CN109880027A - A kind of method that semiconductor surface prepares crosslinking copolymerization organic polymer - Google Patents
A kind of method that semiconductor surface prepares crosslinking copolymerization organic polymer Download PDFInfo
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Abstract
The invention discloses a kind of methods that semiconductor surface prepares copolymerization organic polymer thin film, this method comprises: A1: the grafting solution that the semiconductor chip is placed in cyano-containing vinyl monomer and carboxy vinyl base class monomer semiconductor substrate surface copolymerized grafting: being carried out graft reaction, after grafting, most of cyano spontaneous hydrolysis are amide groups；A2: annealing makes annealing treatment sample obtained by the step A1, and holding temperature is 150~300 DEG C, and soaking time is 30~180min, obtains the thin polymer film containing imide structure.The film with three-dimensional space cross-linked structure is prepared in situ in semiconductor substrate surface in the present invention, improves the structure that the polymer film that traditional Graft Method obtains is mostly " comb shape " or " linear ", improves the performance of existing organic film two-dimensional structure.
Description
Technical field
The invention belongs to the technical field of organic insulator more particularly to a kind of semiconductor surface are prepared in semiconductor surface
The method for preparing crosslinking copolymerization organic polymer.
Background technique
The 3D stacked electronic encapsulation technology being interconnected by semiconductor through hole is one of following most important packing forms.
In semiconductor microactuator channel insulation technology, existing insulating layer mainly includes the inorganic insulation layers such as silica, silicon nitride and organic
Insulating layer.Organic insulator have dielectric constant is low, elasticity modulus is small, it is simple to prepare, it is at low cost, can be used as stress-buffer layer etc.
Advantage has great application prospect in semiconductor fabrication.But prior art is difficult to realize in the microchannel of big depth-to-width ratio
The controllable insulating layer of middle spin coating thickness.This is because with the reduction in microchannel aperture and the increase of depth, traditional spin-coating method without
Method screws out organic matter effectively, or even can block microchannel, and organic film obtained by spin-coating method is micron order thickness.With electronics
The reduction of device size, all kinds of complexity microchannels are gradually promoted for preparing the requirement of precision, are occurred with chemical vapor deposition
Based on film preparation mode.By controlling presoma, specific inorganic, organic film can be prepared in substrate surface.Simultaneously etc.
The use of gas ions enhancing chemical vapor deposition has further expanded its application.However, these chemical vapour deposition techniques are big
Have the defects that film thickness distribution is uneven, step coverage is low in the complicated microchannel of depth-to-width ratio.
In order to meet the needs of nano high-precision manufacture, and is obtained in all kinds of complicated microchannels and shape good insulation
Layer gradually develops the method for obtaining organic insulator using grafting method, such as using electricity grafting poly 4 vinyl pyridine
(P4VP), polymethyl methacrylate (PMMA) or polyacrylic acid (PAA) etc. cover one layer of organic film as insulation in silicon face
Layer uses.However, the film that this kind of grafting is formed is usually " combed " or " line style " structure, both without physics between adjacent molecule chain
Winding effect, is also connected without chemical bond, be easy to cause film thermodynamic property weak.
Summary of the invention
The technical problem to be solved in the present invention is to provide the sides that a kind of semiconductor surface prepares copolymerization organic polymer thin film
Method.This method can obtain the thin polymer film containing imide structure, change " combed " or " line of existing organic polymer thin film
Type " structure improves the performance of film.
To solve the above problems, the technical solution of the present invention is as follows:
A kind of method that semiconductor surface prepares crosslinking copolymerization organic polymer, comprising:
A1: semiconductor substrate surface copolymerized grafting: by the semiconductor chip be placed in cyano-containing vinyl monomer and
The grafting solution of carboxy vinyl base class monomer carries out graft reaction, and after grafting, most of cyano spontaneous hydrolysis are amide groups；
A2: annealing: carrying out annealing to sample obtained by the step A1 makes the carboxyl and amide groups of grafted monomers
Or carboxyl and cyano dehydrating condensation, holding temperature are 150~300 DEG C, soaking time is 30~180min, is obtained containing acid imide
The thin polymer film of structure.
