CN1472371A - Method for modifying planar mono-crystal silicon surface - Google Patents
Method for modifying planar mono-crystal silicon surface Download PDFInfo
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- CN1472371A CN1472371A CNA031321321A CN03132132A CN1472371A CN 1472371 A CN1472371 A CN 1472371A CN A031321321 A CNA031321321 A CN A031321321A CN 03132132 A CN03132132 A CN 03132132A CN 1472371 A CN1472371 A CN 1472371A
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- Prior art keywords
- vinylbenzene
- dull
- stereotyped
- molecular weight
- vinylpyridine
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- 238000000034 method Methods 0.000 title claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 31
- 229910052710 silicon Inorganic materials 0.000 title claims description 31
- 239000010703 silicon Substances 0.000 title claims description 31
- 239000013078 crystal Substances 0.000 title claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 5
- 229920005604 random copolymer Polymers 0.000 claims description 43
- 239000000126 substance Substances 0.000 claims description 43
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 33
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 11
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 230000005059 dormancy Effects 0.000 claims description 8
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 230000001276 controlling effect Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims description 4
- 238000007306 functionalization reaction Methods 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 3
- AMLFJZRZIOZGPW-UHFFFAOYSA-N prop-1-en-1-amine Chemical group CC=CN AMLFJZRZIOZGPW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 6
- -1 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-O Chemical class 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000010189 synthetic method Methods 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 210000004899 c-terminal region Anatomy 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000002977 biomimetic material Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- UCYWSGCXYHZWEY-UHFFFAOYSA-N diiodomethane propane-1,2,3-triol Chemical compound ICI.OCC(O)CO UCYWSGCXYHZWEY-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Abstract
A process for modifying the surface of flat monocrystalline silicon includes such steps as dissolving 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-O (HTEMPO) and azodiisobutylnitrile (AIBN) in styrene and 4-vinyl pyridine, heating at 95 deg.C for 2 hr, polymerizing at 130+/-2 deg.C for 5-48 hr, cooling at -20 deg.C, depositing to obtain the atactic copolymer of styrene and 4-vinylpyridine, ultrasonic washing of flat monocrystalline silicon in water, immersing in mixture of concentrated sulfuric acid and hydrogen peroxide solution, heating at 90 deg.C for 2 hr, washing, drying, preparing DMF solution from said copolymer, coating it on the surface of said monocrystalline silicon, and vacuum heating at 120 deg.C for 6-122 hr to form a polymer brush layer.
Description
One, technical field
The present invention relates to the modification of dull and stereotyped monocrystalline silicon surface, specifically, is a kind of method that vinylbenzene and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers is grafted on dull and stereotyped monocrystalline silicon surface.
Two, background technology
It is to grow up nineteen nineties that the random copolymers that will contain reactable end group, narrow molecular weight distributions, controllable molecular weight is grafted on dull and stereotyped monocrystalline silicon surface method, and this polymer layer is otherwise known as: polymer brush.Many studies have shown that is grafted on the wetting behavior that monocrystalline silicon surface can be controlled monocrystalline silicon surface effectively with random copolymers, and then induce organism self-assembly on the monocrystalline silicon surface, or induce its surperficial macromolecular material generation ordered phase to separate, thereby preparation order thin film, this orderly film is at microelectronics, the cell growth control, the biomimetic material preparation, field such as microreactor and control drug release will be widely used, having higher application and theoretical investigation and be worth, is one of hi-tech of extensively being paid attention at present.
Present technology is with 2,2,6,6-tetramethyl piperidine-1-oxyradical (2,2,6,6-tetramethylpiperidine-l-oxyl, TEMPO) nitroxyl free radical is a raw material, the synthetic earlier end group 2 that contains, 2,6,6-tetramethyl piperidine-1-oxyradical derivative, the random copolymers of synthetic then reactable end group, narrow molecular weight distributions, controllable molecular weight, random copolymers with reactable end group, narrow molecular weight distributions, controllable molecular weight is grafted to the silicon face surface at last, preparation polymer brush sublayer.
Prior art is generally used 2,2,6 of aromatic hydrocarbon alkanisation, 6-tetramethyl piperidine-1-oxyradical (2,2,6,6-tetramethylpiperidine-1-oxyl is TEMPO) as nitroxyl free radical, because 2,2,6,6-tetramethyl piperidine-1-oxyradical price is very high, in addition, and at 2 of preparation aromatic hydrocarbon alkanisation, 2,6, passed through the synthetic and sepn process of multistep during 6-tetramethyl piperidine-1-oxyradical, yield is low, and therefore, this technology is very restricted in actual applications.
