CN103755384B - A kind of method of silicon nanowire array finishing organic molecule - Google Patents
A kind of method of silicon nanowire array finishing organic molecule Download PDFInfo
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- CN103755384B CN103755384B CN201410024915.6A CN201410024915A CN103755384B CN 103755384 B CN103755384 B CN 103755384B CN 201410024915 A CN201410024915 A CN 201410024915A CN 103755384 B CN103755384 B CN 103755384B
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Abstract
The invention discloses a kind of method of silicon nanowire array finishing organic molecule, the method comprises the steps: 1) by the hydrogen fluoride solution process of silicon nano-array surface, obtain the silicon nanowire array after processing; 2) anhydrous and under the condition of starvation, by step 1) obtained silicon nanowire array and grignard reagent react, and obtains the silicon nanowire array of finishing.The method is simple and safe easy, be a kind of effectively build silicon nanowire array-organic molecule group method and present method modify after silicon nanowire array in photoelectrocatalysis, have excellent performance.
Description
Technical field
The present invention relates to field of nanometer material technology, particularly relate to a kind of method of silicon nanowire array finishing organic molecule.
Background technology
Silicon nanowire array is the important construction unit of silicon-based nano device.Silicon nanowire array is the structural motif of the very promising nanoelectronics of a class and sensor component.But in actual applications, the existence of the oxide compound of surface of silicon nanowires is that our institute is undesired, because the zone of oxidation of this defect such as silicon-dioxide, can cause producing uncontrollable surface state (Ossama A. in being with of silicon, J.Am.Chem.Soc.2008,130,17670-17671).
Be that the silicon nanowires H-SiNWs of end group has low recombination-rate surface with hydrogen, but unstable in atmosphere, and chief reason is the formation of unordered zone of oxidation.Lewis group (Ronald L, .J.Phys.Chem.C.2012,116,23569-23576) analyze respectively with hydrogen be end group silicon nanowires H-SiNWs and take methyl as the silicon nanowires CH3-SiNWs of end group, for p-type silicon, CH3-SiNWs array is relative to H-SiNWs array open circuit loss of voltage; For N-shaped silicon, CH3-SiNWs array raises relative to H-SiNWs array open circuit voltage, and wherein the displacement of flat-band potential is relevant with the pseudo-contact shift of interface.The precious full group (Zhang F .Chem.Mater.2011,23,2084-2090) of grandson improves the photoelectric transformation efficiency of solar cell by the surface of methyl SiClx.
But carry out on silicon nanowire array surface at present methylated method be two-step reaction method namely first by surface of silicon nanowires chlorination, then to methylate with grignard reagent react.In this method, chlorination reagent is phosphorus pentachloride, has very strong toxicity, and meet water and can release chlorine, experiment danger is very high; And this two step all requires anhydrous and oxygen-free condition, so harsh experiment condition makes the success ratio of experiment low.
Therefore, be necessary the silicon nanowire array utilizing simple safe chemical modification method to modify to obtain organic molecule at surface of silicon nanowires, and do not use more dangerous phosphorus pentachloride reagent, and directly react with the fresh silicon nanowire array of Grignard reagent and HF process, construct the silicon nanowire array methylating and modify.Meanwhile, different Grignard reagents will obtain the silicon nanowire array of different finishinges, and this will greatly enrich the surface-functionalized modification strategy of silicon.This will be applied to solar cell for silicon nanowire array, photoelectrocatalysis splitting water, and the research and development of sensor field create material conditions and basis with application.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of silicon nanowire array finishing organic molecule, and the silicon nanowire array after present method modification has excellent performance in photoelectrocatalysis.
For solving the problems of the technologies described above, the present invention adopts following technical proposals:
1) hydrogen fluoride solution process is used on silicon nanowire array surface, obtain the silicon nanowire array after processing;
2) anhydrous and under the condition of starvation, by step 1) obtained silicon nanowire array and Grignard reagent react, and obtains the silicon nanowire array of finishing.
