CN100479931C - Method for producing compound thin film of phosphoric acid radicle silane-carbon nanotubes on the surface of single crystal silicon wafers - Google Patents
Method for producing compound thin film of phosphoric acid radicle silane-carbon nanotubes on the surface of single crystal silicon wafers Download PDFInfo
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- CN100479931C CN100479931C CNB2007100370456A CN200710037045A CN100479931C CN 100479931 C CN100479931 C CN 100479931C CN B2007100370456 A CNB2007100370456 A CN B2007100370456A CN 200710037045 A CN200710037045 A CN 200710037045A CN 100479931 C CN100479931 C CN 100479931C
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Abstract
The invention relates to a preparation method for the monocrystalline silicon slice surface phospho silicane-carbon nanomater tube composite membrane, firstly dipping the monocrystalline silicon slice in the water, after being heated and cooled naturally to take out, repeatedly flushing using the deionized water and then drying, and then dipping into the well prepared amino silane solution, assembling the amino silane film on the surface of the substrate, then putting into the cyanidation methane solution containing the phosphorus oxychloride and the 2,3,5-trimethyl pyridine. The phospho group is assembled on the film surface, then the substrate is inputted in the modified carbon nanomater tube suspension liquid, for standing 2-24 hours in 30-90 DEG, then taking out to flush using plenty of deionized water, and drying using nitrogen gas, thereby obtaining an improved monocrystalline silicon slice of the carbon nanomater tube composite membrane deposited on the surface. The invention has simple technology, low cost, no pollution to the environment, and the carbon nanomater tube composite membrane has evident anti friction function and good resistance to wear.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nano-tube coextruded film, relate in particular to a kind of method for preparing phosphate group silicone hydride-rare earth modified carbon nanotube pipe laminated film at monocrystalline silicon sheet surface.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 surface roughness 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 fracture easily take place in face crack under low tensile stress effect, be difficult to satisfy instructions for use, therefore need improve silicon materials surface micro performance with process for modifying surface, to improve the Micro Lub polishing machine of silicon materials.Can improve the antifriction antiwear on monocrystalline silicon substrate surface by self-assembling method at monocrystalline silicon substrate surface preparation self-assembled film at present.
CNT is the seamless hollow tube that is surrounded by the former sub-grid of hexagonal carbon, two ends are covered by hemispheric big fullerene molecule usually, diameter zero point several nanometers to tens nanometers, length then is several to a hundreds of micron, as a kind of new material, the strength ratio steel of CNT is high more than 100 times, and Young's modulus can be up to 1TPa, and proportion has only 1/6 of steel.Because very little, the draw ratio of diameter, CNT is regarded as quasi-one-dimensional nanometer material.Confirmed now that CNT has peculiar electric property, superpower mechanical property, good adsorption property, thereby caused very big attention in the material field.
But CNT nano-grade size and high surface radially can cause its easy reunion, and be dispersed relatively poor, reduced the effective L D ratio of CNT.In addition, the carbon nano tube surface feature is similar to graphite, and insoluble in most solvents, wet performance is poor, is difficult to be formed with effective adhesive with substrate.In order to improve the dispersed of CNT and to increase it and the adhesion of substrate interface, must assemble methods such as active group by surface modification and substrate surface to CNT, improve the interface combination degree between CNT and the substrate surface, obtain the good composite membrane of tribological property.
Find by literature search, publication number is the preparation method that the Chinese invention patent application of CN1403494 discloses a kind of self-assembling ultrathin polymer film, at first by the synthetic membrane material of radical copolymerization, the thin polymer film that utilizes self-assembling technique to prepare to have various surface naturies.The polymer ultra-thin film of preparation has antifriction, anti-wear effect, can be used for the lubricated and protection of Micro Electro Mechanical System.This method be with mol ratio be 0.1～10% silane coupler and monomer with azodiisobutyronitrile with the initator copolymerization, purifying obtains self-assembling polymers; Self assembly film forming in clean substrate, and in inert gas, heat-treated 10～24 hours in 100 ℃～200 ℃.The process conditions of the self-assembled film of this method preparation are relatively loaded down with trivial details, and heat treatment period is also longer, does not also relate to improvement and the research of CNT to film performance.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of monocrystalline silicon sheet surface phosphate group silicone hydride-carbon nano-tube coextruded film is provided, technology is simple, and is with low cost, the thin-film material that preparation has good wear resistance.
