CN1810810A - Process of preparing organic molecular line on the surface of silicon semiconductor - Google Patents
Process of preparing organic molecular line on the surface of silicon semiconductor Download PDFInfo
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- CN1810810A CN1810810A CN 200510111834 CN200510111834A CN1810810A CN 1810810 A CN1810810 A CN 1810810A CN 200510111834 CN200510111834 CN 200510111834 CN 200510111834 A CN200510111834 A CN 200510111834A CN 1810810 A CN1810810 A CN 1810810A
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Abstract
本发明属分子电子器件制备技术领域，具体为一种将有机分子嫁接到硅半导体表面以实现在硅半导体表面制备有机分子线的方法。本发明利用紫外光、等离子体手段对硅半导体表面进行处理，使硅表面产生可供进一步反应的活性点，这些活性点与有机分子上含有的活性官能团进行反应，在硅表面形成牢固的化学键，从而在硅半导体表面制备有机分子线。该方法可以适用于以硅半导体材料为基础的分子电子器件的制备。The invention belongs to the technical field of molecular electronic device preparation, and specifically relates to a method for grafting organic molecules onto the surface of a silicon semiconductor to realize the preparation of organic molecular wires on the surface of the silicon semiconductor. The present invention uses ultraviolet light and plasma means to treat the silicon semiconductor surface, so that the silicon surface generates active points for further reaction, and these active points react with the active functional groups contained on the organic molecules to form firm chemical bonds on the silicon surface, Thus, organic molecular wires are prepared on the surface of silicon semiconductor. The method can be applied to the preparation of molecular electronic devices based on silicon semiconductor materials.
Description
Technical field
The invention belongs to the molecular electronic device preparing technical field, be specifically related to a kind of UV-light or plasma technique of utilizing and handle the silicon semiconductor material surface, the method for organic molecule grafting to silicon face.
Background technology
Electronics is experiencing vacuum electronics and Solid State Electronics after two periods, and current being in the ultra large scale integrated circuit is the microtronics period of feature.The development of super large-scale integration at present is faced with challenge, and these challenge the physical restriction of existing principle, and technical process technology limit is arranged again.At these problems, scientists is being fermented a new change-----molectronics of electronics.Molectronics research be electronics on the molecular level, its target is to use individual molecule, supramolecule or molecular clustering replace Solid State Electronics element assembling logical circuits such as silicon-based semiconductor transistor, and even assemble complete molecular computer.Its research contents comprises the synthetic of various molecular electronic devices, performance test and how they being fitted together to realize certain logic function.Compare with traditional Solid State Electronics, molectronics has powerful advantage.Existing microelectronic processing technology will be near the limit of development after 10 years, and constantly dwindling of live width will make solid electronic device no longer defer to traditional moving law; Simultaneously, live width is dwindled and is also made tooling cost constantly increase.And molectronics is expected to address these problems.1cm in the Pentium computer chip
2Area on can integrated 10
7-10
8Individual electronic component, and molectronics allows on onesize area integrated 10
14Individual unit molecule electronic component, the raising of integrated level will make arithmetic speed greatly improve.Simultaneously, because molectronics adopts mode from bottom to top to assemble logical circuit, employed element is by chemical reaction synthetic in enormous quantities, so cost is compared with traditional photoetching method reduction greatly.In order to grab the commanding elevation of future technology, many developed countries have all formulated the special plan of development nanoelectronics and molecules, have dropped into huge manpower and materials, have also obtained a series of breakthrough simultaneously.
