CN102508410A - Composite nanometer impressing mold plate with sandwich structure and preparation method of composite nanometer impressing mold plate - Google Patents
Composite nanometer impressing mold plate with sandwich structure and preparation method of composite nanometer impressing mold plate Download PDFInfo
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Abstract
The invention provides a novel nanometer impressing mold plate, and discloses a nanometer impressing composite mold plate with a sandwich structure and a preparation method of the nanometer impressing composite mold plate. The composite mold plate comprises three layers of materials with different mechanical properties, the three layers of materials include a plastic supporting layer, an elastic buffering layer and a rigid impressing structure layer, the elastic buffering layer is sandwiched between the plastic supporting layer and the rigid impressing structure layer, and accordingly the sandwich structure is formed; and the upper layer, the middle layer and the lower layer of the sandwich structure can be tightly connected in an adhesion or chemically bonded manner. The composite mold plate with the sandwich structure can effectively solve the problem of large-area defects due to granules in an environment in a nanometer impressing process.
Description
Technical field
The invention belongs to the micro-nano manufacture field, be specifically related to a kind of sandwich structure composite Nano impression block and preparation method thereof.
Background technology
Since the sixties in 20th century, integrated circuit is brought in constant renewal in according to Moore's Law always and is regenerated, and transistor size integrated in the promptly single chip doubled in per 18 months.Along with people's constantly diminishes to what device size in the circuit required, and photoetching technique is about near its physics limit.In order to adapt to the fast development of integrated circuit technique, this time, nano impression also just arose at the historic moment as a figure manufacturing technology of future generation of preparing alternative optical lithography.
Nanometer embossing is at first proposed in nineteen ninety-five by the S. Y. Chou of Princeton university professor, and has obtained very big development in recent years.It is a kind of brand-new nano graph clone method; Than micro-nano manufacturing process such as (utmost point) ultraviolet photolithographic far away, electron/ion beams photoetching; It has characteristics such as ultrahigh resolution, high yield, low cost; High resolving power is because it does not have diffraction phenomena and the scattering phenomenon in the electron beam exposure in the optical exposure, and high yield is can parallel processing as optical exposure because of it, makes hundreds and thousands of devices simultaneously; Low cost is because it does not have complicated technology property and high device fabrication cost; And included in the international semiconductor development blueprint, and caused various countries researchists' extensive concern, can be applicable to numerous areas such as information stores, biomedical product, molectronics, subwavelength optical element.
Current nanometer technology has become the strong instrument of preparation nanostructured in the laboratory, and begins progressively to move towards the commercial production manufacturing from scientific research, becomes one of emerging nano-fabrication technique of most possible realization industrialization.But because this technology from occurring having only short 15 years so far, also has a lot of key issues to remain further research, the technical bottleneck of restriction remains to be captured, the related process lifting that haves much room for improvement.Most important three parts of nano impression can be divided into nano marking press, nano impression glue and nano-imprint stamp.What present nano-imprint stamp mainly used is the hard brittle material of high rigidity such as silicon, silicon dioxide, silicon nitride, again via related process such as beamwriter lithographies at above-mentioned material surface preparation micro-nano structure, its technology is loaded down with trivial details, expensive.Because nanometer embossing is the working mechanism of physics contact; Therefore the molecule that exists in the environment is easy to intercept the template and the substrate of rigidity in moulding process; The two can't be contacted; Cause large-area defective, a very little particle just can produce the defective of tens of times of the areas of particle own.As reduce the area of defective through the pressure that strengthens impression, template is under high pressure broken easily, and the defective that most importantly in the contact process of template and substrate, produces has influenced the yield of finished product greatly.As bringing up to the impression environment degree of extreme cleaning, improved production cost again greatly, caused very important obstruction for the suitability for industrialized production of nano impression.
