CN1715270A - Uv decomposable molecules and a photopatternable monomolecular film formed therefrom - Google Patents
Uv decomposable molecules and a photopatternable monomolecular film formed therefrom Download PDFInfo
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- CN1715270A CN1715270A CN 200510067080 CN200510067080A CN1715270A CN 1715270 A CN1715270 A CN 1715270A CN 200510067080 CN200510067080 CN 200510067080 CN 200510067080 A CN200510067080 A CN 200510067080A CN 1715270 A CN1715270 A CN 1715270A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
- B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/165—Monolayers, e.g. Langmuir-Blodgett
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
Abstract
The invention discloses a method for forming a film pattern; wherein, a superfine film pattern can be easily formed by the working procedure of spraying the drips containing the following compound on a solid phase surface with part function. The compound is provided with a structure which decomposes when being illuminated by infrared light with a long wave length and a structure which is provided with hydrophobic nature or/and lipophobicity.
Description
Technical field
The present invention relates to by the easily decomposed certain molecules of UV light, especially there is those of hydrophobicity and/or oleophobic structure component.This kind of molecule can be used and form monomolecular film, when as image being exposed to low energy UV ray, light-pattern can be carried out and formed.Furthermore, the present invention relates to a kind of methods for forming Thinfilm pattern by using the means such as ink ejecting method for spraying fine droplet, in particular to the method or a kind of method formed with reactive Thinfilm pattern of the formation Thinfilm pattern of a kind of solid state properties that can change solid phase surface.
Background technique
It has been known that there is the methods for being largely used to form patterned film on substrate such as semiconductor substrate.These methods first is that based on dissolving photopolymerizable material in a solvent, the film of this material is then formed by spin coating on a semiconductor substrate.Then obtained film is irradiated by patterned exposure mask with ultraviolet rays (UV), causes to form negative image or positive image in photosensitive polymer film.But the spin coating technique is inefficient, because the polymer material of up to 99 weight % is discarded during application step.
As the improvement of this method, propose to be formed monomolecular thickness can light forming pattern film, pattern can be formed and being exposed to UV ray.These films are referred to as self-assembled monolayer (SAM).The example of such methods is disclosed in: H.Sugimura's etc., in the Scanning probe nanolithography (non-patent document 2) of Micropatterning oforganosilane self-assembled monolayers using vacuum ultraviolet light at 172nm:resolution evaluation by Kelvin-probe force microscopy (non-patent document 1) and H.Sugimura.Compared with the method for using spin coating, using the method for SAM reduce can light forming pattern material waste.This is because only needing minimal amount of light-sensitive material, that is, need to come the amount of the monomolecular film of forming material.
But proposed in the past can light forming pattern SAM have the shortcomings that it is following: they need time exposure in the UV ray of high-energy, to be satisfactorily imaged.This means that they have the treatment effeciency being mutually on duty.Accordingly, it is desirable to provide a kind of improved materials for being used to form SAM, it can be exposed to the relatively long UV light of wavelength by being exposed to low energy UV ray in short time and carry out light pattern and formed.
With it is described above individually Dunkin etc. is in J.Chem.Soc.Perkin Trans.2, (2001), disclose in page 1414 (non-patent document 3): a kind of o- p-Nitrobenzyl derivative absorbs the UV ray of about 254nm.This absorption induction photoisomerization reaction and photolysis reactions.This is explained in following reaction route:
[formula 5]
The first reaction in route above is the intramolecular enolization reaction of o- p-Nitrobenzyl derivative.The enolization reacts inducing molecule intramolecular cyclization reaction in turn.Then, ester group present on benzyl dissociates, and is formed and contains aldehyde radical and nitroso compound as decomposition product.When forming carbamate groups key on benzyl, it is also formed as the amine compounds and carbon dioxide of other decomposition products.
The present inventor has such idea, it being incorporated in this analog derivative comprising degradable structural constituent can be used for carrying out in the SAM that light-pattern is formed, and the pattern can be formed on various types of substrate.There are also such ideas for they, pass through careful MOLECULE DESIGN, it can arrange this kind of SAM, to represent two different surface naturies: being on the one hand hydrophobicity and/or oleophobic property, and on the other hand it is hydrophily, so that when the molecule carries out UV irradiation, the hydrophobicity and/or the separation of oleophobic structure component release hydrophilic.
Recent years, need such technology, wherein by DNA, biomolecule such as antibody and with them there is reactive compound to be fixed on high-densit and high precision pattern solid phase surface, to develop the biosensor from test specimen detection specific biological molecules, and laboratory (lab-on-chip) technology on glass-chip on the chip of the Biochemistry Experiment of progress microsize.
As for the method for the fixed dna on highdensity substrate surface; it is proposed in non-patent document 4 and uses up the self installation monomolecular film for irradiating and there is light to split protecting group under conditions of using the photomask for for example forming hydroxyl pattern; the hydroxyl has specific activity; then the compound of different bases reacts to each other there are four types of having, and extends DNA chain.
But difficulties in terms of adjusting orientation when exposing and reacting using the method for photomask, cause yield low and high manufacturing cost and inadequate detection sensitivity.On the other hand, as the method for forming small Thinfilm pattern on the surface of solid substrate, the means such as ink ejecting method of injection fine droplet is used.The means for spraying fine droplet can make the material for including in drop supply the specific position to substrate by injection drop under conditions of the mobile platform for installing solid phase group on it.
Therefore, in the case of fixing biological molecules under conditions of giving direct pattern or compound, effectively the surface of substrate is pre-processed, such as forms the region that there is reactivity and control solid state properties such as wetability with these biomolecule or compound.According to these methods, it can preferably capture fixed material in the target area and it is prevented to be adhered to other regions.
[non-patent document 1]
Surface Coating Technology (2003), the 169-170 pages
[non-patent document 2]
OYO BUTURI (Applied physics in Japan), Vol.70, page 1182
[non-patent document 3]
J.Chem.Soc., Perkin Trans.2, (2001), page 1414
[non-patent document 4]
The Proceedings of he National Academy of Sciences.Vol.91 (1994) of Pease, A. etc., page 5022 to 5026
Summary of the invention
[technical problems to be solved]
The first purpose of this invention is intended to provide a kind of molecule for inclusion in SAM, which can be used in the low energy UV ray short time by photo-patterning, and UV ray is the relatively long UV ray of wavelength.
Second object of the present invention is intended to provide a kind of molecule that can be formed as various types of SAM and can be used for carrying out various types of substrate photo-patterning.
Third object of the present invention is intended to provide a kind of SAM of tool there are two types of different surfaces property, that is, starts with hydrophobicity and/or oleophobic property property, but is irradiated by UV and be transformed into hydrophilic nature.
Fourth object of the present invention is intended to provide a kind of method that the solid state properties of solid phase surface are controlled by using the means for spraying drop and a kind of method for the formation for controlling conversion zone.
[means solved the problems, such as]
The inventors discovered that, these purposes can be achieved by the following procedure: such a structural constituent is introduced SAM, structural constituent decomposition in the UV light irradiation for being 254-400nm with wavelength, leads to the molecular breakdown, while also including the structural constituent for hydrophobicity and/or oleophobic property in SAM.
Therefore, according to the first aspect of the invention, the present invention provides a kind of molecule, and it includes in the ultraviolet light irradiation time-division formal similarity component (A) for being 254-400nm with wavelength and be hydrophobicity and/or the structural constituent (B) of oleophobic property.
Preferably, structural constituent (A) is o- p-Nitrobenzyl.The structural constituent has an advantage in that and is easy to split when being irradiated with low energy UV light, and the UV light has relatively long wavelength just within the scope of 254-400nm.Preferably, the end group connecting with the benzyl of o- p-Nitrobenzyl should be succinimide.