Molecular electronic device will be the functional element of molecular dimension and nano-scale, and the element that moves under this yardstick will have significant quantum effect and statistical character.The main raw that constitutes molecular electronic device will be organic polymer and bioprotein material.With the functional element that this class material constitutes, will be the assembling on molecular dimension.On the material, still on the package technique, all be the tip of modern science and technology no matter in theory.It needs multi-disciplinary cross development, comprises the joint efforts of subjects such as electronics, physics, chemistry, biology, microtechnique, Surface Science, membrane science, Materials science, comprehensive development.In the early stage molecular device research, the LB membrane technique plays an important role.But the molecular device of LB membrane technique structure is because organic molecule and extraneous simple mechanical contact, less stable, and its contact resistance has had a strong impact on the performance of device with repeatable.In order to get rid of these problems, at the end of functional materials, on purpose introduce the functional groups that some can be used for self-assembly, by self-assembly, make contacting of material and electrode by the chemical bond combination, will be the key point that overcomes the problems referred to above.Therefore, self-assembling technique has caused more and more scientists' attention in recent years, has also obtained attention more and more widely when constructing molecular device.Research at present at most be that end at the organic molecule long-chain with big п conjugated system adds that some can play the group of crocodile clip effect (as SH etc.) so that connect with metallic surface or other functional molecular.For example: no matter the chemical reactivity between sulfydryl-gold surface still is the development that the experimental study angle has promoted molecular electronic device greatly from theory.
Yet the molecular electronic device research work can not only rest on the metallic surface of representing with Jin Wei, and along with the silicon face CHEMICAL DEVELOPMENT, more and more the interest with people's research forwards on the silicon semiconductor material from the metallic surface.Silicon has been well-known most important base mateiral at microelectronic, and in electronic goods, the unicircuit of nearly all microprocessor all depends on monocrystalline silicon piece.People have done a large amount of research to the character and the application potential of silicon chip, and the nineties middle and later periods has been carried out the surface chemistry research work to this material especially.Silicon crystal has similar adamantine structure, and each Siliciumatom passes through sp
3Hybridized orbital links to each other with the Siliciumatom of four vicinities and forms tetrahedral structure.The bond distance of this covalent linkage is 2.35 , bond energy are 226kJmol
-1In this field, early stage research mainly concentrates in the reaction of some unsaturated hydrocarbons.These unsaturated hydrocarbons are by C=C, and the dangling bonds of C ≡ C and diene key and silicon face carries out the addition reaction of similar [2+2] or [4+2].This cycloaddition reaction not only is confined to olefin hydrocarbon molecules.N=N, C=O also is to carry out similar reaction with C ≡ N group.Except these simple unsaturated molecules, similarly the result obtains in benzene and derivative system thereof equally.In organic solution, can produce organic monomolecular film at silicon face by free radical, heating, light-initiated method.First this reaction of example report be that Chidsey in 1993 etc. finish on monocrystalline silicon surface.Alkene is at 100 ℃, and diacyl peroxide catalysis is married and received the H-Si surface, forms high-quality unimolecular film.For the mechanism that unimolecular film under this condition forms, people such as Chidesy have proposed a radical reaction mechanism, and are similar with the mechanism of molecule silane reaction under free radical is got involved to well-known alkene.Chidesy etc. marry the possibility of receiving on the silicon face to alkene in the catalyst-free condition and study.They think after temperature of reaction is greater than 150 ℃, and reaction also can be carried out under the catalyst-free condition, and be sure of to react initial be because the heterolytic fission of H-Si key.Zhu etc. have reported that a kind of simple, novel method is implemented in silicon face with Si-O key grafting organic monomolecular film, that is: allow the alcohol and the silicon face of chlorine end group react under the catalysis of pyridine; This method and they once reported utilizes amine and Si-Cl surface reaction, forms similar with the unimolecular film method of Si-N key grafting.Uv-radiation can promote the silanization of unsaturated hydrocarbon compound, and reaction is at room temperature carried out, and this can be avoided thermal response to cause adverse influence to the characteristic of responsive, small silicon circuit.Chidsey etc. point out to be present in H-Si surface in the aliphatics alkene with ultraviolet radiation, can cause the silicon face alkylation.Afterwards this reaction broadened application is arrived aromatic series substituted olefine and terminal olefin.Allongue etc. have realized phenyl unimolecular film in the densification of H-Si surface graft with electrochemical method.The H-Si surface applies negative voltage in the rare HF solution that contains 4-nitro diazobenzene or 4-bromo diazobenzene to being immersed in, and causes producing aromatic base free radical and N
2, aryl biradical extracts surperficial hydrogen evolution surface free radical, and this free radical and the reaction of another aryl biradical form the Si-C key.
