye. The spectrum of each film is recorded by a reflection spectrometer and converted into CIE chromatic value; the film thickness at different humidity at different cycles was tested using a breath on/off.
The test results are:
the formed film can respond to humidity quickly. When the relative humidity was changed from 10% to 80%, the color changed slightly from blue to green/yellow, and when the relative humidity was increased to 95%, the color changed rapidly from green/yellow to purple. Iridescent blue, green, yellow and pink colors were obtained at different film thicknesses. When the relative humidity is higher than 90%, the film thickness is significantly increased. When the relative humidity is higher than 90%, the film thickness is significantly increased. This transition may be attributed to an increase in water absorption sites upon swelling of the multilayer film. With increasing relative humidity, the proton exchange membrane shows a distinct color change from blue to pink.
The film thickness variation at different relative humidities was tested continuously over 10 cycles with less than 3% variation between cycles. Using the breath on/off test, the mode reveal/hide mode can repeat hundreds of cycles without detectable decrease in sensitivity and speed, indicating excellent reversibility and reproducibility, and the porous surface morphology resulting from liquid nitrogen freezing at high relative humidity also indicates that at high relative humidity the film surface contains more water, and that this humidity-triggered color change is fast, reversible, and compatible with most silicon-based devices.
The results were analyzed as follows: the self-assembled film has high sensitivity to humidity. Based on the performance, the anti-counterfeiting requirement is met
Example 2
Taking a silicon wafer as a substrate, taking deionized water as a solvent, preparing a certain amount of chitosan (a product purchased from Jinhu Chiba products Co., Ltd. in Hengtai county, the viscosity of the chitosan is 100-200 mu M, the deacetylation degree is more than or equal to 95%) into a chitosan solution (CHI) with the concentration of 0.5mg/ml, adjusting the pH of the solution to 4 by using a 0.1M hydrochloric acid solution, preparing a certain amount of carboxymethyl cellulose (a product purchased from Shanghai Aladdin Biotechnology Co., Ltd., the number average molecular weight of the carboxymethyl cellulose is 25000, the viscosity of the carboxymethyl cellulose is 1500-3100mPa.s) into a carboxymethyl cellulose solution (CMC) with the concentration of 0.5mg/ml, and adjusting the pH of the solution to 4 by using a 0.1M hydrochloric acid solution at 25 ℃; hydrochloric acid solutions with pH 4 were prepared and labeled as solution 1, solution 2, solution 3, and solution 4. Placing the cleaned silicon wafer in an ultraviolet curing box for surface activation for 10min, quickly placing in CHI solution for 4min after activation, then placing in solution 1 for 4min, taking out and placing in solution 2 for 4 min; placing in CMC solution for 4min, placing in solution 3 for 4min, taking out, and placing in solution 4 for 4 min; the process is a cycle, and a silicon wafer substrate LBL film is obtained after 25 cycles. The film has a rapid and reversible response to humidity as tested.