Specifically, the step A1 is specifically included:
A101: semiconductor base cleaning: under the conditions of temperature is 10~40 DEG C, using acetone, alcohol and deionized water pair
The semiconductor base is successively cleaned by ultrasonic, and each scavenging period is 5~15min；
A102: semiconductor substrate surface pretreatment: the semiconductor base is immersed in fluorine-containing reagent, soaking time 5
~10min, 10~40 DEG C of soaking temperature, then deionized water is cleaned, dry；
A103: the semiconductor chip: being placed in the grafting solution of configuration by semiconductor substrate surface copolymerized grafting, grafting
10~40 DEG C of temperature, 15~120min of grafting time, then deionized water is cleaned, dry.
Preferably, configuring the grafting solution is specially that 0.05~1g anionic surface is added in 100ml deionized water
Activating agent, 0.5~5ml inorganic acid, the acid of 0.5~5ml fluoride ion or salt, 0.5~10mL vinyl monomer reagent,
0.05~0.5g aromatic diazo salt；
Wherein, the vinyl monomer is selected from carboxy vinyl base class monomer, cyano vinyl base class monomer, amide groups ethylene
The one or more of base class monomer, and the concentration ratio of the carboxy vinyl base class monomer and the cyano vinyl base class monomer is
3:9~1.
Preferably, the carboxy vinyl base class monomer is acrylic acid, methacrylic acid, any one in cinnamic acid.
Preferably, the cyano vinyl base class monomer is acrylonitrile or methacrylonitrile.
Preferably, the fluorine-containing reagent in the step A102 is the aqueous solution of hydrofluoric acid, fluoboric acid or ammonium fluoride.
Preferably, the annealing process is by sample with stove heating to holding temperature, and heating rate is 5~10 DEG C/min,
Then it keeps the temperature, last furnace cooling or taking-up are air-cooled；Or
Sample is directly introduced to arrive in the high temperature furnace of holding temperature, is then kept the temperature, last furnace cooling or taking-up are empty
It is cold.
Preferably, the atmosphere of the annealing is air, argon gas or nitrogen.
The present invention also provides a kind of methods that semiconductor surface prepares crosslinking copolymerization organic polymer, use second containing carboxyl
Alkenyl class monomer and cyano-containing vinyl monomer are grafted in the presence of strong acid and initiator in semiconductor surface, grafting
Afterwards, most of cyano spontaneous hydrolysis are amide groups, obtain be grafted on semiconductor surface containing carboxylic group and cyano or amide
Then the polymer molecular chain of base group is dehydrated carboxyl and cyano dehydrating condensation or carboxyl and amide groups by annealing
Condensation prepares carboxyl and cyano or amide groups intramolecular cyclization, carboxyl and cyano or amide in the surface in situ of semiconductor base
The organic polymer thin film with three-dimensional space cross-linked structure of base intermolecular cross-linking.
In preferred embodiment, the carboxy vinyl base class monomer is acrylic acid, methacrylic acid, any one in cinnamic acid
Kind；The cyano-containing vinyl monomer is acrylonitrile or methacrylonitrile.
Preferably, 10~40 DEG C of the temperature of surface grafting, the carboxy vinyl base class monomer and the cyano vinyl base class
The concentration ratio of monomer is 3:9~1.
The present invention due to using the technology described above, makes it have the following advantages that and actively imitate compared with prior art
Fruit:
(1) present invention is using the reagent of the monomer of base class containing carboxy vinyl and cyano-containing vinyl monomer in semiconductor surface
It is grafted, most of cyano spontaneous hydrolysis are amide groups after grafting, therefore semiconductor substrate surface acquisition contains carboxylic group
With the polymer molecular chain of cyano or amide group, carboxyl and cyano dehydrating condensation or carboxyl are then made by annealing
With amide groups dehydrating condensation, substrate surface be prepared in situ carboxyl and cyano or amide groups intramolecular cyclization, carboxyl and cyano or
The imide organic polymer thin film with three-dimensional space cross-linked structure of amide groups intermolecular cross-linking, improves traditional grafting
The polymer film that method obtains is mostly the structure of " comb shape " or " linear ", improves the properties of film.
