CN105824190A - Preparing method for nanoimprint template - Google Patents
Preparing method for nanoimprint template Download PDFInfo
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- CN105824190A CN105824190A CN201610369964.2A CN201610369964A CN105824190A CN 105824190 A CN105824190 A CN 105824190A CN 201610369964 A CN201610369964 A CN 201610369964A CN 105824190 A CN105824190 A CN 105824190A
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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
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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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
- G03F7/0017—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor for the production of embossing, cutting or similar devices; for the production of casting means
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Abstract
The invention provides a preparing method for a nanoimprint template .The method includes the following steps that a micro-nano original template of a three-dimensional graph structure is provided; a base is coated with sol to serve as a substrate; a complementary graph of the micro-nano three-dimensional graph structure is imprinted on the substrate with the original template through an imprinting technology; the obtained substrate with the complementary graph is used as the template in the follow-up nanoimprint process .The preparing method for the nanoimprint template is high in repeatability, capable of preparing the inorganic template fast at low cost on a large scale and capable of being used in the processes of ultraviolet imprinting and thermal imprinting, the prepared template is high in mechanical strength and reutilization, conformality in the follow-up imprinting process is good, a base material with a higher depth ratio can be obtained by using the template as a mask plate after etching, and the problem that the structure is shallow after etching when photoresist serves as the mask plate can be solved.
Description
Technical field
The present invention relates to nanometer embossing field, particularly relate to a kind of nano-imprint stamp preparation method.
Background technology
The casting technique that nano impression (NIL) technical process is similar in machine-building, solidification glue is under certain supplementary means, and such as heat, ultraviolet, solvent volatilization etc., through flowing, impressing and solidification process, transfer replicates the micro-nano graph structure in template.Compared with other photoetching technique, nanometer embossing has machining accuracy height, operation is simple, production efficiency is high, low cost, the advantage of applicable industrialization production, help the batch machining realizing tens nanofeature live width structures, in fields such as integrated circuit, microfabrication, biosensor, optics, there is broad prospect of application.
In nanoimprinting process, impression block directly determines the quality of coining pattern as the starting vector of embossed features, its quality.Prepare meet high accuracy, high uniformity, high-fidelity, long-life impression block are the key of stamping technique.The most conventional nano impression template can be divided into elastomeric material template and hard template.Common elastomeric material template is polydimethylsiloxane (PDMS) and derivant (h-PDMS, x-PDMS etc.) thereof, and they can obtain by replicating hard caster, has that cost is relatively low, ultraviolet permeability high.The patent documentation of Application No. CN101036086A discloses a kind of nano-imprint stamp carrying out nanoscale impressing in grade structure, and this template by being confined to limit on the matrix part between impression partial the impact of any combination of the defect in the defect in the substrate of photoengraving pattern to be imprinted or on substrate and/or template or in template and this type of defect by the bending of template.But the Young's modulus of this kind of Elastic forming board is relatively low, it is difficult to obtain less characteristic size or yielding under bigger embossing pressure.Therefore, the pressure that uses of this class template is limited in relatively low pressure limit.And in traditional hot embossing process, needing template to have higher mechanical strength, it is clear that elastomeric material template is also unsatisfactory for this requirement.Hard template is usually and obtains micro-nano structure by techniques such as ultraviolet photolithographic, interference lithography, electron beam exposure, X-ray lithography, focused ion beam lithographies on the substrates such as metal (Ni etc.), silicon, carborundum, quartz, sapphire.The patent documentation of Application No. CN101806996A discloses the preparation method of a kind of hard template for nano impression, first in oxalic acid, uses electrochemical process to prepare regular anodised aluminium (AAO) template；Secondly one layer of perfluoro capryl-trichlorosilane (CF it is deposited with on AAO surface3(CF2)5(CH2)2SiCl3) releasing agent；One layer of ultraviolet curable of spin coating or heat solidifiable photoresist on silicon or quartz substrate；Utilize ultraviolet nanometer impressing or hot nanometer embossing that the micro-nano structure of anodic oxidation aluminium formwork is copied to photoresist surface；Finally utilize reactive ion beam etching (RIE), the silicon for nano impression or the quartz hard template of this micro-nano size adjustable can be obtained on silicon or quartz substrate.But, the preparation technology of such hard template is expensive, is difficult to, using it, the requirement that meets commercial production to cost control as impression block.In addition, the embossed metal templates such as nickel can be obtained in conjunction with electroforming process, this kind of technique is documented by the patent documentation of Application No. CN103579421A and CN103576446A, but the electrolyte that relates to of this kind of technique, electroplating parameter are numerous and diverse difficult adjusts, and cost is the most of a relatively high.
Therefore seek a kind of quickly, low cost prepare reusable template, and be applicable to various moulding process, such as hot pressing, ultraviolet stamping etc., particularly important for expanding the application of nano impression.
Summary of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of nano-imprint stamp preparation method, is used for the problem such as complex operation, cost intensive in prior art that solves.
For achieving the above object and other relevant purposes, the present invention provides the preparation method of a kind of nano-imprint stamp, said method comprising the steps of:
The primary template of the 3-D graphic structure with micro-or nano size is provided；
In substrate, coating colloidal sol is as substrate；
Utilize described primary template to be imprinted with technology imprint out the complementary graph of 3-D graphic structure of described micro-or nano size over the substrate and solidify；
The described substrate with described complementary graph obtained is used in follow-up nano-imprint process as template.
Preferably, the 3-D graphic structure of described micro-or nano size is column, taper, pyramid shape, pit shape, inverted cone shape, inverted pyramid shape, raster-like, prism-like structures or the orderly or random structure derived based on above shape.
Preferably, the one during described substrate is glass, quartz, silicon, sapphire；Or being metal or metal alloy, it includes one or more in Al, Fe, Ti, W；Or it is the one in polyethylene terephthalate, Merlon, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer, polyurethane, polrvinyl chloride, polyimides, polydimethylsiloxane；Or it is one or more in polyethylene terephthalate, Merlon, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer, polyurethane, polrvinyl chloride, polyimides, polydimethylsiloxane and SiO2、TiO2、Al2O3、SiNx, the complex of one or more in SiC.
Preferably, the complex of one or more during described colloidal sol is oxide sol, nitride colloidal sol, carbide colloidal sol, boride colloidal sol.
