CN110724908A - Method for modifying surface of inorganic substance substrate - Google Patents

Method for modifying surface of inorganic substance substrate Download PDF

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CN110724908A
CN110724908A CN201911125082.1A CN201911125082A CN110724908A CN 110724908 A CN110724908 A CN 110724908A CN 201911125082 A CN201911125082 A CN 201911125082A CN 110724908 A CN110724908 A CN 110724908A
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substrate
cleaning
cavity
modified organic
inorganic
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孟尚君
芮祥新
李建恒
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Hefei Anderkeming Semiconductor Technology Co Ltd
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Hefei Anderkeming Semiconductor Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation

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Abstract

The invention provides a method for modifying the surface of an inorganic substrate, which comprises a cleaning process and a coating process which are sequentially carried out; the cleaning process comprises the steps of removing organic matters and/or inorganic matters adhered to the surface of the inorganic substance substrate by adopting plasma in the cavity and activating the surface, and the coating process comprises the step of depositing single-layer modified organic substance molecules by adopting a molecular layer deposition mode to realize the surface modification of the inorganic substance substrate. The invention replaces the original soaking method with the method of gas phase surface cleaning and organic film deposition, and is beneficial to achieving the aims of safety, high efficiency, reasonable emission reduction and environmental harm reduction.

Description

Method for modifying surface of inorganic substance substrate
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of semiconductors, and particularly relates to a substrate surface modification method.
[ background of the invention ]
The modification of the substrate is widely applied to industries such as biological research, medical research, chip manufacturing and the like. Typically, the substrate is made of an inorganic material, such as glass, silicon, metal (e.g., stainless steel, aluminum, etc.), ceramic (e.g., Al)2O3、ZrO2、 Si3N4Etc.) and it is the organic molecule that needs to be attached to the substrate surfaceSuch as pharmaceutical molecules, bio-organic molecules, etc. Since most of organic molecules are difficult to attach to the surface of inorganic materials, surface modification of the substrate is essential to improve the adsorption capacity of the organic molecules on the surface thereof.
The materials used for changing the surface properties (modification) of inorganic materials are generally organic substances which have the following characteristics:
① the organic substance has a hydrolyzable group at one end, such as alkoxy (RO-, wherein R may be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.), amino (-NR)1R2Wherein R is1、R2Hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.), halogen (Cl, Br, I, etc.), etc.; these groups readily react with hydroxyl groups on the surface of the mineral substrate to form chemisorptions.
② the other end of the organic substance usually contains organic functional groups, such as amino, epoxy, isocyanate, carboxyl, etc., and is easy to bond with organic molecules or macromolecules (such as protein, DNA, RNA, etc.).
If the organic matter is coated on the surface of an inorganic substrate, the adhesive capacity of organic molecules or macromolecules on the surface of the substrate can be greatly improved, and typical surface modification materials comprise: 3-Aminopropyltriethoxysilane (APTES), 3- (2, 3-glycidoxy) propyltrimethoxysilane (GOPTS), Isocyanatopropyltriethoxysilane (ICPTES), and the like.
Figure BDA0002276571710000021
Structural formula 13-Aminopropyltriethoxysilane (APTES)
Figure BDA0002276571710000022
Structural formula 23- (2, 3-glycidoxy) propyltrimethoxysilane (GOPTS)
Figure BDA0002276571710000023
Isocyanic acid propyltriethoxysilane (ICPTES)
The process of modifying the surface of a substrate is generally divided into two steps: and (5) cleaning and coating.
The reagents for the washing process are varied, but soaking methods are conventionally used, such as the method of soaking in an alkaline solution and ultrasonic rinsing with acetone/clean water (Al/clear water) as disclosed in "Development of a high throughput automated and sizing biochi array technology" of Clinical Chemistry51:7, 1165-2O3Substrates) and surface-treated surfaces for micro applications, surface chemical analysis and fluorescent labeling surfaces, surface-treated surfaces for chemical applications, surface-treated surfaces for chemical reactions and fluorescent labeling surfaces, surface focus 6:20160056, acetone/dichloromethane pretreatment, and surface-treated surfaces for tin oxide films, surface-treated surfaces for chemical reactions, and surface-treated surfaces for chemical reactions, surface Modification, and surface-treated surfaces for chemical reactions, surface coating, surface chemical reactions, and surface-treated surfaces for chemical reactions, surface Modification, and surface treatment, surface Modification, and surface-treated surfaces for surface coatings, and surface-treated surfaces of fish, and surface coatings, and coating, and surface coatings.