Detailed description of the invention
Fig. 1 prepares the method flow diagram of crosslinking copolymerization organic polymer in semiconductor surface for the present invention；
Fig. 2 is to realize that semiconductor surface prepares the schematic diagram of crosslinking copolymerization organic polymer；
Fig. 3 is the specific steps flow chart of A1 in Fig. 1；
Fig. 4 is that original membrane and the decaying of two cluster films after the completion of heat treatment are totally reflected micro ft-ir spectroscopy in embodiment 2
Analysis of spectra；
Fig. 5 is that the Infrared Difference Spectrum of two cluster films and original membrane after being heat-treated in embodiment 2 is analyzed；
Fig. 6 is that original membrane and two cluster films after heat treatment carry out thermogravimetic analysis (TGA) comparison diagram respectively in embodiment 2；
Fig. 7 is the dielectric constant comparison diagram of thin polymer film in embodiment 2；
Fig. 8 is the dielectric loss comparison diagram of thin polymer film in embodiment 2；
Description of symbols: 1- semiconductor base；Segment containing carboxyl in 2- polymer molecular chain；3- polymer molecular chain
In cyano-containing or amide groups segment；4- annealing；The intramolecular cyclization of 5- carboxyl and cyano or amide groups；6- carboxyl and cyanogen
The intermolecular cross-linking of base or amide groups.
Specific embodiment
Below in conjunction with the drawings and specific embodiments to a kind of semiconductor surface preparation copolymerization organic polymer proposed by the present invention
The method of object film is described in further detail.According to following explanation and claims, advantages and features of the invention will more
It is clear.
Embodiment 1
Referring to Fig. 1, in one embodiment, a kind of method that semiconductor surface prepares crosslinking copolymerization organic polymer, half
Conductor substrate can make silicon, germanium or GaAs, this method comprises:
A1: semiconductor substrate surface copolymerized grafting, by the semiconductor chip be placed in cyano-containing vinyl monomer and
The grafting solution of carboxy vinyl base class monomer, 10~40 DEG C of grafting temperature, 15~120min of grafting time makes carboxy vinyl list
Body and cyano vinyl base class monomer are grafted in semiconductor substrate surface, and after grafting, most of cyano spontaneous hydrolysis are amide
Base, then semiconductor surface obtains thin polymer film of the grafting containing carboxylic group and cyano or amide group；
A2: annealing makes annealing treatment sample obtained by step A1, and holding temperature is 150~300 DEG C, when heat preservation
Between be 30~180min, make carboxyl and cyano dehydrating condensation or carboxyl and amide groups dehydrating condensation, on the surface of semiconductor base
Carboxyl and cyano or amide groups intramolecular cyclization, carboxyl and cyano is prepared in situ with amide groups intermolecular cross-linking with three-dimensional space
Between cross-linked structure imide organic polymer thin film.
Preferably, annealing process is by sample with stove heating to holding temperature, and heating rate is 5~10 DEG C/min,
Sample can also be directly introduced to arrive in the high temperature furnace of holding temperature, then kept the temperature, last furnace cooling to room temperature or
It takes out air-cooled.Preferably, the atmosphere of annealing can be air, nitrogen or argon gas.
Referring to Fig. 2, it illustrates the schematic diagrames that semiconductor surface prepares crosslinking copolymerization organic polymer: using second containing carboxyl
The reagent of alkenyl class monomer and cyano-containing vinyl monomer carries out copolymerized grafting on 1 surface of semiconductor base, obtains surface and contains
There are carboxylic group segment 2 and the thin polymer film containing cyano or amide group segment 3, carboxylic is then made by annealing 4
Base and cyano dehydrating condensation or carboxyl and amide groups dehydrating condensation, 1 surface in situ of semiconductor base prepare carboxyl and cyano or
The film with three-dimensional space cross-linked structure of amide groups intramolecular cyclization 5, carboxyl and cyano or amide groups intermolecular cross-linking 6,
Improve the structure that the polymer film that traditional Graft Method obtains is mostly " comb shape " or " linear ".
The method that this example provides may be implemented in semiconductor substrate surface and be prepared in situ with three-dimensional space cross-linked structure
Imide (five yuan or hexatomic ring, that is, cross-linked structure) film.Imide structure, i.e. PMI structure, those skilled in the art are equal
Know that PMI has good mechanical performance and heat resistance, therefore there is acyl prepared by semiconductor substrate surface for the present embodiment
The polymer film performance of imine structure has a distinct increment, and improves product quality, and the organic film of preparation is with higher mechanical strong
Degree, heat resistance, corrosion resistance, while also there is lower dielectric constant and dielectric loss, it can be used as the insulation in semiconductors manufacture
Layer or passivation layer.
