CN109860042A - A kind of method that semiconductor surface prepares self-crosslinking organic polymer - Google Patents
A kind of method that semiconductor surface prepares self-crosslinking organic polymer Download PDFInfo
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- CN109860042A CN109860042A CN201910087448.4A CN201910087448A CN109860042A CN 109860042 A CN109860042 A CN 109860042A CN 201910087448 A CN201910087448 A CN 201910087448A CN 109860042 A CN109860042 A CN 109860042A
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Abstract
The invention discloses a kind of methods that semiconductor surface prepares self-crosslinking organic polymer, this method comprises: semiconductor substrate surface is grafted；Hydrolysis；Annealing.This method uses diazonium salt surface grafting technology, monomer containing cyano is grafted to semiconductor surface, then pass through hydrolysis, cyan-hydrolysis is amide groups and carboxyl, carboxyl and amide groups dehydrating condensation in last annealing process, the film with three-dimensional space cross-linked structure is prepared in situ in substrate surface, 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 self-crosslinking 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 include the inorganic insulation layers such as silica, silicon nitride and it is organic absolutely
Edge layer.Organic insulator has that dielectric constant is low, elasticity modulus is small, it is simple to prepare, at low cost, to can be used as stress-buffer layer etc. excellent
Point has great application prospect in semiconductors manufacture.But prior art is difficult to realize spin coating in the microchannel of big depth-to-width ratio
The controllable insulating layer of thickness.This is because traditional spin-coating method can not make to have with the reduction in microchannel aperture and the increase of depth
Machine object effectively screws out, or even can block microchannel, and organic film obtained by spin-coating method is micron order thickness.With electronic device ruler
Very little reduction, all kinds of complexity microchannels are gradually promoted for preparing the requirement of precision, are occurred based on chemical vapor deposition
Film preparation mode.By controlling presoma, specific inorganic, organic film can be prepared in substrate surface.Plasma simultaneously
The use of enhancing chemical vapor deposition has further expanded its application.However, the big depth-to-width ratio of these chemical vapour deposition techniques
The defect that film thickness distribution is uneven, step coverage is low is deposited in complicated microchannel.
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), the silicon faces such as polymethyl methacrylate (PMMA) or polyacrylic acid (PAA) cover one layer of organic film as insulating layer
It uses.However, the film that this kind of grafting is formed is usually " combed " or " line style " structure, both twined without physics between adjacent molecule chain
Around effect, also it is 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 a kind of methods that semiconductor surface prepares self-crosslinking organic polymer.
This method obtains the thin polymer film containing imide structure, changes " combed " or " line style " knot of existing organic polymer thin film
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 self-crosslinking organic polymer, comprising:
A1: the semiconductor chip semiconductor substrate surface grafting: is placed in the grafting of cyano-containing vinyl monomer
Solution is grafted, and 10~40 DEG C of grafting temperature, 15~120min of grafting time, the long link in semiconductor substrate surface grafting
Structure, the cyano spontaneous hydrolysis after grafting in long-chain are amide groups；
A2: functional group's hydrolysis of grafted films: it is 1~50% that sample obtained by the step A1, which is placed in volume fraction,
It impregnates and is hydrolyzed in acid solution, 10~100 DEG C of hydrolysis temperature, 10~180min of hydrolysis time, by controlling acid solution
Concentration, hydrolysis temperature and hydrolysis time, so that partial amides base is hydrolyzed to carboxyl；
A3: annealing: carrying out annealing to sample obtained by the step A2 takes off carboxyl and amide groups in long-chain
Water condensation, holding temperature are 150~300 DEG C, and soaking time is 5~120min, obtains the polymer thin containing imide structure
Film.
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 impregnated 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 grafting: is placed in configured grafting solution, grafting temperature
10~40 DEG C, 15~120min of grafting time of degree, then deionized water is cleaned, dry.
Specifically, the grafting solution is configured specifically: 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 cyano vinyl base class monomer, 0.05
~0.5g aromatic diazo salt.
Preferably, the cyano vinyl base class monomer is acrylonitrile or methacrylonitrile.
Preferably, the acid solution in the step A2 be selected from one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, fluoboric acid or
It is a variety of.
