CN106206252B - In the method for surface of semiconductor substrates one-step method chemical graft organic film - Google Patents
In the method for surface of semiconductor substrates one-step method chemical graft organic film Download PDFInfo
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- CN106206252B CN106206252B CN201610510595.4A CN201610510595A CN106206252B CN 106206252 B CN106206252 B CN 106206252B CN 201610510595 A CN201610510595 A CN 201610510595A CN 106206252 B CN106206252 B CN 106206252B
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- organic film
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
Abstract
The present invention provides a kind of methods in surface of semiconductor substrates one-step method chemical graft organic film comprising following steps: prepares chemical plating fluid；Semiconductor substrate is placed in the chemical plating fluid, is stood at 0~30 DEG C, completes organic film in the grafting of surface of semiconductor substrates.Compared with prior art, the present invention has following the utility model has the advantages that in 1, method of the invention, in F‑Under the action of, other additional equipments and temperature condition are not needed, uniform thick organic film can be prepared on a semiconductor substrate；2, step is simple, easily operated, and cost is relatively low, is suitable for semiconductor field and industrial production.
Description
Technical field
The present invention relates to a kind of methods in surface of semiconductor substrates one-step method chemical graft organic film, belong to semiconductor core
Piece encapsulation technology field.
Background technique
Due to the extensive potential application in microelectronics, biosensor and field of molecular electronics, in semiconductor surface
It carries out organic modification and has become a hot topic.So becoming in surface of semiconductor substrates preparation organic polymer layers
Extremely important experiment subject under discussion.In recent years, it is very popular using electrochemical method deposition diazonium salt in surface of semiconductor substrates,
Because this method can carry out in aqueous solution, it is easy to carry out for industrial production, and application is than wide.
In the reaction being widely recognized as, such as cation as diazonium tetrafluoroborate can be in saturation mercury electrode, outside
Deposition is completed in the case where making alive 1V.This its mechanism using the method for electricity grafting has had a large amount of research.This is related to
Fracture to the associative key by dinitrogen transfers an electron on diazonium salt.It just will form altogether in electrode surface aryl in this way
Valence link.Further, extra aryl meeting and continue reflection with the aromatic group formed and form complicated polynitrobenzene
Layer.This is a kind of method that a step diversification prepares organic layer on the electrode, but the organic layer prepared is very thin.
Diazonium salt also be used to connect macromolecular on matrix surface.Matrix surface uses diazonium salt treatment first, then again
Cause the growth of organic matter chain with macromole evocating agent.Organic film in order to obtain, fragrant base provide being total to for connection matrix
Valence link makes it form a covalent linkage between macromolecular.Cause poly- in this surface carried out on the basis of diazonium salt
The method for closing reaction can be used various of monomer and carry out on different matrix surfaces, and can obtain thicker film.But this
Kind method needs two steps, in the industrial production using more difficult.
Summary of the invention
For disadvantages mentioned above of the existing technology, the present invention provides one kind in semiconductor surface one-step method chemical graft
The method of organic film, the present invention are added after hydrofluoric acid in the plating solution, and under no any outer plus instrument requirement, diazonium salt can
To be deposited directly to silicon face.
The present invention is achieved by the following technical solutions:
The present invention provides a kind of methods in surface of semiconductor substrates one-step method chemical graft organic film comprising as follows
Step:
Prepare chemical plating fluid；
Semiconductor substrate is placed in the chemical plating fluid, is stood at 0~30 DEG C, completes organic film in semiconductor
The grafting of substrate surface.
Preferably, the semiconductor substrate is element semiconductor or compound semiconductor.
It preferably, include surfactant, acid, organic monomer, diazonium salt and fluorine ion in the chemical plating fluid.
Preferably, the pH value of the chemical plating fluid is 0~4.
Preferably, in the chemical plating fluid, the concentration of surfactant be no more than 20g/L, organic monomer
Concentration should be no more than its solubility, and the concentration of diazonium salt is 0.1~10g/L, and the concentration of fluorine ion is 0.1-8mol/L, sour
Additional amount is subject to the pH value for guaranteeing chemical plating fluid no more than 3.
Preferably, the surfactant be selected from one of dodecyl sodium sulfate and sulfated castor oil or
Two kinds.
Preferably, the acid is selected from least one of hydrochloric acid, sulfuric acid, acetic acid and carbonic acid.
Preferably, the organic monomer is selected from methyl methacrylate, acrylic acid, 2- (perfluoro capryl) methyl-prop
At least one of olefin(e) acid ethyl ester, trifluoroethyl methacrylate, 2,2,2- trifluoroethyl methacrylate.
Preferably, the diazonium salt is in diazonium tetrafluoroborate, pyrazoles diazonium inner salt, triptycene diazonium salt
At least one.
Preferably, the organic film with a thickness of 5nm~3 μm.