Three, summary of the invention
The present invention utilizes cheap 4-hydroxyl-2,2,6, the 6-tetramethyl piperidine is a raw material, prepare 4-hydroxyl-2,2,6 through oxidation step, 6-tetramethyl piperidine-1-oxyradical (T.Kurosaki, K.W.Lee, M.OkawaraJ. Polym.Sci., Polym.Chem.Ed.1972,10,3295), as nitroxyl free radical, cause vinylbenzene and 4-vinylpyridine or vinylbenzene and methyl methacrylate monomer and carry out " activity " radical polymerization with this, preparation hydroxyl or carboxylic, narrow distribution, vinylbenzene that molecular weight is controlled and 4-vinylpyridine and vinylbenzene and methyl methacrylate random copolymers are grafted on monocrystalline silicon surface with them then.This technology has that preparation cost is low, and raw material is easy to get, and separation and purification is simple, is easy to advantages such as control.
Synthetic hydroxyl of the inventive method or carboxyl, narrow distribution, that molecular weight is controlled vinylbenzene and 4-vinylpyridine and vinylbenzene and methyl methacrylate random copolymers synthetic route are:
Annotate: when the vinylbenzene synthetic hydroxyl, narrow distribution, that molecular weight is controlled and 4-vinylpyridine and vinylbenzene and methyl methacrylate random copolymers: I is a Diisopropyl azodicarboxylate;
When the vinylbenzene synthetic carboxylic, narrow distribution, that molecular weight is controlled and 4-vinylpyridine and vinylbenzene and methyl methacrylate random copolymers: I is 4,4 '-azo two (4-cyanopentanoic acid) (4,4 '-Azobis (4-Cyanovaleric Acid, ACA))
The present invention with the synthetic route that vinylbenzene hydroxyl, narrow molecular weight distributions, that molecular weight is controlled and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers are grafted on monocrystalline silicon surface is:
The present invention with the vinylbenzene carboxylic, narrow distribution, that molecular weight is controlled and 4-vinylpyridine and and the methyl methacrylate random copolymers be grafted on the synthetic route of monocrystalline silicon surface:
Technical scheme of the present invention is as follows:
A kind of method of modifying of dull and stereotyped monocrystalline silicon surface, it is made up of the following step:
Vinylbenzene and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers that step 1. preparation is hydroxyl, narrow molecular weight distributions, molecular weight is controlled:
Step 1.1. is 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxyradical (HTEMPO) and Diisopropyl azodicarboxylate (AIBN) dissolve in vinylbenzene and 4-vinylpyridine or vinylbenzene and the methyl methacrylate, the ratio of vinylbenzene/4-vinylpyridine or methyl methacrylate amount of substance is in 0.2 to 0.8 scope, total monomer and 4-hydroxyl-2,2,6, the mass ratio of 6-tetramethyl piperidine-1-oxyradical and Diisopropyl azodicarboxylate is: 500-1,000: 1.8-3: 1, they are inserted in single neck flask of abundant dehydration and deoxygenation, heated 2～4 hours down at 90 ℃～100 ℃, promptly get " covalency dormancy kind " compound
Step 1.2. at 130 ± 2 ℃, after polymerization in 5～48 hours, inserts cooling in ice-salt bath (20 ℃) with " the covalency dormancy kind " of step 1.1 gained, and polyreaction is stopped,
Step 1.3. stops the reaction mixture of polyreaction, separates through the precipitator method, obtains vinylbenzene hydroxyl, narrow molecular weight distributions, that molecular weight is controlled and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers.
The functionalization of the dull and stereotyped monocrystalline silicon surface of step 2
Dull and stereotyped silicon single crystal is inserted in the redistilled water, ultrasonic cleaning 30 minutes, then, put it into the mixing solutions (vitriol oil is 70: 30 with hydrogen peroxide volume ratio) of the hydrogen peroxide composition of the vitriol oil and 30%, 80 ℃～90 ℃ heating 1.5～2.5 hours, clean the high-purity argon gas drying with ether and redistilled water
Step 3. is grafted on monocrystalline silicon surface with hydroxyl or the C-terminal base, narrow molecular weight distributions, that molecular weight is controlled vinylbenzene and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers
Step 3.1. is the polystyrene of the hydroxyl of step 1 gained or C-terminal base, poly-4-vinylpyridine, vinylbenzene and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers, be mixed with 1.5%～4% N, dinethylformamide (DMF) solution, it is coated in the surface of the prepared dull and stereotyped silicon single crystal of step 2 with spin coating method, the monocrystalline silicon piece that is coated with polymer layer is placed in the vacuum drying oven, under vacuum condition, at 6～122 hours (according to embodiment 9) of 120 ℃～122 ℃ heating, the surface that makes polymer graft arrive dull and stereotyped silicon single crystal forms the polymer brush sublayer
Step 3.2. at room temperature quenches the dull and stereotyped silicon single crystal that the surface forms the polymer brush sublayer, use N, dinethylformamide soaked 24 hours, polymers grafted is removed from silicon substrate, under vacuum condition, dry below 60 ℃, promptly making the surface has dull and stereotyped silicon single crystal certain thickness, homogeneous polymer brush layer.