We see from above introduction, and people are by using for reference the organosilane chemistry and in conjunction with some electrology characteristics of silicon substrate material, having createed the method for many silicon face grafting organic groups.Made us expect becoming possibility in the obtained experimental result of silicon face chemical field in recent years just at the more various organic conjugated molecule of silicon face grafting.Organic molecule itself has various and adjustable performance, and is for example big or small, shape, Chemical bond power, conductivity etc.Particularly the organic long-chain molecule of conjugated structure has more its unique charge transport ability.Therefore, the molecular electronic device of exploring based on silicon semiconductor material is that its feasible experiment basis is arranged.The molecular electronic device that particularly develops based on silicon semiconductor material more has two important reasons.The one, silicon semiconductor material is in existing microelectronic widespread use, and development has the better application basis based on the molecular electronic device of silicon semiconductor material in industry member; The 2nd, do not resemble gold element, silicon is a kind of semiconductor material, it has a bandwidth.The existence of this bandwidth provides the space of material novel in design to us just, expands the Application Areas of molecular electronic device.
From above elaboration as can be seen, forming the molecular line that connects by covalent linkage on the surface of silicon semiconductor material is the committed step of development based on the molecular electronic device of silicon semiconductor material.Therefore this research has important scientific meaning for developer molecule electron device and molectronics.
Summary of the invention
The object of the present invention is to provide the method that on silicon face, prepares organic molecular line that a kind of Application Areas is wide, technological operation is easy.
The method that on silicon face, prepares organic molecular line that the present invention proposes, be to utilize UV-light or plasma technique that silicon face is handled, silicon face is produced to supply further reactive activity point, the active function groups that contains on these active sites and the organic molecule reacts, form firm chemical bond at silicon face, thereby at silicon semiconductor surface preparation organic molecular line.Utilize the concrete steps of ultraviolet Technology to be:
Silicon wafer at first passes through the vitriol oil/hydrogen peroxide oxidation, and hydrofluoric acid etch forms silicon-hydrogen bond on the surface; With the UV-irradiation the in＜350nm wavelength region, form living radical at silicon-hydrogen meter face, this free radical and carbon-carbon double bond, triple bond, carbon nitrogen triple bond generation free radical reaction, thereby at the preparation organic molecular line of silicon face.
Utilize the concrete steps of plasma technique to be:
Silicon wafer is placed in the argon plasma system after passing through cleaning, passes through discharge process 28-35 second; Silicon wafer after Cement Composite Treated by Plasma is exposed in the air 5-10 minute, and the surface forms the silicon hydroxyl; Then, with the triethoxy hydrolysis in the silane coupling agent, form firm Si-O-Si key with the hydroxyl on surface; End has the functional group of the reaction of having neither part nor lot in, and organic conjugated molecule or macromolecular chain grafting are arrived the surface, realizes the reaction second time on surface, thereby at silicon face formation organic molecular line.
The inventive method can be used for the preparation of molecular electronic device.
Among the present invention, silicon face can be silicon single crystal (as silicon (100), silicon (111)), polysilicon, non-crystalline silicon or porous silicon.This method also is applicable to other semiconductor material, for example germanium and so on simultaneously.
Among the present invention, can have the organic molecular line of active function groups with the two ends that silicon face reacts, its molecular skeleton is the one or more CH that linked to each other by the saturated carbon hydrogen bond
2Group is formed, and molecular formula is as follows:
R1-(CH
2)n-R2
Wherein R1 is a functional group, can with silicon face generation chemical reaction, generate stable covalent linkage; R2 is close organo-functional group, can react with organic conjugated molecule or the macromolecular material through modification.N is the number of methylene level, can be long chain alkane, also can be 1.
R1 in the molecular line can be that identical group also can be different group with R2.
