CN109880027B - Method for preparing copolymerized and crosslinked organic polymer on surface of semiconductor - Google Patents
Method for preparing copolymerized and crosslinked organic polymer on surface of semiconductor Download PDFInfo
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Abstract
The invention discloses a method for preparing a copolymerized organic polymer film on the surface of a semiconductor, which comprises the following steps: a1: copolymerization and grafting on the surface of a semiconductor substrate: placing the semiconductor substrate in a grafting solution containing a cyano vinyl monomer and a carboxyl vinyl monomer for grafting reaction, wherein most of cyano groups are spontaneously hydrolyzed into amide groups after grafting; a2: and B, annealing, namely annealing the sample obtained in the step A1, wherein the heat preservation temperature is 150-300 ℃, and the heat preservation time is 30-180 min, so that the polymer film containing the imide structure is obtained. The invention prepares the film with the three-dimensional cross-linked structure on the surface of the semiconductor substrate in situ, improves the structure that most of polymer film layers obtained by the traditional grafting method are comb-shaped or linear, and improves the performance of the two-dimensional structure of the existing organic film.
Description
Technical Field
The invention belongs to the technical field of preparation of organic insulating layers on semiconductor surfaces, and particularly relates to a method for preparing a copolymerized and crosslinked organic polymer on a semiconductor surface.
Background
3D stacked electronic packaging technology with interconnections through semiconductor vias is one of the most important packaging forms in the future. In the semiconductor microchannel insulation technology, the conventional insulation layer mainly includes inorganic insulation layers such as silicon dioxide and silicon nitride, and organic insulation layers. The organic insulating layer has the advantages of low dielectric constant, small elastic modulus, simple preparation, low cost, capability of being used as a stress buffer layer and the like, and has great application prospect in semiconductor manufacturing. But the prior art is difficult to realize the spin coating of the insulating layer with controllable thickness in the micro-channel with large depth-width ratio. This is because, with the decrease of the pore size and the increase of the depth of the micro-channel, the traditional spin coating method cannot effectively spin out the organic matter, even block the micro-channel, and the organic film obtained by the spin coating method has a micron-sized thickness. With the reduction of the size of electronic devices, the requirements of various complex microchannels on the preparation precision are gradually improved, and a film preparation mode mainly based on chemical vapor deposition appears. By controlling the precursor, specific inorganic and organic films can be prepared on the surface of the substrate. While the use of plasma enhanced chemical vapor deposition further expands its applications. However, these chemical vapor deposition techniques have the defects of uneven film thickness distribution and low step coverage in complex micro-channels with large aspect ratio.
In order to meet the requirement of nano-scale high-precision manufacturing and obtain well-formed insulating layers in various complex microchannels, methods for obtaining organic insulating layers by using grafting methods are gradually developed, for example, electro-grafted poly-4-vinylpyridine (P4VP), polymethyl methacrylate (PMMA) or polyacrylic acid (PAA) and the like are adopted to cover an organic film on the silicon surface to be used as an insulating layer. However, the film formed by such grafting is usually in a "comb" or "linear" structure, and there is no physical entanglement or chemical bond connection between adjacent molecular chains, which easily causes weak thermodynamic properties of the film.
Disclosure of Invention
The invention aims to provide a method for preparing a copolymerized organic polymer film on the surface of a semiconductor. The method can obtain the polymer film containing the imide structure, changes the comb-shaped or linear structure of the existing organic polymer film, and improves the performance of the film.
In order to solve the problems, the technical scheme of the invention is as follows:
a method for preparing a copolymerized crosslinked organic polymer on a semiconductor surface, comprising:
a1: copolymerization and grafting on the surface of a semiconductor substrate: placing the semiconductor substrate in a grafting solution containing a cyano vinyl monomer and a carboxyl vinyl monomer for grafting reaction, wherein most of cyano groups are spontaneously hydrolyzed into amide groups after grafting;
a2: annealing treatment: and B, annealing the sample obtained in the step A1 to enable the carboxyl and the amido or the carboxyl and the cyano of the grafting monomer to be subjected to dehydration condensation, and keeping the temperature at 150-300 ℃ for 30-180 min to obtain the polymer film containing the imide structure.