For the present embodiment in the manufacturing process for realizing Semiconductor microstructure polymeric layer, being not only prepared for nano-precision can
The organic insulating film of control improves profile pattern simultaneously in crosslinking cyclization process, significantly reduces the surface of organic film
The planarization of roughness, film surface has greater significance to the production application of electronic product.
Further, referring to Fig. 3, step A1 is specifically included:
A101: semiconductor base cleaning, under the conditions of temperature is 10~40 DEG C, using acetone, alcohol and deionized water pair
Semiconductor base is successively cleaned by ultrasonic, and each scavenging period is 5~15min；
A102: semiconductor base is immersed in fluorine-containing reagent by semiconductor substrate surface pretreatment, and soaking time 5~
10min, 10~40 DEG C of soaking temperature, then deionized water is cleaned, dry, hf etching semiconductor base during this, and
It releases electronics and hydrogen ion or releases hydrogen atom；
A103: configuration grafting solution；
A104: semiconductor chip is placed in the solution of the step A103 configuration by semiconductor substrate surface copolymerized grafting,
10~40 DEG C of grafting temperature, 15~120min of grafting time, then deionized water is cleaned, dry；
Wherein, step A103 can be carried out in any time before step A104.
Specifically, the method that step A103 configures grafting solution is specially that 0.05~1g is added in 100ml deionized water
Anionic surfactant, 0.5~5ml inorganic acid, the acid of 0.5~5ml fluoride ion or the vinyl-based list of salt, 0.5~10mL
Reagent, the 0.05~0.5g aromatic diazo salt of body；Aromatic diazo salt is as radical polymerization initiator.
Wherein, vinyl monomer specifically includes carboxy vinyl base class monomer, cyano vinyl base class monomer, amide groups second
Alkenyl class monomer；The ratio of carboxy vinyl base class monomer and cyano vinyl base class monomer is 3:9~1.Amide groups is in crosslinked film
Preparation in, since grafting efficiency in aqueous solution is very slow, can not as individual amide groups supply, can be used as carboxyl and cyanogen
The additive of base monomer uses, and amide groups vinyl monomer is preferably acrylamide.
Preferably, anionic surfactant is dodecyl sodium sulfate, neopelex or dodecyl sulphur
Any one in sour sodium；Inorganic acid is hydrochloric acid, sulfuric acid, nitric acid, any one in fluoboric acid；Fluoride ion acid or salt are hydrogen
Fluoric acid or ammonium fluoride or sodium fluoride；P-nitrophenyl diazonium tetrafluoroborate, hydroxy benzenes tetrafluoro boric acid weight may be selected in aromatic diazo salt
Nitrogen salt.
Preferably, carboxy vinyl base class monomer is acrylic acid, methacrylic acid, any one in cinnamic acid.
Preferably, cyano vinyl base class monomer is acrylonitrile or methacrylonitrile.
Preferably, the fluorine-containing reagent in step A102 is the aqueous solution of hydrofluoric acid, fluoboric acid or ammonium fluoride.
Embodiment 2
The present embodiment is related to the method for preparing crosslinking copolymerization organic polymer in silicon chip surface, the specific steps are as follows:
Step 1): being respectively cleaned by ultrasonic silicon wafer using acetone, alcohol and deionized water, and scavenging period is respectively 15
Minute, it is spare using being dried with nitrogen after taking-up；
Step 2): Si-Hization processing, soaking time are carried out by being placed in the HF solution that volume by volume concentration is 3% on silicon wafer
5min；
Step 3): silicon wafer is taken out from HF solution, is rinsed and is used using a large amount of deionized waters and is dried with nitrogen, and is obtained uniform
The surface Si-H；
Step 4): grafting solution is formulated as follows: the deionized water of 100mL being added in polytetrafluoroethylcontainer container first, so
Sequentially add the methyl-prop of the dodecyl sodium sulfate of 0.1g, the hydrochloric acid of 1mL, the hydrofluoric acid of 1mL, 1mL under magnetic stirring afterwards
The p-nitrophenyl diazonium tetrafluoroborate of olefin(e) acid, the acrylonitrile of 1mL and 0.1g, stirring are stood after twenty minutes, obtain clear solution,
Then the silicon wafer after step 3) cleaning is placed in configured grafting solution, carries out graft reaction at 25 DEG C of room temperature, connects
Branch time 30min.