On the other hand, U.S. Pat 6180239 disclosed a kind of be that the soft impression (in little process, adopting the organic elastomer macromolecular material but not the general designation of one type of printing technology of rigid inorganic material) of key technical feature has low cost, rapid shaping and need not external pressure and can form good the contact with substrate with the Flexible formwork assembly.Yet; Because the low-intensity of the Flexible formwork assembly material that in soft printing technology, uses itself; The raising resolution that some improved soft impression blocks can be limited make the resolution of soft stamping technique pace up and down about 1 micron, though can't obtain the nano-pattern of the following resolution of 100nm always.Chinese patent 200810195525.X has invented a kind of nano impression---and soft impression composite Nano impression block has the resolution of inferior 15 nanometers, and can on curved surface and irregular on-plane surface, impress high-resolution nano-structure.This template is made up of resiliency supported layer and rigid structure embossed layer, combines the advantage of the high resolving power of nano impression rigid template with the flexibility of soft impression Elastic forming board.The resiliency supported layer of this template has adopted soft impression block silicone materials commonly used, makes no impressed pressure condition lower bolster and impression substrate to fit tightly.But silicone materials itself has very strong adhesiveness, is easy to be infected with dust granule, and the while has also increased very big difficulty to the operability of moulding process.
Summary of the invention
In view of above situation, the objective of the invention is to solve as in this type of the contact figure manufacturing technology of nano impression by the caused defect problem of particle, composite Nano impression block a kind of three layers, that have sandwich structure is provided.Another object of the present invention provides the preparation method of this template.
For realizing the foregoing invention purpose, the technical scheme that nano-imprint stamp of the present invention is taked is:
A kind of sandwich structure composite Nano impression block, said template is made up of the material of three layers of different mechanical properties, is respectively the supporting layer of plasticity, the stamping structure layer of flexible cushion and rigidity; Said flexible cushion is formed sandwich structure by between the stamping structure layer of sandwich supporting layer and rigidity in plasticity; Can closely connect through bonding or chemical bonding between following three layers on the said sandwich structure.
Wherein, The supporting layer of said plasticity be glass transition temperature more than the room temperature, pass through ultraviolet light, the thermal plastic high polymer film of thickness between 0.1 to 0.2 millimeter, can be polymethyl methacrylate film, PET mylar, Kapton or the plasticon etc. of ultraviolet light.Elastic cord breaker is for passing through the macromolecular elastomer material of ultraviolet light, and the scope of Young modulus is at 1 ~ 5 N/mm
2Thickness is adjustable; Between 0.1 millimeter to 2 millimeters; Can be copolymer elastomer, chlorobutyl rubber-styrene-grafted copolymer elastomer, ethylene-propylene rubber-styrene-alkene graft copolymerization elastic body, polyurethane elastomer, polyester elastomer or the silicone elastomer etc. that styrene and butadiene, isoprene are formed, siliceous silicone elastomer in the wherein preferred segment.The nano impression structural sheet of rigidity is the high molecular nanometer patterned layer of photocuring, and Young modulus is at 50 N/mm
2More than, thickness is adjustable, and between 30 nanometer to 500 nanometers, material is acrylic ester grafted polysiloxane, the polysiloxane of epoxide group grafting or the polysiloxane of vinyl ether grafting.Curable prepolymer is under ultraviolet lighting; Radical initiator (for acrylic ester grafted polysiloxane) or cationic initiator (for the polysiloxane of epoxide group grafting, the polysiloxane of vinyl ether grafting) initiated polymerization is solidified into rigid macromolecule nano-pattern structural sheet.
Can fluoridize organic molecule or macromolecule adherent layer at lower floor's rigidity nano impression patterned layer surface bond one deck low-surface-energy, thereby in printing process, avoid damaged template, reach the effect of template and substrate good separation.
The method that the present invention prepares said sandwich structure composite Nano impression block may further comprise the steps: the elastic body cushion of at first preparation flexibility; Through oxygen gas plasma or ozone plasticity supporting layer and elastic body buffer-layer surface are handled respectively then, again cushion and supporting layer are combined closely; At last on the impression caster of the nano-pattern of processing by quartz, silicon chip or glass; Pass through spin-coating; Form uniform curable prepolymer film, then cushion simultaneously is covered on the caster, behind the ultraviolet photoetching; Separate caster, obtain the nano impression composite shuttering of said sandwich structure.