Specifically, the step a1 specifically includes:
a101: cleaning a semiconductor substrate: sequentially carrying out ultrasonic cleaning on the semiconductor substrate by adopting acetone, alcohol and deionized water at the temperature of 10-40 ℃, wherein the cleaning time is 5-15 min each time;
a102: semiconductor substrate surface pretreatment: soaking the semiconductor substrate in a fluorine-containing reagent for 5-10 min at the soaking temperature of 10-40 ℃, then washing with deionized water, and drying;
a103: copolymerization and grafting on the surface of a semiconductor substrate: and placing the semiconductor substrate in the prepared grafting solution, wherein the grafting temperature is 10-40 ℃, the grafting time is 15-120 min, and then cleaning and drying with deionized water.
Preferably, the grafting solution is prepared by adding 0.05-1 g of anionic surfactant, 0.5-5 mL of inorganic acid, 0.5-5 mL of acid or salt containing fluorine ions, 0.5-10 mL of vinyl monomer reagent and 0.05-0.5 g of aromatic diazonium salt into 100mL of deionized water;
the vinyl monomer is selected from one or more of carboxyl vinyl monomer, cyano vinyl monomer and amido vinyl monomer, and the concentration ratio of the carboxyl vinyl monomer to the cyano vinyl monomer is 3: 9-1.
Preferably, the carboxyvinyl monomer is any one of acrylic acid, methacrylic acid and cinnamic acid.
Preferably, the cyanovinyl monomer is acrylonitrile or methacrylonitrile.
Preferably, the fluorine-containing reagent in step a102 is an aqueous solution of hydrofluoric acid, fluoroboric acid or ammonium fluoride.
Preferably, the annealing process comprises the steps of heating a sample to a heat preservation temperature along with a furnace, wherein the heating rate is 5-10 ℃/min, then preserving heat, and finally cooling along with the furnace or taking out for air cooling; or
Directly putting the sample into a high-temperature furnace with the heat preservation temperature, preserving the heat, and finally cooling along with the furnace or taking out for air cooling.
Preferably, the atmosphere of the annealing treatment is air, argon or nitrogen.
The invention also provides a method for preparing a copolymerized and crosslinked organic polymer on the surface of a semiconductor, which comprises the steps of using a carboxyl-containing vinyl monomer and a cyano-containing vinyl monomer, grafting on the surface of the semiconductor in the presence of strong acid and an initiator, spontaneously hydrolyzing most of cyano groups into amide groups after grafting to obtain a polymer molecular chain containing carboxyl groups and cyano groups or amide groups grafted on the surface of the semiconductor, and then carrying out dehydration condensation on the carboxyl groups and the cyano groups or the amide groups through annealing treatment, so as to prepare an organic polymer film with a three-dimensional space crosslinking structure, wherein the organic polymer film is formed by intramolecular cyclization of the carboxyl groups and the cyano groups or the amide groups and intermolecular crosslinking of the carboxyl groups and the cyano groups or the amide groups on the surface of a semiconductor substrate.
In a preferred embodiment, the carboxyvinyl monomer is any one of acrylic acid, methacrylic acid and cinnamic acid; the cyano-containing vinyl monomer is acrylonitrile or methacrylonitrile.
Preferably, the surface grafting temperature is 10-40 ℃, and the concentration ratio of the carboxyl vinyl monomer to the cyanovinyl monomer is 3: 9-1.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:
(1) the invention uses the reagents containing carboxyl vinyl monomer and cyano vinyl monomer to graft on the surface of a semiconductor, most of the cyano groups are spontaneously hydrolyzed into amide groups after grafting, thus obtaining a polymer molecular chain containing carboxyl groups and cyano groups or amide groups on the surface of a semiconductor substrate, then carrying out annealing treatment to carry out dehydration condensation on the carboxyl groups and the cyano groups or the amide groups, and preparing an imide-based organic polymer film which has a three-dimensional space cross-linking structure and is formed by intramolecular cyclization of the carboxyl groups and the cyano groups or the amide groups and intermolecular cross-linking of the carboxyl groups and the cyano groups or the amide groups on the surface of the substrate in situ, thereby improving the structure that most of polymer film layers obtained by the traditional grafting method are comb-shaped or linear and improving various performances of the film.