The principle of the invention lies in: diazonium salt can cause emulsion polymerization reaction on the surface of semiconductor substrate, with this in electricity
It is extremely upper to form covalent, consolidation and stable organic film.This method is by aromatic radical initiation reaction, and forming initial time has
Machine layer is then followed by and occurs extending on the aromatic radical of initial secondary organic layer and chain tra nsfer.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, in method of the invention, under the action of F-, other additional equipments and temperature condition are not needed, it can be half
Uniform thick organic film is prepared on conductor substrate；
2, step is simple, easily operated, and cost is relatively low, is suitable for semiconductor field and industrial production.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the simulation schematic diagram of the organic film of surface of semiconductor substrates grafting in the present invention；
Fig. 2 is that 50000 times of SEM photograph is amplified in the organic film section that in the present invention prepared by embodiment 1；
Fig. 3 is that 50000 times of SEM photograph is amplified in the organic film section that in the present invention prepared by embodiment 2；
Fig. 4 is that 200000 times of SEM photograph is amplified in the organic film section that in the present invention prepared by embodiment 3.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
The present embodiment is related to a kind of method in surface of semiconductor substrates one-step method chemical graft organic film, and specific steps are such as
Under:
Step (1): by p-type, resistivity is that each ultrasound is clear in acetone, alcohol, deionized water respectively for 50 Ω/m silicon wafer
It washes 10 minutes；
Step (2): it prepares electrolyte solution (i.e. chemical plating fluid), wherein having the dodecyl sodium sulfate of 10g/L, 10mol/
The hydrochloric acid of L, the acrylic acid of 10mol/L, the pyrazoles diazonium inner salt of 5g/L, the hydrofluoric acid of 5mol/L, pH value 2.
Step (3): the silicon wafer in step (1) is placed in 5h in the electrolyte solution in step (2), temperature is controlled 25
DEG C, without adding any instrument, the model configuration figure of the organic film of preparation is as shown in Figure 1, to measure its section as shown in Figure 2.?
Uniform thick film is obtained under F- ionization, film thickness is at 1 μm or so.
Embodiment 2
This example is related to a kind of method in surface of semiconductor substrates one-step method chemical graft organic film, and specific steps are such as
Under:
Step (1): by p-type, resistivity is that 100 Ω/m GaAs substrate is each in acetone, alcohol, deionized water respectively
Ultrasonic cleaning 10 minutes；
Step (2): preparing chemical plating fluid, wherein have the dodecyl sodium sulfate of 10g/L, the hydrochloric acid of 10mol/L, 5mol/L
Hydroxypropyl polymethacrylic acid methyl ester, the pyrazoles diazonium inner salt of 5g/L, the sodium fluoride of 5mol/L, pH value 2.
Step (3): the GaAs substrate in step (1) is placed in 4h in the electrolyte solution in step (2), temperature control
At 23 DEG C, without adding any instrument, it is as shown in Figure 3 to measure its section.Uniform thick film, film have been obtained under F- ionization
Thickness is in 800nm or so.
Embodiment 3
The present embodiment is related to a kind of method in surface of semiconductor substrates one-step method chemical graft organic film, and specific steps are such as
Under:
Step (1): by N-shaped, resistivity is 1000 Ω/m silicon wafer each ultrasound in acetone, alcohol, deionized water respectively
Cleaning 10 minutes；
Step (2): preparing chemical plating fluid, wherein have the sulfated castor oil of 5g/L, the hydrochloric acid of 5mol/L, the first of 5mol/L
Base acrylic acid trifluoro ethyl ester, the triptycene diazonium salt of 5g/L, the hydrofluoric acid of 5mol/L, pH value 3.
The concentration of surfactant is no more than 20g/L, and the concentration of organic monomer should be no more than its solubility, diazonium salt
Concentration be 0.1~10g/L, the concentration of fluorine ion is 0.1-8mol/L, and sour additional amount is to guarantee the pH value of chemical plating fluid not
Subject to 3.
Comparative example 1
The present embodiment is related to a kind of method in surface of semiconductor substrates one-step method chemical graft organic film, specific steps
It is same as Example 1, it the difference is that only: without containing fluorine ion in the electrolyte solution of this comparative example.In the comparative example, by
In the presence of fluoride-free, organic film can not be formed in surface of semiconductor substrates, surface of semiconductor substrates does not have significant change.
Comparative example 2
The present embodiment is related to a kind of method in surface of semiconductor substrates one-step method chemical graft organic film, specific steps with
Embodiment 1 is identical, the difference is that only: hydrochloric acid is not contained in the electrolyte solution of this comparative example.The electrolyte solution
PH value is 7.In the comparative example, organic matter occurs decomposing in grafting process, and electrolyte solution is unstable, can not carry out effectively
Chemical graft.
Comparative example 3
The present embodiment is related to a kind of method in surface of semiconductor substrates one-step method chemical graft organic film, specific steps with
Embodiment 1 is identical, the difference is that only: not diazonium salt in solution described in this comparative example, then organic monomer can not be in base
Body surface face is grafted, so can not form organic film on semiconductor substrate surface.