The method of modifying of above-mentioned dull and stereotyped monocrystalline silicon surface, can be with 4,4 '-azo two (4-cyanopentanoic acid) replaces Diisopropyl azodicarboxylate to make initiator, so can obtain vinylbenzene carboxylic, narrow molecular weight distributions, that molecular weight is controlled and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers, so the method for modifying of above-mentioned dull and stereotyped monocrystalline silicon surface, step 1.1 and 1.2 also can followingly be carried out:
Vinylbenzene and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers that step 1. preparation is carboxylic, narrow molecular weight distributions, molecular weight is controlled:
Step 1.1. is 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxyradical (HTEMPO) and 4,4 '-azo two (4-cyanopentanoic acid) dissolves in vinylbenzene and 4-vinylpyridine or vinylbenzene and the methyl methacrylate, vinylbenzene and total monomer amount of substance mark compare between 0.2 to 0.8 scope, total monomer and 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxyradical and 4, the ratio of the amount of substance of 4 '-azo two (4-cyanopentanoic acid) is: 500-1,000: 1.8-3: 1, they are inserted in single neck flask of abundant dehydration and deoxygenation, heated 1.5～3 hours down at 90 ℃～100 ℃, promptly get " covalency dormancy kind " compound
Step 1.2. at 130 ± 2 ℃, after polymerization in 5～60 hours, inserts cooling in ice-salt bath (20 ℃) with " the covalency dormancy kind " of step 1.1 gained, and polyreaction is stopped,
So step 2 is item corresponding changes into following carrying out:
The functionalization of the dull and stereotyped monocrystalline silicon surface of step 2
Dull and stereotyped silicon single crystal is inserted redistilled water; ultrasonic cleaning 30 minutes; under argon shield; silicon single crystal is immersed in the anhydrous toluene solution of the amino propylene of 2%3-24 hours; be immersed in the methanol solution of 2% pimelic acid 24 hours then; use methanol rinse at last three times, promptly get the surperficial dull and stereotyped silicon single crystal that contains carboxyl
Other step is constant.
The method of modifying of above-mentioned dull and stereotyped monocrystalline silicon surface, the number-average molecular weight (Mn) of reaction times controlling polymers that can be by regulating step 1.2 is 6,000～60, between 000.
The method of modifying of above-mentioned dull and stereotyped monocrystalline silicon surface can be by the heat-up time of regulating step 3.1, and the thickness of controlling polymers brush layer is between 2.5～9.1nm.
Technology with the existing preparation narrow molecular weight distribution polymer is compared, and the present invention has adopted the method for " activity " radical polymerization to prepare a series of polystyrene, poly-4-vinylpyridine, vinylbenzene and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers on preparation technology.In the preparation process, the initiator system raw material of use is easy to get, the control of simple synthetic method, easy handling.Adopt the polymkeric substance of this kind prepared can have end group, narrow molecular weight distributions, and the molecular weight size can be controlled by controlling reaction time.Number-average molecular weight can be controlled in 6,000g/mol～60, and 000g/mol, molecular weight distributing index is (M between 1.15～1.30
w/ M
n), the thickness of polymer brush sublayer can be controlled by the heat-up time that adjusting is coated with the monocrystalline silicon piece of polymkeric substance, and the thickness of polymer brush sublayer can be between 2.5～9.1nm.
Technology with the existing preparation polymer brush is compared, the preparation process that the present invention has adopted the method for " activity " radical polymerization to come the controlling polymers brush on preparation technology, in preparation, used the HTEMPO initiator system, make thickness, the grafting density of polymer brush sublayer be easy to control, simple synthetic method.The preparation, separation and the purifying complex that exist in the prior art have been solved well, problems such as synthetic cost height.Institute's synthetic polymer brush thickness is at 2.5nm～9.1nm, and surface coverage is 90～95%.
Four, description of drawings
Fig. 1 is the sample of embodiment 1 preparation
1The H-NMR spectrogram;
Fig. 2 is the GPC graphic representation of the hydroxyl sample of embodiment 3 preparations, and the reaction times is 24 hours, and the ■ reaction times is 48 hours, ● the reaction times is 60 hours, and ▲ the reaction times is 70 hours.
Fig. 3 is the XPS spectrum figure of the sample of embodiment 7 preparations, wherein, and angle of departure: (a) 90 ° (b) 75 ° of (c) 60 ° of (d) 45 ° of (e) 30 ° of (f) 10 °; C
1s: 285eV, N
1s: 400eV, O
1s: 532eV, Si
2s: 152eV, Si
29: 100eV.
Fig. 4: A is the atomic force microscope shape appearance figure of the sample of embodiment 7 preparations, and B is the atomic force microscope side elevational view of the sample of embodiment 7 preparations.
Fig. 5: A is the atomic force microscope shape appearance figure of the sample of embodiment 8 preparations, and B is the atomic force microscope side elevational view of the sample of embodiment 8 preparations.
Five, embodiment
Below by embodiment technical scheme of the present invention is further described.
