CN1300369C - Method for preparing self-assenbling monomolecular film in vapor phase and vapor phase assembiling instrument - Google Patents
Method for preparing self-assenbling monomolecular film in vapor phase and vapor phase assembiling instrument Download PDFInfo
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- CN1300369C CN1300369C CNB021383200A CN02138320A CN1300369C CN 1300369 C CN1300369 C CN 1300369C CN B021383200 A CNB021383200 A CN B021383200A CN 02138320 A CN02138320 A CN 02138320A CN 1300369 C CN1300369 C CN 1300369C
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Abstract
The present invention relates to a method for preparing a self-assembled monomolecular film in a vapor phase and a vapor phase assembling apparatus thereof. The present invention is characterized in that fresh basal pieces are put into a vacuum chamber which can be pumped into vacuum in the vapor phase assembling apparatus composed of two vacuum chambers which are connected by a pipeline with a vacuum valve; after being enclosed, the vapor phase assembling apparatus is pumped into vacuum; a substance to be assembled is displaced into the other vacuum chamber in the vapor phase assembling apparatus; the vacuum valve for connecting the two vacuum chambers is opened for a period, and then, is closed, so a product is obtained on the basal piece; the basal piece is a metal film which is freshly prepared, and comprises Au, Ag, Pt, Cu or the single crystals or the silicon chips of the metals; molecules to be assembled comprise thiol and silicon hydride. The method for preparing a self-assembled monomolecular film in a vapor phase and the vapor phase assembling apparatus enable the self-assembled preparation process of a monomolecular film to have the advantages of convenience, simple and available structure, cleanness and rapidity, overcome many cockamamie processes for preparing the self-assembled monomolecular film in a solution at present, greatly shorten film-forming time, reduce pollution and are suitable for the needs of industrialized large-scale production.
Description
Technical field:
The invention belongs to field of nanometer technology, relate to vapour phase processes self-assembled monolayer and vapour phase thereof assembling instrument.
Background technology:
Mention in 97 pages of " SCI " 1999 20 the 1st phases of volume; self-assembled monolayer (Self-Assembled Monolayers; be called for short SAMs) be bioactive molecule by the spontaneous orderly supramolecular system that forms on the out-phase interface that is adsorbed on of chemical bond, its thermodynamic stability is good, the degree of order is high, can be shifted out from the solution transfer after the film forming.This self-assembled monolayer all has the important use potentiality in fields such as nanometer manufacturing, molecular device, molecular biology, materialogy, biological chemistry, microelectron-mechanical and magnetic recording system are lubricated." Science Bulletin " rolled up 449 pages of the 5th phases in 1998 43 and point out that existing unimolecular film self assembling process is all finished in solution, and its film forming principle is by the chemisorption film forming between solid-liquid interface.With alkyl sulfhydryl and these two kinds of modal self assembly molecules of silane is example: in the organic solution of mercaptan or silane, immerse certain substrate (as gold and silver, copper, silicon), the reactive group (siloxy) of reactive group of mercaptan (sulfydryl) or silane and substrate surface material generation successive chemical reaction are at unit molecule mercaptan film or the silane film of substrate surface formation by the compact arranged sequential 2 D of chemical bond connection.The Van der Waals force effect is arranged between molecule in the self-assembled film and the molecule, thereby form fine and close, stable unitary film." JACS " (J.Am.Chem.Soc, 1998,120, the method for 2721-2732) mentioning for preparing the mercaptan film is: dispose certain density thiol solution with solvent in clean container; Then clean fresh substrate is put into this thiol solution, soak and took out afterwards in 24-48 hour, use solvent washing, nitrogen dries up.Obviously, this in solution the procedure of preparation self-assembled monolayer loaded down with trivial details: at first, it needs obtain solution, and to the requirement height of solvent, container cleanliness factor; Substrate must soak the long period in thiol solution; After finishing, self-assembly also needs to use solvent washing; Whole unimolecular film self-assembly preparation process needs the long period.