Example 3
Taking a silicon wafer as a substrate, taking deionized water as a solvent, preparing a certain amount of chitosan (a product purchased from Jinhu Chiba products Co., Ltd., Hengtai county, the viscosity of the chitosan is 100-200 mu M, the deacetylation degree is more than or equal to 95%) into a chitosan solution (CHI) with the concentration of 1mg/ml, adjusting the pH of the solution to 4.5 by using a 0.1M hydrochloric acid solution, preparing a certain amount of carboxymethyl cellulose (a product purchased from Shanghai Aladdin Biotechnology Co., Ltd., the number average molecular weight of the carboxymethyl cellulose is 25000, the viscosity of the carboxymethyl cellulose is 1500-3100mPa.s) into a carboxymethyl cellulose solution (CMC) with the concentration of 1mg/ml, and adjusting the pH of the solution to 4.5 by using a 0.1M hydrochloric acid solution at the temperature of 10 ℃; hydrochloric acid solutions with pH 4.5 were prepared and labeled as solution 1, solution 2, solution 3, and solution 4. Placing the cleaned silicon wafer in an ultraviolet curing box for surface activation for 10min, quickly placing in CHI solution for 5min after activation, then placing in solution 1 for 5min, taking out and placing in solution 2 for 5 min; then placing in CMC solution for 5min, then placing in solution 3 for 5min, taking out and placing in solution 4 for 5 min; the method is a cycle, and a silicon wafer substrate LBL film is obtained after 30 cycles. The film has a rapid and reversible response to humidity as tested.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method based on self-assembly of a silicon wafer substrate hard film with humidity response is characterized by comprising the following specific steps:
1) preparing a deionized water solution of chitosan with the concentration of 0.5-1 mg/ml, and adjusting the pH value of the deionized water solution to 3.5-4.5 by using a hydrochloric acid solution; preparing a deionized water solution of carboxymethyl cellulose with the concentration of 0.5-1 mg/ml, and adjusting the pH of the deionized water solution to 3.5-4.5 by using a hydrochloric acid solution; preparing a plurality of washing hydrochloric acid solutions with the pH value of 3.5-4.5;
2) obtaining a clean silicon wafer substrate;
3) activating the surface of the substrate obtained in step 2);
4) rapidly soaking the activated substrate obtained in the step 3) in the deionized water solution of chitosan obtained in the step 1) for 5-10 min at room temperature, then placing the substrate in one part of the hydrochloric acid solution for cleaning obtained in the step 1) for 4-5 min, and then placing the substrate in the other part of the hydrochloric acid solution for cleaning obtained in the step 1) for 4-5 min; taking out the substrate, soaking the substrate in the deionized water solution of the carboxymethyl cellulose obtained in the step 1) for 4-5 min, then placing the substrate in another part of the hydrochloric acid solution for cleaning obtained in the step 1) for 4-5 min, and then placing the substrate in another part of the hydrochloric acid solution for cleaning obtained in the step 1) for 4-5 min to complete self-assembly of one layer;
5) and (5) repeating the step 4) for 20-30 times to obtain the silicon wafer substrate hard film with humidity response.
2. The method for preparing a silicon wafer substrate hard film having a humidity response according to claim 1, wherein in the step 1):
the viscosity of the chitosan is 100-200 mu m, and the deacetylation degree is more than or equal to 95 percent;
the viscosity of the carboxymethyl cellulose is 1500-;
the concentration of the deionized water solution of the chitosan is the same as that of the deionized water solution of the carboxymethyl cellulose.
3. The method for preparing a silicon wafer substrate hard film having a humidity response according to claim 1, wherein in the step 2): using silicon wafer firstProduct ratio of H2SO4:H2O2Washing with 4:1 acidic solution, washing with deionized water, and then washing with H2O:H2O2:NH4Cleaning with an alkaline cleaning solution with OH being 5:2:1, and then using a volume ratio of H2O:H2O2And (3) putting the silicon wafer into deionized water for cleaning, and putting the cleaned silicon wafer into a vacuum oven for later use.
4. The method for preparing a silicon wafer substrate hard film having a humidity response according to claim 1, wherein in the step 3): placing the clean silicon wafer substrate obtained in the step 2) in a glass vessel, and activating the surface of the substrate in an ultraviolet curing box with the wavelength of 365nm for 5-10 min.
5. The method for preparing a silicon wafer substrate hard film having a humidity response according to any one of claims 1 to 4, wherein in the step 4): the time for each impregnation was the same.
6. The method for preparing a silicon wafer substrate hard film having a humidity response according to any one of claims 1 to 4, wherein in the step 4): during each immersion, the substrate was placed perpendicular to the liquid surface.
7. A silicon wafer substrate hard film having a humidity response prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the silicon wafer substrate hard film having humidity response according to claim 7, wherein: as an anti-counterfeiting or humidity detection material.
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