Step 5): the silicon wafer that grafting is completed is taken out from grafting solution, is cleaned using a large amount of plasma waters, is then used
It is dried with nitrogen.
Step 6): the silicon wafer that grafting is completed is placed in the heat-treatment furnace of argon atmosphere, with stove heating, heating rate is
5 DEG C/min, 200 DEG C of holding temperature, 1 hour is kept the temperature, it is cooling cold using furnace；Then silicon chip surface obtains one group of organic cross-linked polymeric object
Film.
Step 1-5 is repeated, then the silicon wafer that grafting is completed is placed in the heat-treatment furnace of argon atmosphere, with stove heating,
Heating rate is 5 DEG C/min, 300 DEG C of holding temperature, keeps the temperature 1 hour, cooling cold using furnace.Then silicon chip surface obtains another group of friendship
Join organic polymer thin film.
By two groups of polymer thins after the completion of the thin polymer film (original membrane in figure) of existing two-dimensional structure and heat treatment
Film carries out infrared spectrum analysis respectively, and Fig. 4 presents decaying total reflection micro ft-ir spectroscopy analysis, after Fig. 5 is two groups of heat treatment
Film and original membrane differential spectrum analysis.Infrared Difference Spectrum analysis shows, the infrared peak position 1550cm of the generation of imide ring-1With
1376cm-1.Other major absorbance peaks (original membrane): CH3/CH2For 2922cm-1With 2853cm-1, C=O 1657cm-1, phenyl ring
For 1596cm-1,NO2For 1510 and 1342cm-1,CH2For 1458cm-1.Analysis shows heat treatment after film in contain acid imide
The organic polymer thin film that ring structure, i.e. the present embodiment obtain has imide structure.
Thermogravimetic analysis (TGA), i.e. Fig. 6 are carried out to two cluster films after original membrane and heat treatment respectively, can be obtained from figure, three groups
The temperature that film begins with mass loss is respectively: original membrane is 147 DEG C, and the film after 200 DEG C of heat treatments is 254 DEG C, 300 DEG C
Film after heat treatment is 328 DEG C, it can thus be appreciated that the film heat resistance after heat treatment is promoted.Therefore the embodiment obtains
The heat resistance of crosslinking copolymerization organic polymer thin film be greatly improved.
Using the dielectric properties of ellipsometer test polymer film, Fig. 7 is dielectric constant, and Fig. 8 is dielectric loss, Cong Tuzhong
It is found that the film after heat treatment reduces the dielectric constant and dielectric loss of original membrane.Therefore illustrate the embodiment obtains three
The film for tieing up cross-linked structure has lower dielectric constant and dielectric loss, can be used as the insulating layer or passivation in semiconductors manufacture
Layer.
Embodiment 3
The present embodiment is related to the method for preparing crosslinking copolymerization organic polymer insulating layer in silicon chip surface, and specific steps are such as
Under:
Step 1): being respectively cleaned by ultrasonic silicon wafer using acetone, alcohol and deionized water, and scavenging period is respectively 15
Minute, it is spare using being dried with nitrogen after taking-up；
Step 2): NH of the volume by volume concentration for 5% will be placed on silicon wafer4Si-Hization processing is carried out in F solution, when immersion
Between 15min；
Step 3): silicon wafer is taken out from HF solution, is rinsed and is used using a large amount of deionized waters and is dried with nitrogen, and is obtained uniform
The surface Si-H；
Step 4): grafting solution is formulated as follows: the deionized water of 100mL being added in polytetrafluoroethylcontainer container first, so
Sequentially add under magnetic stirring afterwards the lauryl sodium sulfate of 0.1g, the concentrated sulfuric acid of 1mL, the hydrofluoric acid of 1mL, 1mL methyl
The p-nitrophenyl diazonium tetrafluoroborate of acrylic acid, the methacrylonitrile of 1mL and 0.1g, stirring are stood after twenty minutes, are obtained clear
Then silicon wafer after cleaning in step 3) is placed in configured grafting solution, is connect at 25 DEG C of room temperature by clear solution
Branch reaction, grafting time 60min.
Step 5): the silicon wafer that grafting is completed is taken out from grafting solution, is cleaned using a large amount of plasma waters, is then used
It is dried with nitrogen.