The coating process is also generally carried out by dipping methods, such as dipping the substrate in a solution of glutaraldehyde and APTES for coating APTES films as disclosed in "equivalent Binding vs. addition of biomolecular on Silicon Nitride films" by Eurosensors XXV, September 4-7,2011, Development of analytical stage dimension Modification with N-polyamides as disclosed in "Development of simulation Chemistry N-halogen" by J.APPL.POLY. SCI.2012,1-11, dipping the substrate in a solution of toluene and GOTPS for coating GOTPS films, Development of simulation Chemistry 1176(2005) of simulation Chemistry51:7,1165 (2005) for dipping of substrate in a solution of Development of plasma coating solutions and for coating of biological coating films as disclosed in "Development of plasma coating" by dipping of biological coatings.
However, in the conventional soaking method, a large amount of alkaline solution, or alkaline solution with oxidative hydrogen peroxide/ammonia water, or piranha solution and the like are used in the cleaning process, so that the corrosion and the oxidation are strong, and the safety is poor; the recycling rate of the cleaning solution is poor; the cleaning efficiency is low and the cleaning time is long; the conventional cleaning time is at least 2-4 hours. A large amount of solvent is needed in the process of soaking and coating, so that the fire risk is increased, and the harm to the human body is large; the solvent recovery cost is high, and waste is easy to cause; the dipping coating efficiency is low, and generally needs 4 to 8 hours.
Therefore, although the soaking method can basically realize the modification of the inorganic substrate, it has the obvious disadvantages that a large amount of operations are required for the toxic/acidic/alkaline solution, and the solution is difficult to treat and discharge, inefficient and seriously wasted. The surface modification of inorganic substrates requires the development of new processes.
[ summary of the invention ]
The invention provides a method for modifying the surface of an inorganic substance substrate, which replaces the original soaking method with a method of gas phase surface cleaning and organic film deposition, and is beneficial to achieving the aims of safety, high efficiency, reasonable reduction of emission and reduction of environmental damage.
The technical solution of the invention is as follows:
the method for modifying the surface of the inorganic substance substrate is characterized by comprising a cleaning process and a coating process which are sequentially carried out; the cleaning process comprises the steps of removing organic matters and/or inorganic matters adhered to the surface of the inorganic substance substrate by adopting plasma in the cavity and activating the surface, and the coating process comprises the step of depositing single-layer modified organic substance molecules by adopting a molecular layer deposition mode to realize the surface modification of the inorganic substance substrate.
The process of activating the surface includes a process of generating hydroxyl groups on the inorganic substrate sufficient to chemisorb the modified organic component.
The above cleaning process comprises the following steps:
s1-1: cleaning the substrate surface with acetone/anhydrous alcohol to remove organic components;
s1-2: rinsing the surface with ultrapure water to remove dust particles adhering to the surface of the substrate;
s1-3: after drying, putting the base substrate into a cavity, vacuumizing to 1-10 Pa, and introducing O2、H2O、N2、H2、NH3、 N2And O gas or a plurality of O gases, ionizing the gas into plasma by high pressure, and cleaning the surface by means of plasma bombardment or reaction with surface impurities.
The film coating process comprises the following steps:
s2-1: under the condition that the substrate is heated, modified organic matter molecule steam is introduced into the cavity, wherein the pressure of the cavity is 10-10%4Pa, stopping introducing the steam of the modified organic molecules after the monolayer modified organic molecules are uniformly deposited on the surface of the substrate, and blowing the redundant steam in the cavity to be clean to finish the deposition of the monolayer modified organic molecule film.
When a plurality of layers of modified organic molecules need to be deposited, the coating process further comprises the following steps:
s2-2: and (3) repeatedly performing S2-1 to perform the deposition of multiple layers of modified organic molecules on the surface on which the deposition of the single layer of modified organic molecules is completed by reactivating the surface by using gas containing low-power plasma, ozone, water vapor or ammonia gas. The low-power plasma can use one or a mixture of argon, water vapor, nitrogen, ammonia gas, laughing gas and hydrogen as a gas source.
The step S1-3 is performed in the same chamber as the steps S2-1 and S2-2.