The structural constituent, which has an advantage in that, is directly incorporated in the molecule on the substrate surface with suitable functional group by covalent coupling, or the single layer before being adhered on substrate surface through coupling compound, on the substrate surface with suitable functional group, the substrate surface has the functional group that can be reacted with succinimide residue.
Preferred structure component (B) is fluorination chain, and the more preferable fluorination chain is saturation.The chain can be straight chain or branching.In addition, the chain can also be perfluorinated, have the advantages that improve the hydrophobic of the chain.
In the first aspect of the present invention, preferably the molecule has logical formula (I).
[formula 6]
Wherein:
R1Independently indicate hydrogen atom ,-OR6(R6It is the alkyl chain that carbon number is 1 to 10) ,-NH (CO) R7(R7Indicate the alkyl chain that carbon number is 1 to 10 or the alkyl fluorine chain that carbon number is 1 to 10), N (R8)2(R8Indicate that carbon number is 1 to 5 alkyl chain), or-S (R9)(R9Indicate that carbon number is 1 to 10 alkyl chain)；
R2It indicates n-hydroxysuccinimide base (optionally replaced sulfonyl)；
R3Expression-X2-(CH2)n-X1, wherein X2Expression-CH2Or-O-, n are 0 or integer of 1 to 10, and X1Expression-OZ ,-Z or
Wherein:
Y expression-(CH2)-or-O-, Z indicate fluoro-alkyl that carbon number is 1 to 20 and m indicates 0 or integer of 1 to 10；R4Expression-NO2Or hydrogen atom；And R5It is the alkyl that hydrogen atom or carbon number are 1 to 10.
Preferred substituents R1For methoxyl group.Substituent R1Presence has an advantage in that o- p-Nitrobenzyl structural constituent is caused to absorb the UV light in the region 330-360nm, which is the UV light of extremely low energy.
It include preferably-(CH by the fluoroalkyl that the carbon number that Z is indicated is 1 to 202)m(CF2)PF or its branched isomer, wherein m as defined above and p be 0 or 1 to 9 integer.
The preferred molecule of general formula recited above is:
[formula 7]
According to second aspect, the present invention provides a kind of substrate of monomolecular film coating.The film is formed by the molecule comprising structural constituent (B) and structural constituent (A), the structural constituent (B) is hydrophobicity and/or oleophobic property, structural constituent (A) decomposition in the ultraviolet light irradiation for being 254-400nm with wavelength, to be broken a part for the molecule containing structural constituent (B) of exchanging, remaining hydrophilic-structure component (C) is left.
In a manner of identical with first aspect, preferred structure component (A) is o- p-Nitrobenzyl, and structural constituent (B) includes fluorination chain, and the more preferable fluorination chain can be saturation.The fluorination chain is also possible to branching and/or fluoridized.
Preferred hydrophilic structural constituent (C) includes amido or hydroxyl.This kind of group is advantageous, because they can be reacted with succinimide, succinimide is in conjunction with molecule covalent according to a first aspect of the present invention, but the fracture when being irradiated with UV ray, discharges the amido or hydroxyl of relative hydropathy.
The monomolecular film (SAM) of second aspect is by the monomolecular film coated substrate with the coupling compound (D) comprising hydrophilic segment, and then the hydrophilic segment reacts acquisition with molecule according to a first aspect of the present invention.Substrate can be any suitable material, including metal, semiconductor or plastics.
Alternatively, the monomolecular film (SAM) of coated substrate can be formed by molecule according to a first aspect of the present invention completely, if these molecules can satisfactorily be adhered to substrate, for example, by with pre-existing suitable functional group's covalent bond on the surface of a substrate.Specifically, if this formation can be substrate and have the case where hydrophilic surface.
According to the third aspect of the invention we, the present invention provides a kind of method formed to the substrate being coated with according to the monomolecular film of invention described above second aspect progress light-pattern.The method includes the steps of: the UV light for being 254-400nm with wavelength at image irradiates the substrate of the monomolecular film coating by patterned exposure mask, to be broken be coated with molecule at structural constituent (A), thus structural constituent (B) is removed from the coated thin film in irradiated site, the molecule is hydrophilic from being changed into for hydrophobicity and/or oleophobic property.
Furthermore, in order to solve problems described above, reach fourth object of the present invention above, as the result deeply and carefully studied, the inventors discovered that a kind of compound, which includes the structural constituent Y and structural constituent Z can decompose and between X and Z for having reactive structural constituent X, the solid state properties for changing solid phase surface with functional group on a solid surface.This compound can be coated on solid phase surface by way of spraying fine droplet, consistently to control the solid state properties of solid phase surface with micro pattern.In compound described above, make Z reaction structure component, forms conversion zone with the micro pattern on solid phase surface.
In addition, they have found, once after compound recited above is fixed on solid phase surface, Y is decomposed, the solid state properties of solid phase surface or reaction are back to reset condition, and Y is also decomposed, different solid state properties or reaction are provided by the funtion part exposed to the open air on surface.
I.e., according to fourth aspect, the present invention relates to a kind of methods [1] for forming Thinfilm pattern, and this method includes: at least one step of drop is sprayed on the solid phase surface containing funtion part, the drop includes the compound indicated by following formula (O):
[formula 8]
X-Y-Z (O)
Wherein, X indicates there is reactive structural constituent with the funtion part existing for solid phase surface, and Y indicates decomposable structural constituent itself, and Z indicates to can change the structural constituent or reaction structure component of the solid state properties on solid phase surface.In addition, the present invention includes the methods [1] that wherein solid state properties are wetability.Or the present invention relates to a kind of method [3] for being based on [1] or [2], wherein Z includes a kind of structural constituent, selected from including following any one of group: the saturated or unsaturated alkyl chain of substituent group can be contained, the saturated or unsaturated fluorination chain of substituent group, hydroxyl, amino can be contained, urethane ester group, carboxyl, carbonyl, urea groups, sulfonic group, disulfide group, epoxy group, carbodiimide, dimaleoyl imino, n-hydroxysuccinimide base.Or the present invention relates to a kind of method [4] based on [1] to [3] any one, wherein X includes such a structural constituent, selected from including following any one of group: amino, urethane ester group, carboxyl, carbonyl, urea groups, sulfonic group, disulfide group, epoxy group, carbodiimide, dimaleoyl imino, alkoxy silane, silane halide and n-hydroxysuccinimide base.Or the present invention relates to a kind of method [4] based on [1] to [4] any one, wherein Y is the structural constituent with photo absorption property.Or the present invention relates to a kind of methods [6] for being based on [1], wherein the compound is indicated by lower formula (I):
[formula 9]
Wherein:
R1Independently indicate hydrogen atom ,-OR6(R6It is the alkyl chain that carbon number is 1 to 10) ,-NH (CO) R7(R7Indicate the alkyl chain that carbon number is 1 to 10 or the alkyl fluorine chain that carbon number is 1 to 10), N (R8)2(R8Indicate that carbon number is 1 to 5 alkyl chain), or-S (R9)(R9Indicate that carbon number is 1 to 10 alkyl chain)；
R2It indicates n-hydroxysuccinimide base (optionally replaced sulfonyl)；
R3Expression-X2-(CH2)n-X1, wherein X2Expression-CH2Or-O-, n are 0 or integer of 1 to 10, and X1Expression-OZ ,-Z or
Wherein:
Y expression-(CH2)-or-O-, Z indicate fluoro-alkyl that carbon number is 1 to 20 and m indicates 0 or integer of 1 to 10；R4Expression-NO2Or hydrogen atom；And R5It is the alkyl that hydrogen atom or carbon number are 1 to 10.