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 method that semiconductor surface prepares self-crosslinking organic polymer,
It is vinyl-based to carry out semiconductor substrate surface grafting cyano-containing simultaneously first in the solution containing strong acid and initiator
The reaction of monomer and cyano-containing vinyl monomer free radical polymerization, the long link after making the cyano vinyl base class monomer polymerization
Branch is in semiconductor substrate surface, and the cyano spontaneous hydrolysis in long-chain is amide groups, so that semiconductor substrate surface grafting
There is amide group and cyano group on long-chain；
Then, by hydrolysis, and hydrating solution concentration, hydrolysis temperature and hydrolysis time are controlled by partial amides base
It is further hydrolyzed to carboxyl, carboxylic group and amide group are generated in the long-chain of grafting；
Then carboxyl and amide groups dehydrating condensation are made by annealing again, and then is prepared in situ in semiconductor substrate surface
Imide organic polymer thin film with three-dimensional space cross-linked structure.
Preferably, cyano-containing vinyl monomer is acrylonitrile or methacrylonitrile.
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 grafted using cyano-containing vinyl monomer in semiconductor substrate surface, in semiconductor base
Long-chain obtained by surface grafting cyano-containing vinyl monomer free radical polymerization, then cyano spontaneous hydrolysis is amide groups, is obtained
Obtain the organic polymer thin film containing amide group；Later by hydrolysis, control hydrating solution concentration, hydrolysis temperature and
Partial amides base in long-chain is further hydrolyzed to carboxyl by hydrolysis time, then carboxylic group and amide are generated in grafted films
Base group；Then carboxyl and amide groups dehydrating condensation are made by annealing, and then tool is prepared in situ in semiconductor substrate surface
There is the imide organic polymer thin film of three-dimensional space cross-linked structure, it is more to improve the polymer film that traditional Graft Method obtains
For " comb shape " or the structure of " linear ", imide structure can be improved the properties such as the thermodynamic property of film.
Detailed description of the invention
Fig. 1 is the method flow diagram that semiconductor surface of the present invention prepares self-crosslinking organic polymer；
Fig. 2 is to realize that semiconductor surface prepares the schematic diagram of self-crosslinking organic polymer；
Fig. 3 is the specific steps flow chart of A1 in Fig. 1；
Fig. 4 is that the decaying of sample after hydrolyzing in embodiment 2 is totally reflected infrared microscopy spectrogram；
Description of symbols: 1- semiconductor base；The segment of amide-containing group in 2- thin polymer film；3- polymer thin
The segment of cyano-containing group in film；4- hydrolysis；Carboxylic group in 5- thin polymer film；6- annealing process；7- carboxyl
With the intramolecular cyclization of amide groups；The intermolecular cross-linking of 8- carboxyl and amide groups.
Specific embodiment
It is organic poly- that prepared by self-crosslinking to a kind of semiconductor surface proposed by the present invention below in conjunction with the drawings and specific embodiments
The method for closing object is described in further detail.According to following explanation and claims, advantages and features of the invention will be more clear
Chu.
Embodiment 1
Referring to Fig. 1, a kind of method that semiconductor surface prepares self-crosslinking organic polymer, semiconductor base can be silicon,
Germanium or GaAs, this method comprises:
A1: semiconductor chip is placed in the grafting solution of cyano-containing vinyl monomer by semiconductor substrate surface grafting,
10~40 DEG C of grafting temperature, 15~120min of grafting time, while carrying out semiconductor substrate surface grafting cyano-containing vinyl list
The reaction of body and cyano-containing radical polymerizable vinyl monomer, the long-chain after making cyano-containing polymerization of vinyl monomer, which is grafted on, partly leads
Body substrate surface, cyano spontaneous hydrolysis is amide groups after grafting；
A2: sample obtained by step A1 is placed in the acidity that volume fraction is 1~50% by functional group's hydrolysis of grafted films
It impregnates, 10~100 DEG C of hydrolysis temperature, 10~180min of hydrolysis time, is then rinsed using deionized water, drying in solution；This
Procedure division amide groups is hydrolyzed into carboxyl, while being hydrolyzed to amide groups in the process in the cyano that step A1 is not hydrolyzed, this
Sample generates carboxylic group and amide group in grafted films；
A3: annealing makes annealing treatment sample obtained by step A2, and holding temperature is 150~300 DEG C, when heat preservation
Between be 5~120min；This process makes carboxyl and amide groups dehydrating condensation, and then is prepared in situ in semiconductor substrate surface with three
The imide organic polymer thin film of dimension space cross-linked structure.
