CN1670247A - Method for preparing sulfhydryl silane-rare earth nanometer compound membrane on single crystal silicon sheet surface - Google Patents
Method for preparing sulfhydryl silane-rare earth nanometer compound membrane on single crystal silicon sheet surface Download PDFInfo
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- CN1670247A CN1670247A CN 200510023460 CN200510023460A CN1670247A CN 1670247 A CN1670247 A CN 1670247A CN 200510023460 CN200510023460 CN 200510023460 CN 200510023460 A CN200510023460 A CN 200510023460A CN 1670247 A CN1670247 A CN 1670247A
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Abstract
A method is for making mercaptosilicane-tombarthitenanometer coextruded film on the surface of a monocrystalline silicon chip, in which base material is a single-crystal chip with surface treated, employing a self-assemblage process on the surface to make said film, which comprises the following steps: putting the monocrystalline silicon chip into chloroazotic acid, pretreating the chip, washing and drying it, and immersing it into the mercaptosilicane solution for 8 hours, after the flush process, weathering it with nitrogen, then putting it into the self-assemblage solution with tombarthite compound, ethanol, ethylene diamine tetraacetic acid, chlor ammonia, aquacare and aquacare to assemble, and then getting the mercaptosilicane-tombarthite self-assemblage nanometer coextruded film. The invention provides an easy technique, and the tombarthite self-assemblage film made on the surface of the monocrystalline silicon chip can reduce friction and increase wear-resistance dramatically.
Description
Technical field
The present invention relates to a kind of preparation method of organic and inorganic nano compound film, relate in particular to the method that a kind of monocrystalline silicon sheet surface prepares hydrosulphonyl silane self-assembly rare earth nanometer composite film.Belong to the film preparation field.
Background technology
Along with high-tech progress, machine building industry just develops towards the direction of microminiaturization, and this has just related to the friction problem on micromachine surface.Because silicon materials have hardness height, with low cost, advantage such as surfaceness is little, the application in Micro Electro Mechanical System comes into one's own day by day.But not surface treated silicon materials fragility is higher, wearing and tearing of stripping layer and brittle rupture easily take place in surface crack under low tension stress effect, be difficult to satisfy service requirements, therefore need improve silicon materials surface micro performance with process for modifying surface, to improve Micro Lub polishing machine at the bottom of the silicon materials.
Can prepare self-assembled film at monocrystalline silicon sheet surface by self-assembling method at present, improve the antifriction antiwear on rare earth surface.But the process of some self-assembly laminated film preparation is more loaded down with trivial details comparatively speaking, and bigger to the pollution of environment, and friction reducing effect neither be fine.
Find by literature search, publication number is the preparation method that the Chinese invention patent of CN1358804A discloses a kind of solid film surface fatty acid self-composed monomolecular ultrathin lubrication membrane, this method is the unimolecular layer at solid surface self-assembly one deck lipid acid, choose the lipid acid that easily is adsorbed in solid surface, be mixed with dilute solution, the ceramic membrane that makes immersed the lipid acid dilute solution that configures rapidly under room temperature, reacted 24～48 minutes.This method needs the time of 24～96h to prepare precursor solution in the process of preparation self-assembled film, make that so whole film forming period is long, and in the process that substrate is handled, do not relate to concrete grammar, and this method is to have prepared a kind of organic self-assembled film, does not relate to improvement and the research of rare earth element to film performance.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of monocrystalline silicon sheet surface to prepare the method for sulfhydryl silane-rare earth nano compound film, adopt monocrystalline silicon piece as base material, adopt self-assembling method to prepare the sulfhydryl silane-rare earth nano composite membrane on its surface, make it solve the friction problem of micro mechanical system.