Or the present invention relates to a kind of method [7] for being based on [1] to [6] any one above, also include: before injection includes the liquid of the compound indicated by the formula, the fixed compound with the funtion part that can combine X on solid phase surface.Or the present invention relates to a kind of methods [8] based on [1] to [7] above any one, wherein the method for the injection drop is ink ejecting method.Or the present invention relates to a kind of methods [9] based on [8] to [1] above any one, wherein the drop includes solvent, the solvent is selected from such as water, ethyl alcohol, DMF, DMSO, HMPA, pyrrolidinone compounds, any one of dioxanes.Or the present invention relates to a kind of methods [10] based on [1] to [9] above any one, wherein the method for the injection drop includes control method, with the dry drop.
[effect of the invention]
According to the present invention it is possible to provide a kind of molecule for inclusion in SAM, the SAM can be used progress light-pattern in the low energy UV ray short time and be formed, and UV ray is the relatively long UV ray of wavelength.In addition, the present invention can provide such molecule, various types of SAM can be formed as and the light pattern for various types of substrates is formed.It is initially hydrophobicity and/or oleophobic property there are two types of the SAM of different surfaces performance that the present invention, which can also provide tool, but be changed into hydrophily by UV irradiation.
According to the present invention, it is injected on solid phase surface using such a compound as solution, the compound includes having reactive first structure component with the funtion part on solid phase surface, change the second structural constituent of the solid state properties of solid phase surface, and between the first and second structural constituents and is the third structural constituent that can be decomposed.The solid state properties of solid phase surface can be consistently controlled with micro pattern.The formation of conversion zone can also be controlled.Furthermore, the decomposition of the third structural constituent recited above that can be decomposed, the solid state properties for once giving solid phase surface and reactivity can be made to be back to reset condition or new solid state properties and new reactivity, it is to give solid phase surface by funtion part, which is exposed to the open air on the surface by the decomposition.
[preferred embodiment description]
Embodiment of the present invention is described with reference to the drawings.
Return to first aspect present invention as described above, this is related to a kind of molecule in terms of broadest, and it includes in the ultraviolet light irradiation time-division formal similarity component (A) for being 254-400nm with wavelength and be hydrophobicity and/or the structural constituent (B) of oleophobic property.Thus, which includes at least two individual structural constituents.The first part of these structural constituents is labeled as (A), is to be used in the chemical structure decomposed when light irradiation outside the UV of relatively long wavelength of 254-400nm range or part.The structural constituent makes the molecule to UV photaesthesia, thus makes the molecule itself or bigger molecule is to UV photaesthesia, thus can carry out light-pattern and be formed.Structural constituent (A) is coupled in bigger molecule.On the other hand, structural constituent (B) is hydrophobicity and/or oleophobic property, and molecule itself is caused to have this property or these properties.As a result, having the surface nature of hydrophobicity and/or oleophobic property by the monomolecular film that the molecule of first aspect present invention is formed.The property is also possessed by monomolecular film (SAM), and monomolecular film is formed and being coupled molecule according to a first aspect of the present invention with the coupling compound for having been coated with monomolecular film on substrate.
Even if more preferable 30 seconds to 5 minutes, and most preferably 1 to 5 minute, molecule according to a first aspect of the present invention can also carry out light-pattern and be formed when using the low energy UV light radiation short time corresponded in the wavelength in the region 254-400nm, such as 10 seconds to 10 minutes.This shows that can relatively effectively carry out light-pattern forms, and reason is that it only needs relatively low energy to irradiate.
The structural constituent (A) that can be decomposed when being irradiated with UV light is o- p-Nitrobenzyl.The decomposition of above-described this structural constituent is related to the known prior art of Dunkin etc..
Structural constituent (B) is hydrophobicity and/or oleophobic property.The presence of the structural constituent causes the monomolecular film formed by the molecule to be hydrophobicity and/or oleophobic property again.The Sutable examples of structural constituent (B) are long chain hydrocarbon groups and long-chain fluorination carbochain, be can be fluoridized or replaced the mixture of fluorine and hydrogen atom.It is preferred that this chain be saturation and/or branching, i.e., they can have dendritic structure.
The example of this chain includes saturation fluorination chain-(CH2)n(CF2)mCF3,-(CH2)nCF[(CF2)mCF3]2With-(CH2)nC[(CF2)mCF3]3, (wherein n and m is integer, preferably respectively 0 to 10 and 0 to 9).
If structural constituent (A) is o- p-Nitrobenzyl, structural constituent (B) can be easily introduced to the contraposition of benzyl by ehter bond.
If structural constituent (A) is o- p-Nitrobenzyl, the molecule of preferred first aspect present invention has end group of the succinimide structure as benzyl, and reason is its beneficial reactivity.The molecule that the succinimide structure can make easily is coupled on substrate, the substrate has suitable surface reactive group such as hydroxyl or amino, or can be coupled to and being pre-coated with and/or being bound to the coupling compound of single layer of substrate (D) on such substrate, the substrate has with succinimide structure such as hydroxyl or amino with reactive functional group.This can be such that the molecule of first aspect present invention is actually coated on any kind of substrate, on such as surface with the modified golden substrate of amino surface, on the surface of semiconductor substrate such as silicon, on the organic material surface of plastic supporting base or on the surface of insulating substrate.In this way, photodegradable SAM can be prepared.
For example, substrate such as gold thin film can be coated with the single layer of amino silane compounds such as 3- TSL 8330, then the molecule of itself and first aspect present invention is coupled, which includes the o- p-Nitrobenzyl containing succinimide residue.This coupling principle can be such that the molecule of first aspect present invention is widely coated on many different types of substrates, thus form application field for light-pattern.Coupling compound (D) can have alternative substituent group, have reactivity with succinimide residue such as hydroxyl.
This coupling concept is more fully illustrated in Fig. 2 (1) and 2 (2).In these figures, substrate (10) is functioned firstly as the HSCH of coupling compound (D)2CONHCH2(OCH2CH2)6CH2CH2NH2Processing, forms monomolecular film (not shown) on substrate (10).The surface of the film includes reaction amino.Then, for these amino with to react with molecule according to a first aspect of the present invention, the molecule carries succinimide residue in one end, reacts with the amine substituent group one of coupling compound (D), forms carbamate structures.Reacting between coupling compound and molecule according to a first aspect of the present invention can for example carry out in organic solvent such as methylene chloride, use trimethylamine as catalysts.Substrate (10) may, for example, be metal substrate such as gold or silver, because this kind of metal substrate and mercaptan and disulphide have great reactivity.Therefore, coupling compound is easy to react with substrate, forms SAM on the surface of a substrate.A kind of alternative coupling compound will be 11- aminododecane mercaptan.
The molecule of first aspect present invention preferably has logical formula (I).
[formula 10]
Wherein:
R1Independently indicate hydrogen atom ,-OR6(R6It is the alkyl chain that carbon number is 1 to 10) ,-NH (CO) R7(R7Indicate the alkyl chain that carbon number is 1 to 10 or the alkyl fluorine chain that carbon number is 1 to 10), N (R8)2(R8Indicate that carbon number is 1 to 5 alkyl chain), or-S (R9)(R9Indicate that carbon number is 1 to 10 alkyl chain)；
R2It indicates n-hydroxysuccinimide base (optionally replaced sulfonyl)；
R3Expression-X2-(CH2)n-X1, wherein X2Expression-CH2Or-O-, n are 0 or integer of 1 to 10, and X1Expression-OZ ,-Z or
Wherein:
Y expression-(CH2)-or-O-, Z indicate fluoro-alkyl that carbon number is 1 to 20 and m indicates 0 or integer of 1 to 10；R4Expression-NO2Or hydrogen atom；And R5It is the alkyl that hydrogen atom or carbon number are 1 to 10.
This compound effectively decomposes absorbing a small amount of UV ray, and the SAM to be formed can be made to have high surface hydrophobic and/or oleophobic property property.
In formula (I) compound described above, particularly preferably substituent R1It should be methoxyl group (- OCH3).The substituent group is such a structure, and wherein methoxyl group is connected to the contraposition relative to nitro.The substitution causes the compound consumingly to absorb the UV ray in wave-length coverage 330-360nm.Further preferably R5It is hydrogen atom.