Further, the heating temperature of the substrate is 25 to 250 ℃, preferably 100 to 200 ℃, and more preferably 150 to 200 ℃.
Further, the modified organic molecules are placed in a source bottle communicated with the cavity, and modified organic molecule steam is generated by heating the source bottle to 25-150 ℃, wherein the more preferable heating temperature is 80-120 ℃.
Further, the pressure of the cavity is preferably 10-10%4Pa, more preferably 10 to 100 Pa.
Further, the deposition time of the monolayer modified organic molecular thin film is 1 second to 20 minutes, and more preferably 1 minute to 10 minutes.
The invention has the following beneficial effects:
the method replaces the original soaking method with the methods of gas phase surface cleaning and organic film deposition, utilizes the mode of plasma bombardment or reaction with surface impurities to generate enough hydroxyl on the surface of an inorganic substance substrate for adsorbing and modifying organic components, and then effectively combines organic modified organic substance molecules with the inorganic substance substrate through single-layer modified organic substance molecule film deposition.
[ description of the drawings ]
FIG. 1 is a gas circuit diagram of a Molecular Layer Deposition (MLD) system according to an embodiment;
FIG. 2 is a photograph showing contact angles of water drops of the glass substrate of the first example (a) before cleaning (b) and after plating (c);
FIG. 3 is a fluorescent spot coating observation result of the modified glass substrate of the first embodiment under a fluorescent microscope;
FIG. 4 is a photograph showing contact angles of water drops of the glass substrate of comparative example A before (a) cleaning, (b) after (c) plating;
FIG. 5 is a result of observing fluorescent spot coating under a fluorescence microscope on a modified glass substrate of comparative example one;
FIG. 6 is a photograph showing contact angles of water drops of the glass substrate of example two before (a) cleaning, (b) cleaning and after (c) plating;
FIG. 7 is a fluorescent spot coating observation result under a fluorescent microscope on the modified glass substrate of example two;
FIG. 8 is a photograph showing contact angles of water drops of the glass substrate of the comparative example after (a) cleaning, before (b) cleaning, and after (c) plating;
FIG. 9 is a result of observing fluorescent spot coating under a fluorescence microscope on a modified glass substrate of a comparative example II;
FIG. 10 is a photograph showing contact angles of water droplets on a silicon wafer substrate of example III before (a) cleaning, (b) cleaning and after (c) plating;
FIG. 11 is a photograph showing contact angles of water droplets on the glass substrate of example four after (a) cleaning, (b) cleaning, (c) plating a first film and (d) plating a second film;
fig. 12 shows the observation result of the fluorescent dot coating under a fluorescence microscope on the modified glass substrate of example four.
Wherein all colors are not shown.
[ detailed description ] embodiments
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
The following examples are not provided to limit the scope of the present invention, nor are the steps described to limit the order of execution, and the directions described are limited to the drawings. Modifications of the invention which are obvious to those skilled in the art in view of the prior art are also within the scope of the invention as claimed.
In this document, "/" means "or" unless otherwise specified; "substrate" is essentially the same as "base" and "substrate" is an analogous expression to "base"; "ultrapure water" means water having a resistivity of not less than 18.2 M.OMEGA.cm; acetone/anhydrous alcohol means that acetone is used first and then anhydrous alcohol is used for thorough cleaning.
The method for modifying the surface of the inorganic substance substrate is characterized by comprising a cleaning process and a coating process which are sequentially carried out; the cleaning process comprises the steps of removing organic matters and/or inorganic matters adhered to the surface of the inorganic substance substrate by adopting plasma in the cavity and activating the surface, and the coating process comprises the step of depositing single-layer modified organic substance molecules by adopting a molecular layer deposition mode to realize the surface modification of the inorganic substance substrate. The process of activating the surface includes a process of making the inorganic substrate generate hydroxyl groups, sufficient to generate hydroxyl groups for adsorption of the modified organic component. The cleaning process and the coating process can be carried out in the same cavity, and can also be carried out in different cavities, and the efficiency can be improved more favorably when the cleaning process and the coating process are carried out in the same cavity.
The above cleaning process comprises the following steps:
s1-1: cleaning the substrate surface with acetone/anhydrous alcohol to remove organic components;
s1-2: rinsing the surface with ultrapure water to remove dust particles adhering to the surface of the substrate;
s1-3: after drying, putting the base substrate into a cavity, vacuumizing to 1-10 Pa, and introducing O2、H2O、N2、H2、NH3、 N2And O gas or a plurality of O gases, ionizing the gas into plasma by high pressure, and cleaning the surface by means of plasma bombardment or reaction with surface impurities.