Step 6): the silicon wafer that grafting is completed is placed in the heat-treatment furnace of argon atmosphere, with stove heating, heating rate is
5 DEG C/min, 200 DEG C of holding temperature, 1 hour is kept the temperature, it is cooling cold using furnace.Then it is thin to obtain organic cross-linked polymeric object for silicon chip surface
Film.
Embodiment 4
The present embodiment is related to a kind of method in silicon chip surface preparation high-performance crosslinking copolymerization organic polymer insulating layer, tool
Steps are as follows for body:
Step 1): being respectively cleaned by ultrasonic silicon wafer using acetone, alcohol and deionized water, and scavenging period is respectively 15
Minute, it is spare using being dried with nitrogen after taking-up；
Step 2): the processing of Si-Hization is carried out by being placed in the HF solution that volume by volume concentration is 5% on silicon wafer, soaking time
5min；
Step 3): silicon wafer is taken out from HF solution, is rinsed and is used using a large amount of deionized waters and is dried with nitrogen, and is obtained uniform
The surface Si-H；
Step 4): grafting solution preparation method is as follows: polytetrafluoroethylcontainer container is added in the deionized water of 100mL first
In, the first of the lauryl sodium sulfate of 0.1g, the hydrochloric acid of 1mL, the hydrofluoric acid of 1mL, 1mL is then sequentially added under magnetic stirring
Base acrylic acid, the methacrylonitrile of 1mL, the acrylamide of 0.1g and 0.1g p-nitrophenyl diazonium tetrafluoroborate, stirring 20
It is stood after minute, obtains clear solution, then the silicon wafer after cleaning in step 3) is placed in configured grafting solution,
Graft reaction, grafting time 60min are carried out at 25 DEG C of room temperature.
Step 5): the silicon wafer that grafting is completed is taken out from grafting solution, is cleaned using a large amount of plasma waters, is then used
It is dried with nitrogen.
Step 6): the silicon wafer that grafting is completed is placed in the heat-treatment furnace of argon atmosphere, with stove heating, heating rate is
5 DEG C/min, 200 DEG C of holding temperature, 1 hour is kept the temperature, it is cooling cold using furnace.Then it is thin to obtain organic cross-linked polymeric object for silicon chip surface
Film.
Based on the above embodiments it is found that a kind of semiconductor surface provided by the invention prepares crosslinking copolymerization organic polymer
Method, using the monomer of base class containing carboxy vinyl and cyano-containing vinyl monomer, in the presence of strong acid and initiator, in semiconductor
Surface is grafted, and after grafting, most of cyano spontaneous hydrolysis is amide groups, obtain be grafted on semiconductor surface contain carboxyl
Then the polymer molecular chain of group and cyano or amide group makes carboxyl and cyano dehydrating condensation by annealing, or
Carboxyl and amide groups dehydrating condensation, the surface in situ of semiconductor base prepare carboxyl and cyano or amide groups intramolecular cyclization,
The organic polymer thin film with three-dimensional space cross-linked structure of carboxyl and cyano or amide groups intermolecular cross-linking.
Carboxy vinyl base class monomer is preferably acrylic acid, methacrylic acid, any one in cinnamic acid；Cyano-containing ethylene
Base class monomer is preferably acrylonitrile or methacrylonitrile；10~40 DEG C of the temperature of surface grafting, the carboxy vinyl base class monomer
Concentration ratio with the cyano vinyl base class monomer is 3:9~1.
Embodiments of the present invention are explained in detail above in conjunction with attached drawing, but the present invention is not limited to above-mentioned implementations
Mode.Even if to the present invention, various changes can be made, if these variations belong to the model of the claims in the present invention and its equivalent technologies
Within enclosing, then still fall within the protection scope of the present invention.
Claims (11)
1. a kind of method that semiconductor surface prepares crosslinking copolymerization organic polymer characterized by comprising
A1: the semiconductor chip semiconductor substrate surface copolymerized grafting: is placed in cyano-containing vinyl monomer and carboxyl
The grafting solution of vinyl monomer carries out graft reaction, and after grafting, most of cyano spontaneous hydrolysis are amide groups；
A2: annealing: carrying out annealing to sample obtained by the step A1 makes the carboxyl and amide groups or carboxylic of grafted monomers
Base and cyano dehydrating condensation, holding temperature are 150~300 DEG C, and soaking time is 30~180min, is obtained containing imide structure
Thin polymer film.