The present invention is achieved by the following technical solutions, method is as follows: at first monocrystalline silicon piece is carried out pre-treatment, monocrystalline silicon piece is immersed in the chloroazotic acid, use electric furnace heating chloroazotic acid, be 5～6 hours heat-up time, naturally cooling at room temperature, monocrystalline silicon piece is taken out, wash repeatedly with deionized water, it is dry to put into drying basin, monocrystalline silicon piece after will handling then immerses in the hydrosulphonyl silane solution for preparing, left standstill 6～8 hours, and used chloroform after the taking-up respectively, acetone, behind the deionized water rinsing, dry up with nitrogen and to place the rare earth self-assembly solution for preparing, under 80～100 ℃, assembled 10～12 hours, and promptly obtained sulfhydryl silane-rare earth self-assembled nanometer film.
The component volumetric molar concentration of the hydrosulphonyl silane solution that the present invention adopts is: hydrosulphonyl silane 0.1～1.0mmol/L, solvent are benzole soln.
The weight percentages of components of the rare earth self-assembly solution that the present invention adopts is: ethanol content: 60%～80%, rare earth compound: 4.5%～7%, ethylenediamine tetraacetic acid (EDTA) (EDTA): 1%～4%, ammonium chloride: 2%～5%, urea: 10%～25%, nitric acid: 0.5%～1.5%.
Rare earth compound of the present invention is a kind of in Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or the cerium oxide.
Processing method of the present invention is simple, and cost is low, environmentally safe.At the monocrystalline silicon piece substrate surface, contain hydrolyzable active group in the hydrosulphonyl silane molecule, can build Si-O by chemistry combines with the base material with active group Si-OH, form one deck self-assembled film at substrate surface, and in the hydrosulphonyl silane molecule-the SH group has reactive behavior, and the number of chemical reaction can take place.With surface-assembled after the hydrosulphonyl silane bottom substrate inserts earth solution ,-SH group and rare earth element generation complex reaction, thus form one deck rare earth nanometer film again on the silane surface.
Rare earth self-assembly solution allocation among the present invention is simple, and the sulfhydryl silane-rare earth nano thin-film that is self-assembled into has and is evenly distributed advantages such as film forming densification.The rare earth self-assembly composite membrane of monocrystalline silicon sheet surface preparation can be with frictional coefficient 0.8 during from no film be reduced to about 0.1, have fairly obvious antifriction function.The rare earth self-assembled film also has good wear resistance in addition, is expected to become micromachine ideal boundary lubricant film.
Embodiment
Below technical scheme of the present invention is further described but component that technical characterictic of the present invention is not limited to provide in following examples and parameter by specific embodiment.
Embodiment 1:
At first, monocrystalline silicon piece is carried out pre-treatment, monocrystalline silicon piece is immersed in the chloroazotic acid, use electric furnace heating chloroazotic acid, be 5 hours heat-up time, and naturally cooling takes out monocrystalline silicon piece at room temperature, washes repeatedly with deionized water, and it is dry to put into drying basin.Monocrystalline silicon piece after handling is immersed in the hydrosulphonyl silane solution for preparing, left standstill 8 hours, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl group methyl dimethoxysilane 0.5mmol/L, and solvent is a benzole soln; After using chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up with nitrogen and to be placed in the rare earth self-assembly solution for preparing, under 80 ℃, assembled 12 hours, promptly obtain sulfhydryl silane-rare earth self-assembled nanometer film.
The weight percentages of components of the rare earth self-assembly solution that the present invention adopts is: ethanol content: 60%, and Lanthanum trichloride: 5%, ethylenediamine tetraacetic acid (EDTA): 4%, ammonium chloride: 5%, urea: 25%, concentrated hydrochloric acid: 1%.
Adopt SPM-9500 atomic force microscope, L116E type measurement of elliptically polarized li instrument and PHI-5702 type x-photoelectron spectroscopy (XPS) to characterize surface topography, thickness and the chemical ingredients of film.Adopt the little frictional behaviour survey meter of the point pure slip of contact MEASUREMENTS OF THIN frictional coefficient.