It is further preferred that described colloidal sol is the one in diamond like carbon colloidal sol, TiO 2 sol, silica sol, alumina sol, ferrum oxide colloidal sol, Indium sesquioxide. colloidal sol, zinc oxide colloidal sol, oxide sol, silicon nitride colloidal sol, boron nitride colloidal sol, titanium nitride colloidal sol, carborundum colloidal sol, titanium carbide colloidal sol, zirconium carbide colloidal sol, titanium boride colloidal sol, zirconium boride colloidal sol, tantalum boride colloidal sol；Or be pucherite complex sol, FTO complex sol, ITO complex sol, Sialon complex sol, ZrB2-SiC complex sol, TiB2-Al2O3One in complex sol, TiC-SiC complex sol, BN-TiN complex sol.
Preferably, described stamping technique is hot press printing technology or ultraviolet stamping technology.
Preferably, the mode applying pressure impressing in described stamping technique is that flat impressing, roller are to plate impressing or roll-to-roll impressing.
Preferably, when described stamping technique is hot press printing technology, using described colloidal sol spin coating on the substrate as substrate；Then described primary template it is placed in above described colloidal sol and applies pressure impressing；Heat and keep making the solvent of described colloidal sol volatilize and forming gel, after cooling, taking described primary template off；Drive away Organic substance in described gel by heat treatment subsequently and realize solidification.
In such scheme, it is preferable that it is that 500-5000 per minute turns that described colloidal sol is spin-coated on described suprabasil spin speed；The pressure size applied is 0.1-1.0MPa；Heating-up temperature is 150-250 DEG C, and heated hold time is 10-150 minute；Cool down reached temperature and be 20-80 DEG C；Heat treatment temperature is 200-1500 DEG C, and heat treatment time is 1-3 hour.
Preferably, when described stamping technique is ultraviolet stamping technology, use the colloidal sol spin coating to ultraviolet-sensitive on the substrate as substrate；Then described primary template it is placed in above described colloidal sol and applies pressure impressing；Described colloidal sol is made to take described primary template off after solidifying by ultraviolet light irradiation.
In such scheme, it is preferable that it is that 500-5000 per minute turns that described colloidal sol is spin-coated on described suprabasil spin speed；The pressure size applied is 0.1-1.0MPa；Ultraviolet light irradiation power is 1-100mW/cm2, exposure time is the 1-600 second.
Preferably, described method also includes, utilize described primary template be imprinted with technology imprint out over the substrate described micro-or nano size 3-D graphic structure complementary graph and solidify after, the described substrate surface with described 3-D graphic structure is carried out moditied processing.
Preferably, described moditied processing includes: oxygen plasma treatment, ald dense layer material or monolayer deposit hydrophilic or hydrophobic membrane.
Preferably, described follow-up nano-imprint process is heat cure, hot padding, ultraviolet stamping or Microcontact printing.
Preferably, the mode applying pressure impressing in described follow-up nano-imprint process is that flat impressing, roller are to plate impressing or roll-to-roll impressing.
For achieving the above object and other relevant purposes, the present invention also provides for a kind of nano-imprint stamp utilizing above-mentioned nano-imprint stamp preparation method to obtain, including the complementary graph of the 3-D graphic structure by the described micro-or nano size obtained after the impressing solidification of described colloidal sol.
For achieving the above object and other relevant purposes, the present invention also provides for a kind of utilizing above-mentioned nano-imprint stamp as the lithographic method of mask plate, comprises the steps:
The primary template of the 3-D graphic structure with micro-or nano size is provided；
Coating colloidal sol in substrate；
Described primary template is placed in described colloidal sol pressure applied above impressing, and is heating and curing or is solidified by ultraviolet light irradiation, then remove described primary template, form the complementary graph of the 3-D graphic structure of described micro-or nano size at described substrate surface；
The substrate that surface is formed described complementary graph performs etching process, obtains the substrate with 3-D graphic structure.
Preferably, the complex of one or more during described colloidal sol is oxide sol, nitride colloidal sol, carbide colloidal sol, boride colloidal sol.
It is further preferred that described colloidal sol is the one in diamond like carbon colloidal sol, TiO 2 sol, silica sol, alumina sol, ferrum oxide colloidal sol, Indium sesquioxide. colloidal sol, zinc oxide colloidal sol, oxide sol, silicon nitride colloidal sol, boron nitride colloidal sol, titanium nitride colloidal sol, carborundum colloidal sol, titanium carbide colloidal sol, zirconium carbide colloidal sol, titanium boride colloidal sol, zirconium boride colloidal sol, tantalum boride colloidal sol；Or be pucherite complex sol, FTO complex sol, ITO complex sol, Sialon complex sol, ZrB2-SiC complex sol, TiB2-Al2O3One in complex sol, TiC-SiC complex sol, BN-TiN complex sol.
Preferably, the pressure limit of described impressing is 0.1-30MPa, and heating temperature range is 60-300 DEG C, and ultraviolet light irradiation power is 1-100mW/cm2, exposure time is the 1-600 second.
As it has been described above, the nano-imprint stamp preparation method of the present invention, have the advantages that
1, the nano-imprint stamp preparation method repeatability of the present invention is high, can quickly, on a large scale, low cost prepares inorganic matter template and can be used for the process such as ultraviolet stamping, hot padding.
2, the template obtained by nano-imprint stamp preparation method of the present invention has higher mechanical strength, can be repeated several times use, and reusing is high.
3, the conformality in follow-up moulding process of the template obtained by the inventive method is good, hot pressing or ultraviolet stamping repeatedly after pattern dimension almost keep consistent, and structural penalties is little after multi-impression.
4, the template obtained by the inventive method is inorganic material, compared with photoresist, the substrate such as silicon, sapphire relatively has higher etching selection ratio, use as mask plate and can obtain the base material of higher depth ratio after over etching, the predicament that after being prevented effectively from the etching that photoresist brings as mask plate, structure is shallower.
Accompanying drawing explanation
Fig. 1 is shown as the preparation method schematic diagram of a kind of nano-imprint stamp that the present invention provides.
Fig. 2 a-2e is shown as the concrete preparation flow schematic diagram of a kind of nano-imprint stamp that the present invention provides.
Fig. 3 be shown as the present invention provide utilize nano-imprint stamp of the present invention as the schematic diagram of the lithographic method of mask plate.
Fig. 4 is shown as the surface topography SEM figure of PDMS template in the embodiment of the present invention one.
Fig. 5 is shown as in the embodiment of the present invention one TiO prepared2The surface topography SEM figure of gel sample.
Fig. 6 is shown as in the embodiment of the present invention one TiO prepared2The surface topography SEM figure of template.
Fig. 7 a, 7b, 7c show and respectively use prepared TiO in the embodiment of the present invention one2Template flat board hot pressing once, five times, the surface topography SEM figure of etfe film that obtains after ten times.
Fig. 8 is shown as in the embodiment of the present invention one TiO prepared2Template surface topography SEM figure after ten hot pressing.