In the compound of logical formula (I) described above, it is further preferred that substituent group Z is-(CH2)m(CF2)PF or its branched isomer, wherein m as defined above and p be 0 or 1 to 9 integer.
If molecule according to a first aspect of the present invention is coated on the substrate with water-wetted surface as single layer (SAM), obtained monomolecular film coated substrate can directly carry out being formed by the light pattern for being exposed to UV ray.Therefore, UV ray will divide the molecule, the water-wetted surface of exposing substrates after rinsing at structural constituent (A).The region for shielding the monomolecular film of irradiation retains hydrophobicity and/or oleophobic property due to structural constituent (B).As a result, the substrate of this coating can prove there is two different surface naturies.That is, being hydrophilic surface nature in the region for carrying out UV irradiation, and they do not carry out other regions of UV irradiation as hydrophobicity and/or the surface nature of oleophobic property.
Alternatively, molecule according to a first aspect of the present invention can be coupled on a surface of the substrate, as illustrated in Fig. 2 (2) by coupling compound (D).Obtained SAM has carbamate structures.When the UV ray for wavelength being, for example, 365nm irradiates the surface SAM by photomask, the photodegradation of SAM is relatively rapidly carried out, and about 30 seconds to 5 minutes, and carbamate structures decompose.Then, the surface of film is rinsed with suitable solvent such as water, and the original amino of coupling compound (D) reappears on the membrane surface, as Fig. 2 (3) is illustrated.As a result, between the UV irradiation zone and non-irradiated site domain of the substrate of SAM coating, there are big surface energy difference.
According to described above, monomolecular film or SAM have been obtained, the wetability of solution and solvent can have been changed significantly and being carried out into image UV irradiation.For example, when using the molecule recited above containing succinimide residue, by flowing back in acetonitrile as a solvent, these molecules can with hydroxy thiol, such as 11- hydroxydodecanoic thiol reaction.The reaction generates dithio-carbamate.Then, which can be fixed on golden substrate, be formed on monomolecular film.Then, the UV light irradiation which can be 254-400nm with wavelength, to carry out dissociation reaction.The reaction leads to the fracture of succinimide derivatives, only leaves 11- hydroxydodecanoic mercaptan, and there are hydroxyls on its film surface, so that the irradiation zone of SAM is hydrophilic.On the other hand, SAM non-irradiated region due to structural constituent (B) presence and be left hydrophobicity and/or oleophobic property.
As described above, the second aspect of the present invention provides a kind of substrate of monomolecular film coating.The film is formed by the molecule comprising structural constituent (B) and structural constituent (A), the structural constituent (B) is hydrophobicity and/or oleophobic property, structural constituent (A) decomposition in the ultraviolet light irradiation for being 254-400nm with wavelength, to be broken a part for the molecule containing structural constituent (B) of exchanging, remaining hydrophilic-structure component (C) is left.
It should be understood that the monomolecular film (SAM) being deposited on substrate is that there are two types of the high functionalized layers of possible surface nature for tool, two kinds of possible surface naturies are the hydrophobicitys and/or oleophobic property property started, and carry out the hydrophilic nmature after UV irradiation.These properties can make the substrate of this monomolecular film coating be suitable for being formed by light-pattern that UV is irradiated.Structural constituent (A) and structural constituent (B) are identical as described in first aspect present invention above.Thus, unless the monomolecular film of second aspect of the present invention be particularly described it is as follows, can be using the upper surface of molecule description of first aspect present invention.
When turning to remaining hydrophilic-structure component (C), which is hydrophilic, such as amido or hydroxyl.The fracture of structural constituent (A) caused by the group is irradiated by UV releases.The fracture is especially illustrated in Fig. 2 (2) and 2 (3).According to the figure, the UV irradiation of the substrate of the monomolecular film coating of Fig. 2 (2) leads to the fracture of o- p-Nitrobenzyl structure.After rinsing residue, the coupling compound (D) that amine replaces is remained in the region of monomolecular film, and it is hydrophilic for having been subjected to irradiation.On the contrary, chain-OCH of the region of shielding UV ray due to constituting structural constituent (B)2CH2(CF2)5CF3And keep hydrophobic.
It is preferred that the monomolecular film in second aspect of the present invention can be obtained by then reacting hydrophilic parts with molecule according to a first aspect of the present invention with coupling compound (D) coated substrate comprising hydrophilic parts.Alternatively, when substrate surface has been hydrophily, the substrate of monomolecular film coating according to a second aspect of the present invention can be obtained simply by being coated with molecule formation SAM according to a first aspect of the present invention on substrate.
As long as the substrate of monomolecular film coating has carried out light-pattern and formed, then can for example be suitable for the spin coating or ink jet printing of solution by routine techniques such as selectivity, the polymer solution containing functional material is applied to its surface.Functional material will be deposited on figuratum monomolecular film, return permission functional material pattern easy to form.
As described above, the present invention provides a kind of method that substrate progress light-pattern to monomolecular film as described above coating is formed in the third aspect.The method includes the steps of: the UV light for being 254-400nm with wavelength at image irradiates the substrate of the monomolecular film coating by patterned exposure mask, to be broken be coated with molecule at structural constituent (A), thus structural constituent (B) is removed from the coated thin film in irradiated site, they are hydrophilic from being changed into for hydrophobicity and/or oleophobic property.
Carrying out the technology that light-pattern is formed using light irradiation and mask is known for the technical staff in photolithographic techniques field.
It should be understood that method according to a third aspect of the present invention allows only to need to be coated with monomolecular film on substrate and carry out light-pattern and formed.Therefore, this method solve when passing through spin application using conventional photosensitive polymer material, in the application background technique the problem of so-called essence waste.Furthermore, the two-phase method provided by the present invention for forming monomolecular film, molecule including design and synthesis according to a first aspect of the present invention, its have simultaneously can UV degrading texture and hydrophobicity and/or oleophobic structure component, then both structures are coupled with coupling compound (D) by the hydrophilic segment on the former.The two-phase method is provided can be with widely applied technology for various substrate types progress light-pattern formation.
The compound (compound (O)) of fourth aspect present invention is indicated by following formula (O):
[formula 11]
X-Y-Z (O)
Its end, which is provided with, has reactive structure X with the functional group on solid phase surface.For example, the surface of substrate has a large amount of hydroxyl when glass substrate is used as solid phase substrate.X can be such as alkoxy silane or silane halide-SiL (wherein, L indicates alkoxy or halogen ion, and n indicates 1 to 4 integer).L portion is water dispersible as a result, and is coupled with hydroxyl, and compound (O) is caused to be fixed on solid phase surface.
X is conveniently selected from solid phase material and fixed compound on the surface, in addition to alkoxy silane recited above or silane halide.X is not particularly limited, as long as the functional group with solid phase surface has reactivity.But it is preferably selected from high reaction structure, such as includes any one of following group: amino, urethane ester group, carboxyl, carbonyl, urea groups, sulfonic group, disulfide group, epoxy group, carbodiimide, dimaleoyl imino, alkoxy silane, silane halide and n-hydroxysuccinimide base.
According to the fourth aspect of the invention, the drop including compound recited above (O) is injected on the solid phase surface containing functional group.Here, the functional group that solid phase surface is possessed can be functional group possessed by the functional group as possessed by solid phase material itself or the compound as being fixed on solid phase surface in advance.When solid phase surface is glass substrate recited above, the hydroxyl as possessed by glass substrate can be used as to the functional group of solid phase surface.In addition, will have and be fixed on solid phase surface in advance before with the compound of X coupling functional group in drop of the injection including compound (O) when the functional group that solid phase material is not coupled with X.