The film coating process comprises the following steps:
s2-1: under the condition that the substrate is heated, modified organic matter molecule steam is introduced into the cavity, wherein the pressure of the cavity is 10-10%4Pa, stopping introducing the steam of the modified organic molecules after the monolayer modified organic molecules are uniformly deposited on the surface of the substrate, and blowing the redundant steam in the cavity to be clean to finish the deposition of the monolayer modified organic molecule film.
When a plurality of layers of modified organic molecules need to be deposited, the coating process further comprises the following steps:
s2-2: and (3) repeatedly performing S2-1 to perform the deposition of multiple layers of modified organic molecules on the surface on which the deposition of the single layer of modified organic molecules is completed by reactivating the surface by using gas containing low-power plasma, ozone, water vapor or ammonia gas.
The heating temperature of the substrate is 25-250 ℃, preferably 100-200 ℃, and more preferably 150-200 ℃.
Modified organic molecules are placed in a source bottle communicated with the cavity, modified organic molecule steam is generated by heating the source bottle to 25-150 ℃, and the preferable heating temperature is 80-120 ℃.
The pressure of the cavity is preferably 10-10000 Pa, and more preferably 10-100 Pa.
The deposition time of the monolayer modified organic molecular film is 1 second to 20 minutes, and more preferably 1 minute to 10 minutes.
Example one
A glass substrate surface modification method includes:
and (3) cleaning: cleaning the glass substrate by using a mixed solution of acetone and absolute ethyl alcohol to remove organic components on the surface; then, washing the surface with ultrapure water to remove dust particles adhered to the surface; drying the substrate, placing the substrate in a cavity for Molecular Layer Deposition (MLD) coating, vacuumizing, heating the substrate to 150 ℃, and introducing O2And ionizing the gas into a plasma state, and cleaning the surface of the glass substrate in a plasma bombardment mode.
In the present example, a Molecular Layer Deposition (MLD) coating system is shown in fig. 1; the valve of the water source bottle is closed, the valve of the oxygen bottle is opened, O2The flow rate of the cleaning solution is 300sccm, the pressure of the cavity is 60Pa, the power of the radio frequency plasma is 300W, and the cleaning time is 1 min.
Film coating process: o is2After being purged, heating the GOPTS source bottle to 90 ℃ to gasify the GOPTS and introduce the GOPTS into the cavity, controlling the pressure of the cavity to be 80Pa by controlling a butterfly valve, and setting the deposition time to be 5 min; and then closing the GOPTS source bottle, and purging redundant steam in the cavity to be clean, so that the deposition of the single-layer GOPTS film is completed.
The whole modification process takes 16 minutes (1 minute cleaning, 5 minutes purging, 5 minutes coating and 5 minutes purging), no liquid is discharged in the whole process, and the discharged gas only comprises argon or nitrogen (carrier gas), oxygen (plasma source) and GOPTS vapor, can be simply treated by a tail gas treatment system, and then is recycled or discharged into the atmosphere.
Glass substrate modification effect:
(1) contact Angle analysis of Water droplets
Under the condition that the surface of the glass substrate is not cleaned, due to the pollution of organic matters and inorganic matters, the contact angle of a water drop is larger (>50 degrees, as shown in figure 2a), after the cleaning is finished, the surface of the substrate has strong hydrophilicity, the contact angle of a water drop experiment is almost 0 (as shown in figure 2b), after a layer of GOPTS is coated on the surface, the surface becomes hydrophobic, and the contact angle of the water drop is larger (>50 degrees, as shown in figure 2 c).
(2) Homogeneity analysis
The fluorescent agent is an organic molecule (such as rhodamine B, rhodamine 123, rhodamine 110, and the like; in the example, the rhodamine 110 is taken as an example), is easy to adsorb on the surface of an organic substance, but not adsorb on the surface of an inorganic substance, and emits fluorescence under the irradiation of light with certain wavelength. Based on the properties of the phosphor, it can be determined whether the surface of the substrate has been deposited with a surface modifier. The uniformity of the deposition of the modified organic molecules can be analyzed by spot coating of the fluorescent agent and observation of the spot coating under a fluorescence microscope. The surface modifier of the present embodiment is GOPTS, and as the density of the surface covered by the GOPTS increases, more fluorescer molecules will be adsorbed on the surface, and emit stronger light under illumination. Upon analysis, the mean fluorescence intensity of the fluorescent spot coating exceeded 77 (readings from the image analysis software), as shown in FIG. 3.