R1 group in the molecular line can be a carbon-carbon double bond, carbon carbon triple bond, and unsaturated functional groups such as carbon nitrogen triple bond, the easy and silicon face generation free radical reaction of these functional groups forms stable covalent linkage on the surface.
R1 group in the molecular line also can be the triethoxy functional group in the silane coupling agent.
R2 group in the molecular line can be organo-functional groups such as hydroxyl, carboxyl, ester group.
Among the present invention, said conjugated polymer or macromolecular material can be the conjugated polymers with specified propertys such as luminous, conductions.Have conduction, luminous conjugated molecule can be a benzene, thiophene phenol, furans, the pyrroles, pyridine, dipyridyl, fluorenes and derivative etc. thereof has the molecule of conjugated structure.The organic conjugated molecule of modified or polymer can be to have hydroxyl, carboxyl, ester group, the organic conjugated molecule or the polymer of carboxylic acid halides isoreactivity group.
Among the present invention, the terminal unreacted organo-functional group of organic molecular line and organic conjugated molecule or high molecular reaction through modifying can be amino and carboxyl, the acid amides reaction of amino and acyl chlorides, also can be contracting and reacting the esterification of ester group and hydroxyl of carboxyl and hydroxyl.
Be used for the polymer of grafting to the surface, its repeating unit number from 1 to 1000, between the 1-100, best between 1-30 more fortunately.
Can test by the following method at the formed organic molecular line of silicon face: the test of deionized water contact angle can obtain the surface tension data, and then judges the length and hydrophilic, the oleophylic performance of surface molecular line.The XPS photoelectron spectrum provides the key bound energy of surface molecular line, and the information of UPS photoelectron spectrum valence link track can help to obtain the surface molecular line and become key information; The infrared vibrational spectrum that the surface molecular line is provided of attenuated total reflectance attenuated total refraction can obtain the information of each functional group in the surface molecular line.
Can prepare organic molecular line at silicon face by this reaction.This method is applicable to the preparation of molecular electronic device.
The inventive method mainly connects by covalent linkage on the silicon semiconductor surface, is prepared into organic molecular line, expanded the Application Areas of electronic molecules device, and it is easy and simple to handle, and technology is simple, and control easily.
Embodiment
By the following examples the present invention is further specified:
Embodiment 1:
After silicon chip acetone, ether, ethanol and washed with de-ionized water and ultrasonication, through the vitriol oil/hydrogen peroxide oxidation, the hydrofluoric acid corrosion generates silicon-hydrogen bond on silicon face.This wafer that has silicon-hydrogen bond is placed in the quartz container of nitrogen protection, puts into simultaneously a certain amount of 10-amino-1-hendecene solution in container, solution amount is not too many, just wet surface and form a skim on the surface and be advisable.The quartz reaction container that sample will be housed then is placed on following the irradiation about 12 hours of low pressure mercury lamp of 254-nm.Free radical reaction takes place by two keys and surface in 10-amino-1-hendecene molecule, generates stable silicon-carbon bond, and the other end keeps the amino group that reacts.This lip-deep amino group further with benzoic acid molecule in carboxylic group react, and with this simplest conjugated system grafting of phenyl ring to silicon face, form required organic molecular line.Then, obtain the information of surface molecular line through surface contact angle XPS, UPS, attenuated total reflectance attenuated total refraction infrared test.
Embodiment 2:
Other can further react with acyl chlorides benzene through the surface that 10-amino-1-hendecene is modified as embodiment 1.Amino in the olefin hydrocarbon molecules and the acid chloride functional groups generation amidate action on the benzene.
Embodiment 3:
Other is as embodiment 1, and 10-amino-1-11-alkene molecule can be 10-carboxyl-1-hendecene molecule.Can be further through the surface of this molecular modification and the phenol molecular reaction.Hydroxyl generation condensation reaction in carboxyl in the olefin hydrocarbon molecules and the phenol molecule.