In the above-mentioned preparation process; Curable prepolymer is with during the macromolecular elastomer material contacts; Can effectively infiltrate through in the elastomeric material, solidify the crosslink polymer network of back formation and the network of elastomer molecules chain formation and constituted the macromolecule interpenetrating networks, thereby combine closely the material of cushion and two-layer different chemical of embossed layer and physical property through the method for chemical bonding; Form unified wholely, prevent this and two-layerly peel off each other.
The invention provides novel nano impression block of a kind of flexibility and preparation method thereof, the beneficial effect that compared with prior art has is:
(1) three layers of composite Nano impression block of the present invention; Adopt the nano-pattern embossed layer of the rigidity crosslinked polymer material of curing as template lower floor; Thereby overcome the shortcoming that soft printing technology can not reach very high resolution (below the 100nm), can obtain high resolving power, Hi-Fi nanostructured; By the cushion that the macromolecular elastomer material constitutes, can make template and substrate under no external pressure condition, realize fitting tightly; The supporting layer that is made up of the thermal plastic high polymer film plays the usefulness of protection to cushion, and external pressure also can apply through supporting layer, is delivered to uniformly on the whole impression face through cushion.
(2) apply among the present invention less than 0.1 atmospheric impression pressure; Particle in the environment can make cushion prolong granule-morphology generation deformation; Particle dents in the cushion; The deformation that is caused by particle is limited to the size of particle itself, has solved in the nanometer embossing this difficult problem that the stamping structure ratio of defects that the environment particle causes is high effectively.
(3) solve extremely this difficult problem of cleaning of nano impression industry, batch process, can reduce cost, improve the product yield effectively.
Description of drawings
Fig. 1 is the diagrammatic cross-section of sandwich structure composite Nano impression block structure of the present invention.
Fig. 2 is sandwich structure composite Nano impression block of the present invention and particle interaction synoptic diagram.
Fig. 3 is the comparison diagram of particle to two kinds of dissimilar template moulding process generation defectives, (a) uses the traditional silicon template; (b) use sandwich structure composite Nano impression block of the present invention.
Fig. 4 utilizes the nanostructured impression electron scanning micrograph of sandwich structure composite Nano impression block of the present invention, (a) 200nm cycle, 100nm live width lattice structure; (b) the 200nm cycle, 100nm live width optical grating construction.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is explained further details.
The structure of the composite Nano impression block of sandwich structure of the present invention is seen Fig. 1, successively by the supporting layer of plasticity, and these three layers of formations of the stamping structure layer of flexible cushion and rigidity.Can also fluoridize adherent layer at nano-pattern embossed layer surface bond one deck low-surface-energy of lower floor: through in oxygen gas plasma or ozone environment; Be oxidized to silicon dioxide to siloxane; Si-OH group on the silicon dioxide and the reaction of perfluoro trichlorosilane form and fluoridize the organic molecule adherent layer; Also can pass through CHF
3, CF
4Fluoridize the macromolecule adherent layer Deng what gas directly formed the similar teflon of one deck on nano-pattern structural sheet surface under plasmoid.
In moulding process; When flexible three layers of composite shuttering contact with the substrate that is coated with curable low viscosity macromolecule prepolymer; The capillary force of liquid makes the flexible macromolecule composite shuttering can depend on the fluctuations of substrate, fits tightly with substrate, need not to apply external force.The rigidity imprint nano patterned layer of template lower floor then possesses the favorable mechanical mechanical property; Keep nanostructured not because of generations deformation such as the pressure that produces in the moulding process, capillary force, destruction such as subside, thus completion high resolving power, Hi-Fi nano impression; The supporting layer of plasticity is covered on the elastic cord breaker, and elastic cord breaker is shielded, and avoids in the moulding process, and cushion and other material adhere to each other; When the particulate blockage template in the environment contacts with substrate; When applying less than 0.1 atmospheric pressure to composite shuttering, cushion can be according to coating of particles generation deformation, and particle is recessed in the cushion; Therefore the large-area defective that caused owing to particle originally; Be limited to the size of particle itself, reduced the defect problem of nano impression effectively, as shown in Figure 2.External pressure also is applied on the whole impression face through cushion uniformly.In composite shuttering and the substrate base applying process, because capillary action is filled up the space between the concavo-convex nanostructured of composite shuttering patterned layer, form the nano-pattern complementary with the formwork structure layer at the low viscosity macromolecule prepolymer between template and the substrate.At this moment, make the macromolecule prepolymer that forms nanostructured further be cured as rigid structure through initiation means such as illumination, heating.After removing composite shuttering, finally on complicated shape substrates such as plane or curved surface, obtain the nanostructured complementary with the formwork structure layer.