2. the method that semiconductor surface according to claim 1 prepares crosslinking copolymerization organic polymer, which is characterized in that institute
Step A1 is stated to specifically include:
A101: semiconductor base cleaning: under the conditions of temperature is 10~40 DEG C, using acetone, alcohol and deionized water to described
Semiconductor base is successively cleaned by ultrasonic, and each scavenging period is 5~15min；
A102: semiconductor substrate surface pretreatment: the semiconductor base is immersed in fluorine-containing reagent, and soaking time 5~
10min, 10~40 DEG C of soaking temperature, then deionized water is cleaned, dry；
A103: the semiconductor chip semiconductor substrate surface copolymerized grafting: is placed in the grafting solution of configuration, grafting temperature
10~40 DEG C, 15~120min of grafting time, then deionized water is cleaned, dry.
3. the method that semiconductor surface according to claim 2 prepares crosslinking copolymerization organic polymer, which is characterized in that match
Set the grafting solution be specially in 100ml deionized water be added 0.05~1g anionic surfactant, 0.5~5ml without
Machine acid, the acid of 0.5~5ml fluoride ion or salt, the reagent of 0.5~10mL vinyl monomer, 0.05~0.5g aromatic diazo
Salt；
Wherein, it is vinyl-based to be selected from carboxy vinyl base class monomer, cyano vinyl base class monomer, amide groups for the vinyl monomer
The one or more of monomer, and the concentration ratio of the carboxy vinyl base class monomer and the cyano vinyl base class monomer is 3:9
~1.
4. the method that semiconductor surface according to claim 3 prepares crosslinking copolymerization organic polymer, which is characterized in that institute
Carboxy vinyl base class monomer is stated as any one in acrylic acid, methacrylic acid, cinnamic acid.
5. the method that semiconductor surface according to claim 3 prepares crosslinking copolymerization organic polymer, which is characterized in that institute
Stating cyano vinyl base class monomer is acrylonitrile or methacrylonitrile.
6. the method that semiconductor surface according to claim 2 prepares crosslinking copolymerization organic polymer, which is characterized in that institute
State the aqueous solution that the fluorine-containing reagent in step A102 is hydrofluoric acid, fluoboric acid or ammonium fluoride.
7. the method that semiconductor surface according to claim 1 prepares crosslinking copolymerization organic polymer, which is characterized in that institute
Stating annealing process is by sample with stove heating to holding temperature, and heating rate is 5~10 DEG C/min, is then kept the temperature, finally with furnace
Cooling is taken out air-cooled；Or
Sample is directly introduced to arrive in the high temperature furnace of holding temperature, is then kept the temperature, last furnace cooling or taking-up are air-cooled.
8. the method that semiconductor surface according to claim 1 prepares crosslinking copolymerization organic polymer, which is characterized in that institute
The atmosphere for stating annealing is air, argon gas or nitrogen.
9. a kind of method that semiconductor surface prepares crosslinking copolymerization organic polymer, which is characterized in that using containing carboxy vinyl
Class monomer and cyano-containing vinyl monomer are grafted in the presence of strong acid and initiator in semiconductor surface, after grafting,
Most of cyano spontaneous hydrolysis are amide groups, obtain be grafted on semiconductor surface containing carboxylic group and cyano or amide groups base
Then the polymer molecular chain of group makes carboxyl and cyano dehydrating condensation or carboxyl and amide groups dehydrating condensation by annealing,
Carboxyl and cyano or amide groups intramolecular cyclization, carboxyl and cyano or amide groups molecule are prepared in the surface in situ of semiconductor base
Between the organic polymer thin film with three-dimensional space cross-linked structure that is crosslinked.
10. the method that semiconductor surface according to claim 9 prepares crosslinking copolymerization organic polymer, which is characterized in that
The carboxy vinyl base class monomer is acrylic acid, methacrylic acid, any one in cinnamic acid；The cyano-containing is vinyl-based
Monomer is acrylonitrile or methacrylonitrile.
11. the method that semiconductor surface according to claim 9 prepares crosslinking copolymerization organic polymer, which is characterized in that
The concentration ratio of 10~40 DEG C of the temperature of surface grafting, the carboxy vinyl base class monomer and the cyano vinyl base class monomer is
3:9~1.
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| CN112103176B (en) * | 2020-09-11 | 2023-12-22 | 上海交通大学 | Method for covalent grafting dielectric film on semiconductor surface |
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