Any one of following group: amino, urethane ester group, carboxyl are preferably selected from by the functional group that solid phase surface is possessed, carbonyl, urea groups, sulfonic group, mercapto, sulfenyl, disulfide group, epoxy group, carbodiimide, dimaleoyl imino, alkoxy silane, silane halide and n-hydroxysuccinimide (NHS) base.
The method for being not particularly limited the fixed compound with these functional groups.But for example, the end group opposite with these functional groups and functional group's coupling can be used to form the SAM corresponding to solid phase material-SiLn as described above, such as (wherein, L indicates alkoxy or halogen ion, and n is 1 to 4 integer.) mercapto, sulfenyl, disulfide group and other.It is possible thereby to form SAM, and make to include that the solution of the compound is contacted and fixed with solid phase surface.
Compound (O) is provided with structure Z, can change the solid state properties of solid phase surface or the reaction property in the end relative to X.
The solid state properties of solid phase surface can for example respond wetability, heat and pressure, structure, viscosity, bonding force, water imbibition, elasticity and other.Particularly, the structure with wetability is preferred for Z.Control wetability such as hydrophobicity, hydrophily, hydrophobicity and lipophilicity absorb in the region for needing fixed solid phase surface in which can make the compatible materials to be fixed.On the other hand, it can prevent from for they being fixed on other regions.For Z, the structure for controlling good wettability is e.g. following；As giving solid phase surface hydrophobic structure, what is enumerated is saturated or unsaturated alkyl chain optionally with substituent group, and optionally with the saturated or unsaturated fluorination chain of substituent group.As giving solid phase surface hydrophilic structure, what is enumerated is hydroxyl and amino.
Meanwhile for Z, sound response structure is that have the functional group of high response.The group is for example selected from hydroxyl, amino, urethane ester group, carboxyl, carbonyl, urea groups, sulfonic group, disulfide group, epoxy group, carbodiimide, dimaleoyl imino, n-hydroxysuccinimide base.In addition, Z can be diluted in suitable solvent, and it is not particularly limited, as long as being sprayed as drop.These are avidin such as with biological affinity, biotin, antigen, the molecule of antibody and a-protein.
Compound (O) for fourth aspect present invention is between X and Z, and possessing is that can divide formal similarity Y in itself.The decomposability of Y allows to be broken Z from solid phase surface by decomposing Y after fixed compound (O).This method can make the solid phase property and reaction property once given by Z be back to reset condition.In addition, the decomposition of Y can make solid phase surface receive new solid state properties and reactivity by the atom newly exposed to the open air.The method for being not particularly limited decomposition.But this can be realized as follows.Make to include that the solution with the compound for decomposing Y property is contacted with solid phase surface.Or the solution including this compound is applied on solid phase surface by droplet ejection device.
It is preferred that Y is the structure with photoresponse.Thus Y is easily decomposed to solid phase surface exposure light.In addition, Y can only be decomposed in the partial region of fixed compound (O) when using suitable mask.
Refer to a preferred embodiment of the lower formula (I) as compound above (O).
[formula 12]
Wherein:
R1Independently indicate hydrogen atom ,-OR6(R6It is the alkyl chain that carbon number is 1 to 10) ,-NH (CO) R7(R7Indicate the alkyl chain that carbon number is 1 to 10 or the alkyl fluorine chain that carbon number is 1 to 10), N (R8)2(R8Indicate that carbon number is 1 to 5 alkyl chain), or-S (R9)(R9Indicate that carbon number is 1 to 10 alkyl chain)；
R2It indicates n-hydroxysuccinimide base (optionally replaced sulfonyl)；
R3Expression-X2-(CH2)n-X1, wherein X2Expression-CH2Or-O-, n are 0 or integer of 1 to 10, and X1Expression-OZ ,-Z or
Wherein:
Y expression-(CH2)-or-O-, Z indicate fluoro-alkyl that carbon number is 1 to 20 and m indicates 0 or integer of 1 to 10；R4Expression-NO2Or hydrogen atom；And R5It is the alkyl that hydrogen atom or carbon number are 1 to 10.
In the compound, R2, it is NHS residue, or the NHS residue containing sulfonyl, plays structure X, and be easy for compound (I) to be fixed on solid phase surface, precondition is that amino is present on solid phase surface as functional group.R3 including fluorite chain plays structure Z, and the solid state properties of solid phase surface are changed into hydrophobicity and/or oleophobic property.
In addition, the compound is decomposed by absorbing the extreme ultraviolet of long wavelength such as 254nm to 400nm, preferably decomposed by reaction shown in Fig. 4.Thus, once compound (I) is fixed on solid phase surface (10), just give solid phase surface hydrophobicity and/or oleophobic property property.Then, radiating ultraviolet light removes the structure Z including fluorite chain from solid phase surface, the solid state properties on surface is changed into again hydrophilic.
For the compound indicated by upper formula (I), it is mentioned that the compound indicated by lower formula (II) and (III).
[formula 13]
[formula 14]
As for the method for the injection drop for fourth aspect present invention, what is referred to has micropipette, differential orchestration and ink ejecting method.For being formed accurately pattern, ink ejecting method is particularly preferred.Ink-jet is using various for spraying the method for drop, the pressure injection including using pressure elements, the thermojet using thermal element and the static excitation using the electrostatic force between oscillating plate and electrode.Preferably for temperature sensitive biological substance, pressure injection and static excitation can be used, do not have high-temperature effect to the liquid of injection.
It is not particularly limited the solvent of the compound (I) for fourth aspect present invention, precondition is that it is liquid, can be sprayed by droplet ejection device.However, it is preferred to it is such solvent or compound, with to the high solubility of compound (I) and there is low saturated vapor pressure, i.e., low boiling point and it is not easy drying.As for solvent, what is referred to has such as DMF, DMSO, HNPA, pyrrolidinone compounds solvent and proton polar solvent such as dioxanes.
In addition, in the method for fourth aspect present invention, when spraying drop, it is preferred to use control the device of dry drop.It is easy the dry drop sprayed by droplet ejection device, reason is a small amount of volume.Therefore, in order to guarantee the functional group reactions time enough on structure X and solid phase surface, preferably extend the time of dry drop.As for the mode for controlling dry drop, it is mentioned that as example: shortening the mode of distance between drop, spray the mode of drop (solvent or solution) again before dry drop, the mode of coating material is added, with in the case where injection method, the mode of the movement speed of the platform of solid phase is installed in delay.
Specific embodiment
Following embodiment provides further details of content of the invention.It should be noted, however, that the present invention is never limited to the detailed description of these embodiments.It will be apparent to those skilled in the art that can to embodiment, many variations and modifications may be made without leaving the spirit and scope of the present invention, and they fall into the range of appended claim.
[first embodiment]
(synthesis of following compound 1)
[formula 15]
According to synthetic method shown in Fig. 1 and its reaction step 1-4, prepare compound 1.
For the substance (white solid) synthesized in the reaction step (1),1H NMR、13The spectroscopic data of C NMR, MS etc. are as follows, which is confirmed as 4- (1H, 1H, 2H, 2H- perfluor octyloxy) -3- Methoxy-benzaldehyde (yield 30%).
1H NMR (300MHz, CDCl3) 9.87 (s, 1H, Ar-H), 7.48-7.43 (m, 2H, Ar-H), 6.99 (d, 1H, Ar-H), 4.43-4.38 (t, 2H), 3.93 (s, 3H), 2.81-2.69 (m, 2H)；13CNMR (75MHz, CDCl3) 191.28,153.26,150.35,131.28,126.90,1112.34,110.02,61.54,56.47,31.82,31.54,31.25；MS(ES+)499([M+H]+, 55), 454 (20), 391 9220,279 (5), 241 (5).
For the substance (yellow solid) synthesized in the reaction step (2),1H NMR、13The spectroscopic data of C NMR, elemental analysis etc. is as follows, which is confirmed as 2- nitro -4- (1H, 1H, 2H, 2H- perfluor octyloxy) -5- Methoxy-benzaldehyde (yield 80%).