The result who characterizes shows thickness at the silane that is self-assembled on the monocrystalline silicon piece between 5～7nm, and the thickness of laminated film is between 15～45nm.XPS spectrum figure shows contain the Rare Earth Lanthanum element in the film that monocrystalline silicon sheet surface is self-assembled into, and by the analysis to its bound energy numerical value, shows that the Rare Earth Lanthanum element is that mode by chemical bonding is assembled into the organosilane surface.And do not observe the index of hydrosulphonyl silane, thus the surface coverage of monocrystalline silicon piece one deck rare earth nanometer composite film.On a little frictional behaviour survey meter of the pure slip of contact, measure the frictional coefficient of clean monocrystalline silicon piece and monocrystalline silicon sheet surface self-assembly rare earth composite membrane respectively.The rare earth self-assembly composite membrane of monocrystalline silicon sheet surface preparation can be with frictional coefficient 0.8 during from no film be reduced to about 0.1, have fairly obvious antifriction function.
Embodiment 2:
At first, monocrystalline silicon piece is carried out pre-treatment, monocrystalline silicon piece is immersed in the chloroazotic acid, use electric furnace heating chloroazotic acid, be about 6 hours heat-up time, and naturally cooling takes out monocrystalline silicon piece at room temperature, washes repeatedly with deionized water, and it is dry to put into drying basin.Monocrystalline silicon piece after handling is immersed in the hydrosulphonyl silane solution for preparing, left standstill 6 hours, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl group methyl dimethoxysilane 0.1mmol/L, and solvent is a benzole soln; After using chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up with nitrogen and to be placed in the rare earth self-assembly solution for preparing, under 90 ℃, assembled 11 hours, promptly obtain sulfhydryl silane-rare earth self-assembled nanometer film.
The weight percentages of components of the rare earth self-assembly solution that the present invention adopts is: ethanol content: 80%, and Lanthanum trichloride: 4.5%, ethylenediamine tetraacetic acid (EDTA): 1%, ammonium chloride: 2%, urea: 12%, concentrated hydrochloric acid: 0.5%.
Adopt the characterization method among the embodiment 1 that film quality is estimated.
The result who characterizes shows thickness at the silane that is self-assembled on the monocrystalline silicon piece between 5～8nm, and the thickness of laminated film is between 15～50nm.XPS spectrum figure shows at monocrystalline silicon sheet surface and has been self-assembled into the organosilane film that contains mercapto groups, can't see the index of silicon-dioxide, so the surface of monocrystalline silicon piece has all covered the organosilane film of one deck densification.The film surface of assembling in earth solution contains the Rare Earth Lanthanum element, and the index of observed element sulphur very a little less than, so the surface coverage of monocrystalline silicon piece the rare earth nanometer composite film of one deck densification.
Embodiment 3:
At first, monocrystalline silicon piece is carried out pre-treatment, monocrystalline silicon piece is immersed in the chloroazotic acid, use electric furnace heating chloroazotic acid, be about 5 hours heat-up time, and naturally cooling takes out monocrystalline silicon piece at room temperature, washes repeatedly with deionized water, and it is dry to put into drying basin.Monocrystalline silicon piece after handling is immersed in the hydrosulphonyl silane solution for preparing, left standstill 7 hours, the component volumetric molar concentration of hydrosulphonyl silane solution is: 3-sulfydryl propyl trimethoxy silicane 1.0mmol/L, and solvent is a benzole soln; After using chloroform, acetone, deionized water rinsing respectively after the taking-up, dry up with nitrogen and to be placed in the rare earth self-assembly solution for preparing, under 100 ℃, assembled 10 hours, promptly obtain sulfhydryl silane-rare earth self-assembled nanometer film.
The weight percentages of components of the rare earth self-assembly solution that the present invention adopts is: ethanol content: 65%, and Cerium II Chloride: 7%, ethylenediamine tetraacetic acid (EDTA): 2.5%, ammonium chloride: 4%, urea: 20%, concentrated hydrochloric acid: 1.5%.