Preferably, described method also comprises the steps
3) to step 2) silicon nanowire array of finishing that obtains washs, dry, described washing solvent used is tetrahydrofuran (THF) or ethanol.
Preferably, step 1) described in the mass concentration of hydrogen fluoride solution be 1% ~ 15%, preferably, the mass concentration of described hydrogen fluoride solution is 10%.
Preferably, step 2) described in the strength of solution of Grignard reagent be 0.5 ~ 3mol/L, preferably, the strength of solution of described Grignard reagent is 1mol/L; Described Grignard reagent is selected from methylmagnesium-chloride, methyl-magnesium-bromide, methylpyridinium iodide magnesium, ethylmagnesium chloride or ethylmagnesium bromide.
Preferably, step 2) described in temperature of reaction be 60 ~ 90 DEG C, preferably, described temperature of reaction is 70 DEG C; The described reaction times is 1 ~ 144h, and preferably, the described reaction times is 8h.
Preferably, step 2) described in the anhydrous and condition of starvation refer to that reaction is carried out in the organic solvent of drying; Described organic solvent is selected from tetrahydrofuran (THF), ethanol or acetone.
Preferably, the inventive method prepares the silicon nanowire array that methyl is modified.
Beneficial effect of the present invention is as follows:
The invention provides a kind of method of silicon nanowire array surface being carried out to organic molecule modification.The method is simple and safe easy, is a kind of method effectively building silicon nanowire array-organic molecule group.Adopt the new page that single stage method directly will be opened the surperficial alkylation of silicon nanowire array with the strategy of grignard reagent react and modified.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail;
Fig. 1 is the schema of silicon nanowire array finishing methyl;
Fig. 2 is the In situ ATR-FTIR of the silicon nanowire array having modified methyl;
Fig. 3 is the ATR-FTIR constituency spectrum of the silicon nanowire array having modified methyl.
Embodiment
For understanding the present invention better, will further illustrate the solution of the present invention below by specific embodiment, protection scope of the present invention should comprise the full content of claim, but is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, except silicon nanowire array, if no special instructions, all can obtain from commercial channels.
Embodiment 1
Silicon nanowire array used in embodiment prepares by the following method:
1. the preparation of silicon nanowire array: adopt the metal ion Assisted Chemical Etching Process method (Peng reported in existing document, Q.Chem.Eur.J.2006,12,7942-7947.) (metal-assisted electrolesschemical etching method) prepare silicon nanowires.
(P's N (100) crystal orientation monocrystalline silicon piece adulterates, resistivity 0.01-0.02 Ω cm) use chromic acid lotion (potassium bichromate 5g, vitriol oil 100ml, the mixing solutions of water 10ml) soak one hour, washed with de-ionized water is used after taking-up, re-use the organism on the ultrasonic removing surface of acetone, then use deionized water rinsing removing acetone.It is 20% that silicon chip after cleaning is immersed hydrofluoric acid containing concentration, etches, bath temperature 50 DEG C in the mixing etching solution of silver nitrate concentration 0.04M.After having etched rear use deionized water rinsing silicon chip surface, to be immersed in chloroazotic acid one hour, the Ag particle that removing is residual, re-used washed with de-ionized water silicon chip.
2. prepare the silicon nanowire array that methyl is modified
Silicon nanowire array is soaked 15 minutes in the HF solution of 10%; Under drying temperature is 50 DEG C and pressure is the condition of 1000Pa, silicon nanowire array after above-mentioned immersion is placed in vacuum drying oven dry 3 hours, obtain the silicon nanowire array after drying treatment, silicon nanowire array is placed in three-necked bottle, repeat to vacuumize logical nitrogen three times, in three-necked bottle, inject the tetrahydrofuran solution of the methylmagnesium-chloride of 1mol/L
20mL, stirs, and reacts 8 hours under 80 DEG C of conditions, obtains the silicon nanowire array that methyl is modified; Cooled by products therefrom, with dehydrated alcohol, anhydrous tetrahydro furan rinses three times respectively, rear preservation to be dried.