Drawings
FIG. 1 is a flow chart of a method for preparing a copolymerized crosslinked organic polymer on a semiconductor surface according to the present invention;
FIG. 2 is a schematic diagram of the preparation of a co-crosslinked organic polymer on the surface of a semiconductor;
FIG. 3 is a flowchart illustrating the detailed procedure A1 in FIG. 1;
FIG. 4 is an attenuated total reflection micro-IR spectrum of the original film and the two groups of films after the heat treatment in example 2;
FIG. 5 is an infrared difference spectrum analysis of the two sets of films after heat treatment and the original film in example 2;
FIG. 6 is a comparison graph of the thermogravimetric analysis of the original film and the two groups of films after heat treatment in example 2;
FIG. 7 is a graph showing a comparison of dielectric constants of polymer films in example 2;
FIG. 8 is a graph of dielectric loss versus polymer film of example 2;
description of reference numerals: 1-a semiconductor substrate; 2-a carboxyl-containing segment in the polymer molecular chain; 3-a cyano-or amido-containing segment in the polymer molecular chain; 4-annealing treatment; intramolecular cyclization of the 5-carboxyl group with the cyano or amide group; intermolecular crosslinking of 6-carboxyl groups with cyano or amide groups.
Detailed Description
The method for preparing the copolymerized organic polymer film on the surface of the semiconductor, which is provided by the invention, is further described in detail with reference to the accompanying drawings and specific examples. Advantages and features of the present invention will become apparent from the following description and from the claims.
Example 1
Referring to fig. 1, in one embodiment, a method for preparing a co-crosslinked organic polymer on a semiconductor surface, the semiconductor substrate being silicon, germanium or gallium arsenide, the method comprising:
a1: carrying out copolymerization and grafting on the surface of a semiconductor substrate, placing the semiconductor substrate in a grafting solution containing a cyano vinyl monomer and a carboxyl vinyl monomer, grafting at the grafting temperature of 10-40 ℃ for 15-120 min, so that the carboxyl vinyl monomer and the cyano vinyl monomer are grafted on the surface of the semiconductor substrate, and after grafting, most of cyano groups are spontaneously hydrolyzed into amide groups, so that a polymer film grafted with carboxyl groups and cyano groups or amide groups is obtained on the surface of the semiconductor;
a2: and (B) annealing, namely annealing the sample obtained in the step A1, keeping the temperature at 150-300 ℃, keeping the temperature for 30-180 min, and performing dehydration condensation on carboxyl and cyano groups or carboxyl and acylamino to prepare the imide-based organic polymer film with a three-dimensional cross-linking structure, wherein the imide-based organic polymer film is formed by intramolecular cyclization of carboxyl and cyano groups or acylamino and intermolecular cross-linking of carboxyl and cyano groups and acylamino on the surface of the semiconductor substrate in situ.
Preferably, the annealing treatment process is to heat the sample to the heat preservation temperature along with the furnace, the temperature rise rate is 5-10 ℃/min, or the sample can be directly put into a high-temperature furnace with the heat preservation temperature, then the heat preservation is carried out, and finally the sample is cooled to the room temperature along with the furnace or taken out for air cooling. Preferably, the atmosphere of the annealing treatment may be air, nitrogen or argon.
Referring to fig. 2, a schematic of the preparation of a co-crosslinked organic polymer on a semiconductor surface is shown: the preparation method comprises the steps of carrying out copolymerization grafting on the surface of a semiconductor substrate 1 by using a reagent containing a carboxyl vinyl monomer and a cyano vinyl monomer to obtain a polymer film of which the surface contains a carboxyl group chain segment 2 and a cyano group or amido group chain segment 3, then carrying out dehydration condensation on carboxyl and cyano groups or carboxyl and amido groups through annealing treatment 4, and preparing a film with a three-dimensional space crosslinking structure, wherein the film is formed by intramolecular cyclization 5 of carboxyl and cyano groups or amido groups and intermolecular crosslinking 6 of carboxyl and cyano groups or amido groups, on the surface of the semiconductor substrate 1 in situ, so that the structure of most of polymer films obtained by the traditional grafting method in a comb shape or a linear shape is improved.
The method provided by the embodiment can realize in-situ preparation of the imide (five-membered ring or six-membered ring, namely, a cross-linked structure) film with a three-dimensional cross-linked structure on the surface of the semiconductor substrate. The PMI structure is known to those skilled in the art to have good mechanical properties and heat resistance, so that the performance of the polymer film with the imide structure prepared on the surface of the semiconductor substrate in the embodiment is greatly improved, the product quality is improved, and the prepared organic film has high mechanical strength, heat resistance and corrosion resistance, and also has low dielectric constant and dielectric loss, and can be used as an insulating layer or a passivation layer in semiconductor manufacturing.