Adopt the laboratory apparatus among the embodiment 1 that film is estimated, the result of sign shows: between 5～7nm, the thickness of laminated film is between 15～40nm at the thickness of the silane that is self-assembled on the monocrystalline silicon piece.XPS spectrum figure shows contain the rare earth Ce elements in the laminated film that monocrystalline silicon sheet surface is self-assembled into, and by analyzing the variation of its bound energy, can learn that the rare earth Ce elements is assembled into the surface of substrate by the mode of chemical bonding, and do not observe the index of silicon-dioxide, so the surface of monocrystalline silicon piece has all covered one deck rare earth nanometer composite film.
Claims (2)
1, a kind of monocrystalline silicon sheet surface prepares the method for sulfhydryl silane-rare earth nano compound film, it is characterized in that, at first monocrystalline silicon piece is immersed in and heats 5～6 hours in the chloroazotic acid, naturally cooling at room temperature, with monocrystalline silicon piece taking-up deionized water rinsing, dry back is immersed in the hydrosulphonyl silane solution for preparing, left standstill 6～8 hours, taking out the flushing back dries up with nitrogen, place the rare earth self-assembly solution for preparing, under 80～100 ℃, assembled 10～12 hours, and promptly obtained sulfhydryl silane-rare earth self-assembled nanometer film; Wherein, the component volumetric molar concentration of described hydrosulphonyl silane solution is: hydrosulphonyl silane 0.1～1.0mmol/L, solvent are benzole soln; The weight percentages of components of described rare earth self-assembly solution is: ethanol: 60%～80%, and rare earth compound: 4.5%～7%, ethylenediamine tetraacetic acid (EDTA): 1%～4%, ammonium chloride: 2%～5%, urea: 10%～25%, nitric acid: 0.5%～1.5%.
2, the method for preparing the sulfhydryl silane-rare earth nano compound film according to the monocrystalline silicon sheet surface of claim 1 is characterized in that described rare earth compound is a kind of in Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide, the cerium oxide; Hydrosulphonyl silane is a kind of in 3-sulfydryl propyl group methyl dimethoxysilane, the 3-sulfydryl propyl trimethoxy silicane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100364911C (en) * | 2006-03-23 | 2008-01-30 | 上海交通大学 | Preparation method of amine silicon sheet monocrystalline silane-rare earth nanometer film on surface |
| CN101359581B (en) * | 2008-09-25 | 2010-12-01 | 张彩根 | Silicon carbide boat cleaning method |
| CN102219556A (en) * | 2011-04-14 | 2011-10-19 | 上海交通大学 | Method for preparing dopamine-rare earth laminated film on surface of monocrystalline wafer |
| CN106987833A (en) * | 2017-03-07 | 2017-07-28 | 新乡学院 | The preparation method of aluminum alloy surface silane lanthanum salt composite membrane |
-
2005
- 2005-01-20 CN CN 200510023460 patent/CN1670247A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100364911C (en) * | 2006-03-23 | 2008-01-30 | 上海交通大学 | Preparation method of amine silicon sheet monocrystalline silane-rare earth nanometer film on surface |
| CN101359581B (en) * | 2008-09-25 | 2010-12-01 | 张彩根 | Silicon carbide boat cleaning method |
| CN102219556A (en) * | 2011-04-14 | 2011-10-19 | 上海交通大学 | Method for preparing dopamine-rare earth laminated film on surface of monocrystalline wafer |
| CN106987833A (en) * | 2017-03-07 | 2017-07-28 | 新乡学院 | The preparation method of aluminum alloy surface silane lanthanum salt composite membrane |
| CN106987833B (en) * | 2017-03-07 | 2019-04-12 | 新乡学院 | Aluminum alloy surface silane-lanthanum salt composite membrane preparation method |
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