Fig. 9 is shown as in the embodiment of the present invention two the surface topography SEM figure after the ultraviolet stamping adhesive curing prepared.
Figure 10 is shown as in the embodiment of the present invention one TiO prepared2Template surface topography SEM figure after ten ultraviolet stampings.
Figure 11 is shown as in the embodiment of the present invention six the cross section SEM figure of the patterned sapphire substrate prepared.
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be understood other advantages and effect of the present invention easily by the content disclosed by this specification.The present invention can also be carried out by the most different detailed description of the invention or apply, and the every details in this specification can also carry out various modification or change based on different viewpoints and application under the spirit without departing from the present invention.It should be noted that, in the case of not conflicting, the feature in following example and embodiment can be mutually combined.
It should be noted that, diagram provided in following example illustrates the basic conception of the present invention the most in a schematic way, component count, shape and size when only showing the assembly relevant with the present invention rather than implement according to reality in the most graphic are drawn, during its actual enforcement, the kenel of each assembly, quantity and ratio can be a kind of random change, and its assembly layout kenel is likely to increasingly complex.
Referring to Fig. 1, the present invention provides the preparation method of a kind of nano-imprint stamp, said method comprising the steps of:
S11 provides the primary template of the 3-D graphic structure with micro-or nano size；
S12 in substrate coating colloidal sol as substrate；
S13 utilizes described primary template to be imprinted with technology and imprints out the complementary graph of 3-D graphic structure of described micro-or nano size over the substrate and solidify；
The described substrate with described complementary graph obtained is used in follow-up nano-imprint process by S14 as template.
Specifically preparation flow, refers to Fig. 2 a-Fig. 2 e.
The most as shown in Figure 2 a, the primary template 101 that step S11 provides has the 3-D graphic structure of micro-or nano size, the 3-D graphic structure of described micro-or nano size can be column, taper, pyramid shape, pit shape, inverted cone shape, inverted pyramid shape, raster-like, prism-like structures or based on above shape derivative in order or random structure, figure is only the signal of one of which typical structure.Material for primary template 101 is not particularly limited, can be silicon, quartz, sapphire, it is also possible to be the polymeric material such as the metals such as nickel, copper, chromium or polydimethylsiloxane (PDMS), polyimides (PI), politef (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), fluorinated ethylene propylene copolymer (FEP).
Step S12 as shown in Figure 2 b, coating colloidal sol 202 in substrate 201.Substrate 201 used can be inorganic substrates, such as sheet metal, glass, quartz, silicon, sapphire etc., or such as the complex of transparent polymer material and transparent polymer material with transparent inorganic material at the bottom of organic group, it is preferable that can be the one in glass, quartz, silicon, sapphire；Or being metal or metal alloy, it includes one or more in Al, Fe, Ti, W；Or it is polyethylene terephthalate (PET), Merlon (PC), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer (PFA), polyurethane (PU), polrvinyl chloride (PVC), polyimides (PI), one in polydimethylsiloxane (PDMS), or it is polyethylene terephthalate (PET), Merlon (PC), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer (PFA), polyurethane (PU), polrvinyl chloride (PVC), polyimides (PI), one or more in polydimethylsiloxane (PDMS) and SiO2、TiO2、Al2O3、SiNx, the complex of one or more in SiC.Colloidal sol 202 used is the complex of one or more in oxide sol, nitride colloidal sol, carbide colloidal sol, boride colloidal sol, it is preferable that can be diamond like carbon colloidal sol, titanium dioxide (TiO2) colloidal sol, silicon oxide (SiO2) colloidal sol, aluminium oxide (Al2O3) colloidal sol, ferrum oxide (Fe2O3) colloidal sol, Indium sesquioxide. (In2O3) colloidal sol, zinc oxide (ZnO) colloidal sol, oxide (WO3) colloidal sol, silicon nitride (Si3N4) colloidal sol, boron nitride (BN) colloidal sol, titanium nitride (TiN) colloidal sol, carborundum (SiC) colloidal sol, titanium carbide (TiC) colloidal sol, zirconium carbide (ZrC) colloidal sol, titanium boride (TiB2) colloidal sol, zirconium boride (ZrB2) colloidal sol, tantalum boride (TaB2) one in colloidal sol, or be pucherite (BiVO4) complex sol, FTO (F:SnO2) complex sol, ITO (In:SnO2) complex sol, Sialon (SiAlON) complex sol, ZrB2-SiC complex sol, TiB2-Al2O3One in complex sol, TiC-SiC complex sol, BN-TiN complex sol.Preferably, can be coated in substrate 201 by colloidal sol 202 with certain spin speed by the way of spin coating, spin speed can be that 500-5000 per minute turns.
Step S13 refers to 2c-2e.Wherein said stamping technique is preferably hot press printing technology or ultraviolet stamping technology.
When described stamping technique is hot press printing technology, described colloidal sol 202 is spin-coated in described substrate 201 after substrate, described primary template 101 is placed in above described colloidal sol 202 and applies pressure impressing；Heat and keep making the solvent of described colloidal sol 202 volatilize and form gel, after cooling, taking described primary template 101 off；Drive away Organic substance in described gel by heat treatment subsequently and realize solidification.Preferably, the pressure size of applying is 0.1-1.0MPa；Heating-up temperature is 150-250 DEG C, and heated hold time is 10-150 minute；Cool down reached temperature and be 20-80 DEG C；Heat treatment temperature is 200-1500 DEG C, and heat treatment time is 1-3 hour.
When described stamping technique is ultraviolet stamping technology, the colloidal sol 202 to ultraviolet-sensitive is used to be spin-coated in described substrate 201 as substrate；Such as at TiO2, use titanate esters, zincic acid ester etc. reacts with 3-butenoic acid during the configuration of ZnO isosol to obtain the sour four-3-butenoic acid ester of titanium (zinc) and ethanol, add the most wherein appropriate Isobutyl 2-propenoate as reactive diluent, ethylene glycol divinyl ether and cyclohexyl vinyl ether etc. as fluorochemical monomers such as cross-linking agent, trifluoroethyl vinyl ethers and 17 last of the ten Heavenly stems (fluorine) acrylate as light trigger, obtain the colloidal sol of ultraviolet-sensitive.The colloidal sol prepared by above-mentioned similar approach in principle i.e. contains the colloidal sol of light trigger etc., is all ultraviolet-sensitive colloidal sol, is not limited only to the TiO of citing2, ZnO two kinds.Then described primary template 101 it is placed in above described colloidal sol 202 and applies pressure impressing；Described colloidal sol 202 is made to take described primary template 101 off after solidifying by ultraviolet light irradiation.Preferably, the pressure size of applying is 0.1-1.0MPa；Ultraviolet light irradiation power is 1-100mW/cm2, exposure time is the 1-600 second.