In the manufacturing process of the semiconductor microstructure polymer layer, the nano-scale precision-controllable organic insulating film is prepared, the surface smoothness is improved in the cross-linking cyclization process, the surface roughness of the organic film is greatly reduced, and the planarization of the surface of the film has great significance for the production and application of electronic products.
Further, referring to fig. 3, step a1 specifically includes:
a101: cleaning a semiconductor substrate, namely sequentially ultrasonically cleaning the semiconductor substrate by adopting acetone, alcohol and deionized water at the temperature of 10-40 ℃, wherein the cleaning time is 5-15 min each time;
a102: the method comprises the following steps of (1) pretreating the surface of a semiconductor substrate, namely soaking the semiconductor substrate in a fluorine-containing reagent for 5-10 min at the soaking temperature of 10-40 ℃, then cleaning with deionized water, and drying, wherein hydrofluoric acid etches the semiconductor substrate in the process, and electrons and hydrogen ions or hydrogen atoms are released;
a103: preparing a grafting solution;
a104: carrying out copolymerization and grafting on the surface of a semiconductor substrate, placing a semiconductor substrate in the solution prepared in the step A103, wherein the grafting temperature is 10-40 ℃, the grafting time is 15-120 min, and then washing and drying with deionized water;
wherein step a103 may be performed at any time prior to step a 104.
Specifically, the method for preparing the grafting solution in the step A103 comprises the steps of adding 0.05-1 g of anionic surfactant, 0.5-5 mL of inorganic acid, 0.5-5 mL of acid or salt containing fluorine ions, 0.5-10 mL of reagent of vinyl monomers and 0.05-0.5 g of aromatic diazonium salt into 100mL of deionized water; aromatic diazonium salts as free radical polymerization initiators.
The vinyl monomer specifically comprises a carboxyl vinyl monomer, a cyano vinyl monomer and an amido vinyl monomer; the ratio of the carboxyl vinyl monomer to the cyanovinyl monomer is 3: 9-1. In the preparation of a crosslinked film, an amide group is not supplied as a separate amide group because the grafting efficiency in an aqueous solution is low, and the amide group can be used as an additive to a carboxyl group and cyano group monomer.
Preferably, the anionic surfactant is any one of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate or sodium dodecyl sulfate; the inorganic acid is any one of hydrochloric acid, sulfuric acid, nitric acid and fluoboric acid; the fluorine-containing ion acid or salt is hydrofluoric acid or ammonium fluoride or sodium fluoride; the aromatic diazonium salt can be selected from p-nitrobenzene tetrafluoroborate diazonium salt and hydroxybenzene tetrafluoroborate diazonium salt.
Preferably, the carboxyvinyl monomer is any one of acrylic acid, methacrylic acid and cinnamic acid.
Preferably, the cyanovinyl monomer is acrylonitrile or methacrylonitrile.
Preferably, the fluorine-containing reagent in step a102 is an aqueous solution of hydrofluoric acid, fluoroboric acid, or ammonium fluoride.
Example 2
The embodiment relates to a method for preparing a copolymerized and crosslinked organic polymer on the surface of a silicon wafer, which comprises the following specific steps:
step 1): ultrasonic cleaning is carried out on the silicon wafer by using acetone, alcohol and deionized water respectively, the cleaning time is 15 minutes respectively, and the silicon wafer is taken out and dried by using nitrogen for standby;
step 2): placing the silicon wafer in HF solution with the volume ratio concentration of 3% for Si-H treatment, and soaking for 5 min;
step 3): taking the silicon wafer out of the HF solution, washing the silicon wafer by using a large amount of deionized water, and drying the silicon wafer by using nitrogen to obtain a uniform Si-H surface;
step 4): the grafting solution was prepared as follows: firstly, 100mL of deionized water is added into a polytetrafluoroethylene container, then 0.1g of sodium dodecyl sulfate, 1mL of hydrochloric acid, 1mL of hydrofluoric acid, 1mL of methacrylic acid, 1mL of acrylonitrile and 0.1g of p-nitrophenyltetrafluoroborate diazonium salt are sequentially added under magnetic stirring, the mixture is stirred for 20 minutes and then stands to obtain a clear solution, and then the silicon wafer cleaned in the step 3) is placed into a prepared grafting solution to carry out grafting reaction at the room temperature of 25 ℃ for 30 minutes.