Embodiment one: contain hydroxy end groups, vinylbenzene amount of substance mark is the preparation of poly-(vinylbenzene-r-4-vinylpyridine) random copolymers of 0.66
Polyreaction through vacuumize-toast for three times-carry out in the single port flask after the applying argon gas cyclical operation.With 0.61g 4-hydroxyl-2; 2; 6; 6-tetramethyl piperidine oxyradical (HTEMPO) and 0.287g Diisopropyl azodicarboxylate (AIBN) mixture are dissolved in (ratio of their amount of substance is 500: 2: 1) in 63.7g vinylbenzene and the 27.6g 4-vinylpyridine mixing solutions, are injected under argon shield in the single port flask.Under argon shield, earlier 90 ℃ of-95 ℃ of following stirring heating 1.5～3 hours, then, control reaction temperature was 130 ± 2 ℃, react after 48 hours, cools off with ice-salt bath, and polyreaction is stopped.Behind the reaction terminating, polymkeric substance is that precipitation agent is handled with the mixed solvent dissolving (volume ratio is 1/1) of dehydrated alcohol and toluene with normal hexane, is settled out polymkeric substance, and drying gets polymkeric substance 62 g.
Molecular weight of poly-(vinylbenzene-r-4-vinylpyridine) random copolymers and molecular weight distribution are with adopting GPC instrument (Waters244) to measure, polystyrene standards is a standard, tetrahydrofuran (THF) (THF) is moving phase (down together), recording its weight-average molecular weight is 76,400g/mol, number-average molecular weight is 58, and 768g/mol, molecular weight distributing index are 1.20 (M
w/ Mn).The composition of multipolymer characterizes (DMSO-d with Broker A (CE)-300 nuclear magnetic resonance analyser
6Be solvent), see accompanying drawing 1, (2,6 of pyridine rings are gone up 2H to the composition of multipolymer (the amount of substance mark of 4-vinylpyridine) with 8.3ppm
A) peak area of locating and the peak area at 6.3ppm place ratio (on the pyridine ring 3,5,2H; 2,6 2H on the phenyl ring) obtain.Corresponding and the 1.1ppm (G) of 12 H on the end group HTEMPO.
Calculating its vinylbenzene amount of substance mark is 0.66.
Embodiment two: contain carboxyl end groups, vinylbenzene amount of substance mark is the preparation of 0.52 poly-(vinylbenzene-r-4-vinylpyridine) random copolymers
Polyreaction through vacuumize-toast for three times-carry out in the single port flask after the applying argon gas cyclical operation.With 0.61g4-hydroxyl-2; 2; 6; 6-tetramethyl piperidine oxyradical (HTEMPO) and 0.327g 4; 4 '-azo two (4-cyanopentanoic acid) mixture is dissolved in that (ratio of their amount of substance is 1 in 88.4g vinylbenzene and the 89.25g 4-vinylpyridine mixing solutions; 000: 3: 1), under argon shield, be injected in the single port flask.Under argon shield, stirred 1.5～3 hours down at 90 ℃-95 ℃ earlier, then, control reaction temperature is 130 ± 2 ℃, reacts after 5 hours, with the cooling of ice-salt bath polyreaction is stopped.Behind the reaction terminating, polymkeric substance is the precipitation agent precipitation with the mixed solvent dissolving (volume ratio is 1/1) of dehydrated alcohol and toluene, normal hexane, obtain the 35g multipolymer, its weight-average molecular weight is 6,800g/mol, number-average molecular weight is 6, and 018g/mol, molecular weight distributing index are 1.30 (M
w/ Mn), vinylbenzene amount of substance mark is 0.52.
Embodiment three: the preparation of poly-(vinylbenzene-r-4-vinylpyridine) random copolymers of compositions hydroxyl or carboxyl end groups, different and different molecular weight size
Synthetic method like employing and embodiment one and the embodiment two-phase, amount of substance ratio by vinylbenzene and 4-vinylpyridine in the change monomer, can prepare different poly-(vinylbenzene-r-4-vinylpyridine) random copolymerss of forming, when the ratio of the amount of substance of vinylbenzene in the monomer and 4-vinylpyridine was respectively 8/2,6/4,4/6,3/7 and 2/8, vinylbenzene amount of substance mark was respectively 0.72,0.58,0.43,0.28 and 0.2 in the prepared multipolymer.By the controlled polymerization time, the multipolymer that can prepare the different molecular weight size, when polymerization time in 5 hours to 48 hours scope, the weight-average molecular weight that can control prepared multipolymer is 6,800g/mol-76,400g/mol scope, number-average molecular weight is 6,018g/mol-58, the 768g/mol scope, molecular weight distributing index is at 1.13-1.30 (M
w/ Mn) scope is seen shown in Figure 2ly, and as seen from Figure 2, along with the prolongation of polymerization time, the molecular weight of polymkeric substance increases.Can obtain poly-(vinylbenzene-r-4-vinylpyridine) random copolymers of compositions contain hydroxy end groups, different and different molecular weight size with embodiment one similar synthetic method; Can obtain containing carboxyl end groups, the different composition and poly-(vinylbenzene-r-4-vinylpyridine) random copolymers of different molecular weight size with synthetic method like the embodiment two-phase.