For realizing this purpose, in the technical scheme of the present invention, the monocrystalline silicon piece that adopts surface process nano-cerium oxide polishing adopts self-assembling method to prepare phosphate group silicone hydride-rare earth modified carbon nanotube pipe laminated film as base material on its surface, makes it solve the friction problem of micro mechanical system.
Method of the present invention is specific as follows: at first monocrystalline silicon piece is carried out preliminary treatment, monocrystalline silicon piece is immersed in the chloroazotic acid, use electric furnace heating chloroazotic acid, heated 5～6 hours down at 120 ℃, naturally cooled off 7～8 hours 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 handling is immersed in the amino silane solution for preparing, left standstill 12 hours, after using absolute methanol, deionized water rinsing respectively after the taking-up, dry up to be placed on nitrogen and contain phosphorous oxychloride and 2,3, reaction is 20 minutes in the acetonitrile solution of 5-trimethylpyridine, takes out the back and uses a large amount of deionized water rinsings, obtains the film substrate that surface-assembled has phosphate group.
Again CNT is at room temperature immersed and soak 2～4 hours in the rare-earth modifier, filter the back oven dry.The CNT that processing obtains is put into N by 0.05～0.15mg/ml, and in dinethylformamide (DMF) dispersant, ultrasonic wave disperseed (40W) 1～4 hour, obtained steady suspension.Then surface-assembled there is the film substrate of phosphate group to immerse in the carbon nano tube suspension for preparing, left standstill 2～24 hours at 30～90 ℃, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, so just obtains the monocrystalline silicon piece that there is phosphate group silicone hydride-carbon nano-tube coextruded film on the surface.
The percent by volume of amino silane is 0.5～2% in the amino silane solution that the present invention adopts, and solvent is an absolute methanol.The component percent by volume of the acetonitrile solution that the present invention adopts is: phosphorous oxychloride 15～25%, 2,3,5-trimethylpyridine 15～25%, acetonitrile 50～70%.
The weight percentages of components of rare-earth modifier of the present invention is: rare earth compound 0.1～2%, alcohol 95～97%, ethylenediamine tetra-acetic acid 0.05～0.5%, ammonium chloride 0.1～1%, nitric acid 0.02～0.5%, urea 0.03～1%.
CNT of the present invention comprises single wall, double-walled or multi-walled carbon nano-tubes.
Rare earth compound of the present invention is a kind of in lanthanum chloride, cerium chloride, lanthana or the cerium oxide.
Process 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 amino silane molecules, can build Si-O by chemistry and combine with base material with active group Si-OH, form the silane self-assembled film that one deck has amino group at substrate surface; With surface-assembled the substrate of amino silane insert and contain phosphorous oxychloride and 2,3, in the acetonitrile solution of 5-trimethylpyridine, leave standstill a period of time after, film surface will be assembled phosphate group.After again it being inserted carbon nano tube suspension, substrate surface is with deposition of carbon nanotubes.
The configuration of rare-earth modifier among the present invention is simple, the carbon nano-tube coextruded film of monocrystalline silicon substrate surface preparation can be with coefficient of friction 0.8 during from no film be reduced to about 0.08, have fairly obvious antifriction function.Carbon nano-tube coextruded film also has good wear resistance in addition, is expected to become the desirable boundary lubricant film of micromachine.
The specific embodiment
Below by specific embodiment technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
Embodiment 1:
CNT: SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes that Nanometer Port Co., Ltd., Shenzhen produces.