Step 5): and taking the grafted silicon wafer out of the grafting solution, cleaning the silicon wafer by using a large amount of plasma water, and then blowing the silicon wafer by using nitrogen.
Step 6): placing the grafted silicon wafer in a heat treatment furnace in an argon atmosphere, heating along with the furnace, keeping the temperature for 1 hour at the temperature rising rate of 5 ℃/min and the temperature of 200 ℃, and cooling by adopting furnace cooling; a set of crosslinked organic polymer films is obtained on the surface of the silicon wafer.
Repeating the steps 1-5, then placing the grafted silicon wafer in a heat treatment furnace in an argon atmosphere, heating along with the furnace, keeping the temperature at 300 ℃ for 1 hour at the heating rate of 5 ℃/min, and cooling by adopting furnace cooling. Another set of crosslinked organic polymer films is obtained on the surface of the silicon wafer.
The existing two-dimensional structure polymer film (original film in the figure) and the two groups of polymer films after heat treatment are respectively subjected to infrared spectrum analysis, fig. 4 shows the attenuated total reflection micro-infrared spectrum analysis, and fig. 5 shows the difference spectrum analysis of the two groups of heat-treated films and the original film. Infrared difference spectrum analysis shows that the infrared peak position of the generated imide ring is 1550cm-1And 1376cm-1. Other major absorption peaks (original film): CH (CH)3/CH2Is 2922cm-1And 2853cm-1And C is 1657cm ═ O-1The benzene ring is1596cm-1,NO2Is 1510 and 1342cm-1,CH2Is 1458cm-1. Analysis showed that the film after heat treatment contained an imide ring structure, i.e., the organic polymer film obtained in this example had an imide structure.
The thermogravimetric analysis was carried out on the original film and the two groups of films after heat treatment, respectively, i.e. fig. 6, from which it can be seen that the temperatures at which the three groups of films start to lose mass are: the original film is 147 ℃, the film after heat treatment at 200 ℃ is 254 ℃, and the film after heat treatment at 300 ℃ is 328 ℃, so that the heat resistance of the film after heat treatment is improved. Therefore, the heat resistance of the copolymerized crosslinked organic polymer film obtained in this example was greatly improved.
Dielectric properties of the polymer film were measured using an ellipsometer, fig. 7 is a dielectric constant, and fig. 8 is a dielectric loss, and it can be seen from the graph that the heat-treated film reduced the dielectric constant and the dielectric loss of the original film. Therefore, the three-dimensional cross-linked structure thin film obtained in this example has a low dielectric constant and low dielectric loss, and can be used as an insulating layer or a passivation layer in semiconductor manufacturing.
Example 3
The embodiment relates to a method for preparing a copolymerized and crosslinked organic polymer insulating layer on the surface of a silicon wafer, which comprises the following specific steps:
step 1): ultrasonic cleaning is carried out on the silicon wafer by using acetone, alcohol and deionized water respectively, the cleaning time is 15 minutes respectively, and the silicon wafer is taken out and dried by using nitrogen for standby;
step 2): placing the silicon wafer on NH with the volume ratio concentration of 5%4Carrying out Si-H treatment in the solution F for 15 min;
step 3): taking the silicon wafer out of the HF solution, washing the silicon wafer by using a large amount of deionized water, and drying the silicon wafer by using nitrogen to obtain a uniform Si-H surface;
step 4): the grafting solution was prepared as follows: firstly, 100mL of deionized water is added into a polytetrafluoroethylene container, then 0.1g of sodium dodecyl sulfate, 1mL of concentrated sulfuric acid, 1mL of hydrofluoric acid, 1mL of methacrylic acid, 1mL of methacrylonitrile and 0.1g of p-nitrophenyltetrafluoroboric acid diazonium salt are sequentially added under magnetic stirring, stirred for 20 minutes and then kept stand to obtain a clear solution, and then the silicon wafer cleaned in the step 3) is placed into a prepared grafting solution, and a grafting reaction is carried out at room temperature of 25 ℃ for 60 minutes.
Step 5): and taking the grafted silicon wafer out of the grafting solution, cleaning the silicon wafer by using a large amount of plasma water, and then blowing the silicon wafer by using nitrogen.
