CN102508408B - Dual-solidification nanoimprint lithography transporting layer material - Google Patents
Dual-solidification nanoimprint lithography transporting layer material Download PDFInfo
- Publication number
- CN102508408B CN102508408B CN201110331249.7A CN201110331249A CN102508408B CN 102508408 B CN102508408 B CN 102508408B CN 201110331249 A CN201110331249 A CN 201110331249A CN 102508408 B CN102508408 B CN 102508408B
- Authority
- CN
- China
- Prior art keywords
- layer material
- nano impression
- transfer layer
- group
- impression glue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a dual-solidification nanoimprint lithography transporting layer material and belongs to the technical field of micro-nanometer processing. The transporting layer material comprises at least two types of reactive groups based on different polymerization crosslinking mechanisms, wherein one of the groups is same as a polymerizable reactive group in nanoimprint lithography glue; at least one of the composition ingredients of the transporting layer material is simultaneously linked with the two types of reactive groups; after the transporting layer material is spun on a substrate to form a film, one type of reactive group is selectively polymerized to form a solidified cross-linked network firstly; the other type of group and the same kind of group in the nanoimprint lithography glue are simultaneously polymerized in a nanoimprint lithography solidification step; and the transporting layer and the solidified nanoimprint lithography glue layer are tightly combined by a chemical bond. The dual-solidification nanoimprint lithography transporting layer material disclosed by the invention not only can further transport the nanoimprint lithography structure onto the substrate, but also can improve the adhesion performance of the nanoimprint lithography glue material and the substrate.
Description
Technical field
The invention belongs to micro-nano manufacture field, be specifically related to the nano impression transfer layer material of a kind of pair of curing type.
Background technology
Nanometer embossing (openly US Patent No. 6180239) is that the Stephen Y. Chou professor of middle nineteen nineties in the last century U.S. Princeton Nanostructure Lab of university is exposed the restriction of wavelength for traditional photoetching process, reached the limit (~ 30nm) of preparing micro-structure, cannot further obtain less size, and proposed to be similar to a kind of technology of macromolecule mold pressing, and successfully prove by this technology and can on semi-conductor silicon chip, obtain the structural unit that size is less than 10nm.Nano impression is a kind of nanostructured preparation method of physical contact formula, similar to macromolecule mould technology, the impression block with nanostructured, be pressed in thermoplastics type's macromolecule of heating and melting or be pressed in curable prepolymer liquid film, and then make to impress the cooling or curing molding of glue, after impression finishes, also need template separated with impression glue, i.e. the demoulding.There are a lot of nanostructureds on general impression block surface, and substrate surface is smooth plane, therefore the specific area of template is much larger than substrate, if do not done pre-service, impressing the interaction force of glue and template, is mainly Van der Waals force, by the interaction force much larger than impression glue and substrate, when this will cause the demoulding, impression glue is stripped down from substrate by template.US Patent No. 2008217813 discloses a kind of by carrying out release treatment on impression block surface, and the unimolecular layer of bonding one deck perfluoro alkane can significantly reduce the surface tension of template, effectively solves the technology of the problem of peeling off.For further reducing the acting force between impression glue and template, be convenient to the demoulding, in impression glue, added the low surface-active components (US Patent No. 6334960) such as organosiloxane, fluorine material.Although organosiloxane, fluorine material etc. have reduced the adhesion of impression glue to template, also reduced the adhesion of impression glue to substrate.Especially the impression glue material to curing type, once the impression glue adhesion after solidifying, in template, because it forms cross-linked network, can not, by any solvent cleaning, can pollute template, damage.For the impression glue material of curing type, document Nano Letters 2005,5,179-182 adopts coupling agent to strengthen the adhesiveness of impression glue material and substrate.Coupling agent is a kind of a kind of compound that is usually used in strengthening bond properties between different materials, and it possesses the reactive group of two types, can carry out chemical reaction by respectively with two kinds of different materials, and two kinds of different materials are got up by chemical bond and link.As coupling agent acrylate chlorosilane, chlorine silicon key can with conventional silicon, the silicon hydroxyl reaction of silicon dioxide substrates, form Si-O-Si key, and the acrylate group of the other end can carry out bonding with the acrylate group that esters of acrylic acid curing type impresses in glue.But it is loaded down with trivial details generally to process backing material process with coupling agent, backing material is had to special requirement simultaneously, as the coupling agent of chlorosilane is only suitable in the material that has silicon hydroxyl.