Additionally, the mode applying pressure impressing in described stamping technique can be that flat impressing, roller are to plate impressing or roll-to-roll impressing.
One of preferred version as the present invention, the preparation method of described nano-imprint stamp also includes, utilize described primary template be imprinted with technology imprint out over the substrate described micro-or nano size 3-D graphic structure complementary graph and solidify after, the described substrate surface with described complementary graph is carried out moditied processing.Preferably, described moditied processing includes: carries out oxygen plasma treatment at described substrate surface, carries out ald dense layer material or the monolayer hydrophilic or hydrophobic membrane of deposition at described substrate surface.
It addition, in step S14, described follow-up nano-imprint process is preferably heat cure, hot padding, ultraviolet stamping or Microcontact printing.Wherein, heat cure impressing refers to note liquid polymer and uses heating or spontaneous curing mode curing molding on template, and hot padding refers to be placed in substrate template, can be macromolecule membrane, inorganic matter sol pellicle etc., raises temperature-curable imprinting moulding.Preferably, the mode applying pressure impressing in described follow-up nano-imprint process is that flat impressing, roller are to plate impressing or roll-to-roll impressing.
Such as, when nano-imprint stamp the inventive method prepared is used for ultraviolet stamping technique, ultra-violet curing glue can be coated in required substrate, with the nano-imprint stamp of the inventive method gained, solidification glue is imprinted, after ultraviolet light irradiates and solidifies, template is separated with substrate, obtain desired structure；When nano-imprint stamp the inventive method prepared is used for heat curing process, moulding by casting or ejection forming technique is utilized to be poured or injected into by liquid polymer on the nano-imprint stamp of the inventive method gained, utilize heating or spontaneous curing mode to be separated with polymer by described nano-imprint stamp again after it solidifies, obtain desired structure；When nano-imprint stamp the inventive method prepared is used for thermal imprint process, as used the thermal imprint process of flat impressing, with the nano-imprint stamp of the inventive method gained and required substrate contact, under pressure, rise high-temperature, imprint out the substrate with microscale features within a certain period of time；When nano-imprint stamp the inventive method prepared is used for Microcontact printing technique, " ink " molecule is made to spread over nano-imprint stamp surface, the base material of impression block contact subsequently, then transfer " ink " molecule is to substrate surface, ideally forms self-assembly monolayer.It addition, pressure mode be roller to plate or roll-to-roll time, use the nano-imprint stamp of the inventive method gained and required substrate contact, the thin film with microscale features can be imprinted out under the conditions of certain pressure, roller speed, temperature, draft angle etc..
The present invention also provides for a kind of nano-imprint stamp utilizing above-mentioned nano-imprint stamp preparation method to obtain, including the complementary graph of the 3-D graphic structure by the described micro-or nano size obtained after the impressing solidification of described colloidal sol.
Additionally, refer to Fig. 3, the present invention also provides for a kind of lithographic method utilizing above-mentioned nano-imprint stamp, comprises the steps:
S31 provides the primary template of the 3-D graphic structure with micro-or nano size；
S32 is coating colloidal sol in substrate；
Described primary template is placed in described colloidal sol pressure applied above impressing by S33, and is heating and curing or is solidified by ultraviolet light irradiation, then removes described primary template, forms the complementary graph of the 3-D graphic structure of described micro-or nano size at described substrate surface；
S34 is formed with the substrate of described complementary graph and performs etching process surface, obtains the substrate with 3-D graphic structure.
Wherein, step S31 and step S32 are basically identical with step S12 with step S11 of preceding method, and the 3-D graphic structure of described micro-or nano size can be column, taper, pyramid shape, pit shape, inverted cone shape, inverted pyramid shape, raster-like, prism-like structures or the orderly or random structure derived based on above shape.Material for primary template is not particularly limited, can be silicon, quartz, sapphire, it is also possible to be the polymeric material such as the metals such as nickel, copper, chromium or polydimethylsiloxane (PDMS), polyimides (PI), politef (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), fluorinated ethylene propylene copolymer (FEP).Colloidal sol used is the complex of one or more in oxide sol, nitride colloidal sol, carbide colloidal sol, boride colloidal sol, it is preferable that can be diamond like carbon colloidal sol, titanium dioxide (TiO2) colloidal sol, silicon oxide (SiO2) colloidal sol, aluminium oxide (Al2O3) colloidal sol, ferrum oxide (Fe2O3) colloidal sol, Indium sesquioxide. (In2O3) colloidal sol, zinc oxide (ZnO) colloidal sol, oxide (WO3) colloidal sol, silicon nitride (Si3N4) colloidal sol, boron nitride (BN) colloidal sol, titanium nitride (TiN) colloidal sol, carborundum (SiC) colloidal sol, titanium carbide (TiC) colloidal sol, zirconium carbide (ZrC) colloidal sol, titanium boride (TiB2) colloidal sol, zirconium boride (ZrB2) colloidal sol, tantalum boride (TaB2) one in colloidal sol, or be pucherite (BiVO4) complex sol, FTO (F:SnO2) complex sol, ITO (In:SnO2) complex sol, Sialon (SiAlON) complex sol, ZrB2-SiC complex sol, TiB2-Al2O3One in complex sol, TiC-SiC complex sol, BN-TiN complex sol.Preferably, can be coated in substrate by colloidal sol with certain spin speed by the way of spin coating, spin speed can be that 500-5000 per minute turns.Described substrate is chosen according to reality etching demand, includes but not limited to silicon, silicon oxide, silicon nitride, quartz, glass, sapphire, metal-oxide, elemental metals and alloy thereof etc..
In step S33, it is preferable that the pressure limit of described impressing is 0.1-30MPa, heating temperature range is 60-300 DEG C, and ultraviolet light irradiation power is 1-100mW/cm2, exposure time is the 1-600 second.
In step S34, described etching processing can be dry etching, such as oxygen plasma etch, reactive ion etching, sense coupling, particle beam etching and wet etching etc..
Embodiment one
The present embodiment utilizes the nano-imprint stamp preparation method of the present invention, prepares TiO2Template, and this template is used for flat board hot pressing for periodic patterning etfe film, its process is as follows:
1, offer has the PDMS template of micron bowl configurations as primary template, wherein said micron bowl configurations is that the pit of multiple same shape is periodically ordered to be arranged to make up, each pit depth is 2.45 μm, a diameter of 2.4 μm, cycle is 3 μm, at a distance of 3 μm between the center of the most each pit to the center of the pit being adjacent.Utilizing scanning electron microscope (SEM) to observe the surface topography of this PDMS template, the SEM of gained schemes as shown in Figure 4.