Earlier monocrystalline silicon piece is carried out preliminary treatment, monocrystalline silicon piece is immersed in the chloroazotic acid, use electric furnace heating chloroazotic acid, heated 5～6 hours down at 120 ℃, cooled off 7～8 hours naturally 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 handling is immersed in the amino silane solution for preparing, left standstill 12 hours, use absolute methanol, deionized water rinsing after the taking-up respectively, dry up to be placed on nitrogen and contain phosphorous oxychloride and 2,3, reaction is 20 minutes in the acetonitrile solution of 5-trimethylpyridine, takes out the back and uses a large amount of deionized water rinsings, obtains the film substrate that surface-assembled has phosphate group.
At room temperature CNT is immersed in the rare-earth modifier and soaked 2 hours, filter the back oven dry.The CNT that processing is obtained is put into N by 0.05mg/ml then, dinethylformamide (DMF) dispersant, and ultrasonic wave disperseed (40W) 1 hour, obtained steady suspension.
There is the film substrate of phosphate group to immerse in the carbon nano tube suspension for preparing surface-assembled, under 30 ℃, left standstill 2 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, so just obtains the monocrystalline silicon piece that there is phosphate group silicone hydride-carbon nano-tube coextruded film on the surface.
Wherein in the amino silane solution of Cai Yonging amino silane percent by volume be 0.5%, solvent is an absolute methanol; The component percent by volume of acetonitrile solution is: phosphorous oxychloride 15%, 2,3,5-trimethylpyridine 15%, acetonitrile 70%.
Each weight percentages of components is as follows in the rare-earth modifier that present embodiment adopts: rare earth compound 0.3%, ethanol 97%, ethylenediamine tetra-acetic acid 0.4%, ammonium chloride 0.8%, nitric acid 0.5%, urea 1%.
Adopt SPM-9500 AFM (AFM), JEM-2010 SEM (SEM) and PHI-5702 type X-photoelectron spectrograph (XPS) to characterize the surface topography and the chemical composition of the composite membrane that obtains.Adopt the little frictional behaviour measuring instrument of the pure slip of some contact to measure the composite membrane coefficient of friction.
The XPS resolution chart shows at monocrystalline silicon sheet surface has successfully assembled the amino silane film; The amino silane film is presented to contains phosphorous oxychloride and 2,3, after reaction a period of time, observing film surface by XPS has P elements, and the assembled phosphate group of having gone up of film surface is described in the acetonitrile solution of 5-trimethylpyridine; The SEM picture sees clearly that then CNT is deposited on the surface of monocrystalline silicon piece, has formed carbon nano-tube coextruded film.On a little frictional behaviour measuring instrument of the pure slip of contact, measure the coefficient of friction of clean monocrystalline silicon piece and monocrystalline silicon sheet surface self assembly carbon nano-tube compound film respectively.The carbon nano-tube coextruded film of monocrystalline silicon sheet surface preparation can be with coefficient of friction 0.8 during from no film be reduced to about 0.12, have fairly obvious antifriction function.
Embodiment 2:
CNT: SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes that Nanometer Port Co., Ltd., Shenzhen produces.
Earlier monocrystalline silicon piece is carried out preliminary treatment, monocrystalline silicon piece is immersed in the chloroazotic acid, use electric furnace heating chloroazotic acid, heated 5～6 hours down at 120 ℃, cooled off 7～8 hours naturally 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 handling is immersed in the amino silane solution for preparing, left standstill 12 hours, after using absolute methanol, deionized water rinsing respectively after the taking-up, dry up to be placed on nitrogen and contain phosphorous oxychloride and 2,3, reaction is 20 minutes in the acetonitrile solution of 5-trimethylpyridine, takes out the back and uses a large amount of deionized water rinsings, obtains the film substrate that surface-assembled has phosphate group.
At room temperature CNT is immersed in the rare-earth modifier and soaked 3 hours, filter the back oven dry.The CNT that processing obtains is put into N by 0.1mg/ml then, and in dinethylformamide (DMF) dispersant, ultrasonic wave disperseed (40W) 2 hours, obtained steady suspension.
There is the film substrate of phosphate group to immerse in the carbon nano tube suspension for preparing surface-assembled, under 60 ℃, left standstill 12 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, so just obtains the monocrystalline silicon piece that there is phosphate group silicone hydride-carbon nano-tube coextruded film on the surface.