Step 6): and (3) placing the grafted silicon wafer in a heat treatment furnace in an argon atmosphere, heating along with the furnace, keeping the temperature for 1 hour at the temperature rising rate of 5 ℃/min and the temperature of 200 ℃, and cooling by adopting furnace cooling. A crosslinked organic polymer film is obtained on the surface of the silicon wafer.
Example 4
The embodiment relates to a method for preparing a high-performance copolymerized crosslinked organic polymer insulating layer on the surface of a silicon wafer, which comprises the following specific steps:
step 1): ultrasonic cleaning is carried out on the silicon wafer by using acetone, alcohol and deionized water respectively, the cleaning time is 15 minutes respectively, and the silicon wafer is taken out and dried by using nitrogen for standby;
step 2): placing the silicon wafer in an HF solution with the volume ratio concentration of 5% for Si-H treatment, and soaking for 5 min;
step 3): taking the silicon wafer out of the HF solution, washing the silicon wafer by using a large amount of deionized water, and drying the silicon wafer by using nitrogen to obtain a uniform Si-H surface;
step 4): the preparation method of the grafting solution comprises the following steps: firstly, 100mL of deionized water is added into a polytetrafluoroethylene container, then 0.1g of sodium dodecyl sulfate, 1mL of hydrochloric acid, 1mL of hydrofluoric acid, 1mL of methacrylic acid, 1mL of methacrylonitrile, 0.1g of acrylamide and 0.1g of p-nitrophenyltetrafluoroborate diazonium salt are sequentially added under magnetic stirring, the mixture is stirred for 20 minutes and then stands to obtain a clear solution, then the silicon wafer cleaned in the step 3) is placed into a prepared grafting solution, and grafting reaction is carried out at room temperature of 25 ℃, and the grafting time is 60 minutes.
Step 5): and taking the grafted silicon wafer out of the grafting solution, cleaning the silicon wafer by using a large amount of plasma water, and then blowing the silicon wafer by using nitrogen.
Step 6): and (3) placing the grafted silicon wafer in a heat treatment furnace in an argon atmosphere, heating along with the furnace, keeping the temperature for 1 hour at the temperature rising rate of 5 ℃/min and the temperature of 200 ℃, and cooling by adopting furnace cooling. A crosslinked organic polymer film is obtained on the surface of the silicon wafer.
As can be seen from the above embodiments, the present invention provides a method for preparing a copolymerized crosslinked organic polymer on a semiconductor surface, which comprises grafting a carboxyl-containing vinyl monomer and a cyano-containing vinyl monomer onto a semiconductor surface in the presence of a strong acid and an initiator, wherein after grafting, most of the cyano groups are spontaneously hydrolyzed into amide groups to obtain polymer molecular chains containing carboxyl groups and cyano groups or amide groups grafted onto the semiconductor surface, and then annealing to dehydrate and condense the carboxyl groups and the cyano groups or the carboxyl groups and the amide groups, thereby preparing an organic polymer film having a three-dimensional crosslinked structure in which intramolecular cyclization of the carboxyl groups and the cyano groups or the amide groups or intermolecular crosslinking of the carboxyl groups and the cyano groups or the amide groups is performed on the surface of a semiconductor substrate in situ.
The carboxyl vinyl monomer is preferably any one of acrylic acid, methacrylic acid and cinnamic acid; the cyano-containing vinyl monomer is preferably acrylonitrile or methacrylonitrile; the temperature of surface grafting is 10-40 ℃, and the concentration ratio of the carboxyl vinyl monomer to the cyanovinyl monomer is 3: 9-1.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments. Even if various changes are made to the present invention, it is still within the scope of the present invention if they fall within the scope of the claims of the present invention and their equivalents.
Claims (11)
1. A method for preparing a copolymerized and crosslinked organic polymer on the surface of a semiconductor, which is characterized by comprising the following steps:
a1: copolymerization and grafting on the surface of a semiconductor substrate: placing the semiconductor substrate in a grafting solution containing a cyano vinyl monomer and a carboxyl vinyl monomer for grafting reaction, wherein most of cyano groups are spontaneously hydrolyzed into an amide group after grafting;
a2: annealing treatment: and B, annealing the sample obtained in the step A1 to enable the carboxyl and the amido or the carboxyl and the cyano of the grafting monomer to be subjected to dehydration condensation, and keeping the temperature at 150-300 ℃ for 30-180 min to obtain the polymer film containing the imide structure.