2, by TiO2Colloidal sol is spun in the substrate of glass of cleaning as substrate, TiO2Colloidal sol thickness is 5 μm, and spin speed is 1000 turns per minute, and spin speed mainly affects colloidal sol thickness, and integrity and cull thickness to stamping structure have an impact, and can be adjusted according to the needs of actual stamping structure.
3, by the pre-processed PDMS template with micron bowl configurations, i.e. primary template, cover and be coated with TiO2On the substrate of colloidal sol, apply the uniform pressure of 0.25MPa, and be heated to 250 DEG C, keep 2 hours, make TiO2The solvent of colloidal sol volatilizees and forms TiO2Gel.
4, PDMS template being separated with substrate after cooling, form the column structure of the micron level complementary with described micron bowl configurations the most on the glass substrate, its height is 2.16 μm.The SEM reacting this sample surface morphology schemes as shown in Figure 5, it is seen that the TiO obtained2Gel sample has the size penalty of about 10% in each dimension relative to PDMS template.Main reason is that TiO2Colloidal sol solvent volatilization during crosslinking curing makes between granule more densely cross-linked, thus has a fixed structure atrophy.
5, by gained TiO2Gel sample is annealed in air atmosphere, and annealing conditions is that the speed of 2 DEG C/min is warming up to 450 DEG C of holdings 2 hours, can drive away TiO by heat treatment2Organic substance in gel realizes solidification, obtains TiO after cooling2Template, the now TiO of gained2The SEM of template schemes as shown in Figure 6, it is seen that at the TiO of gained after Overheating Treatment2Template the cycle keep constant in the case of, the further atrophy of size.Main cause is still solvent volatilization in heat treatment process, and structure is the most solid, although have certain size to lose, but greatly improves the mechanical strength of template so that keep good repeatable usability during follow-up hot pressing and ultraviolet pressure.Utilize this feature, it is also possible to obtain the fast Template less than caster structure, alleviate the difficulty of processing of smaller szie template.
6, by above-mentioned prepared TiO2Template proceeds surface moditied processing.The power that oxygen gas plasma machine uses is 50W, and gas flow is 0.5L/min, and etch period is 60 seconds.Then unimolecule deposition is used to show that hydrophobic surface separates with material after being suitable to.Detailed process is will to appeal the TiO after oxygen plasma treatment2Template is placed in airtight chamber, injects 2 μ L trichlorine n-perfluoro-octyl silane in the chamber, is warming up to 100 DEG C and keeps 10 minutes.I.e. form the unimolecule silicon fluoride of one layer of self assembly at template surface, the stripping of follow-up template and sample can be beneficial to.
By above-mentioned prepared TiO2Template is as impression block for using the thermal imprint process manufacturing cycle patterning etfe film of flat impressing, and method is as follows:
First clean etfe film is placed on the platform of flat-bed press, by TiO2Template has pattern one to be placed face down on etfe film, is then heated to 170 DEG C, applies the pressure of 0.4MPa at its two ends, keeps 25 minutes, after reducing to room temperature, by TiO2Template separates with etfe film, i.e. obtains periodic patterning etfe film.
Utilize the method that same TiO is used for multiple times2Template manufacturing cycle patterning etfe film, the etfe film pattern dimension obtained almost keeps consistent.Fig. 7 a, Fig. 7 b and Fig. 7 c respectively use TiO2Template flat board hot pressing once, five times, the etfe film SEM figure that obtains after ten times.It will be seen that through once, five times, the physical dimension of the etfe film obtained after ten times is the most unchanged in figure.The structure of template makes to imprint that to obtain the aperture of structure closely related with the degree of depth, although cannot test the degree of depth of impressing pit, but the external diameter of its impressing ETFE pit and TiO2Template base diameter is more or less the same, it was demonstrated that pit depth and TiO2The height of the column structure in template is also more or less the same.Fig. 8 is TiO2Template SEM figure after ten hot pressing, it is seen that little through repeatedly hot padding rear pattern plate structural penalties, conformality is preferable.
Embodiment two
The TiO that embodiment one is prepared by the present embodiment2Template patterns photoresist structure for ultraviolet stamping manufacturing cycle, and its preparation process is as follows:
Ultraviolet stamping glue is coated in the quartz glass substrate of cleaning, and ultraviolet stamping glue thickness is 5 μm.
TiO prepared by embodiment one2Template is placed in ultraviolet stamping chamber, then is placed face down on described TiO by being coated with the one of ultraviolet stamping glue in quartz glass substrate2On template, apply the uniform pressure of 0.25MPa, and with ultraviolet light irradiation, irradiation power is 100mW/cm2, exposure time 500 seconds.
After ultraviolet stamping adhesive curing, by TiO2Template separates with ultraviolet stamping glue, i.e. forms the bowl configurations of micron level, pit depth 1.370 μm, diameter 1.535 μm, cycle 3 μm in quartz glass substrate, and the SEM of resulting structures schemes, as shown in Figure 9.Utilize the method that TiO is used for multiple times2The pattern dimension that template obtains is almost without significant change.If it should be noted that the inorganic matter template of the absorbable ultraviolet light of the template utilizing the inventive method to prepare then can only be stamped in when ultraviolet stamping in the substrate of the saturating ultraviolet lights such as quartz, and the transparent inorganic thing template not absorbing ultraviolet light can imprinting when ultraviolet stamping in any planar substrates.Figure 10 is TiO2Template SEM figure after ten ultraviolet stampings, it is seen that little through repeatedly ultraviolet stamping rear pattern plate structural penalties, conformality is preferable.
Embodiment three
The present embodiment utilizes the nano-imprint stamp preparation method of the present invention, prepares ZnO template, and for flat board hot pressing for periodic patterning etfe film, its preparation process is as follows:
1, offer has the PDMS template of micron bowl configurations as primary template, wherein said micron bowl configurations is that the pit of multiple same shape is periodically ordered to be arranged to make up, each pit depth is 2.45 μm, a diameter of 2.4 μm, cycle is 3 μm, at a distance of 3 μm between the center of the most each pit to the center of the pit being adjacent.Utilizing scanning electron microscope (SEM) to observe the surface topography of this PDMS template, the SEM of gained schemes as shown in Figure 4
2, being spun on by ZnO colloidal sol in the substrate of glass of cleaning is 5 μm as substrate, ZnO colloidal sol thickness, and spin speed is 500 turns per minute.
3, by the pre-processed PDMS template with micron bowl configurations, i.e. primary template, cover on the substrate being coated with ZnO colloidal sol, apply the uniform pressure of 0.4MPa, and it is heated to 250 DEG C, keep 150 minutes, make the solvent of ZnO colloidal sol volatilize and form ZnO gel.