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, the principle of the present embodiment is to be connect using cyano-containing vinyl monomer on 1 surface of semiconductor base
Branch, at the same cyano-containing vinyl monomer in 1 surface aggregate of semiconductor base at long-chain, after making cyano-containing polymerization of vinyl monomer
Long-chain be grafted on semiconductor substrate surface, after grafting, cyano spontaneous hydrolysis be amide groups, obtain thin polymer film, the polymerization
There are the molecule segment 2 of amide-containing, the molecule segment 3 of cyano-containing in object film；Later by hydrolysis 4, by remaining cyano
It is hydrolyzed to amide groups, and partial amides base is hydrolyzed to by carboxyl by control hydrolysis concentration, hydrolysis temperature and hydrolysis time, is made
Carboxylic group 5 and amide group 3 are generated in grafted films；Then identical strand or different molecular are made by annealing 6
Carboxyl and amide groups dehydrating condensation on chain, carboxyl and amide groups carry out the molecule of intramolecular cyclization 7 and carboxyl and amide groups
Between be crosslinked 8, realize and the imide film with three-dimensional space cross-linked structure be prepared in situ in semiconductor substrate surface, improve
The organic film that traditional Graft Method obtains is mostly the structure of " comb shape " or " linear ".
Method provided in this embodiment 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
Know PMI have good mechanical performance and heat resistance, therefore the formation of imide structure for the present embodiment semiconductor-based
The polymer film performance with imide structure of bottom surface preparation has a distinct increment, and improves product quality, preparation it is organic
Film mechanical strength with higher, heat resistance, corrosion resistance, while also there is lower dielectric constant and dielectric loss, it can be used as
Insulating layer or passivation layer in semiconductors manufacture.
The present embodiment realizes in the manufacturing process of Semiconductor microstructure organic layer, and it is controllable to be not only prepared for nano-precision
Organic insulating film is crosslinked in cyclization process and improves profile pattern simultaneously, significantly reduces the surface roughness of organic film,
The planarization of 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 scavenging period is 5~15min；
A102: semiconductor substrate surface pretreatment impregnates semiconductor base in fluorine-containing reagent, 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, grafting by semiconductor substrate surface grafting
10~40 DEG C of temperature, 15~120min of grafting time, then deionized water is cleaned, dry；
Wherein, step A103 can be carried out in any time before A104.
Further, step A103 configure grafting solution method be specially in 100ml deionized water be added 0.05~
1g anionic surfactant, 0.5~5ml inorganic acid, the acid of 0.5~5ml fluoride ion or salt, 0.5~10mL cyano vinyl
Base class monomer, 0.05~0.5g aromatic diazo salt；Initiator of the aromatic diazo salt as free radical polymerization.
Wherein, cyano vinyl base class monomer can be acrylonitrile or methacrylonitrile；Anionic surfactant can be used
Any one in dodecyl sodium sulfate, neopelex or lauryl sodium sulfate；Inorganic acid has hydrochloric acid, sulphur
Acid, nitric acid, fluoboric acid；Fluoride ion acid or salt have hydrofluoric acid, ammonium fluoride, sodium fluoride；P-nitrophenyl may be selected in aromatic diazo salt
Diazonium tetrafluoroborate, hydroxy benzenes diazonium tetrafluoroborate.
Further, the acid solution in step A2 is one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, fluoboric acid or more
Kind.
Further, 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 a kind of method that silicon chip surface prepares self-crosslinking organic polymer, 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): silicon wafer is placed in the HF solution that volume by volume concentration is 3% and carries out the processing of Si-Hization, 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, silicon chip surface
Obtain the surface uniform Si-H；
Step 4): grafting solution is formulated as follows: the deionized water of 100mL being added in polytetrafluoroethylcontainer container first, so
Sequentially added under magnetic agitation afterwards the dodecyl sodium sulfate of 0.1g, the hydrochloric acid of 1mL, the hydrofluoric acid of 1mL, 2mL acrylonitrile and
The p-nitrophenyl diazonium tetrafluoroborate of 0.1g, stirring obtain clear solution after ten minutes；The silicon wafer that step 3) is obtained is placed
In configured grafting solution, graft reaction, grafting time 30min 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.