In the amino silane solution that present embodiment adopts amino silane percent by volume be 1.5%, solvent is an absolute methanol.The component percent by volume of acetonitrile solution is: phosphorous oxychloride 20%, 2,3,5-trimethylpyridine 20%, acetonitrile 60%.
Each weight percentages of components in the rare-earth modifier that present embodiment adopts: rare earth compound 0.5%, ethanol 97%, ethylenediamine tetra-acetic acid 0.2%, ammonium chloride 1%, nitric acid 0.5%, urea 0.8%.
Adopt the characterization method among the embodiment 1 that film quality is estimated.
The XPS resolution chart shows at monocrystalline silicon sheet surface has successfully assembled the amino silane film; The amino silane film is presented to contains phosphorous oxychloride and 2,3, after reaction a period of time, observing film surface by XPS has P elements, and the assembled phosphate group of having gone up of film surface is described in the acetonitrile solution of 5-trimethylpyridine; The SEM picture sees clearly that then CNT is deposited on the surface of monocrystalline silicon piece, has formed carbon nano-tube coextruded film; The carbon nano-tube coextruded film of monocrystalline silicon sheet surface preparation can be with coefficient of friction 0.8 during from no film be reduced to about 0.1, have fairly obvious antifriction function.
Embodiment 3:
CNT: SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes that Nanometer Port Co., Ltd., Shenzhen produces.
Earlier monocrystalline silicon piece is carried out preliminary treatment, monocrystalline silicon piece is immersed in the chloroazotic acid, use electric furnace heating chloroazotic acid, heated 5～6 hours down at 120 ℃, cooled off 7～8 hours naturally 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 handling is immersed in the amino silane solution for preparing, left standstill 12 hours, after using absolute methanol, deionized water rinsing respectively after the taking-up, dry up to be placed on nitrogen and contain phosphorous oxychloride and 2,3, reaction is 20 minutes in the acetonitrile solution of 5-trimethylpyridine, takes out the back and uses a large amount of deionized water rinsings, obtains the film substrate that surface-assembled has phosphate group.
At room temperature CNT is immersed in the rare-earth modifier and soaked 4 hours, filter the back oven dry.The CNT that processing obtains is put into N by 0.15mg/ml then, dinethylformamide (DMF) dispersant, ultrasonic wave disperseed (40W) 4 hours, obtained steady suspension.
There is the film substrate of phosphate group to immerse in the carbon nano tube suspension for preparing surface-assembled, under 90 ℃, left standstill 24 hours, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, so just obtains the monocrystalline silicon piece that there is phosphate group silicone hydride-carbon nano-tube coextruded film on the surface.
In the amino silane solution that the present invention adopts amino silane percent by volume be 2%, solvent is an absolute methanol.The component percent by volume of acetonitrile solution is: phosphorous oxychloride 25%, 2,3,5-trimethylpyridine 25%, acetonitrile 50%.
The proportioning of the rare-earth modifier that present embodiment adopts: rare earth compound 1%, ethanol 96%, ethylenediamine tetra-acetic acid 0.5%, ammonium chloride 1%, nitric acid 0.5%, urea 1%.
The XPS resolution chart shows at monocrystalline silicon sheet surface has successfully assembled the amino silane film; The amino silane film is presented to contains phosphorous oxychloride and 2,3, after reaction a period of time, observing film surface by XPS has P elements, and the assembled phosphate group of having gone up of film surface is described in the acetonitrile solution of 5-trimethylpyridine; The SEM picture sees clearly that then CNT is deposited on the surface of monocrystalline silicon piece, has formed carbon nano-tube coextruded film.The carbon nano-tube coextruded film of monocrystalline silicon sheet surface preparation can be with coefficient of friction 0.8 during from no film be reduced to about 0.08, have fairly obvious antifriction function.