1H NMR (300MHz, CDCl3) 7.64 (s, 1H, Ar-H), 7.43 (s, 1H, Ar-H), 4.47-4.43 (t, 2H), 4.01 (s, 3H), 2.86-2.69 (m, 2H)；13C NMR (75MHz, CDCl3) 188.08,154.01,151.17,126.77,110.71,108.91,91.23,62.28,57.17,31.78,31.48,31.21；MS(ES+)544([M+H]+, 100), 514 (15), 410 (15), 282 (10), 178 (10)；For C16H10F13O5The analytical calculation of N: C35.35%, H1.85%, N2.57% survey C35.35%, H1.95%, N2.75%.
For the substance (solid) synthesized in the reaction step (3),1H NMR and13The spectroscopic data of C NMR is as follows, which is confirmed as 2- nitro -4- (1H, 1H, 2H, 2H- perfluor octyloxy) -5- methoxyl group-benzylalcohol (yield 70%).
1H NMR (300MHz, CDCl3) 7.74 (s, 1H, Ar-H), 7.22 (s, 1H, Ar-H), 4.98 (s, 2H), 4.40-4.35 (t, 2H), 3.99 (s, 3H), 2.82-2.65 (m, 2H), 2.62 (br.s, 1H)；13CNMR (75MHz, CDCl3) 154.80,146.79,139.89,133.75,111.82,110.56,63.18,56.90,31.80,31.54,31.26.
For the substance (faint yellow solid) synthesized in the reaction step (4),1H NMR、13The spectroscopic data of C NMR, MS, elemental analysis etc. is as follows, which is confirmed as compound 1 (yield 62%).
1H NMR (300MHz, CDCl3) 7.80 (s, 1H, Ar-H), 7.23 (s, 1H, Ar-H), 5.99 (s, 2H), 4.41-4.37 (t, 2H), 4.05 (s, 3H), 2.87 (s, 4H), 2.80-2.68 (m, 2H)；13CNMR (75MHz, CDCl3) 168.88,155.07,151.81,147.36,139.23,126.89,110.54,109.49,69.48,62.09,57.08,31.76,31.51,31.23,25.86；MS(FAB)686([M]+, 8), 528 (100)；HRMS(ES+).It is calculated as C21H15N2O9F13Na 709.0468, actual measurement 709.0473；For C21H15N2O9F13Analytical calculation: C36.73%, H2.20%, N4.08% survey C36.45%, H2.35%, N4.25%.
[the second embodiment]
Gold thin film is formed on surface by sputtering at silicon substrate.Individually, thiol solution is prepared and the 11- aminododecane mercaptan of 1mM is dissolved in ethyl alcohol.Then, the substrate for being provided with gold thin film thereon is impregnated in the thiol solution of room temperature 12 hours.Then ethyl alcohol rinse substrate is used, is then dried under nitrogen flowing.This causes the SAM film of 11- aminododecane mercaptan to be formed in the gold surface of substrate.
Then, in the anhydrous methylene chloride that the compound 1 for 150mg being synthesized and being purified in embodiment 1 is dissolved in 100ml, the solution that concentration is about 2mM is formed, and the triethylamine of 2ml is dissolved in the solution being consequently formed, thus prepares the solution of compound 1.Then, the above-mentioned substrate (hereinafter referred to as " amino surface substrate ") on the surface thereof with amido functional group is impregnated in half a day in the solution at room temperature thus prepared in room temperature, makes to react progress between the succinimide ester of compound 1 and the amino of amino surface substrate.The reaction icon is in Fig. 2 (1) and 2 (2).After reaction, with dichloromethane substrate, then dried by flowing nitrogen.Thus the SAM chain modified by the fluorination of the molecular composition respectively with structure as shown in Figure 2 is formed on the surface of a substrate.
The contact angle on SAM (monomolecular film) surface being consequently formed is measured, and advance angle (water) is about 90 to 100 °.The variation for thinking the angle of measurement is the change due to being fluorinated the molecule coating state of chain modified SAM.
Then, the UV for being 365nm with wavelength is fluorinated the chain modified surface the SAM different time (1 minute, 5 minutes, 10 minutes etc.) by photomask irradiation.The energy profile of used UV ray is shown in Figure 3.The energy of UV ray is about 30mW/cm2.UV irradiation causes decomposition reaction shown in Fig. 2 (2) and 2 (3) to occur, as a result, by decomposing the SAM for being formed have the amino of the representation as shown in Fig. 2 (3) on the surface.
After UV irradiation, the variation of surface contact angle (advance angle (water)) is measured in four different locations that SAM was illuminated with the surface of ethyl alcohol rinse substrate.The results are shown in Table 1 for measurement.Result as shown in Table 1 is classified as follows.When SAM is illuminated 1 to 5 minute, contact angle is reduced to about 50 °, shows that the decomposition of the SAM of coupling is basically completed within this time range.Since when only covering 11- aminododecane mercaptan, the contact angle on the surface SAM of measurement is about 43 °, it is believed that remove most fluorination chain by irradiation.
In addition, SAM is impregnated in water with after rinse step irradiating, then it is taken out.The surface of SAM is observed immediately after.It observes that water droplet is retained in and turns out to be hydrophilic nmature, place with the UV irradiated surface SAM.Separately-aspect, shielding UV irradiation, be hydrophobic position, keep repel water the surface SAM.
[comparative example]
The silicon substrate for being coated with solid film for being used as donor substrate in embodiment 2 is impregnated in the HS (CH containing 1mM2)2(CF2)9CF3Dichloromethane solution in.Then UV irradiation is carried out in a manner of being similar to embodiment 2, and analyzes wettability of the surface.As a result, the contact angle before UV processing is 110 ° for water, and it is about 109 ° in the contact angle of UV irradiation after five minutes, there is no variation.This is confirmed by HS (CH2)2(CF2)9The SAM of formation is difficult to by UV photodegradation (right column for being shown in Table 1).
Table 1
| Embodiment 2 | Comparative example | ||||
| Compound 1 | CF3(CF2)9(CH2)2SH | ||||
| The region of measurement | 1 | 2 | 3 | 4 | |
| C.A(°) | C.A(°) | C.A(°) | C.A(°) | C.A(°) | |
| UV0 minutes | 95 | 97 | 102 | 98 | 110 |
| UV1 minutes | 67 | 67.8 | 66 | 69 | 109 |
| UV5 minutes | 53.1 | 53 | 52.6 | 53.1 | 109 |
| UV10 minutes | 50 | 49.5 | 49.7 | 50.9 | 108 |
| UV20 minutes | 50.5 | 50.1 | 50.8 | 51.4 | 104 |
| UV30 minutes | 48.5 | 49.7 | 48.8 | 48.9 | 105 |
| UV60 minutes | 49.2 | 49.7 | 50.1 | 51.1 | 103 |
By above description, it is to be understood that the present invention provides a kind of self installation single layer (SAM) material, monomolecular film can be formed on the substrate, and it can carry out light-pattern by the exposure of the suitable short time of low energy UV ray and be formed.The SAM material of offer can be applied to various types of substrate by suitable coupling compound.Before irradiation, SAM material is hydrophobicity and/or oleophobic property.But the structural constituent fracture that irradiation will be responsible for this property is fallen, and hydrophilic functional group is left.Therefore, the irradiation of SAM material substantially changes the surface nature of the substrate of SAM coating.
[embodiment 3]
In this embodiment, it is described as the solution of the compound (referred to as compound (II)) of upper formula (II), by spraying to control the wetability of solid phase surface.Compound (II) includes the n-hydroxysuccinimide base as structure X, as structure Y have can the structure of photodegradation property the solid state properties of solid phase surface are changed into hydrophobicity and/or oleophobic property as the fluorination chain of structure Z.