Step 6): the silicon wafer being grafted is placed in the H that volume ratio is 10%2SO4It is hydrolyzed in solution, hydrolysis temperature
It 50 DEG C, is taken out after 1h, using being dried with nitrogen.
Step 7): the silicon wafer that hydrolysis 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.With being furnace-cooled to silicon chip extracting, silicon wafer table after room temperature
Face obtains organic cross-linked polymeric object film.
Sample after hydrolysis is subjected to infrared analysis, Fig. 4 is decaying total reflection infrared microscopy spectrogram, 1733cm in figure-1With
1684cm-1For carboxyl peak, 1652cm-1For amide base peak, for the film layer based on amide groups, grafted nature is also found in other
Phenyl ring (1592cm-1) and nitro (1509cm-1, 1338cm-1), after showing hydrolysis, silicon chip surface contains carboxylic group and acyl
Amine groups.Carboxyl and amide groups dehydrating condensation can be made by annealing later, carboxyl and amide groups carry out molecule inner ring
The intermolecular cross-linking of change and carboxyl and amide groups, obtains the film containing imide ring structure.
Embodiment 3
The present embodiment is related to a kind of method that silicon chip surface prepares self-crosslinking organic polymer, 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): 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): preparing grafting solution, and grafting solution is formulated as follows: polytetrafluoro is added in the deionized water of 100mL first
In ethylene container, then sequentially added under magnetic agitation the lauryl sodium sulfate of 0.2g, the concentrated sulfuric acid of 1mL, 1mL hydrogen fluorine
The p-nitrophenyl diazonium tetrafluoroborate of acid, the methacrylonitrile of 2mL and 0.2g, stirring are stood after ten minutes, and it is molten to obtain clarification
Liquid；Silicon wafer 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.
Step 6): the silicon wafer after step 5) cleaning is placed in the H that volume ratio is 5%2SO4In 5% HCl mixed liquor
It is hydrolyzed, 50 DEG C of hydrolysis temperature, is taken out after 1h, using being dried with nitrogen.
Step 7): the silicon wafer that hydrolysis 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, with being furnace-cooled to silicon chip extracting after room temperature, it is organic that silicon chip surface obtains crosslinking
Thin polymer film.
Based on the above embodiments it is found that a kind of semiconductor surface provided by the invention prepares the side of self-crosslinking organic polymer
Method, first in the solution containing strong acid and initiator simultaneously carry out semiconductor substrate surface grafting cyano-containing vinyl monomer and
The reaction of cyano-containing vinyl monomer free radical polymerization makes to be grafted on containing the long-chain after the cyano vinyl base class monomer polymerization
Semiconductor substrate surface, then cyano spontaneous hydrolysis is amide groups, so that semiconductor substrate surface has finally been grafted amide groups base
Group and cyano group；
Then, by hydrolysis, control hydrating solution concentration, hydrolysis temperature and hydrolysis time by partial amides base into
One one-step hydrolysis is carboxyl, while remaining cyano is decomposed into amide groups, and carboxylic group and amide group are generated in grafted films；
Then carboxyl and amide groups dehydrating condensation are made by annealing again, and then is prepared in situ in semiconductor substrate surface
Imide organic polymer thin film with three-dimensional space cross-linked structure.
Wherein, cyano-containing vinyl monomer is preferably acrylonitrile or methacrylonitrile.
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 among protection scope of the present invention.