Summary of the invention:
The present invention proposes a kind of easy, quick method-vapour phase processes for preparing self-assembled monolayer, and the employed instrument of this method-vapour phase assembling instrument.
Vapour phase assembling instrument of the present invention, it is characterized in that this assembling instrument is used for preparing self-assembled monolayer in vapour phase, it is made of two vacuum chambers 3 and 6 that are connected with pipeline 4 two ends that have vacuum valve 5, the vacuum chamber 6 of one of them vacuum-pumping has the arm 7 that is used to vacuumize, and this arm 7 is provided with vacuum valve 8; Be respectively equipped with on the vacuum chamber 3 and 6 for picking and placeing opening 2 that sample operation uses and 9 and sealing cover 1 and 10.
The present invention prepares the method for self-assembled monolayer in vapour phase, it is characterized in that: the vacuum chamber 6 of fresh substrate being put into the vacuum-pumping of two vacuum chambers that are connected with pipeline 4 two ends, wherein have the vacuum valve 5 that connects two vacuum chambers on the pipeline 4, vacuumize behind the vacuum valve 5 of two vacuum chambers of sealing connection; Close vacuumizing on the vacuum chamber 6 that is positioned at vacuum-pumping after vacuumizing with the vacuum valve 8 on the arm 7; Pipette and wait to assemble the material of molecule to another vacuum chamber 3 of assembling in the instrument, after the sealing, the vacuum valve 5 that connects two vacuum chambers was opened 10 seconds-600 seconds, closed the vacuum valve 5 that connects two vacuum chambers, promptly obtain product on the substrate in the vacuum chamber 6 of vacuum-pumping; Described substrate is the metallic membrane of prepared fresh, comprises Au, Ag, Pt, Cu, perhaps the monocrystalline of these several metals or silicon chip; The described material of assembling molecule of waiting comprises mercaptan and silane.
Everyly can prepare its self-assembled monolayer by method provided by the invention by the spontaneous molecule that forms orderly supramolecular system on the out-phase interface that is adsorbed on of chemical bond.
Compare with the method for preparing self-assembled monolayer in the existing solution, though ultimate principle is roughly the same: by waiting to assemble the reactive group and the substrate surface material generation successive chemical reaction of molecule and waiting to assemble Van der Waals force effect between the molecule, in the unimolecular film of the spontaneous formation of substrate surface by the compact arranged sequential 2 D of chemical bond connection, but because the present invention has adopted vapour phase processes, the a lot of complicated processes that make existing solution method prepare self-assembled monolayer are simplified: at first, vapour phase processes of the present invention does not need obtain solution; Secondly, whole sample making course just needs several minutes altogether, need in solvent, soak 24-48 hour unlike existing solution method, thus shortened film formation time greatly, thus the chance that unimolecular film is polluted also reduced; Once more, prepare in the process of self-assembled monolayer in existing solution method, because the soak time of substrate in solution is longer, easy some the unnecessary molecules of physical adsorption in unimolecular film surface that assembling, therefore need use solvent washing after assembling finishes, and only need several minutes with the process that vapour phase processes prepares unimolecular film, the film surface is difficult for adsorbing unnecessary molecule, after assembling finishes, do not need to use solvent washing, when reducing operation, solved the pollution problem that solvent easily brings again like this.Vapour phase processes of the present invention and device thereof make easy, the easy row of the self-assembly preparation process of unimolecular film, clean, quick, have shortened film formation time greatly, have reduced pollution, can adapt to the needs that large-scale industrialization is produced.
Description of drawings:
Fig. 1 is the basic structure synoptic diagram of vapour phase assembling instrument of the present invention;
Fig. 2 is the structural representation of a kind of concrete vapour phase assembling instrument that uses among the embodiment.
Fig. 3, Fig. 4 are respectively the six carbon list mercaptan that prepare among embodiment scanning tunnel microscope (STM) scanning images at the self-assembled film on golden film surface, and wherein the sweep limit of Fig. 3 is 100nm * 100nm, and the sweep limit of Fig. 4 is 30nm * 30nm; The scale on next door is an altitude scale.