(pretreatment of substrate surface)
Firstly, as shown in figure 5,11- aminododecane mercaptan is fixed on a surface of the substrate.The compound can be coupled with the n-hydroxysuccinimide of compound (II).Substrate is silicon and first passing through evaporation is coated with gold thin film in advance.Gold thin film is also to be formed by sputtering.
11- aminododecane mercaptan is dissolved in ethyl alcohol, becomes the solution of 1mM, and substrate is impregnated in this solution.Then the substrate is rinsed with ethyl alcohol, then dried under nitrogen flowing.Substrate surface is covered by amino and becomes hydrophilic.
(fixed compound (II))
Then, the compound I of 150mg is dissolved in the anhydrous DMSO (dimethyl sulfoxide) of 100mL, becomes the solution of about 2mM, and the trimethylamine of 2mL is added.
As shown in fig. 6, the solution is added into the ink reservoir of inkjet type injection apparatus after deaerating to solution, and it is injected on the designated position of amino substrate surface recited above.
After spraying herein, with DMSO rinse substrate, then dried by flowing nitrogen.As a result, compound (II) is only fixed on the region of injection drop, and hydrophobicity and/or oleophobic property property are given by the fluorination chain that CF is indicated.On the other hand, the region for not spraying drop has hydrophily, and reason is that amino holding exposes to the open air.
Extend water on the surface and by micro- sem observation.Observation result is shown in Fig. 7 to 10.According to Fig. 7 and 8, it was demonstrated that water flows out in the region of injection compound (II) solution.In addition, in figures 9 and 10, it was demonstrated that polar organic solvent such as ethyl alcohol also flows out, and is shown to be printed patterns and sprays the region of compound (II) solution, and liquid is not adhere to substrate surface.
(fixed amino protecting group)
Then, as shown in figure 11, the DMSO solution of such as 9- fluorine prenyl methyl succinimide base carbonic ester is for example injected in by ink ejecting method etc. to the region for not spraying compound (II).In addition, compound (II) substrate for forming pattern is impregnated in the solution, so that amino protecting group is reacted and fixed.For amino protecting group, what is referred to has N- succinimido carbonic acid benzyl ester, di-t-butyl diamino acid ester group and N- tertbutyloxycarbonyl imidazoles.
(decomposition of chemical compounds (II))
Then, as shown in figure 12, with 308nm UV radiation supporting base surface.Reaction dissolved compound (II) as shown in Figure 4 as a result, and the fluorination chain indicated by CF is removed from substrate surface, expose amino to the open air again, and show hydrophilic nmature in this region.Then, reaction amino and the solution reaction for being dissolved with NHS ester (NHS-LC-LC- biotin, the reagent prepared by Pierce Inc.), form the micro- pattern for being covered with biotin.In addition, on this pattern, such as fixed HRP (horseradish peroxidase) enzyme molecule with streptavidin conjugation, micro- pattern of enzyme monomolecular film easy to form.
[Detailed description of the invention]
[Fig. 1]
Fig. 1 show the synthesis of molecule (compound 1) according to a first aspect of the present invention.
[Fig. 2]
Fig. 2 show molecule according to a first aspect of the present invention and is adhered to covalent bonding and their fractures when carrying out UV irradiation later of the coupling compound (D) of substrate in advance.
[Fig. 3]
Fig. 3 show the Energy distribution of UV ray, can be used to expose the substrate of monomolecular film coating according to a second aspect of the present invention.
[Fig. 4]
Fig. 4 show the explanation for the photoresponse in fourth aspect present invention.
[Fig. 5]
Fig. 5 show the figure being fixed on amino on solid phase surface.
[Fig. 6]
Fig. 6 show the figure that compound (II) is fixed on to the amino on solid phase surface.
[Fig. 7]
Fig. 7 show the figure of the water outflow property of observation compound (II).
[Fig. 8]
Fig. 8 show the figure of the water outflow property of observation compound (II).
[Fig. 9]
Fig. 9 show the figure of the water outflow property of observation compound (II).
[Figure 10]
Figure 10 show the figure of the water outflow property of observation compound (II).
[Figure 11]
Figure 11 show the figure to the fixed amino protecting group of the amino of solid phase surface.
[Figure 12]
Figure 12 show the figure of the decomposition of chemical compounds (II) and irradiating UV to solid phase surface.
Claims (32)
1. a kind of molecule, it includes structural constituents (A) and structural constituent (B), structural constituent (A) decomposition in the ultraviolet light irradiation for being 254-400nm with wavelength, the structural constituent (B) are hydrophobicity and/or oleophobic property.
2. molecule according to claim 1, wherein the structural constituent (A) is o- p-Nitrobenzyl.
3. molecule according to claim 2, wherein the end group connecting with the benzyl of the o- p-Nitrobenzyl is succinimide.
4. according to claim 1 to molecule described in 3 any one, wherein the structural constituent (B) includes fluorination chain.
5. molecule according to claim 4, wherein the fluorination chain is saturation.
6. according to molecule described in claim 4 or claim 5, wherein the fluorination chain is branching and/or fluoridized.
7. according to claim 1 to molecule described in 6 any one, with following general formula (1):
[formula 1]
Wherein:
R1Independently indicate hydrogen atom ,-OR6(R6It is the alkyl chain that carbon number is 1 to 10) ,-NH (CO) R7(R7Indicate the alkyl chain that carbon number is 1 to 10 or the alkyl fluorine chain that carbon number is 1 to 10), N (R8)2(R8Indicate that carbon number is 1 to 5 alkyl chain), or-S (R9)(R9Indicate that carbon number is 1 to 10 alkyl chain)；
R2It indicates n-hydroxysuccinimide base (optionally replaced sulfonyl)；
R3Expression-X2-(CH2)n-X1, wherein X2Expression-CH2Or-O-, n are 0 or integer of 1 to 10, and X1Expression-OZ ,-Z or
Wherein:
Y expression-(CH2)-or-O-, Z indicate fluoro-alkyl that carbon number is 1 to 20 and m indicates 0 or integer of 1 to 10；R4Expression-NO2Or hydrogen atom；And R5It is the alkyl that hydrogen atom or carbon number are 1 to 10.
8. molecule according to claim 7, wherein R1For-OCH3。
9. wherein Z is-(CH according to claim 7 or molecule according to any one of claims 82)m(CF2)PF or its branched isomer, wherein m is as defined above, and the integer that p is 0 or 1 to 9.
10. being following compound according to claim 1 to molecule described in 9 any one:
[formula 2]
11. a kind of substrate of monomolecular film coating, the film is formed by the molecule comprising structural constituent (B) and structural constituent (A), the structural constituent (B) is hydrophobicity and/or oleophobic property, structural constituent (A) decomposition in the ultraviolet light irradiation for being 254-400nm with wavelength, to be broken a part for the molecule containing structural constituent (B) of exchanging, remaining hydrophilic-structure component (C) is left.
12. the substrate of monomolecular film coating according to claim 11, wherein the structural constituent (A) is o- p-Nitrobenzyl.
13. according to claim 11 or claim 12 described in monomolecular film coating substrate, wherein the structural constituent (B) includes fluorination chain.
14. the substrate of monomolecular film coating according to claim 13, wherein the fluorination chain is saturation.
15. according to claim 13 or claim 14 described in monomolecular film coating substrate, wherein the fluorination chain is branching and/or fluoridized.
16. the substrate of the coating of monomolecular film described in 1 to 15 any one according to claim 1, wherein the hydrophilic structure component (C) includes amido or hydroxyl.
17. the substrate of the coating of monomolecular film described in 1 to 16 any one according to claim 1, it is obtained by the following method: with the monomolecular film coated substrate of the coupling compound (D) comprising hydrophilic segment, then make the hydrophilic segment with reacted according to claim 1 to molecule described in 11 any one so that the coupling compound (D) is in conjunction with molecule covalent.