In situ ATR-FTIR (ATR-IR) analysis is carried out to the silicon nanowire array that the methyl obtained is modified, see Fig. 2, two absorption peaks are had as can be seen from Figure 2 between 2700 ~ 3000, choose separately in this interval carry out ATR-FTIR characterize see Fig. 3, in Fig. 3, the position at peak and peak type feature are symmetric and anti-symmetric stretching vibration peak 2876 and the 2960cm-1 of typical methyl, illustrate that methyl is bonded to silicon chip surface (Boukherroub., Langmuir, 1999,15,3831-3835).
Embodiment 2
As different from Example 1 methylmagnesium-chloride is replaced with methyl-magnesium-bromide, obtain the silicon nanowire array that methyl is modified.
Embodiment 3
As different from Example 1 methylmagnesium-chloride is replaced with methylpyridinium iodide magnesium, obtain the silicon nanowire array that methyl is modified.
Embodiment 4
As different from Example 1 methylmagnesium-chloride is replaced with the silicon nanowire array that ethylmagnesium bromide obtains ethyl modification.
Embodiment 5
As different from Example 1 methylmagnesium-chloride is replaced with the silicon nanowire array that ethyl phosphonium iodide magnesium obtains ethyl modification.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (6)
1. a method for silicon nanowire array finishing organic molecule, is characterized in that, comprises
Following steps:
1) hydrogen fluoride solution process is used on silicon nanowire array surface, obtain the silicon nanowire array after processing;
2) anhydrous and under the condition of starvation, by step 1) obtained silicon nanowire array and Grignard reagent react, and obtains the silicon nanowire array of finishing.
2. method according to claim 1, is characterized in that: described method also comprises the steps
3) to step 2) silicon nanowire array of finishing that obtains washs, dry, described washing solvent used is tetrahydrofuran (THF) or ethanol.
3. method according to claim 1 and 2, is characterized in that: step 1) described in the mass concentration of hydrogen fluoride solution be 1% ~ 15%.
4. method according to claim 3, is characterized in that: step 2) described in the strength of solution of Grignard reagent be 0.5 ~ 3mol/L; Described Grignard reagent is selected from methylmagnesium-chloride, methyl-magnesium-bromide, methylpyridinium iodide magnesium, ethylmagnesium chloride or ethylmagnesium bromide.
5. method according to claim 4, is characterized in that: step 2) described in temperature of reaction be 60 ~ 90 DEG C; The described reaction times is 1 ~ 144h.
6. method according to claim 5, is characterized in that: step 2) described in the anhydrous and condition of starvation refer to that reaction is carried out in the organic solvent of drying; Described organic solvent is selected from tetrahydrofuran (THF), ethanol or acetone.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102260493A (en) * | 2010-10-15 | 2011-11-30 | 中国科学院理化技术研究所 | Silicon nanowire-organic functional compound composite and preparation method thereof |
| CN102851022A (en) * | 2012-09-27 | 2013-01-02 | 苏州大学 | Preparation method of fluorescent silica nanoparticles |
| CN102928391A (en) * | 2012-10-11 | 2013-02-13 | 中国科学院理化技术研究所 | Silicon nanowire ordered array-based pH fluorescence sensor and manufacturing method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102260493A (en) * | 2010-10-15 | 2011-11-30 | 中国科学院理化技术研究所 | Silicon nanowire-organic functional compound composite and preparation method thereof |
| CN102851022A (en) * | 2012-09-27 | 2013-01-02 | 苏州大学 | Preparation method of fluorescent silica nanoparticles |
| CN102928391A (en) * | 2012-10-11 | 2013-02-13 | 中国科学院理化技术研究所 | Silicon nanowire ordered array-based pH fluorescence sensor and manufacturing method and application thereof |
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