4, after cooling, PDMS template is separated with substrate, form the column structure of micron level the most on the glass substrate.
5, above-mentioned gained ZnO gel sample uses under air atmosphere the speed of 2 DEG C/min be warming up to 450 DEG C keep 2 hours, after cooling, obtain ZnO template.
Being used for using the thermal imprint process manufacturing cycle patterning etfe film of flat impressing using above-mentioned prepared ZnO template as impression block, method is as follows:
Clean etfe film is placed on the platform of flat-bed press, pattern one is had to be placed face down on etfe film ZnO template, it is then heated to 170 DEG C, the pressure of 0.4MPa is applied at its two ends, keep 25 minutes, after reducing to room temperature, ZnO template is separated with etfe film, i.e. obtain periodic patterning etfe film.Utilize the method that ZnO template is used for multiple times, obtain pattern dimension almost without significant change.
Embodiment four
The ZnO template that embodiment three is prepared by the present embodiment is used for ultraviolet stamping manufacturing cycle patterning photoresist structure, and its preparation process is as follows:
Ultraviolet stamping glue is coated in the quartz glass substrate of cleaning, and ultraviolet stamping glue thickness is 5 μm.
ZnO template embodiment three prepared is placed in ultraviolet stamping chamber, then is placed face down on ZnO template by being coated with the one of ultraviolet stamping glue in quartz glass substrate, applies the uniform pressure of 0.25MPa, and with ultraviolet light irradiation, irradiation power is 100mW/cm2, exposure time 500 seconds.
After ultraviolet stamping adhesive curing, ZnO template is separated with ultraviolet stamping glue, in quartz glass substrate, i.e. form the bowl configurations of micron level, pit depth 1.370 μm, diameter 1.535 μm, cycle 3 μm.Utilize the method to be used for multiple times pattern dimension that ZnO template obtains is almost without significant change.
Embodiment five
The present embodiment utilizes the nano-imprint stamp preparation method of the present invention, prepares SiO2Template, and pattern photoresist structure for ultraviolet stamping manufacturing cycle, its preparation process is as follows:
1, offer has the PDMS template of micron bowl configurations as primary template, wherein said micron bowl configurations is that the pit of multiple same shape is periodically ordered to be arranged to make up, each pit depth is 2.45 μm, a diameter of 2.4 μm, cycle is 3 μm, at a distance of 3 μm between the center of the most each pit to the center of the pit being adjacent.
2, by SiO2Colloidal sol is spun in the substrate of glass of cleaning as substrate, SiO2Colloidal sol thickness is 5 μm, and spin speed is 1000 turns per minute.
3, by the pre-processed PDMS template with micron bowl configurations, i.e. primary template, cover and be coated with SiO2On the substrate of colloidal sol, apply the uniform pressure of 0.4MPa, and be heated to 250 DEG C, keep 120 minutes, make SiO2The solvent of colloidal sol volatilizees and forms SiO2Gel.
4, after cooling, PDMS template is separated with substrate, form the column structure of micron level the most on the glass substrate.
5, by above-mentioned gained SiO2Gel sample uses the speed of 2 DEG C/min to be warming up to 500 DEG C of holdings 3 hours under air atmosphere, obtains SiO after cooling2Template.
Above-mentioned prepared SiO2Template as impression block for ultraviolet stamping manufacturing cycle pattern photoresist structure:
Ultraviolet stamping glue is coated in the substrate of cleaning, and ultraviolet stamping glue thickness is 5 μm.
The substrate being coated with ultraviolet stamping glue is placed in ultraviolet stamping chamber, then by prepared SiO2Template structured one is placed face down in the substrate being coated with ultraviolet stamping glue, applies the uniform pressure of 0.25MPa, and with ultraviolet light irradiation, irradiation power is 100mW/cm2, exposure time 800 seconds.
After ultraviolet stamping adhesive curing, by SiO2Template separates with ultraviolet stamping glue, i.e. forms the bowl configurations of micron level, SiO in substrate2Template can be used for multiple times, and the pattern dimension obtained is almost without significant change.
Embodiment six
The present embodiment utilizes the inventive method to prepare ZnO gel template, and is used for etching preparation patterned sapphire substrate as mask plate, and its preparation process is as follows:
1, offer has the PDMS template of nano-pillar structure as primary template, wherein said nano-pillar structure is that the pillar of multiple same shape is periodically ordered to be arranged to make up, each pillar height is 600nm, a diameter of 700nm, cycle is 1 μm, at a distance of 1 μm between the center of the most each pillar to the center of the pillar being adjacent.
2, being spun on by ZnO colloidal sol in the sapphire substrates of cleaning is 1 μm as substrate, ZnO colloidal sol thickness, and spin speed is 3000 turns per minute.
3, by the pre-processed PDMS template with nano-pillar structure, i.e. primary template, cover on the substrate being coated with ZnO colloidal sol in step 2, apply the uniform pressure of 0.25MPa, and be heated to 250 DEG C, keep 2 hours.
4, after cooling, PDMS template is separated with substrate, in sapphire substrates, i.e. form nanometer hole shape structure.
5, the substrate with hole shape structure being placed in inductive coupling type reactive ion etching intracavity and perform etching 20 minutes, pressure is 2.0Pa, and power is 1.6kW, and voltage is 250V, and base reservoir temperature is maintained at 70 DEG C, and etching gas is the Ar of 10%, the Cl of 20%2, the BCl of 80%3, flow velocity is 55sccm.
6, the sample above-mentioned etching terminated takes out, and i.e. obtains required patterned sapphire substrate.
The cross section SEM figure of the patterned sapphire substrate that the method obtains, as shown in figure 11, etching depth is 572nm, and using organic impressing glue to obtain constructional depth as mask plate etching is 247nm, hence it is evident that visible employing mask plate of the present invention can etch the substrate obtaining higher depth ratio.
Embodiment seven
The present embodiment utilizes ultraviolet stamping to prepare TiO2Template, and this template is used for flat board hot pressing for periodic patterning etfe film, its process is as follows:
1, offer has the PDMS template of micron bowl configurations as primary template, wherein said micron bowl configurations is that the pit of multiple same shape is periodically ordered to be arranged to make up, each pit depth is 2.45 μm, a diameter of 2.4 μm, cycle is 3 μm, at a distance of 3 μm between the center of the most each pit to the center of the pit being adjacent.