18. the substrate of monomolecular film coating according to claim 17, wherein the substrate is formed by metal, semiconductor or plastics.
19. according to claim 17 or claim 18 described in monomolecular film coating substrate, wherein the hydrophilic segment is amido or hydroxyl.
20. the substrate of the coating of monomolecular film described in 1 to 15 any one according to claim 1, is defined wherein forming any one of molecule such as claims 1 to 10 of the film.
21. the substrate of monomolecular film coating described in 1 to 15 any one or claim 20 according to claim 1, wherein the substrate has water-wetted surface before with the monomolecular film coating.
22. the monomolecular film being coated on a kind of substrate described in 1 to 21 any one according to claim 1 carries out the method that light-pattern is formed, method includes the following steps: the UV light for being 254-400nm with wavelength at image irradiates the substrate of the monomolecular film coating by patterned exposure mask, to be broken be coated with molecule at structural constituent (A), thus it is removed from coated thin film in irradiated site structural constituent (B), they are hydrophilic from being changed into for hydrophobicity and/or oleophobic property.
23. a kind of method for forming Thinfilm pattern, this method includes that at least one step of drop is sprayed on the solid phase surface containing funtion part, and the drop includes the compound indicated by following formula (O):
[formula 3]
X-Y-Z (O)
Wherein, X indicates there is reactive structural constituent with the funtion part existing for solid phase surface, and Y indicates decomposable structural constituent itself, and Z indicates to can change the structural constituent or active structure component of the solid state properties on solid phase surface.
24. according to the method for claim 23, wherein the solid state properties are wetabilitys.
25. the method according to claim 23 or 24, wherein Z includes such a structural constituent, selected from including following any one of group: the optionally saturated or unsaturated alkyl chain containing substituent group, the optionally saturated or unsaturated fluorination chain containing substituent group, hydroxyl, amino, urethane ester group, carboxyl, carbonyl, urea groups, sulfonic group, disulfide group, epoxy group, carbodiimide, dimaleoyl imino, n-hydroxysuccinimide base.
26. wherein X includes such a structural constituent according to method described in claim 23 to 25 any one, selected from including any one of following groups: amino, urethane ester group, carboxyl, carbonyl, urea groups, sulfonic group, disulfide group, epoxy group, carbodiimide, dimaleoyl imino, alkoxy silane, silane halide and n-hydroxysuccinimide base.
27. wherein Y is the structural constituent with photo absorption property according to method described in claim 23 to 26 any one.
28. according to the method for claim 23, wherein the formula (O) is represented as following compound:
[formula 4]
Wherein:
R1Independently indicate hydrogen atom ,-OR6(R6It is the alkyl chain that carbon number is 1 to 10) ,-NH (CO) R7(R7Indicate the alkyl chain that carbon number is 1 to 10 or the alkyl fluorine chain that carbon number is 1 to 10) ,-N (R8)2(R8Indicate that carbon number is 1 to 5 alkyl chain), or-S (R9)(R9Indicate that carbon number is 1 to 10 alkyl chain)；
R2It indicates n-hydroxysuccinimide base (optionally replaced sulfonyl)；
R3Expression-X2-(CH2)n-X1, wherein X2Expression-CH2Or-O-, n are 0 or integer of 1 to 10, and X1Expression-OZ ,-Z or
Wherein:
Y expression-(CH2)-or-O-, Z indicate fluoro-alkyl that carbon number is 1 to 20 and m indicates 0 or integer of 1 to 10；R4Expression-NO2Or hydrogen atom；And R5It is the alkyl that hydrogen atom or carbon number are 1 to 10.
29. this method also includes following step according to method described in claim 23 to 28 any one: before injection includes the liquid for the compound that formula (I) is indicated, the fixed compound with the funtion part that can combine X on solid phase surface.
30. according to method described in claim 23 to 29 any one, wherein the method for the injection drop is ink ejecting method.
31., wherein the drop includes solvent, the solvent is selected from such as water, ethyl alcohol, DMF, DMSO, HMPA, pyrrolidinone compounds, any one of dioxanes according to method described in claim 23 to 30 any one.
32. according to method described in claim 23 to 31 any one, wherein the method for the injection drop includes control method, with the dry drop.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0409606A GB2413553A (en) | 2004-04-29 | 2004-04-29 | UV decomposable molecules and a photopatternable monomolecular film formed therefrom |
| GB0409606.1 | 2004-04-29 | ||
| JP2004295100 | 2004-10-07 |
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| CN1715270A true CN1715270A (en) | 2006-01-04 |
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| CN 200510067080 Pending CN1715270A (en) | 2004-04-29 | 2005-04-27 | Uv decomposable molecules and a photopatternable monomolecular film formed therefrom |
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| GB (1) | GB2413553A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101071118B (en) * | 2006-05-08 | 2013-01-02 | 精工爱普生株式会社 | Electronic device substrate, method for manufacturing substrate, compound, method for manufacturing same |
| CN108795210A (en) * | 2017-05-05 | 2018-11-13 | 斯沃奇集团研究和开发有限公司 | Oil-proofing agent and the grease proofing method for using this oil-proofing agent |
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| CN110198946A (en) * | 2017-01-31 | 2019-09-03 | 株式会社尼康 | Compound, pattern formed with substrate, photodegradation coupling agent, pattern forming method and transistor manufacturing method |
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| CN111153462B (en) * | 2020-01-14 | 2021-04-30 | 南京大学 | Method for degrading perfluorinated compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4369244A (en) * | 1980-08-11 | 1983-01-18 | Minnesota Mining And Manufacturing Company | Imaging process and article employing photolabile, blocked surfactant |
| JP3705657B2 (en) * | 1996-09-05 | 2005-10-12 | 信越化学工業株式会社 | Process for producing N, N-dialkylcarbamic acid 2-nitrobenzyl esters |
| EP1415001A4 (en) * | 2001-07-13 | 2008-02-20 | Ambergen Inc | Nucleotide compositions comprising photocleavable markers and methods of preparation thereof |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101071118B (en) * | 2006-05-08 | 2013-01-02 | 精工爱普生株式会社 | Electronic device substrate, method for manufacturing substrate, compound, method for manufacturing same |
| CN110198946A (en) * | 2017-01-31 | 2019-09-03 | 株式会社尼康 | Compound, pattern formed with substrate, photodegradation coupling agent, pattern forming method and transistor manufacturing method |
| US11225461B2 (en) | 2017-01-31 | 2022-01-18 | Nikon Corporation | Compound, substrate for pattern formation, photodegradable coupling agent, pattern formation method, and transistor production method |
| CN110198946B (en) * | 2017-01-31 | 2022-04-26 | 株式会社尼康 | Compound, substrate for pattern formation, photodegradable coupling agent, pattern formation method, and method for manufacturing transistor |
| TWI767983B (en) * | 2017-01-31 | 2022-06-21 | 日商尼康股份有限公司 | Compound, substrate for forming a pattern, photolytic coupling agent, method for forming a pattern and method for producing a transistor |
| CN108795210A (en) * | 2017-05-05 | 2018-11-13 | 斯沃奇集团研究和开发有限公司 | Oil-proofing agent and the grease proofing method for using this oil-proofing agent |
| US11117162B2 (en) | 2017-05-05 | 2021-09-14 | The Swatch Group Research And Development Ltd | Epilamization agent comprising a cleavable linking group and epilamization method using such an epilamization agent |
| CN108795210B (en) * | 2017-05-05 | 2022-02-25 | 斯沃奇集团研究和开发有限公司 | Oil-repellent agent and oil-repellent method using the same |
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| Publication number | Publication date |
|---|---|
| GB0409606D0 (en) | 2004-06-02 |
| GB2413553A (en) | 2005-11-02 |
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