For photoetching technique and nanometer embossing, it is easy that the little structure plan of preparation aspect ratio is all prepared the structure plan that aspect ratio is large, therefore at photoresist (IEEE JOURNAL OF SOLID-STATE CIRCUITS, VOL. SC-15, NO. 4, AUGUST 1980) or nano impression glue (US Patent No. 6334960) and substrate between introduced one deck polymeric membrane transfer layer.Duplicature system can be the little structure plan of aspect ratio forming on photoresist or impression glue, method by selectivity plasma etching is enlarged into the structure plan that aspect ratio is large on macromolecule membranous layer, and structure plan can be copied on substrate more reliably.In the macromolecular material forming at carbon, hydrogen, oxygen, introduce the ability that can effectively improve material antioxygen gas plasma etching containing the component of element silicon.The macromolecule membranous layer of lower floor is the macromolecular material of carbon, hydrogen, oxygen composition, upper layer of material and subsurface material have selectivity to oxygen plasma etching, the speed of upper layer film etching is less than the speed of lower membrane etching, therefore the structure plan forming in upper layer film can be used as mask, by oxygen plasma etching, transfer in lower membrane, the aspect ratio of patterning is exaggerated simultaneously.The general silicon components of introducing is organosiloxane material, and poor adhesion between upper layer film and transfer layer can have been caused in its extremely low surface.Current nano impression glue material mostly is ultraviolet light curing nano impression glue material.
Summary of the invention
The object of the invention is to solve in current nanometer embossing, the problem that impression glue material may be peeled off by template in knockout course, in order to strengthen the adhesive capacity of nano impression glue material and substrate, provide a kind of can two curing nano impression transfer layer materials, by forming covalent bond with impression glue in solidification process, curing impression glue is linked on transfer layer material.
For achieving the above object, the technical scheme that the present invention takes is:
A pair curing type nano impression transfer layer material, comprises at least two kinds of reactive groups based on different polymerization crosslinking mechanism in described transfer layer material, a kind of group is wherein identical with the polymerizable reactive group in nano impression glue; And in the formation component of transfer layer material, at least there is a kind of component and link two kinds of described reactive groups simultaneously.
For nano impression transfer layer material, it is on substrate after film forming, first adopt the polymerization of ultraviolet lighting or heating that wherein a kind of group is reacted, form curing cross-linked network structure, this structure not only can prevent that in nano impression spin coating process after a while, organic solvent, to the dissolving of transfer layer material and swelling, also can improve the mechanical mechanics property of transfer layer material, the tolerance of enhanced etching, prevent in etching process nanostructured lodging.Another unreacted radical, prints in solidification process and identical curing groups reaction in nano impression glue in nano impression glue laminated, forms cross-linked network, make nano impression glue by covalent bonds on transfer layer material.Because transfer layer material is containing organosiloxane, have larger surface free energy, and backing material there is good adhesion, therefore by two curing transfer layers, finally can improve nano impression glue for the adhesion property of substrate.
Nano impression transfer layer material provided by the invention, can strengthen the adhesive capacity of nano impression glue and substrate, solved and in current nanometer embossing, impressed the problem that glue material may be peeled off by template in knockout course, in the process of nano impression, be with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is composition and the curing mechanism schematic diagram that the embodiment of the present invention 1 is applicable to the two curing transfer layer material of acrylic ester type impression glue material.
Fig. 2 is composition and the curing mechanism schematic diagram that the embodiment of the present invention 2 is applicable to the two curing transfer layer material of epoxide resin type impression glue material.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further details.
Current ultraviolet light curing nano impression materials is mainly the acrylic ester prepolymer causing based on free radical and the epoxy prepolymer causing based on kation.For this two classes ultraviolet light curing nano impression glue material, the present embodiment has related to two kinds of two curing transfer layer materials.