(3) Elemental composition analysis
The XPS elemental analysis shows that the cleaned glass substrate has the surface elements: 6.9% C, 62.6% O, 23.6% Si, 0.3% N, 3.9% B, 1.0% Na, 1.2% Al, 0.5% K. After deposition by GOPTS, the elemental composition of the surface becomes: 17.5 percent of C, 52.4 percent of O, 20.1 percent of Si, 0.7 percent of N, 5.2 percent of B,1.0 percent of Na, 1.7 percent of Al and 1.2 percent of K, and the content of C is obviously improved.
Comparative example 1
Surface modification method of conventional glass substrate:
and (3) cleaning: cleaning a glass substrate by using a mixed solution of acetone and absolute ethyl alcohol to remove organic components on the surface, and then washing the surface by using ultrapure water to remove dust particles adhered to the surface; thereafter, the glass substrate was immersed in the piranha solution, heated to 90 ℃, and immersed for 2 hours. The piranha solution is 70% (v/v) concentrated sulfuric acid and 30% (v/v) hydrogen peroxide.
Film coating process: diluting GOPTS with toluene to obtain 2% (v/v) solution, immersing the glass substrate treated by the piranha solution into the toluene solution of GOPTS, heating to 50 ℃, soaking for 4 hours, taking out the glass substrate from the solution, and sequentially washing with toluene and pure water to finish modification.
The whole modification process takes 6 hours, the discharged liquid comprises concentrated sulfuric acid, hydrogen peroxide (cleaning liquid) and a toluene solution containing GOPTS, and the discharged gas contains toluene vapor.
Glass substrate modification effect:
(1) under the condition that the surface of the glass substrate is not cleaned, due to the pollution of organic matters and inorganic matters, the contact angle of a water drop is relatively large (>50 degrees, as shown in figure 4a), after the piranha solution is treated, the contact angle of a water drop experiment is almost 0 (as shown in figure 4b), and the result of the piranha solution treatment for 2 hours is comparable to the result of the plasma treatment for 1 min; when the immersion plating film is 4 hours, the contact angle of a water drop experiment reaches more than 50 degrees (as shown in figure 4c), and the surface modification result of the GOPTS solution after immersion for 4 hours is similar to the result of MLD film deposition for 5 min.
(2) Homogeneity analysis
Through the fluorescent agent spot coating and the fluorescent point coating test under a fluorescent microscope, the fluorescent brightness is about 70 and is smaller than the brightness deposited by the MLD film, as shown in FIG. 5.
(3) Elemental composition analysis
From XPS elemental analysis, it can be seen that, compared to the deposited GOPTS of example one (17.5% C, 52.4% O, 20.1% Si, 0.7% N, 5.2% B, 1.0% Na, 1.7% Al, 1.2% K), the composition of the surface after soaking in the GOPTS solution is: 23.5% C, 53.7% O, 20.8% Si, 0.7% N, 0.9% B, 0.5% Al, the compositions are very close.
Example two
A method of modifying a glass substrate comprising:
and (3) cleaning: cleaning the glass substrate by acetone/absolute ethyl alcohol to remove organic components on the surface; then, washing the surface with ultrapure water to remove dust particles adhered to the surface; drying the substrate, placing the substrate in a cavity for Molecular Layer Deposition (MLD) coating, vacuumizing, heating the substrate to 140 ℃, and introducing H2O/O2And ionizing the gas into a plasma state, and cleaning the surface by means of plasma bombardment.
In the present example, a Molecular Layer Deposition (MLD) coating system is shown in fig. 1; h2O/O2The flow rate of the cleaning solution is 200/300sccm, the pressure of the cavity is 100Pa, the power of the radio frequency plasma is 300W, and the cleaning time is 3 min.
Film coating process: and after purging, heating the APTES source bottle to 90 ℃, gasifying the APTES, introducing the gasified APTES into the vacuum cavity, controlling the pressure of the cavity to be 100Pa by controlling a butterfly valve, and depositing for 5min, then closing the APTES source bottle, and purging redundant steam in the cavity to complete the deposition of the single-layer APTES film.