Embodiment four: contain hydroxy end groups, vinylbenzene amount of substance mark is the preparation of 0.55 poly-(vinylbenzene-r-methyl methacrylate) random copolymers
Polyreaction through vacuumize-toast for three times-carry out in the single port flask after the applying argon gas cyclical operation.With 0.61g4-hydroxyl-2; 2; 6; 6-tetramethyl piperidine oxyradical and 0.32g Diisopropyl azodicarboxylate mixture are dissolved in the solution that 50.6g vinylbenzene and 49.7g methyl methacrylate form (ratio of their amount of substance is 500: 1.8: 1), are injected under argon shield in the single port flask.Under argon shield, stirred 2 hours down at 90 ℃ earlier, then, control reaction temperature is 130 ± 2 ℃ of reactions 5 hours.With the cooling of ice-salt bath polyreaction is stopped.Behind the reaction terminating, polymkeric substance dissolves with dry toluene, is that precipitation agent is handled with normal hexane, is settled out 21 g polymkeric substance.The weight-average molecular weight of multipolymer is 10,000g/mol, and number-average molecular weight is 8,700g/mol, molecular weight distributing index are 1.15 (M
w/ Mn), cinnamic amount of substance mark is 0.55.
Embodiment five: contain carboxyl end groups, vinylbenzene amount of substance mark is the preparation of poly-(vinylbenzene-r-methyl methacrylate) random copolymers of 0.41
Polyreaction through vacuumize-toast for three times-carry out in the single port flask after the applying argon gas cyclical operation.With 0.61g 4-hydroxyl-2; 2; 6; 6-tetramethyl piperidine oxyradical (HTEMPO) and 0.446g 4; 4 '-azo two (4-cyanopentanoic acid) mixture is dissolved in the solution that 33.2g vinylbenzene and 48.8g methyl methacrylate form (ratio of their amount of substance is 500: 2.2: 1), injects the single port flask under argon shield.Under argon shield, heated 3 hours down at 100 ℃ earlier, then, control reaction temperature is 130 ± 2 ℃, reacts 48 hours.With the cooling of ice-salt bath polyreaction is stopped.Behind the reaction terminating, polymkeric substance dissolves with dry toluene, is that precipitation agent is handled with normal hexane, is settled out the 57g polymkeric substance.The weight-average molecular weight of multipolymer is 68,000g/mol, and number-average molecular weight is 53,968g/mol, molecular weight distributing index are 1.26 (M
w/ Mn), cinnamic amount of substance mark is 0.41.
Embodiment six: the preparation of poly-(vinylbenzene-r-methyl methacrylate) random copolymers of compositions hydroxyl or carboxyl end groups, different and different molecular weight size
Adopt the synthetic method similar with embodiment four, five, amount of substance ratio by vinylbenzene and 4-methyl methacrylate in the change monomer, can prepare different poly-(vinylbenzene-r-methyl methacrylate) random copolymerss of forming, when the ratio of the amount of substance of vinylbenzene in the monomer and methyl methacrylate was 8/2,7/3,6/4,4/6,3/7 and 2/8, vinylbenzene amount of substance mark was respectively 0.75,0.68,0.61,0.41,0.33 and 0.25 in the prepared multipolymer.By the controlled polymerization reaction times, the multipolymer that can prepare the different molecular weight size, when polymerization time in 5 hours to 48 hours scope, the weight-average molecular weight that can control prepared multipolymer is 10,000g/mol-68,000g/mol scope, number-average molecular weight is 8,700g/mol-53, the 968g/mol scope, molecular weight distributing index is at 1.13-1.26 (M
w/ Mn) scope.Can obtain poly-(vinylbenzene-r-methyl methacrylate) random copolymers of compositions contain hydroxy end groups, different and different molecular weight size with embodiment four similar synthetic methods; Can obtain containing carboxyl end groups, the different composition and poly-(vinylbenzene-r-methyl methacrylate) random copolymers of different molecular weight size with embodiment five similar synthetic methods.
Embodiment seven: the hydroxylation of dull and stereotyped monocrystalline silicon surface is handled
Dull and stereotyped silicon single crystal is inserted in the redistilled water, ultrasonic cleaning 30 minutes, then, put it into the mixing solutions (vitriol oil is 70: 30 with hydrogen peroxide volume ratio) of the hydrogen peroxide composition of the vitriol oil and 30%, 80 ℃～90 ℃ heating 1.5～2.5 hours, clean the high-purity argon gas drying with ether and redistilled water.
Embodiment eight: the carboxylated processing of dull and stereotyped monocrystalline silicon surface
Dull and stereotyped silicon single crystal is inserted redistilled water; ultrasonic cleaning 30 minutes; under argon shield; silicon single crystal is immersed in the anhydrous toluene solution of the amino propylene of 2%3-24 hours; be immersed in the methanol solution of 2% pimelic acid 24 hours then; use methanol rinse at last three times, promptly get the surperficial dull and stereotyped silicon single crystal that contains carboxyl.