Claims (10)
1. a kind of method that semiconductor surface prepares self-crosslinking organic polymer characterized by comprising
A1: the semiconductor chip semiconductor substrate surface grafting: is placed in the grafting solution of cyano-containing vinyl monomer
It is grafted, 10~40 DEG C of grafting temperature, 15~120min of grafting time, is grafted upper backbone in semiconductor substrate surface,
Cyano spontaneous hydrolysis after grafting in long-chain is amide groups；
A2: sample obtained by the step A1 functional group's hydrolysis of grafted films: is placed in the acidity that volume fraction is 1~50%
It impregnates and is hydrolyzed in solution, 10~100 DEG C of hydrolysis temperature, 10~180min of hydrolysis time, pass through the dense of control acid solution
Degree, hydrolysis temperature and hydrolysis time, make partial amides base be hydrolyzed to carboxyl；
A3: annealing: carrying out annealing to sample obtained by the step A2 makes carboxyl and amide groups dehydration in long-chain contract
It closes, holding temperature is 150~300 DEG C, and soaking time is 5~120min, obtains the thin polymer film containing imide structure.
2. the method that semiconductor surface according to claim 1 prepares self-crosslinking organic polymer, which is characterized in that described
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 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 impregnated 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 grafting: is placed in configured grafting solution, 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 self-crosslinking organic polymer, which is characterized in that configuration
The grafting solution specifically: it is inorganic that 0.05~1g anionic surfactant, 0.5~5ml are added in 100ml deionized water
Acid, the acid of 0.5~5ml fluoride ion or salt, 0.5~10mL cyano vinyl base class monomer, 0.05~0.5g aromatic diazo salt.
4. the method that semiconductor surface according to claim 3 prepares self-crosslinking organic polymer, which is characterized in that described
Cyano vinyl base class monomer is acrylonitrile or methacrylonitrile.
5. the method that semiconductor surface according to claim 1 prepares self-crosslinking organic polymer, which is characterized in that described
Acid solution in step A2 is selected from one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, fluoboric acid or a variety of.
6. the method that semiconductor surface according to claim 2 prepares self-crosslinking organic polymer, feature is in the step
Fluorine-containing reagent in rapid A102 is the aqueous solution of 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
The 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, most
Furnace cooling or taking-up are air-cooled afterwards；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 self-crosslinking organic polymer, feature is in described to move back
The atmosphere of fire processing is air, argon gas or nitrogen.
9. a kind of method that semiconductor surface prepares self-crosslinking organic polymer, which is characterized in that
Carry out semiconductor substrate surface grafting cyano-containing vinyl monomer simultaneously first in the solution containing strong acid and initiator
And the reaction of cyano-containing vinyl monomer free radical polymerization, the long-chain after making the cyano vinyl base class monomer polymerization are grafted on
Semiconductor substrate surface, and the cyano spontaneous hydrolysis in long-chain is amide groups, so that the long-chain of semiconductor substrate surface grafting
It is upper that there is amide group and cyano group；
Then, by hydrolysis, and hydrating solution concentration, hydrolysis temperature and hydrolysis time are controlled by partial amides base into one
One-step hydrolysis is carboxyl, and carboxylic group and amide group are generated in the long-chain of grafting；
Then carboxyl and amide groups dehydrating condensation are made by annealing again, and then is prepared in situ and has in semiconductor substrate surface
The imide organic polymer thin film of three-dimensional space cross-linked structure.
10. the method that semiconductor surface according to claim 9 prepares self-crosslinking organic polymer, which is characterized in that contain
Cyano vinyl base class monomer is acrylonitrile or methacrylonitrile.
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| CN112103176A (en) * | 2020-09-11 | 2020-12-18 | 上海交通大学 | Method for covalently grafting dielectric film on surface of semiconductor |
| CN112201565A (en) * | 2020-09-11 | 2021-01-08 | 上海交通大学 | Method for covalently grafting fluorine-free nano-pore low-k dielectric film on surface of semiconductor |
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| CN108912377A (en) * | 2018-07-24 | 2018-11-30 | 常州储能材料与器件研究院 | A kind of polymer ultra-thin film and preparation method thereof, hybrid film, application |
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| CN101595170A (en) * | 2006-12-19 | 2009-12-02 | 法国原子能委员会 | Under non-electrochemical conditions in the method for solid support thing surface preparation organic membrane, the solid support thing that obtains thus and the preparation complete utensil |
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| CN112201565A (en) * | 2020-09-11 | 2021-01-08 | 上海交通大学 | Method for covalently grafting fluorine-free nano-pore low-k dielectric film on surface of semiconductor |
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