The concrete making step of the sandwich structure composite Nano impression block of this instance:
1. PET and polysiloxane are sticked together, two kinds of implementation methods are arranged:
(a) with Sylgard 184 polysiloxane and its mixed with 10:1 of initiating agent; Mixed solution utilizes sol evenning machine evenly to be coated on the PET of arbitrary dimension, and the adjusting of mixed solution thickness is by the decision of even glue time and sol evenning machine rotating speed, and the PET that even glue is accomplished puts among the baking oven; Oven interior vacuumizes and kept one hour; Remove the bubble in the mixed solution, heated oven internal temperature to 60 degree keeps after 5 hours polysiloxane being solidified.
(b) utilize sol evenning machine on antiseized silicon chip, evenly to apply the mixed solution (10:1) of one deck Sylgard 184 polysiloxane and its initiating agent; The antiseized silicon chip that even glue is accomplished is put among the baking oven; Oven interior vacuumizes and kept one hour; Remove the bubble in the mixed solution, heated oven internal temperature to 60 degree keeps after 5 hours polysiloxane being solidified.Take polysiloxane off and the oxygen reaction ion processing is carried out on the polysiloxane surface with reactive ion etching machine.The parameter of handling is: O
25sccm, 30W, 3Pa, 10s.After handling, that one side of handling is tiled on the PET of identical size at once,
2. again with 2000 rev/mins; 40 seconds parameter applies the ultra-violet curing glue of one deck 150nm on caster through sol evenning machine; The composite membrane of PET and polysiloxane is tiled in fast on silicon chip and takes off fast; Take the composite membrane of PET and polysiloxane behind the uv-exposure off, so just be made into sandwich structure composite Nano impression block with the mother matrix inverse structure.
The sandwich structure composite Nano impression block of present embodiment utilization preparation solves the concrete processing step of impression defect problem:
1. utilize sol evenning machine on required substrate with 3000 rev/mins, evenly applied the impression glue of last layer 100nm thickness in 40 seconds.
2. three layers of nano-imprint stamp that will prepare are tiled on the substrate, and through the capillary force of micro-nano structure and the natural absorption affinity of polysiloxane, template and substrate are fitted naturally.
3. the solidified imprinting glue of exerting pressure, this process can realize through two kinds of methods:
(a) apply 0.025Pa pressure at the template supporting layer, and make public with the 200W ultraviolet mercury lamp simultaneously.
(b) apply 0.025Pa pressure at the template supporting layer, remove pressure after 1 second, make public with the 200W ultraviolet mercury lamp again.
4. take template off, accomplish moulding process.
5. utilize reactive ion etching that structure is transferred on the substrate.
Above-mentioned three layers of multifunction formboard realize that in moulding process the principle of figure transfer is: through natural adhesive attraction and the capillary action realization template of structural sheet and the seamless applying of substrate of PDMS, again through the pressurization to supporting layer, realize the transfer of figure.Three layers of multifunction formboard realize that in moulding process the principle of fix the defect problem is: through to the pressurization operation of PET supporting layer and the effect of PDMS cushion; Force circumgranular impression glue around particle, to be gathered; Finally be covered in the particle top; It is minimum that the defect level that particle is brought reduces to, and Fig. 3 has shown the effect contrast figure.The principle of three layers of multifunction formboard method (b) in the process of solidified imprinting glue of exerting pressure is: force the cushion can be according to coating of particles generation deformation through exerting pressure at nano impression; Particle is recessed in the cushion; Therefore the large-area defective that caused owing to particle originally; Be limited to the size of particle itself, reduced the defect problem of nano impression effectively, as shown in Figure 4.
Claims (7)
1. a sandwich structure composite Nano impression block is characterized in that said template is made up of the material of three layers of different mechanical properties, is respectively the supporting layer of plasticity, the stamping structure layer of flexible cushion and rigidity; Said flexible cushion is formed sandwich structure by between the stamping structure layer of sandwich supporting layer and rigidity in plasticity; Closely connect through bonding or chemical bonding between following three layers on the said sandwich structure.