Embodiment nine: poly-(vinylbenzene-r-4-vinylpyridine) random copolymers of hydroxyl is grafted on monocrystalline silicon surface
The 2%N of poly-(vinylbenzene-r-4-vinylpyridine) random copolymers of hydroxyl or carboxyl, dinethylformamide (DMF) solution, with 3,500 rev/mins rotating speed, be rotated on the dull and stereotyped monocrystalline silicon surface that is coated in hydroxyl or carboxyl, the monocrystalline silicon piece that is coated with polymer layer is placed in the vacuum drying oven, under vacuum condition, 120 ℃ of heating 48 hours, allow hydroxyl on the polymkeric substance be diffused into dull and stereotyped monocrystalline silicon surface and with its on hydroxyl reaction, make polymer graft arrive the surface of dull and stereotyped silicon single crystal, form the polymer brush sublayer.Then, silicon substrate at room temperature quenches.Use N, dinethylformamide soaked 24 hours, made not have polymers grafted to remove from silicon substrate vacuum-drying.
Can prepare dull and stereotyped monocrystalline silicon surface through as above step certain thickness, homogeneous polymer brush layer is arranged.
The elementary composition of polymer brush sublayer measured with x-ray photoelectron spectroscopy (XPS), film thickness is measured with angle x-ray photoelectron spectroscopy (XPS) or ellipsometer test, the result as shown in Figure 3, its surface topography and all the thick perceived noisiness in side measure (the Nanoscope IIIMultiMode of Digital company type atomic force microscope) with atomic force microscope (AFM).Probe Si
3N
4, in room temperature and atmosphere, measure with contact mode, the results are shown in Figure 4.Illustrate: 1, all square thick perceived noisiness formula:
Calculate Z
AveHeight flat average in the given area; Z
jThe height value of certain point; Always counting in the given area of N.
2, surface coverage [Γ (mg/m
2)] calculate with formula, Γ=hp, ρ are the density of polymkeric substance, h is the thickness of brush layer.
Embodiment ten: poly-(vinylbenzene-r-methyl methacrylate) the random copolymers brush of preparation
Poly-(vinylbenzene-r-methyl methacrylate) random copolymers 2%N with hydroxyl or carboxyl, dinethylformamide (DMF) solution, with 3,500 rev/mins rotating speed, be rotated on the dull and stereotyped monocrystalline silicon surface that is coated in hydroxyl or carboxyl, the monocrystalline silicon piece that is coated with polymer layer is placed in the vacuum drying oven, under vacuum condition, 120 ℃ of heating 48 hours, allow hydroxyl on the polymkeric substance be diffused into dull and stereotyped monocrystalline silicon surface and with its on hydroxyl reaction, make polymer graft arrive the surface of dull and stereotyped silicon single crystal, form the polymer brush sublayer.Then, silicon substrate at room temperature quenches.Use N, dinethylformamide soaked 24 hours, made not have polymers grafted to remove from silicon substrate vacuum-drying.
The elementary composition of polymer brush sublayer measured with x-ray photoelectron spectroscopy (XPS), film thickness is measured with angle x-ray photoelectron spectroscopy (XPS) or ellipsometer test, poly-(vinylbenzene-r-methyl methacrylate) random copolymers brush surface pattern and r.m.s. roughness are measured (the Nanoscope III MultiMode of Digital company type atomic force microscope), probe Si with atomic force microscope (AFM)
3N
4, in room temperature, under the atmosphere, measure with contact mode, the results are shown in Figure 5.
Embodiment 11: the preparation of the copolymer brush sublayer of different thickness
Adopt the similar methods of embodiment seven, eight, by controlling heat-up time, the copolymer brush sublayer that can prepare different grafting densities and different thickness when being controlled at heat-up time 6 hours to 122 hours, can prepare the grafting layer thickness in the copolymer brush sublayer of 2.5nm to the 9.1nm scope.
Embodiment 12: different poly-(vinylbenzene-r-4-vinylpyridine) random copolymerss of forming are grafted to dull and stereotyped monocrystalline silicon surface, the interfacial energy of control silicon face.
The copolymer grafted that vinylbenzene amount of substance mark is different are at monocrystalline silicon surface, can prepare different surfaces can the monocrystalline silicon surface of modification, can control surface can be at 42mJ/cm2 between the 51mJ/cm2.
By measuring three kinds of liquid: water, methylene iodide and glycerol are used the Young-Good-Girifalco-Fowkes equation at the contact angle (seeing Table 1) of each polymer surfaces:
γ
Lv(1+cosθ
e)＝2[(γ
L LWγ
s LW)
1/2+(γ
L -γ
s +)
1/2+(γ
l +γ
s -)
1/2]
Calculate the interfacial energy of polymer brush sublayer.Table 2 has been listed the interfacial energy of poly-(vinylbenzene-r-4-vinylpyridine) random copolymers brush layer of different compositions.