Embodiment:
Embodiment 1:
(1) at first make a vapour phase assembling instrument that stopping property as shown in Figure 1 is good: it is made of two vacuum chambers 3 and 6, and one of them vacuum chamber 6 is connected to an arm 7 that can be connected with pumped vacuum systems, and arm 7 is provided with vacuum valve 8; Two vacuum chambers 3 are connected with two ends that have the pipe 4 of vacuum valve 5 respectively with 6; Vacuum chamber 3 and 6 is respectively equipped with for picking and placeing opening 2 that sample operation uses and 9 and sealing cover 1 and 10.
(2) preparation of substrate: used substrate in the present embodiment is under ultrahigh vacuum(HHV), is about the golden film of high purity (99.999%) prepared fresh that gold becomes of 100nm at mica surface evaporation last layer thickness; Also can adopt the high purity metal that comprises Ag, Pt, Cu, perhaps Qing Jie metal single crystal or silicon chip.
(3) preparation self-assembled monolayer:
Before the experiment beginning, all vacuum valves are all closed.
Open the sealing cover 10 of the vacuum chamber 6 of vacuum-pumping, fresh substrate is put into vacuum chamber 6 by opening 9, close sealing cover 10; Open the valve 8 on the arm 7, vacuumize several minutes (such as 3-5 minute, vacuum need not too high), valve-off 8 then;
Open the sealing cover 1 of another vacuum chamber 3, the small vessels that fills the mercaptan drop is put into vacuum chamber 3 by opening 2, close sealing cover 1;
Open the vacuum valve 5 that connects between two vacuum chambers 3 and 6, make two vacuum chamber close vacuum valve 5 after 30 seconds; For mercaptan, the time of this two vacuum chamber generally can be controlled in 10-120 second, if the time is too short, can not have time enough to grow by molecular film, and oversize then easily causing of time pollutes.
From vacuum chamber 6 product is taken out, (STM) does scanning to product with scanning tunnel microscope.Fig. 3, Fig. 4 are respectively the six carbon list mercaptan that prepare in present embodiment scanning tunnel microscope (STM) scanning images at the self-assembled film on golden film surface, and wherein the sweep limit of Fig. 3 is 100nm * 100nm, and the sweep limit of Fig. 4 is 30nm * 30nm; The scale on next door is an altitude scale.Can be clear that in the drawings and the 1119th page of (Chem.Rev.1997 of " chemistry comment " 97 volumes in 1997,97, the peculiar identical hole of self-composed monomolecular mercaptan film (pinholes) structure that scanning tunnel microscope photo that 1117-1127) mention in the paper and appended is shown, the while can also be seen the atom phase of mercaptan in Fig. 4.Explanation has been assembled unit molecule mercaptan film on substrate gold film thus.
Embodiment 2:
Be optimization experiment; present embodiment adopted a kind of on Fig. 1 basis improved vapour phase assembling instrument as shown in Figure 2; characteristics are to have increased by two arms 11 and 13 that vacuum valve 12,14 is housed respectively on therein the vacuum chamber 3; be used for logical nitrogen; make in the vacuum chamber 3 to be full of nitrogen protection, pollute thereby reduce.
The preparation of substrate, identical with embodiment 1;
Before the experiment beginning, all vacuum valves are all closed;
Open sealing cover 1; the small vessels that fills silane droplets is put into vacuum chamber 3 by opening 2; close sealing cover 1; on an arm 11 of this vacuum chamber 3, connect nitrogen; open the vacuum valve 12 and 14 on arm 11 and 13 subsequently; logical nitrogen is closed vacuum valve 12 and 14 after 10 minutes, make in the vacuum chamber 3 to be full of nitrogen protection, pollutes thereby reduce.
Open the vacuum valve 5 that connects two vacuum chambers 3,6, make two vacuum chamber close vacuum valve 5 after 600 seconds.Because the saturation steam of the saturation steam pressure ratio mercaptan of silane forces down, so make the built-up time of two vacuum chamber do suitable increase in the present embodiment.