The whole modification process takes 18 minutes (3 minutes cleaning, 5 minutes purging, 5 minutes depositing, 5 minutes purging), no liquid is discharged, and the discharged gas only comprises argon or nitrogen (carrier gas), oxygen (plasma source), water vapor (plasma source) and APTES vapor, and can be recycled or discharged into the atmosphere after being treated by a simple tail gas treatment system.
(1) Under the condition that the surface of the glass substrate is not cleaned, due to the pollution of organic matters and inorganic matters, the contact angle of a water drop is larger (>50 degrees, as shown in figure 6a), after the cleaning is finished, the surface of the substrate has strong hydrophilicity, the contact angle of a water drop experiment is almost 0 (as shown in figure 6b), after a layer of GOPTS is coated on the surface, the surface becomes hydrophobic, and the contact angle of the water drop is larger (>50 degrees, as shown in figure 6 c).
(2) Homogeneity analysis
By the fluorescent agent spotting and the fluorescent spotting test under a fluorescence microscope, it can be found that the average fluorescence luminance of the fluorescent spotting exceeds 75, as shown in fig. 7.
(3) Elemental composition analysis
The XPS elemental analysis shows that the cleaned glass substrate has the surface elements: 6.9% C, 62.6% O, 23.6% Si, 0.3% N, 3.9% B, 1.0% Na, 1.2% Al, 0.5% K. After APTES deposition, the elemental composition of the surface becomes: 16.4% of C, 49.1% of O, 19.8% of Si, 5.6% of N, 5.2% of B, 1.0% of Na, 1.7% of Al and 1.2% of K, and the content of N is obviously improved.
Comparative example No. two
Surface modification method of conventional glass substrate:
and (3) cleaning: cleaning the glass substrate by acetone/absolute ethyl alcohol to remove organic components on the surface, and then washing the surface by ultrapure water to remove dust particles adhered to the surface; thereafter, the glass substrate was immersed in the piranha solution, heated to 90 ℃, and immersed for 2 hours. The piranha solution is 70% (v/v) concentrated sulfuric acid and 30% (v/v) hydrogen peroxide.
Film coating process: diluting APTES with toluene to obtain 2% (v/v) solution, soaking the glass substrate treated with the piranha solution in toluene to 50 deg.C for 4 hr, taking out the glass substrate, and washing with toluene and pure water successively to complete modification.
The whole modification process takes 6 hours, the discharged liquid comprises concentrated sulfuric acid and hydrogen peroxide (cleaning liquid) and a toluene solution containing APTES, and the discharged gas comprises toluene vapor.
Glass substrate modification effect:
(1) under the condition that the surface of the glass substrate is not cleaned, due to the pollution of organic matters and inorganic matters, the contact angle of a water drop is relatively large (>50 degrees, as shown in figure 8a), after the piranha solution is treated, the contact angle of a water drop experiment is almost 0 (as shown in figure 8b), and the result of the piranha solution treatment for 2 hours is comparable to the result of the plasma treatment for 1 min; when the immersion plating film is 4 hours, the contact angle of a water drop experiment reaches more than 50 degrees (as shown in figure 8c), and the surface modification result of the APTES solution after immersion for 4 hours is similar to the result of MLD film deposition for 5 min.
(2) Homogeneity analysis
Through the fluorescent agent spot coating and the fluorescent point coating test under a fluorescent microscope, the fluorescent brightness is about 70 and is smaller than the brightness deposited by the MLD film, as shown in FIG. 9.
(3) Elemental composition analysis
From XPS elemental analysis, it was found that, compared to APTES deposited in example two (16.4% C, 49.1% O, 19.8% Si, 5.6% N, 5.2% B, 1.0% Na, 1.7% Al, 1.2% K), the surface element composition after immersion in APTES solution was: 16.0% C, 55.4% O, 22.5% Si, 4.7% N, 0.9% B, 0.5% Al, the N content being slightly less than the N content of the surface after MLD film deposition.
EXAMPLE III
A silicon wafer substrate modification method comprises the following steps:
and (3) cleaning: to silicon chip substrateCleaning with acetone and anhydrous alcohol to remove organic components on the surface; then, washing the surface with ultrapure water to remove dust particles adhered to the surface; drying the substrate, placing the substrate in a cavity for Molecular Layer Deposition (MLD) coating, vacuumizing, heating the substrate to 140 ℃, and introducing H2O/O2And ionizing the gas into a plasma state, and cleaning the surface by means of plasma bombardment.