Table 1 water, glycerol and methylene iodide are at the different contact angle polymer brush (vinylbenzene of forming on poly-(vinylbenzene-r-4-vinylpyridine) grafting laminar surface
Water glycerol methylene iodide amount of substance mark)
1.00 92.0 76.0 37.0
0.78 88.4 72.6 34.4
0.69 86.5 70.4 31.8
0.61 84.4 67.9 30.1
0.55 82.2 65.6 28.2
0.38 80.1 63.6 26.3
0.32 78.2 61.3 24.8
0.22 76.2 58.5 23.0
0.00 72.5 55.0 20.5
Table 2, surface energy polymeric brush (the benzene second of poly-(vinylbenzene-r-4-vinylpyridine) grafting layer
γ γ
LWγ
ABγ
+γ
-The amount mark of olefinic substance)
1.00 41.00 41.00 0.00 0.00 1.10
0.78 42.57 42.31 0.26 0.01 1.69
0.69 43.93 43.47 0.46 0.03 1.92
0.61 45.06 44.18 0.88 0.09 2.17
0.55 46.14 44.95 1.19 0.13 2.64
0.38 47.17 45.68 1.49 0.18 3.18
0.32 48.19 46.23 1.96 0.27 3.54
0.22 49.43 46.84 2.59 0.45 3.72
0.00 51.00 47.60 3.40 0.58 5.01
Illustrate: 1, according to the Young-Good-Girifalco-Fowkes equation:
γ
Lv(1+cos θ
e)=2[(γ
L LWγ
s LW)
1/2+ (γ
L -γ
s +)
1/2+ (γ
l +γ
s -)
1/2] calculate the interfacial energy of polymer brush sublayer.
2, each parameter of known water is: γ
LW=21.8, γ=72.8, and γ
+=γ
-=25.5mJ/m
2
Each parameter of glycerol is: γ
LW=34, γ=64, γ
+=5.3, and γ
-=42.5mJ/m
2
Each parameter of methylene iodide is: γ
LW=50.8, γ=50.8, γ
+=0, and γ
-=0mJ/m
2
Claims (4)
1. the method for modifying of a dull and stereotyped monocrystalline silicon surface is characterized in that it is made up of the following step:
Vinylbenzene and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers that step 1. preparation is hydroxyl, narrow molecular weight distributions, molecular weight is controlled:
Step 1.1. is 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxyradical (HTEMPO) and Diisopropyl azodicarboxylate (AIBN) dissolve in vinylbenzene and 4-vinylpyridine or vinylbenzene and the methyl methacrylate, vinylbenzene compares in 0.2 to 0.8 scope with the amount of substance mark of total monomer, total monomer and 4-hydroxyl-2,2,6, the ratio of the amount of substance of 6-tetramethyl piperidine-1-oxyradical and Diisopropyl azodicarboxylate is: 500-1,000: 1.8-3: 1, they are inserted in single neck flask of abundant dehydration and deoxygenation, heated 1.5～3 hours down at 90～100 ℃, promptly get " covalency dormancy kind " compound
Step 1.2. at 130 ± 2 ℃, through after the polymerization in 5-48 hour, inserts cooling in ice-salt bath (20 ℃) with " the covalency dormancy kind " of step 1.1 gained, and polyreaction is stopped,
Step 1.3. stops the reaction mixture of polyreaction, separates through the precipitator method, obtains vinylbenzene hydroxyl, narrow molecular weight distributions, that molecular weight is controlled and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers,
The functionalization of the dull and stereotyped monocrystalline silicon surface of step 2
Dull and stereotyped silicon single crystal is inserted in the redistilled water, ultrasonic cleaning 30 minutes, then, put it into the mixing solutions (vitriol oil is 70: 30 with hydrogen peroxide volume ratio) of the hydrogen peroxide composition of the vitriol oil and 30%, 80 ℃～90 ℃ heating 1.5～2.5 hours, clean the high-purity argon gas drying with ether and redistilled water
Step 3. is grafted on monocrystalline silicon surface with vinylbenzene narrow molecular weight distributions, that molecular weight is controlled and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers
Step 3.1. is the polystyrene of step 1 gained, poly-4-vinylpyridine, vinylbenzene and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers are mixed with 1～4% N, dinethylformamide (DMF) solution, it is coated in the surface of the prepared dull and stereotyped silicon single crystal of step 2 with spin coating method, the monocrystalline silicon piece that is coated with polymer layer is placed in the vacuum drying oven, under vacuum condition, at 6～122 hours (according to embodiment 11) of 120 ℃～122 ℃ heating, the surface that makes polymer graft arrive dull and stereotyped silicon single crystal forms the polymer brush sublayer
Step 3.2. at room temperature quenches the dull and stereotyped silicon single crystal that the surface forms the polymer brush sublayer, use N, dinethylformamide soaked 24 hours, polymers grafted is removed from silicon substrate, under vacuum condition, dry below 60 ℃, promptly making the surface has dull and stereotyped silicon single crystal certain thickness, homogeneous polymer brush layer.