2, metatitanic acid ethanol ester and methacrylic acid or 3-butenoic acid being reacted with 1:4 mixed in molar ratio and obtain methacrylic acid titanate or metatitanic acid four-3-butenoic acid salt and ethanol, decompression rotary evaporation removes all or part of ethanol.Rear addition appropriate reactive diluent Isobutyl 2-propenoate is to reach to be suitable to the suitable viscosity of spin coating, and ethylene glycol divinyl ether and cyclohexyl vinyl ether etc. are as cross-linking agent, the fluorochemical monomers such as the trifluoroethyl vinyl ethers or 17 last of the ten Heavenly stems (fluorine) acrylate that are subsequently adding 2wt% are as light trigger, mix homogeneously.It is passed through argon 3min to get rid of dissolved oxygen, i.e. obtains the TiO of ultraviolet-sensitive2Colloidal sol.It should be noted that the method how obtaining the colloidal sol to ultraviolet-sensitive is not restricted by the present invention.
3, by the above-mentioned TiO to ultraviolet-sensitive2Colloidal sol is spun in the substrate of glass of cleaning as substrate, TiO2Colloidal sol thickness is 5 μm, and spin speed is 1000 turns per minute, and spin speed spin speed mainly affects colloidal sol thickness, and integrity and cull thickness to stamping structure have an impact, and can be adjusted according to the needs of actual stamping structure.
4, by the pre-processed PDMS template with micron bowl configurations, i.e. primary template, cover and be coated with TiO2On the substrate of colloidal sol, apply the uniform pressure of 0.25MPa, use ultra violet lamp (power 100mW/cm2) 4min make TiO2Colloidal sol solidify to form TiO2Gel.
5, PDMS template is separated with substrate, form the column structure of the micron level complementary with described micron bowl configurations, TiO the most on the glass substrate2A fixed structure atrophy is there is in colloidal sol during crosslinking curing.
6, by the TiO after gained ultraviolet light polymerization2Sample is annealed in air atmosphere, and annealing conditions is that the speed of 2 DEG C/min is warming up to 450 DEG C of holdings 2 hours, can drive away TiO by heat treatment2In Organic substance, obtain TiO after cooling2Template.
7, by above-mentioned prepared TiO2Template proceeds surface moditied processing.The power that oxygen gas plasma machine uses is 50W, and gas flow is 0.5L/min, and etch period is 60s.Then unimolecule deposition is used to show that hydrophobic surface separates with material after being suitable to.Detailed process is will to appeal the TiO after oxygen plasma treatment2Template is placed in airtight chamber, injects 2 μ L trichlorine n-perfluoro-octyl silane in the chamber, is warming up to 100 DEG C and keeps 10min.I.e. form the unimolecule silicon fluoride of one layer of self assembly at template surface, the stripping of follow-up template and sample can be beneficial to.
By above-mentioned prepared TiO2Template is as impression block for using the thermal imprint process manufacturing cycle patterning etfe film of flat impressing, and method is as follows:
First clean etfe film is placed on the platform of flat-bed press, by TiO2Template has pattern one to be placed face down on etfe film, is then heated to 170 DEG C, applies the pressure of 31.4MPa at its two ends, keeps 25 minutes, after reducing to room temperature, by TiO2Template separates with etfe film, i.e. obtains periodic patterning etfe film.
Embodiment eight
The present embodiment utilizes the nano-imprint stamp preparation method of the present invention, prepares SiC template, and for flat board hot pressing for periodic patterning etfe film, its preparation process is as follows:
1, offer has the PDMS template of micron bowl configurations as primary template, wherein said micron bowl configurations is that the pit of multiple same shape is periodically ordered to be arranged to make up, each pit depth is 2.45 μm, a diameter of 2.4 μm, cycle is 3 μm, at a distance of 3 μm between the center of the most each pit to the center of the pit being adjacent.
2, being spun on by SiC predecessor colloidal sol in the refractory ceramics substrate of cleaning is 5 μm as substrate, SiC colloidal sol thickness, and spin speed is 500 turns per minute.
3, by the pre-processed PDMS template with micron bowl configurations, i.e. primary template, cover on the substrate being coated with SiC predecessor colloidal sol, apply the uniform pressure of 1.0MPa, and it is heated to 150 DEG C, keep 150 minutes, make the solvent of SiC forerunner's colloidal sol volatilize and form SiC predecessor gel.
4, after cooling, PDMS template is separated with substrate, form the column structure of micron level the most on the glass substrate.
5, above-mentioned gained SiC predecessor gel sample uses under Ar atmosphere the speed of 3 DEG C/min be warming up to 1500 DEG C keep 1 hour, after cooling, obtain SiC template.
Being used for using the thermal imprint process manufacturing cycle patterning etfe film of flat impressing using above-mentioned prepared SiC template as impression block, method is as follows:
Clean etfe film is placed on the platform of flat-bed press, pattern one is had to be placed face down on etfe film SiC template, it is then heated to 170 DEG C, the pressure of 0.4MPa is applied at its two ends, keep 25 minutes, after reducing to room temperature, SiC template is separated with etfe film, i.e. obtain periodic patterning etfe film.Utilize the method that SiC template is used for multiple times, obtain pattern dimension almost without significant change.
In sum, the nano-imprint stamp preparation method repeatability of the present invention is high, can quickly, on a large scale, low cost prepares inorganic matter template and can be used for the process such as ultraviolet stamping, hot padding；Obtained template has higher mechanical strength, can be repeated several times use, and reusing is high；Obtained template conformality in follow-up moulding process is good, hot pressing or ultraviolet stamping repeatedly after pattern dimension almost keep consistent, and structural penalties is little after multi-impression.In addition, template obtained by the inventive method is inorganic material, compared with photoresist, the substrate such as silicon, sapphire relatively has higher etching selection ratio, use as mask plate and can obtain the base material of higher depth ratio after over etching, the predicament that after being prevented effectively from the etching that photoresist brings as mask plate, structure is shallower.So, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by any person skilled in the art.Therefore, art has all equivalence modification or changes that usually intellectual is completed under without departing from disclosed spirit and technological thought such as, must be contained by the claim of the present invention.
Claims (20)
1. the preparation method of a nano-imprint stamp, it is characterised in that said method comprising the steps of:
The primary template of the 3-D graphic structure with micro-or nano size is provided；
In substrate, coating colloidal sol is as substrate；
Utilize described primary template to be imprinted with technology imprint out the complementary graph of 3-D graphic structure of described micro-or nano size over the substrate and solidify；
The described substrate with described complementary graph obtained is used in follow-up nano-imprint process as template.
The preparation method of nano-imprint stamp the most according to claim 1, it is characterised in that: the 3-D graphic structure of described micro-or nano size is column, taper, pyramid shape, pit shape, inverted cone shape, inverted pyramid shape, raster-like, prism-like structures or the orderly or random structure derived based on above shape.