In the present example, a Molecular Layer Deposition (MLD) coating system is shown in fig. 1; h2O/O2The flow rate of the cleaning solution is 200/300sccm, the pressure of the cavity is 100Pa, the power of the radio frequency plasma is 300W, and the cleaning time is 3 min.
Film coating process: and after purging, heating the APTES source bottle to 90 ℃, gasifying the APTES, introducing the gasified APTES into the vacuum cavity, controlling the pressure of the cavity to be 100Pa by controlling a butterfly valve, and depositing for 5min, then closing the APTES source bottle, and purging redundant steam in the cavity to complete the deposition of the single-layer APTES film.
The whole modification process takes 18 minutes (3 minutes of cleaning, 5 minutes of purging, 5 minutes of depositing, 5 minutes of purging), no liquid is discharged, the discharged gas only comprises argon or nitrogen (carrier gas), oxygen (plasma source), water vapor (plasma source) and APTES vapor, and the gas can be recycled or discharged into the atmosphere after being simply treated by a tail gas treatment system.
(1) Under the condition that the surface of the silicon wafer substrate is not cleaned, due to the pollution of organic matters and inorganic matters, the contact angle of a water drop is larger (45 degrees, shown in figure 10a), after the cleaning is finished, the surface of the substrate has strong hydrophilicity, the contact angle of a water drop experiment is almost 0 (shown in figure 10b), after a layer of APTES is coated on the surface, the surface becomes hydrophobic, and the contact angle of the water drop is larger (34 degrees, shown in figure 10 c).
(2) Elemental composition analysis
The XPS elemental analysis shows that the surface elements of the cleaned silicon wafer substrate are: 2.2% C, 31.9% O, 65.9% Si, 0% N. After APTES deposition, the elemental composition of the surface becomes: 16.8 percent of C, 26.9 percent of O, 50.4 percent of Si and 5.9 percent of N, and the content of N is obviously improved.
Note: the silicon wafer substrate cannot be used for taking a fluorescence photograph, and the modification degree cannot be expressed by the fluorescence photograph.
Example four
A glass substrate surface modification method includes:
and (3) cleaning: cleaning the glass substrate by using acetone and absolute ethyl alcohol to remove organic components on the surface; then, washing the surface with ultrapure water to remove dust particles adhered to the surface; drying the substrate, placing the substrate in a cavity for Molecular Layer Deposition (MLD) coating, vacuumizing, heating the substrate to 150 ℃, and introducing O2And ionizing the gas into a plasma state, and cleaning the surface of the glass substrate in a plasma bombardment mode.
In the present example, a Molecular Layer Deposition (MLD) coating system is shown in fig. 1; the valve of the water source bottle is closed, the valve of the oxygen bottle is opened, O2The flow rate of the cleaning solution is 300sccm, the pressure of the cavity is 60Pa, the power of the radio frequency plasma is 300W, and the cleaning time is 1 min.
The first layer film coating process: o is2After being purged, heating the GOPTS source bottle to 90 ℃ to gasify the GOPTS and introduce the GOPTS into the cavity, controlling the pressure of the cavity to be 80Pa by controlling a butterfly valve, and setting the deposition time to be 5 min; and then closing the GOPTS source bottle, and purging redundant steam in the cavity to be clean, so that the deposition of the single-layer GOPTS single-layer film is completed.
And (3) secondary activation process: after GOPTS is purged, opening a water source bottle valve to enable water vapor to be introduced into the cavity, controlling the pressure of the cavity to be 30Pa by controlling a butterfly valve, and setting the deposition time to be 1 min; the water source bottle is then closed and excess steam in the cavity is purged clean.
In the second film coating process, after water vapor is purged, opening a GOPTS source bottle (90 ℃), introducing the GOPTS into the cavity, controlling the pressure of the cavity at 80Pa by controlling a butterfly valve, and depositing for 5 min; and then closing the GOPTS source bottle, and purging redundant steam in the cavity to be clean, so that the deposition of the second layer of GOPTS single-layer film is completed.
The whole modification process takes 32 minutes (1 minute cleaning, 5 minutes purging, 5 minutes coating, 5 minutes purging, 1 minute reactivation, 5 minutes purging, 5 minutes secondary coating, 5 minutes purging), no liquid is discharged in the whole process, and the discharged gas only comprises argon or nitrogen (carrier gas), oxygen (plasma source), water vapor and GOPTS vapor, can be treated by a tail gas treatment system, and then is recycled and discharged into the atmosphere.
Glass substrate modification effect:
(1) contact Angle analysis of Water droplets
Under the condition that the surface of the glass substrate is not cleaned, due to the pollution of organic matters and inorganic matters, the contact angle of a water drop is larger (>50 degrees, as shown in figure 11a), after the cleaning is finished, the surface of the substrate has strong hydrophilicity, the contact angle of a water drop experiment is almost 0 (as shown in figure 11b), after a layer of GOPTS is coated on the surface, the surface becomes hydrophobic, the contact angle of the water drop is larger (>50 degrees, as shown in figure 11c), after a second layer of GOPTS is coated, the surface is more hydrophobic, and the contact angle of the water drop is larger (> 55 degrees, as shown in figure 11 d).
(2) Homogeneity analysis
The fluorescence brightness was found to exceed 80 by the fluorescent spot coating and the fluorescent spot coating test under the fluorescence microscope, as shown in fig. 12.
(3) Elemental composition analysis
From XPS elemental analysis, it can be seen that, compared with the single-layer GOPTS vacuum coating (example one, 17.5% C, 52.4% O, 20.1% Si, 0.7% N, 5.2% B, 1.0% Na, 1.7% Al, 1.2% K), the surface elements after two-layer coating are: 22.1% C, 53.5% O, 19.4% Si, 0.6% N, 2.8% B, 0.7% Na, 0.9% Al. The content of C is improved.

Claims (10)

1. The method for modifying the surface of the inorganic substance substrate is characterized by comprising a cleaning process and a coating process which are sequentially carried out; the cleaning process comprises the steps of removing organic matters and/or inorganic matters adhered to the surface of the inorganic substance substrate by adopting plasma in the cavity and activating the surface, and the coating process comprises the step of depositing single-layer modified organic substance molecules by adopting a molecular layer deposition mode to realize the surface modification of the inorganic substance substrate.
2. The method of claim 1, wherein the surface activation process comprises a process that generates hydroxyl groups on the inorganic substrate.
3. The method of claim 1, wherein the cleaning process comprises the steps of:
s1-1: cleaning the substrate surface with acetone/anhydrous alcohol to remove organic components;
s1-2: rinsing the surface with ultrapure water to remove dust particles adhering to the surface of the substrate;
s1-3: after drying, putting the substrate into a cavity, vacuumizing to 1-10 Pa, and introducing O2、H2O、N2、H2、NH3、N2And O gas or a plurality of O gases, ionizing the gas into plasma by high pressure, and cleaning the surface by means of plasma bombardment or reaction with surface impurities.
4. The method of claim 1 or 3, wherein the coating process comprises the steps of:
s2-1: under the condition that the substrate is heated, modified organic matter molecule steam is introduced into the cavity, and the pressure of the cavity is 10-10%4Pa, stopping introducing the steam of the modified organic molecules after the monolayer modified organic molecules are uniformly deposited on the surface of the substrate, and blowing the redundant steam in the cavity to be clean to finish the deposition of the monolayer modified organic molecule film.
5. The method of claim 4, wherein the step S1-3 is performed in the same chamber as the step S2-1.
6. The method of claim 4, wherein the substrate is heated at a temperature of 25-250 ℃.
7. The method for modifying the surface of an inorganic substrate according to claim 4, wherein the modified organic molecules are placed in a source bottle communicated with the cavity, and the vapor of the modified organic molecules is generated by heating the source bottle to a temperature of 25 to 150 ℃.
8. The method of claim 4, wherein the pressure in the chamber is 10-10 during the modification process4Pa。
9. The method of claim 4, wherein the deposition time of the monolayer modified organic molecular film is 1 second to 20 minutes.
10. The method of claim 4, wherein the coating process further comprises:
s2-2: and (3) repeatedly performing S2-1 to perform the deposition of multiple layers of modified organic molecules on the surface on which the deposition of the single layer of modified organic molecules is completed by reactivating the surface by using gas containing low-power plasma, ozone, water vapor or ammonia gas.
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