At last, product in the vacuum chamber 6 is taken out.Adopt the method identical to test, prove that resulting product is the self-composed monomolecular silane film with embodiment 1.
Claims (3)
1, a kind of vapour phase assembling instrument, it is characterized in that this assembling instrument is used for preparing self-assembled monolayer in vapour phase, it is by two vacuum chambers (3 that are connected with the pipeline that has vacuum valve (5) (4) two ends, 6) constitute, the vacuum chamber of one of them vacuum-pumping (6) has the arm (7) that is used to vacuumize, and this arm (7) is provided with vacuum valve (8); Be respectively equipped with on two vacuum chambers (3,6) for picking and placeing opening (2,9) and the sealing cover (1,10) thereof that sample operation is used.
2, vapour phase assembling instrument as claimed in claim 1, being characterised in that wherein not have has increased by two arms (11,13) that vacuum valve (12,14) are housed respectively on the vacuum chamber (3) that vacuumizes arm (7).
3, a kind of method that in vapour phase, prepares self-assembled monolayer, it is characterized in that: the vacuum chamber (6) of fresh substrate being put into the vacuum-pumping of two vacuum chambers that pipeline (4) two ends are connected, wherein have the vacuum valve (5) that connects two vacuum chambers on the pipeline (4), vacuumize behind the vacuum valve (5) of two vacuum chambers of sealing connection; Close vacuumizing on the vacuum chamber (6) that is positioned at vacuum-pumping after vacuumizing with the vacuum valve (8) on the arm (7); Pipette and wait to assemble the material of molecule to another vacuum chamber (3) of assembling in the instrument, after the sealing, the vacuum valve (5) that connects two vacuum chambers was opened 10 seconds-600 seconds, closed the vacuum valve (5) that connects two vacuum chambers, promptly obtain product on the substrate in the vacuum chamber (6) of vacuum-pumping; Described substrate is the metallic membrane of prepared fresh, comprises Au, Ag, Pt, Cu, perhaps the monocrystalline of these several metals or silicon chip; The described material of assembling molecule of waiting comprises mercaptan and silane.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021383200A CN1300369C (en) | 2002-09-20 | 2002-09-20 | Method for preparing self-assenbling monomolecular film in vapor phase and vapor phase assembiling instrument |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021383200A CN1300369C (en) | 2002-09-20 | 2002-09-20 | Method for preparing self-assenbling monomolecular film in vapor phase and vapor phase assembiling instrument |
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| CN1483851A CN1483851A (en) | 2004-03-24 |
| CN1300369C true CN1300369C (en) | 2007-02-14 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01228539A (en) * | 1988-03-08 | 1989-09-12 | Fuji Photo Film Co Ltd | Formation of built-up film |
| CN1081933A (en) * | 1992-08-08 | 1994-02-16 | 东南大学 | A kind of molding press for unimolecular film |
| WO1997038802A1 (en) * | 1996-04-12 | 1997-10-23 | The Texas A & M University System | Polymeric self-assembled mono- and multilayers and their use in photolithography |
| CN1358804A (en) * | 2001-12-17 | 2002-07-17 | 中国科学院兰州化学物理研究所 | Method for preparing solid film surface fatty acid self-composed monomolecular ultrathin lubrication membrane |
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2002
- 2002-09-20 CN CNB021383200A patent/CN1300369C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01228539A (en) * | 1988-03-08 | 1989-09-12 | Fuji Photo Film Co Ltd | Formation of built-up film |
| CN1081933A (en) * | 1992-08-08 | 1994-02-16 | 东南大学 | A kind of molding press for unimolecular film |
| WO1997038802A1 (en) * | 1996-04-12 | 1997-10-23 | The Texas A & M University System | Polymeric self-assembled mono- and multilayers and their use in photolithography |
| CN1358804A (en) * | 2001-12-17 | 2002-07-17 | 中国科学院兰州化学物理研究所 | Method for preparing solid film surface fatty acid self-composed monomolecular ultrathin lubrication membrane |
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