The preparation method of nano-imprint stamp the most according to claim 1, it is characterised in that: described substrate is the one in glass, quartz, silicon, sapphire；Or it is metal or metal alloy, including one or more in Al, Fe, Ti, W；Or it is the one in polyethylene terephthalate, Merlon, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer, polyurethane, polrvinyl chloride, polyimides, polydimethylsiloxane；Or it is one or more in polyethylene terephthalate, Merlon, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer, polyurethane, polrvinyl chloride, polyimides, polydimethylsiloxane and SiO2、TiO2、Al2O3、SiNx, the complex of one or more in SiC.
The preparation method of nano-imprint stamp the most according to claim 1, it is characterised in that: described colloidal sol is the complex of one or more in oxide sol, nitride colloidal sol, carbide colloidal sol, boride colloidal sol.
The preparation method of nano-imprint stamp the most according to claim 1, it is characterised in that: described colloidal sol is the one in diamond like carbon colloidal sol, TiO 2 sol, silica sol, alumina sol, ferrum oxide colloidal sol, Indium sesquioxide. colloidal sol, zinc oxide colloidal sol, oxide sol, silicon nitride colloidal sol, boron nitride colloidal sol, titanium nitride colloidal sol, carborundum colloidal sol, titanium carbide colloidal sol, zirconium carbide colloidal sol, titanium boride colloidal sol, zirconium boride colloidal sol, tantalum boride colloidal sol；Or be pucherite complex sol, FTO complex sol, ITO complex sol, Sialon complex sol, ZrB2-SiC complex sol, TiB2-Al2O3One in complex sol, TiC-SiC complex sol, BN-TiN complex sol.
The preparation method of nano-imprint stamp the most according to claim 1, it is characterised in that: described stamping technique is hot press printing technology or ultraviolet stamping technology.
The preparation method of nano-imprint stamp the most according to claim 1, it is characterised in that: the mode applying pressure impressing in described stamping technique is that flat impressing, roller are to plate impressing or roll-to-roll impressing.
The preparation method of nano-imprint stamp the most according to claim 1, it is characterised in that: when described stamping technique is hot press printing technology, using described colloidal sol spin coating on the substrate as substrate；Then described primary template it is placed in above described colloidal sol and applies pressure impressing；Heat and keep making the solvent of described colloidal sol volatilize and forming gel, after cooling, taking described primary template off；Drive away Organic substance in described gel by heat treatment subsequently and realize solidification.
The preparation method of nano-imprint stamp the most according to claim 8, it is characterised in that: it is that 500-5000 per minute turns that described colloidal sol is spin-coated on described suprabasil spin speed；The pressure size applied is 0.1-1.0MPa；Heating-up temperature is 150-250 DEG C, and heated hold time is 10-150 minute；Cool down reached temperature and be 20-80 DEG C；Heat treatment temperature is 200-1500 DEG C, and heat treatment time is 1-3 hour.
The preparation method of nano-imprint stamp the most according to claim 1, it is characterised in that: when described stamping technique is ultraviolet stamping technology, use the colloidal sol spin coating to ultraviolet-sensitive on the substrate as substrate；Then described primary template it is placed in above described colloidal sol and applies pressure impressing；Described colloidal sol is made to take described primary template off after solidifying by ultraviolet light irradiation.
The preparation method of 11. nano-imprint stamps according to claim 10, it is characterised in that: it is that 500-5000 per minute turns that described colloidal sol is spin-coated on described suprabasil spin speed；The pressure size applied is 0.1-1.0MPa；Ultraviolet light irradiation power is 1-100mW/cm2, exposure time is the 1-600 second.
The preparation method of 12. nano-imprint stamps according to claim 1, it is characterized in that: also include, utilize described primary template be imprinted with technology imprint out over the substrate described micro-or nano size 3-D graphic structure complementary graph and solidify after, the described substrate surface with described complementary graph is carried out moditied processing.
The preparation method of 13. nano-imprint stamps according to claim 12, it is characterised in that: described moditied processing includes: oxygen plasma treatment, ald dense layer material or monolayer deposit hydrophilic or hydrophobic membrane.
The preparation method of 14. nano-imprint stamps according to claim 1, it is characterised in that: described follow-up nano-imprint process is heat cure, hot padding, ultraviolet stamping or Microcontact printing.
The preparation method of 15. nano-imprint stamps according to claim 1, it is characterised in that: the mode applying pressure impressing in described follow-up nano-imprint process is that flat impressing, roller are to plate impressing or roll-to-roll impressing.
16. 1 kinds of nano-imprint stamps, it is characterized in that: described nano-imprint stamp utilizes the preparation method of the nano-imprint stamp according to any one of claim 1-15 to obtain, including the complementary graph of the 3-D graphic structure by the described micro-or nano size obtained after the impressing solidification of described colloidal sol.
17. 1 kinds of lithographic methods, it is characterised in that said method comprising the steps of:
The primary template of the 3-D graphic structure with micro-or nano size is provided；
Coating colloidal sol in substrate；
Described primary template is placed in described colloidal sol pressure applied above impressing, and is heating and curing or is solidified by ultraviolet light irradiation, then remove described primary template, form the complementary graph of the 3-D graphic structure of described micro-or nano size at described substrate surface；
The substrate that surface is formed described complementary graph performs etching process, obtains the substrate with 3-D graphic structure.
18. lithographic methods according to claim 17, it is characterised in that: described colloidal sol is the complex of one or more in oxide sol, nitride colloidal sol, carbide colloidal sol, boride colloidal sol.
19. lithographic methods according to claim 17, it is characterised in that: described colloidal sol is the one in diamond like carbon colloidal sol, TiO 2 sol, silica sol, alumina sol, ferrum oxide colloidal sol, Indium sesquioxide. colloidal sol, zinc oxide colloidal sol, oxide sol, silicon nitride colloidal sol, boron nitride colloidal sol, titanium nitride colloidal sol, carborundum colloidal sol, titanium carbide colloidal sol, zirconium carbide colloidal sol, titanium boride colloidal sol, zirconium boride colloidal sol, tantalum boride colloidal sol；Or be pucherite complex sol, FTO complex sol, ITO complex sol, Sialon complex sol, ZrB2-SiC complex sol, TiB2-Al2O3One in complex sol, TiC-SiC complex sol, BN-TiN complex sol.
20. lithographic methods according to claim 17, it is characterised in that: the pressure limit of described impressing is 0.1-30MPa, and heating temperature range is 60-300 DEG C, and ultraviolet light irradiation power is 1-100mW/cm2, exposure time is the 1-600 second.
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