The principle of the invention lies in: diazonium salt can cause emulsion polymerization reaction on the surface of semiconductor substrate, with this in electricity
It is extremely upper to form covalent, consolidation and stable organic film.This method is by aromatic radical initiation reaction, and forming initial time has
Machine layer is then followed by and occurs extending on the aromatic radical of initial secondary organic layer and chain tra nsfer.Therefore, in method of the invention,
In F-Under the action of, other additional equipments and temperature condition are not needed, uniform thickness can be prepared on a semiconductor substrate
Organic film；Step is simple, easily operated, and cost is relatively low, is suitable for semiconductor field and industrial production.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (6)
1. a kind of method in surface of semiconductor substrates one-step method chemical graft organic film, which comprises the steps of:
Prepare chemical plating fluid；
Semiconductor substrate is placed in the chemical plating fluid, is stood at 0~30 DEG C, completes organic film in semiconductor substrate
The grafting on surface；
The semiconductor substrate be include element semiconductor or compound semiconductor；
It include surfactant, acid, organic monomer, diazonium salt and fluorine ion in the chemical plating fluid；
The pH value of the chemical plating fluid is not more than 3；
In the chemical plating fluid, the concentration of surfactant is no more than 20g/L, and the concentration of diazonium salt is 0.1~10g/L, fluorine
The concentration of ion is 0.1~8mol/L.
2. as described in claim 1 in the method for surface of semiconductor substrates one-step method chemical graft organic film, which is characterized in that
The surfactant is selected from one or both of dodecyl sodium sulfate and sulfated castor oil.
3. as described in claim 1 in the method for surface of semiconductor substrates one-step method chemical graft organic film, which is characterized in that
The acid is selected from least one of hydrochloric acid, sulfuric acid, acetic acid and carbonic acid.
4. as described in claim 1 in the method for surface of semiconductor substrates one-step method chemical graft organic film, which is characterized in that
The organic monomer is selected from methyl methacrylate, acrylic acid, 2- (perfluoro capryl) ethyl methacrylate, methacrylic acid three
At least one of fluorine ethyl ester, 2,2,2- trifluoroethyl methacrylate.
5. as described in claim 1 in the method for surface of semiconductor substrates one-step method chemical graft organic film, which is characterized in that
The diazonium salt is selected from least one of diazonium tetrafluoroborate, pyrazoles diazonium inner salt, triptycene diazonium salt.
6. as described in claim 1 in the method for surface of semiconductor substrates one-step method chemical graft organic film, which is characterized in that
The organic film with a thickness of 5nm~3 μm.
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| CN106505032A (en) * | 2016-12-14 | 2017-03-15 | 华进半导体封装先导技术研发中心有限公司 | A kind of manufacture method of the through-hole structure of semiconductor device |
| CN112103176B (en) * | 2020-09-11 | 2023-12-22 | 上海交通大学 | Method for covalent grafting dielectric film on semiconductor surface |
Citations (4)
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| CN101622376A (en) * | 2007-01-30 | 2010-01-06 | 朗姆研究公司 | Composition and methods for forming metal films on semiconductor substrates using supercritical solvents |
| CN101842856A (en) * | 2007-08-31 | 2010-09-22 | 泽塔科尔公司 | Methods of treating a surface to promote binding of molecule(s) of interest, coatings and devices formed therefrom |
| WO2010112610A3 (en) * | 2009-04-02 | 2010-12-09 | Commissariat à l'énergie atomique et aux énergies alternatives | Method for modifying the surface energy of a solid |
| CN102083921A (en) * | 2008-07-01 | 2011-06-01 | 埃其玛公司 | Method of preparing an electrical insulation film and application for the metallization of through-vias |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7030040B2 (en) * | 2002-10-31 | 2006-04-18 | Intel Corporation | Selectively growing a polymeric material on a semiconductor substrate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101622376A (en) * | 2007-01-30 | 2010-01-06 | 朗姆研究公司 | Composition and methods for forming metal films on semiconductor substrates using supercritical solvents |
| CN101842856A (en) * | 2007-08-31 | 2010-09-22 | 泽塔科尔公司 | Methods of treating a surface to promote binding of molecule(s) of interest, coatings and devices formed therefrom |
| CN102083921A (en) * | 2008-07-01 | 2011-06-01 | 埃其玛公司 | Method of preparing an electrical insulation film and application for the metallization of through-vias |
| WO2010112610A3 (en) * | 2009-04-02 | 2010-12-09 | Commissariat à l'énergie atomique et aux énergies alternatives | Method for modifying the surface energy of a solid |
Non-Patent Citations (1)
| Title |
|---|
| Direct Covalent Grafting of Conjugated Molecules onto Si, GaAs, and Pd Surfaces from Arydiazonium Salts;Michael P. Stewart et. al;《J. AM. CHEM. SOC.》;20031216;第370-378页 |
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