2. a kind of sandwich structure composite Nano impression block according to claim 1; It is characterized in that; The supporting layer of said plasticity be glass transition temperature more than the room temperature, pass through ultraviolet light, the thermal plastic high polymer film of thickness between 0.1 to 0.2 millimeter, like polymethyl methacrylate film, PET mylar, Kapton, plasticon etc.
3. a kind of sandwich structure composite Nano impression block according to claim 1; It is characterized in that the material of the stamping structure layer of said rigidity is acrylic ester grafted polysiloxane, the polysiloxane of epoxide group grafting or the polysiloxane of vinyl ether grafting.
4. a kind of sandwich structure composite Nano impression block according to claim 3 is characterized in that, lower surface bonding one deck low-surface-energy of said rigidity stamping structure layer is fluoridized organic molecule or macromolecule adherent layer.
5. a kind of sandwich structure composite Nano impression block according to claim 1; It is characterized in that; Said flexible cushion is copolymer elastomer, chlorobutyl rubber-styrene-grafted copolymer elastomer, ethylene-propylene rubber-styrene-alkene graft copolymerization elastic body, polyurethane elastomer, polyester elastomer or the silicone elastomer that styrene and butadiene, isoprene are formed, siliceous silicone elastomer in the preferred segment.
6. the preparation method of a sandwich structure composite Nano impression block as claimed in claim 1 is characterized in that this method may further comprise the steps: the elastic body cushion of at first preparation flexibility; Through oxygen gas plasma or ozone plasticity supporting layer and elastic body buffer-layer surface are handled respectively then, again cushion and supporting layer are combined closely; At last on the impression caster of the nano-pattern of processing by quartz, silicon chip or glass; Pass through spin-coating; Form uniform curable prepolymer film, the one side with cushion is covered on the caster then, behind the ultraviolet photoetching; Separate caster, obtain the nano impression composite shuttering of said sandwich structure.
7. utilize the technology of sandwich structure composite Nano impression block as claimed in claim 1, it is characterized in that this technology may further comprise the steps:
(1) utilize sol evenning machine on required substrate, evenly to apply the certain thickness impression glue of last layer;
(2) described sandwich structure composite Nano impression block is tiled on the substrate;
(3) the solidified imprinting glue of exerting pressure, this process can realize through two kinds of methods:
A) on the supporting layer of template, apply certain pressure, and make public with ultraviolet mercury lamp simultaneously;
B) on the supporting layer of template, apply certain pressure, remove pressure, make public with ultraviolet mercury lamp again;
(4) take template off, accomplish moulding process;
(5) utilize etching apparatus that the structure of impression is transferred on the substrate.
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| CN105835279A (en) * | 2016-05-06 | 2016-08-10 | 中国科学院合肥物质科学研究院 | Machining template used for manufacturing flexible micro-hole sound absorbing film and manufacturing method for flexible micro-hole sound absorbing film |
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| US10649327B2 (en) | 2016-10-17 | 2020-05-12 | Shandong University Of Science And Technology | Mold with cavities for nanoimprint lithography and method of imprinting same |
| CN109177134A (en) * | 2018-08-15 | 2019-01-11 | 信利光电股份有限公司 | A kind of imprint mold preparing diffusion sheet and a kind of diffusion sheet |
| CN109656098A (en) * | 2018-12-04 | 2019-04-19 | 上海安翰医疗技术有限公司 | Production method, nano impression Elastic forming board and the component of nano impression Elastic forming board |
| CN111142330A (en) * | 2020-01-21 | 2020-05-12 | 冷水江市京科电子科技有限公司 | Screen printing plate processing method for preventing screen penetration |
| CN111142330B (en) * | 2020-01-21 | 2023-04-07 | 冷水江市京科电子科技有限公司 | Screen printing plate processing method for preventing screen penetration |
| CN112829479A (en) * | 2020-12-22 | 2021-05-25 | 中国科学院苏州纳米技术与纳米仿生研究所广东(佛山)研究院 | Stamp for fine circuit printing and printing method |
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Application publication date: 20120620 |