2. the method for modifying of dull and stereotyped monocrystalline silicon surface according to claim 1 is characterized in that:
Vinylbenzene and 4-vinylpyridine or vinylbenzene and methyl methacrylate random copolymers that step 1. preparation is carboxylic, narrow molecular weight distributions, molecular weight is controlled:
Step 1.1. is 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxyradical (HTEMPO) and 4,4 '-azo two (4-cyanopentanoic acid) dissolves in vinylbenzene and 4-vinylpyridine or vinylbenzene and the methyl methacrylate, vinylbenzene and total monomer amount of substance mark compare between 0.2 to 0.8 scope, total monomer and 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxyradical and 4, the ratio of the amount of substance of 4 '-azo two (4-cyanopentanoic acid) is: 500-1,000: 1.8-3: 1, they are inserted in single neck flask of abundant dehydration and deoxygenation, heated 1.5～3 hours down at 90 ℃～100 ℃, promptly get " covalency dormancy kind " compound
Step 1.2. at 130 ± 2 ℃, after polymerization in 5～60 hours, inserts cooling in ice-salt bath (20 ℃) with " the covalency dormancy kind " of step 1.1 gained, and polyreaction is stopped,
So step 2 is item corresponding changes into following carrying out:
The functionalization of the dull and stereotyped monocrystalline silicon surface of step 2
Dull and stereotyped silicon single crystal is inserted redistilled water; ultrasonic cleaning 30 minutes; under argon shield; silicon single crystal is immersed in the anhydrous toluene solution of the amino propylene of 2%3-24 hours; be immersed in the methanol solution of 2% pimelic acid 24 hours then; use methanol rinse at last three times, promptly get the surperficial dull and stereotyped silicon single crystal that contains carboxyl
Other step is constant.
3. the method for modifying of dull and stereotyped monocrystalline silicon surface according to claim 1 and 2 is characterized in that: the number-average molecular weight of the reaction times controlling polymers by regulating step 1.2 is 6,000～60, between 000.
4. the method for modifying of dull and stereotyped monocrystalline silicon surface according to claim 1 and 2, it is characterized in that: by the heat-up time of regulating step 3.1, the thickness of controlling polymers brush layer is between 2.5～9.1nm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457832C (en) * | 2006-12-04 | 2009-02-04 | 浙江大学 | Method for preparing water-dispersive carbon black adopting surface graft modification method |
| CN102030482A (en) * | 2010-10-13 | 2011-04-27 | 中国科学院化学研究所 | Method for preparing nanometer patterning bipolymer brush |
| CN104350109A (en) * | 2011-12-12 | 2015-02-11 | 威斯特法伦·威廉姆斯明斯特大学 | Functionalised silicon nanoparticles |
| CN105237660A (en) * | 2015-10-28 | 2016-01-13 | 复旦大学 | Polymer with stable nitroxide free radical as terminal group, and preparation method thereof |
| CN105355262A (en) * | 2015-11-25 | 2016-02-24 | 深圳市乐普泰科技股份有限公司 | Transparent conducting film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457832C (en) * | 2006-12-04 | 2009-02-04 | 浙江大学 | Method for preparing water-dispersive carbon black adopting surface graft modification method |
| CN102030482A (en) * | 2010-10-13 | 2011-04-27 | 中国科学院化学研究所 | Method for preparing nanometer patterning bipolymer brush |
| CN102030482B (en) * | 2010-10-13 | 2012-08-08 | 中国科学院化学研究所 | Method for preparing nanometer patterning bipolymer brush |
| CN104350109A (en) * | 2011-12-12 | 2015-02-11 | 威斯特法伦·威廉姆斯明斯特大学 | Functionalised silicon nanoparticles |
| CN104350109B (en) * | 2011-12-12 | 2016-11-09 | 威斯特法伦·威廉姆斯明斯特大学 | The nano silicon particles of functionalization |
| CN105237660A (en) * | 2015-10-28 | 2016-01-13 | 复旦大学 | Polymer with stable nitroxide free radical as terminal group, and preparation method thereof |
| CN105237660B (en) * | 2015-10-28 | 2018-06-12 | 复旦大学 | The polymer of a kind of end group for stable nitrogen-oxygen free radical and preparation method thereof |
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| CN105355262B (en) * | 2015-11-25 | 2018-07-03 | 深圳市乐普泰科技股份有限公司 | Transparent conductive film and preparation method thereof |
| CN109186561A (en) * | 2018-09-19 | 2019-01-11 | 南京大学 | A kind of evaluation method of subglacial lake volume change |
| CN109186561B (en) * | 2018-09-19 | 2020-10-02 | 南京大学 | Method for estimating volume change of under-ice lake |
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