Embodiment 1
For acrylate UV-curing nano impression material, the two curing transfer layer material the present invention relates to, by acroleic acid esterification poly-(melamine-
co-formaldehyde), the composition such as polyvinylphenol, benzene sulfonic acid, glycol monoethyl ether, wherein acroleic acid esterification poly-(melamine-
co-formaldehyde), polyvinylphenol is the main body composition of two curing materials, acroleic acid esterification poly-(melamine-
co-formaldehyde) upper chain is simultaneously connected to the acrylate group of free redical polymerization and melamine etherificate group that can polycondensation.Benzene sulfonic acid is acid catalyst, and glycol monoethyl ether is solvent.Poly-(melamine-
co-formaldehyde) and polyvinylphenol be conventional compositions of thermosetting resin, (Journal of Photopolymer Science and Technology Volume 3 in photoetching process, Number 3 (1990) 355 – 373), the conventional fertile material of doing antireflection transfer layer, has the advantages that physical strength is high, etch resistance is good.In the present embodiment, adopted acroleic acid esterification poly-(melamine-
co-formaldehyde) with polyvinylphenol under benzene sulfonic acid catalysis, carry out polycondensation reaction, its reaction mechanism as shown in Figure 1, poly-(melamine-
co-formaldehyde) ehter bond on adds thermal decomposition and produces methylene kation under strong acid, and this kation can electrophilic addition, form carbon-oxygen bond, form carbon-carbon bond with phenyl ring with phenolic hydroxyl group, due to poly-(melamine-
co-formaldehyde) and polyvinylphenol all have highdensity reactive group, therefore after heat curing, this material forms the structure of the network of high-crosslinking-degree, simultaneously the not polymerization of initiating methacrylates of hydrogen ion, acrylate is linked on cross-linked network, in unreacted state.In the solidification process of upper strata ultraviolet light curing nano impression glue material, acrylate group on two curing materials is initiated and the acrylate group copolymerization impressing in glue simultaneously, form cross-linked network, the rete of nano impression is linked at and is transmitted on tunic by covalent bond.
The acroleic acid esterification that specifically consists of total mass ratio 6% of the two curing transfer layer material of acrylic ester type impression glue material gather (melamine-
co-formaldehyde), 4% polyvinylphenol, 0.1% benzene sulfonic acid, 89.9% glycol monoethyl ether, by spin-coating, on substrate, form homogeneous film, in temperature 200
ounder C, toast 1 minute, cooling after, can be used as transfer layer, proceed imprint step.
Embodiment 2
For epoxy resin ultraviolet light curing nano impression materials, the two curing transfer layer material the present invention relates to, by epoxy-acrylate prepolymer, acrylate cross linked dose, benzophenone, methyl methacrylate etc., formed, wherein epoxy-acrylate prepolymer, acrylate cross linked dose are the main body compositions of two curing materials, on epoxy-acrylate prepolymer, chain is connected to the acrylate group of free redical polymerization and the epoxide group of kation ring-opening polymerization simultaneously, benzophenone is optical free radical initiating agent, and methyl methacrylate is reactive solvents.After two curing materials are coated on substrate, first carry out uv-exposure, under free radical causes, acrylate group addition polymerization, forms high density cross-linked network structure, and its reaction mechanism as shown in Figure 2.Because free radical does not cause epoxide group ring-opening polymerization, epoxide group is linked on cross-linked network, in unreacted state.In the solidification process of upper strata ultraviolet light curing nano impression glue material, the epoxide group on two curing materials is initiated and the epoxide group ring opening copolymer impressing in glue simultaneously, forms cross-linked network, and the rete of nano impression is linked at and is transmitted on tunic by covalent bond.
The epoxy-acrylate prepolymer that specifically consists of total mass ratio 6% of the two curing transfer layer material of epoxide resin type impression glue material, 4% acrylate cross linked dose, 0.3% benzophenone, 89.7% methyl methacrylate, by spin-coating, on substrate, form homogeneous film, at room temperature, in blanket of nitrogen, uv-exposure, exposure dose 100mJ/cm
2, after having exposed, can be used as transfer layer, proceed imprint step.