Embodiment 4:
Other is as embodiment 1, and 10-amino-1-hendecene molecule can be 10-ester group-1-hendecene molecule.Can be further through the surface of this molecular modification and the phenol molecular reaction.Hydroxyl generation esterification in ester group in the olefin hydrocarbon molecules and the phenol molecule.
Embodiment 5:
Other is as embodiment 1-4, and the ethylene linkage in the molecular line also can be carbon-to-carbon triple bond or carbon-nitrogen triple bond, the same with ethylene linkage they with the surface free radical reaction takes place all, form stable carbon-to-carbon covalent linkage.
Embodiment 6:
Other also can be thiophene phenol as embodiment 1-4 as the conjugate unit benzene in the benzoic acid molecule of further reaction, furans, pyrroles, pyridine, dipyridyl, fluorenes and derivative equiconjugate unit thereof.
Embodiment 7:
Other is as embodiment 1-4, also can be through perhydroxyl radical as the benzoic acid molecule of further reaction, carboxyl, the macromolecular chain of carboxylic acid halides isoreactivity base group modification.
Embodiment 8:
After silicon chip acetone, ether, ethanol and washed with de-ionized water and ultrasonication, it is exposed moments later with taking out after the Ar Cement Composite Treated by Plasma to be placed in the air in plasma reactor, and silicon face becomes hydroxyl after the peroxy radical of Cement Composite Treated by Plasma exposes in air.And then put into end amido modified silane coupling agent (APTE) solution is arranged.The hydroxyl of triethoxy hydrolysis and silicon face reacts, and generates the Si-O-Si key.Terminal amino that keeps and the reaction of single fluorenic acid generation acid amides, thus in grafting on the silicon face organic conjugated molecule, the formation organic molecular line.Then obtain surface molecular line information through methods such as surface contact angle XPS, UPS, attenuated total reflectance attenuated total refraction are infrared.
Embodiment 9:
Other are as embodiment 8, and the silicon face that APTE modifies can be by the amino fluorenes molecule generation amidate action of modifying with acyl chlorides.
Embodiment 10:
Other is as embodiment 8, and can select end is the silane coupling agent and the silicon surface reaction of hydroxyl.Surface through this molecular modification can be by oh group and the fluorenic acid molecule generation esterification that keeps.
Embodiment 11:
Other also can be thiophene phenol as embodiment 8-10 as the conjugate unit fluorenes in the fluorenes molecule of further reaction, furans, pyrroles, pyridine, dipyridyl and derivative equiconjugate unit thereof.
Embodiment 12:
Other is as embodiment 8-11, and further the fluorenes molecule of reaction also can be through carboxyl, the macromolecular chain of carboxylic acid halides isoreactivity base group modification.
Claims (9)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775004B (en) * | 2009-01-14 | 2012-11-21 | 国家纳米科学中心 | Organic molecular line and preparation method |
| CN101728480B (en) * | 2008-10-17 | 2013-05-08 | 南亚科技股份有限公司 | Resistive Random Access Memory Structure and Manufacturing Method |
| US8487290B2 (en) | 2008-09-25 | 2013-07-16 | Nanya Technology Corp. | RRAM with improved resistance transformation characteristic and method of making the same |
| CN108034350A (en) * | 2018-01-31 | 2018-05-15 | 青岛沙木新材料有限公司 | Spary coating type damping material |
-
2005
- 2005-12-22 CN CN 200510111834 patent/CN1810810A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8487290B2 (en) | 2008-09-25 | 2013-07-16 | Nanya Technology Corp. | RRAM with improved resistance transformation characteristic and method of making the same |
| CN101728480B (en) * | 2008-10-17 | 2013-05-08 | 南亚科技股份有限公司 | Resistive Random Access Memory Structure and Manufacturing Method |
| CN101775004B (en) * | 2009-01-14 | 2012-11-21 | 国家纳米科学中心 | Organic molecular line and preparation method |
| CN108034350A (en) * | 2018-01-31 | 2018-05-15 | 青岛沙木新材料有限公司 | Spary coating type damping material |
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