2. The method for preparing a copolymerized and crosslinked organic polymer on the surface of a semiconductor according to claim 1, wherein the step a1 specifically comprises:
a101: cleaning a semiconductor substrate: sequentially carrying out ultrasonic cleaning on the semiconductor substrate by adopting acetone, alcohol and deionized water at the temperature of 10-40 ℃, wherein the cleaning time is 5-15 min each time;
a102: semiconductor substrate surface pretreatment: soaking the semiconductor substrate in a fluorine-containing reagent for 5-10 min at the soaking temperature of 10-40 ℃, then washing with deionized water, and drying;
a103: copolymerization and grafting on the surface of a semiconductor substrate: and placing the semiconductor substrate in a prepared grafting solution, wherein the grafting temperature is 10-40 ℃, the grafting time is 15-120 min, and then cleaning with deionized water and drying.
3. The method for preparing a copolymerized and crosslinked organic polymer on the surface of a semiconductor according to claim 2, wherein the step of preparing the grafting solution is to add 0.05 to 1g of anionic surfactant, 0.5 to 5mL of inorganic acid, 0.5 to 5mL of acid or salt containing fluorine ions, 0.5 to 10mL of reagent containing vinyl monomers, and 0.05 to 0.5g of aromatic diazonium salt to 100mL of deionized water;
the vinyl monomer is selected from one or more of carboxyl vinyl monomer, cyano vinyl monomer and amido vinyl monomer, and the concentration ratio of the carboxyl vinyl monomer to the cyano vinyl monomer is 3: 9-1.
4. The method for preparing the copolymerized and crosslinked organic polymer on the surface of the semiconductor of claim 3, wherein the carboxyl vinyl monomer is any one of acrylic acid, methacrylic acid and cinnamic acid.
5. The method for preparing a copolymerized crosslinked organic polymer on the surface of a semiconductor according to claim 3, wherein the cyanovinyl monomer is acrylonitrile or methacrylonitrile.
6. The method for preparing the copolymerized and crosslinked organic polymer on the surface of the semiconductor of claim 2, wherein the fluorine-containing reagent in step a102 is an aqueous solution of hydrofluoric acid, fluoroboric acid or ammonium fluoride.
7. The method for preparing the copolymerized and crosslinked organic polymer on the surface of the semiconductor according to claim 1, wherein the annealing treatment comprises heating the sample to a holding temperature with a furnace at a heating rate of 5-10 ℃/min, holding the temperature, and finally cooling with the furnace or taking out for air cooling; or
Directly putting the sample into a high-temperature furnace with the heat preservation temperature, preserving the heat, and finally cooling along with the furnace or taking out for air cooling.
8. The method for preparing the copolymerized and crosslinked organic polymer on the surface of the semiconductor of claim 1, wherein the annealing atmosphere is air, argon or nitrogen.
9. A method for preparing a copolymerized and crosslinked organic polymer on the surface of a semiconductor is characterized in that a vinyl monomer containing carboxyl and a vinyl monomer containing cyano are used, grafting is carried out on the surface of the semiconductor in the presence of strong acid and an initiator, most of the cyano is spontaneously hydrolyzed into amide after grafting, a polymer molecular chain containing a carboxyl group and a cyano or amide group is obtained, the polymer molecular chain is grafted on the surface of the semiconductor and is subjected to dehydration condensation of the carboxyl and the cyano or the amide, or the carboxyl and the amide, and an organic polymer film with a three-dimensional space crosslinking structure, wherein the organic polymer film is formed by intramolecular cyclization of the carboxyl and the cyano or the amide and intermolecular crosslinking of the carboxyl and the cyano or the amide, is prepared on the surface of a semiconductor substrate in situ.
10. The method for preparing the copolymerized and crosslinked organic polymer on the surface of the semiconductor of claim 9, wherein the carboxyl vinyl monomer is any one of acrylic acid, methacrylic acid and cinnamic acid; the cyano-containing vinyl monomer is acrylonitrile or methacrylonitrile.
11. The method for preparing the copolymerized and crosslinked organic polymer on the surface of the semiconductor according to claim 9, wherein the temperature of surface grafting is 10-40 ℃, and the concentration ratio of the carboxyl vinyl monomer to the cyanovinyl monomer is 3: 9-1.
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