Acrylate UV-curing impression glue material is in LOL(Microchem company) on transfer layer and two curing transfer layers of the present invention impression afterwards the experimental result of the demoulding show, LOL transfer layer has occurred that serious impression glue is stripped from problem, and two curing transfer layer is without any peeling off problem.
Owing to forming cross-linked network after two curing transfer layer material cured, can not be dissolved in any solvent, therefore cannot be applicable to metal lifts off technique.In the present invention, lower floor at two curing materials introduces one deck thermoplastic macromolecule material again, as the soluble layer that lifts off, as LOL(Microchem company) transfer layer material or polymethylmethacrylate for lifting off, as lifting off layer, after having impressed, by etching, nanostructured is delivered on substrate by lifting off layer, after deposited metal film, complete and lift off technique.
Claims (4)
1. a two curing type nano impression block, comprise substrate and ultraviolet curing type nano impression glue, ultraviolet curing type nano impression glue is acrylic ester type or epoxide resin type, it is characterized in that, between described substrate and ultraviolet curing type nano impression glue, also have the two curing type transfer layers of one deck, in this transfer layer material, do not contain organosiloxane, in transfer layer material, comprise at least two kinds of reactive groups based on different polymerization crosslinking mechanism, a kind of group is wherein identical with the polymerizable reactive group in nano impression glue: when described ultraviolet curing type nano impression glue is acrylic ester type, this group is acrylate group, when described ultraviolet curing type nano impression glue is epoxide resin type, this group is epoxide group, and in the formation component of transfer layer material, at least there is a kind of component and link described two kinds of reactive groups based on different polymerization crosslinking mechanism simultaneously.
2. a kind of pair of curing type nano impression block according to claim 1, it is characterized in that, when described ultraviolet curing type nano impression glue is acrylic ester type, poly-(melamine-co-formaldehyde) and polyvinylphenol that the principal ingredient of described transfer layer material is acroleic acid esterification; When described ultraviolet curing type nano impression glue is epoxide resin type, the principal ingredient of described transfer layer material is epoxy-acrylate prepolymer and acrylate cross linked dose.
3. a kind of pair of curing type nano impression block according to claim 1 and 2, is characterized in that, also has one deck thermoplastic macromolecule material between described substrate and transfer layer.
4. the method for preparation a kind of pair of curing type nano impression block as claimed in claim 2, is characterized in that, comprises the steps: that (1) utilizes the method for spin-coating that transfer layer material is formed to homogeneous film on substrate; (2) when described ultraviolet curing type nano impression glue is acrylic ester type, pass through heated baking, make the polyvinylphenol polymerizing curable in transfer layer material, transfer layer material forms cross-linked structure, and another reactive group acrylate group is still in unreacted state, then in nano impression glue laminated prints solidification process, acrylate group reaction, make nano impression glue by covalent bonds on transfer layer material; When described ultraviolet curing type nano impression glue is epoxide resin type, pass through uv-exposure, make acrylate cross linked dose of polymerizing curable in transfer layer material, transfer layer material forms cross-linked structure, and epoxide group in another reactant epoxy-acrylate prepolymer is still in unreacted state, then in nano impression glue laminated prints solidification process, the epoxide group in epoxy-acrylate prepolymer reacts, make nano impression glue by covalent bonds on transfer layer material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110331249.7A CN102508408B (en) | 2011-10-27 | 2011-10-27 | Dual-solidification nanoimprint lithography transporting layer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110331249.7A CN102508408B (en) | 2011-10-27 | 2011-10-27 | Dual-solidification nanoimprint lithography transporting layer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102508408A CN102508408A (en) | 2012-06-20 |
| CN102508408B true CN102508408B (en) | 2014-09-10 |
Family