Claims (2)
1, a kind of preparation method of monocrystalline silicon sheet surface phosphate group silicone hydride-carbon nano-tube coextruded film, it is characterized in that at first monocrystalline silicon piece being immersed in the chloroazotic acid, use electric furnace heating chloroazotic acid, heated 5～6 hours down at 120 ℃, naturally cooled off 7～8 hours 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 handling is immersed in the amino silane solution for preparing, left standstill 12 hours, use absolute methanol, deionized water rinsing after the taking-up respectively, dry up to be placed on nitrogen then and contain phosphorous oxychloride and 2,3, reaction is 20 minutes in the acetonitrile solution of 5-trimethylpyridine, takes out the back and uses deionized water rinsing, obtains the film substrate of surface with phosphate group;
Again CNT is at room temperature immersed and soak 2～4 hours in the rare-earth modifier, filter the back oven dry, the CNT that processing obtains is put into N by 0.05～0.15mg/ml, in the dinethylformamide dispersant, the 40W ultrasonic wave disperseed 1～4 hour, obtain stable carbon nano tube suspension, then surface-assembled there is the film substrate of phosphate group to immerse in the carbon nano tube suspension for preparing, left standstill 2～24 hours at 30～90 ℃, take out and use a large amount of deionized water rinsings, the flushing back dries up with nitrogen, obtains the monocrystalline silicon piece that there is phosphate group silicone hydride-carbon nano-tube coextruded film on the surface;
Wherein, the percent by volume of amino silane is 0.5～2% in the described amino silane solution, and solvent is an absolute methanol; The component percent by volume of described acetonitrile solution is: phosphorous oxychloride 15～25%, 2,3,5-trimethylpyridine 15～25%, acetonitrile 50～70%; The weight percentages of components of described rare-earth modifier is: rare earth compound 0.1～2%, alcohol 95～97%, ethylenediamine tetra-acetic acid 0.05～0.5%, ammonium chloride 0.1～1%, nitric acid 0.02～0.5%, urea 0.03～1%; Described rare earth compound is a kind of in lanthanum chloride, cerium chloride, lanthana, the cerium oxide.
2, the preparation method of monocrystalline silicon sheet surface phosphate group silicone hydride-carbon nano-tube coextruded film as claimed in claim 1 is characterized in that described CNT is single wall, double-walled or multi-walled carbon nano-tubes.
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| CNB2007100370456A CN100479931C (en) | 2007-02-01 | 2007-02-01 | Method for producing compound thin film of phosphoric acid radicle silane-carbon nanotubes on the surface of single crystal silicon wafers |
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| CNB2007100370456A CN100479931C (en) | 2007-02-01 | 2007-02-01 | Method for producing compound thin film of phosphoric acid radicle silane-carbon nanotubes on the surface of single crystal silicon wafers |
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| CN102383197B (en) * | 2010-09-02 | 2013-12-11 | 北大方正集团有限公司 | Method for processing substrates with process gas |
| CN102092957A (en) * | 2010-12-08 | 2011-06-15 | 上海交通大学 | Preparation method of phosphate silane-carbon nanotube composite film on surface of quartz substrate |
| CN102584334A (en) * | 2012-01-13 | 2012-07-18 | 上海交通大学 | Method for preparing graphene composite thin film on surface of silicon slice |
| CN102582148B (en) * | 2012-02-15 | 2014-11-12 | 上海交通大学 | Method for preparing phosphoryl silane-carbon nano tube composite thin film on surface of titanium alloy |
| CN103296127B (en) * | 2012-02-27 | 2016-01-06 | 浙江启鑫新能源科技股份有限公司 | The preparation method of rare earth modified carbon nanotube silicon solar cell |
| CN103232266B (en) * | 2013-04-18 | 2015-07-15 | 上海交通大学 | Preparation method of silicon substrate surface oxidized carbon-nanotube self-assembly composite film |
| CN104908423B (en) * | 2015-06-26 | 2016-08-24 | 京东方科技集团股份有限公司 | A kind of film manufacturing method and system |
| KR102399680B1 (en) * | 2015-08-19 | 2022-05-19 | 에스케이이노베이션 주식회사 | Method for evaluating quality of carbon nanotube |
| CN110451454B (en) * | 2019-07-17 | 2022-04-22 | 湘潭大学 | Cross-scale friction-reducing wear-resisting modification method and characterization method for monocrystalline silicon surface |
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