ID=46220510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110331249.7A Active CN102508408B (en) | 2011-10-27 | 2011-10-27 | Dual-solidification nanoimprint lithography transporting layer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102508408B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107924121B (en) | 2015-07-07 | 2021-06-08 | 亿明达股份有限公司 | Selective surface patterning via nanoimprinting |
| JP7011386B2 (en) * | 2016-11-16 | 2022-01-26 | キヤノン株式会社 | Adhesion layer forming composition and article manufacturing method |
| CN106918997B (en) * | 2017-03-28 | 2019-10-11 | 南雄市毅豪化工有限公司 | Photosensitive polymer combination, photocuring pattern and the method for forming photocuring pattern |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006301559A (en) * | 2005-03-22 | 2006-11-02 | Fuji Photo Film Co Ltd | Material and method for pattern forming and pattern |
| JP2007041107A (en) * | 2005-08-01 | 2007-02-15 | Nippon Kayaku Co Ltd | Photosensitive resin composition and cured product thereof |
| CN1916034A (en) * | 2006-08-25 | 2007-02-21 | 南京大学 | Solidifiable composition material by ultraviolet light and application |
| CN101501080A (en) * | 2006-08-04 | 2009-08-05 | 三菱化学株式会社 | Insulating layer, electronic device, field effect transistor, and polyvinylthiophenol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6334960B1 (en) * | 1999-03-11 | 2002-01-01 | Board Of Regents, The University Of Texas System | Step and flash imprint lithography |
-
2011
- 2011-10-27 CN CN201110331249.7A patent/CN102508408B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006301559A (en) * | 2005-03-22 | 2006-11-02 | Fuji Photo Film Co Ltd | Material and method for pattern forming and pattern |
| JP2007041107A (en) * | 2005-08-01 | 2007-02-15 | Nippon Kayaku Co Ltd | Photosensitive resin composition and cured product thereof |
| CN101501080A (en) * | 2006-08-04 | 2009-08-05 | 三菱化学株式会社 | Insulating layer, electronic device, field effect transistor, and polyvinylthiophenol |
| CN1916034A (en) * | 2006-08-25 | 2007-02-21 | 南京大学 | Solidifiable composition material by ultraviolet light and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102508408A (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101610185B1 (en) | Ultra-thin polymeric adhesion layer | |
| KR101621381B1 (en) | Process and method for modifying polymer film surface interaction | |
| JP5084728B2 (en) | Method and composition for bonding materials together | |
| US9744715B2 (en) | Method for producing patterned materials | |
| CN103279009B (en) | A kind of flexible ultraviolet impressing composite shuttering and preparation method thereof | |
| CN101923279B (en) | Nano-imprint template and preparation method thereof | |
| CN101872115A (en) | Methods and processes for modifying polymer material surface interactions | |
| EP2136933A1 (en) | Method for imprint lithography utilizing an adhesion primer layer | |
| JP2004002702A (en) | Prepolymer material, polymer material, imprinting process and its use | |
| CN109311663B (en) | Layered microstructure, mold for preparing layered microstructure and preparation method of mold | |
| CN102508408B (en) | Dual-solidification nanoimprint lithography transporting layer material | |
| WO2021182049A1 (en) | Photocurable resin composition for imprint molding, resin mold, method for forming pattern using said resin mold, composite material having said resin mold, method for producing said composite material, and method for producing optical member | |
| CN104932197B (en) | Expansion polymerization imprinting adhesive for nanoimprint | |
| Sun | Recent progress in low temperature nanoimprint lithography | |
| CN102206297A (en) | Low polymer for ultraviolet light cured coating and printing ink, and preparation method thereof | |
| TW201100263A (en) | Nano-imprint stemplate and mthod for manufacturing the same | |
| CN103279011A (en) | Thiol-ene ultraviolet light curing nano imprinting material | |
| KR101132372B1 (en) | Resin composition for preparing of reversal imprint mold, and reversal imprint method using the mold | |
| CN102508409B (en) | Ultraviolet-light-assisted thermocuring nanoimprint lithography technology and material | |
| CN101923283A (en) | Nano-imprint resist and nano-imprint method adopting same | |
| Pina-Hernandez et al. | Easy duplication of stamps using UV-cured fluoro-silsesquioxane for nanoimprint lithography | |
| Zhang et al. | A Novel nanoimprint lithography thiol-ene resist for sub-70 nm nanostructures | |
| KR101321104B1 (en) | Method of producing stamp for nano-imprint | |
| Xia et al. | A dual-curable transfer layer for adhesion enhancement of a multilayer UV-curable nanoimprint resist system | |
| TW201100457A (en) | Nano-imprint resist and nanoimprinting lithography method using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |