CN103869611A - Method for manufacturing three-layer composite structured transparent soft mold for full-chip nano-imprint lithography in situ - Google Patents
Method for manufacturing three-layer composite structured transparent soft mold for full-chip nano-imprint lithography in situ Download PDFInfo
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Abstract
The invention discloses a method for manufacturing a three-layer composite structured transparent soft mold for full-chip nano-imprint lithography in situ. The method comprises the following steps: manufacturing a master pattern, and performing anti-adhesion treatment on the master pattern; coating the master pattern with a characteristic structure layer, and coating the pre-cured characteristic structure layer with an elastic supporting layer; compounding a rigid confinement layer and liquid-state PDMS, performing preliminary curing and demolding, and finally completely curing. The soft mold is high in consistency, high in service durability and suitable for large-scale production, and error compensation is contained in the use process.
Description
Technical field
The invention belongs to technical field of micro-nano manufacture, be specifically related to the transparent soft mold original position of full wafer nano impression three-layer composite structure manufacture method.
Background technology
Nano-imprint lithography (NIL) is that a kind of mould that uses is realized its patterned micro-nano process technology by the stress deformation of resist.Compared with other micro-nano manufacture method, NIL has high resolving power, low cost and large-duty feature, especially has more outstanding advantage in large area micro-nano rice structure and complex three-dimensional micro nano structure manufacture view.Along with nano-imprint lithography is in the widespread use in the fields such as high brightness photon crystal LED, compact disk medium (HDD), optical component (optical waveguide, microlens array, grating), micro-fluidic device, more and more urgent for the demand of large area, the whole audience, Integral wafer nano-imprinting technology and device.At present, the method that realizes large-area nano impression mainly contains three kinds: the first is to adopt stepping to repeat nano-imprint process (Step-and-repeat NIL); The second is to adopt to roll imprint process (Roll NIL); The third is to adopt single step Integral wafer nano-imprinting.Repeat nano-imprint process and roll imprint process and realize large-area graphs method and compare with adopting stepping, adopt full wafer wafer (wafer yardstick, wafer scale) nano impression (Full wafer NIL, Wafer-level NIL, Wafer scale NIL) have that throughput rate is high, cost is low, all significant advantages such as even high conformity of figure, and be applicable to the advantage of various soft hard substrate.
Inventor has applied for a patent " apparatus and method of Integral wafer nano-imprinting " (publication number: 102096315A) in 2010, the method is a kind of method of single step Integral wafer nano-imprinting, its ultimate principle is, introduce the soft mold that a kind of three-layer composite structure is transparent, moulding process adopts from mold center position to the two side directions method of homogeneity Microcontact printing gradually, mould structure based on new also adopts under the auxiliary force of impression of gas and capillary force acting in conjunction, realizing force of impression is uniformly distributed, eliminate air blister defect, and under little force of impression, realize copying of figure.Knockout course employing mould is continuous " opening " formula releasing process from wafer two side direction centers, under the acting in conjunction of pull of vacuum and horizontal force, adopting small knockout press can realize the large area demoulding (avoids on the one hand the large area contact demoulding simultaneously to need larger knockout press, causes mould and copy pattern to cause damage; Avoid on the other hand the one-sided open-type demoulding, because die deformation causes greatly short defect in serviceable life).Moulding process and knockout course be all take template center as axis of symmetry, template evenly, symmetrical stressed, the quality of complex (greatly boost productivity with) carried out in impression and knockout course both sides simultaneously.On the basis of this patented technology, inventor also applied for utility model patent " a kind of Full wafer photo nanoimprint lithography machine " (publication number: 202205025U) in 2011.
Inventor has applied for a patent of invention " for compound soft mold and the manufacture method of non-smooth substrate wafer level nano impression " (application number: 102854741A) in 2012, this soft mold comprises feature structure layer, rigidity limiting layer and resiliency supported layer, and manufacture method comprises (1) manufacture master mold; (2) manufacture and in conjunction with rigidity limiting layer and resiliency supported layer; (3) make feature structure layer; (4) in conjunction with feature structure layer and rigidity limiting layer; (5) demoulding.The method is the transparent soft mold of three-layer composite structure related in patent " apparatus and method of Integral wafer nano-imprinting " (publication number: 102096315A), and a solution is provided.But this compound soft mold and manufacture method have the following disadvantages: the feature structure layer material fluororesin relating in (1) the method and resiliency supported layer material PDMS or PET are low-surface-energy material, adopt transparent coupling agent that two functional layers are carried out to compound operability very poor; (2) between feature structure layer and resiliency supported layer, undertaken bondingly by coupling agent, the coating method of coupling agent, the overall depth of parallelism that curing mode can have influence on composite die, use durability degree; (3) due to the thickness of each layer of three layers of compound soft mold itself tens to hundreds of micron dimension, between feature structure layer and resiliency supported layer, undertaken bonding by coupling agent, the material properties of coupling agent layer, physical property, geometric parameter can affect the overall performance of three layers of composite transparent soft mold, impact impression quality; (4) compound soft mold, between the layers in recombination process, adopts Direct Bonding or the bonding mode of coupling agent, is easy to cause interlayer bubble residual, destroys self overall depth of parallelism of composite die, and the workplace flatness of composite die feature structure layer.
For Integral wafer nano-imprinting, the parallelism error between die-face and substrate workplace is very large to full wafer impression quality influence.Because contact area is very large between workplace in Integral wafer nano-imprinting process simultaneously, there is error amplification.Patent " for compound soft mold and the manufacture method of non-smooth substrate wafer level nano impression " (application number: 102854741A) described compound soft mold and manufacture method, while being applied in the related imprinting apparatus of patent " apparatus and method of Integral wafer nano-imprinting " (publication number: 102096315A) and method, also there is following obviously weak point: the overall parallelism error of the transparent soft mold self of (1) three-layer composite structure, in moulding process, easily cause discontinuity on resist (especially for 4 English inch and above wafer scale full wafer impression), the coining pattern film thickness of keeping on file is inconsistent, affect subsequent etching technique, (2) deviations from planarity of the transparent soft mold workplace of three-layer composite structure, in the moulding process of non-smooth substrate, is equivalent to the large area contact of two warped surface, can, along with the fluctuating of warped surface, cause local noncontact defect, reduces yield rate, (3) because stamp work process essence is under the vacuum-pressure of gas circuit is assisted, impel the transparent soft mold deformation-recovery of three-layer composite structure, the bubble of introducing between layers in the transparent soft mold manufacturing process of three-layer composite structure is residual or cohesive strength is lower, can greatly reduce the serviceable life of the transparent soft mold of three-layer composite structure.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide the transparent soft mold original position of full wafer nano impression three-layer composite structure manufacture method, consistance is high, useful life longevity good, use procedure comprises error compensation.
To achieve these goals, the present invention adopts following technical solution:
The transparent soft mold of three-layer composite structure for full wafer nano impression, comprise rigid support layer, rigid support layer adopts borate glass AF45 or AF32,200 microns of thickness, on rigid support layer, be followed successively by feature structure layer and elastic cord breaker, feature structure layer adopts hard PDMS(H-PDMS), 50～80 microns of thickness; Elastic cord breaker adopts PDMS, 400～500 microns of thickness; The transparent soft mold of three-layer composite structure utilizes Full wafer photo nanoimprint lithography machine to realize original position manufacture.
The transparent soft mold original position of three-layer composite structure manufacture method for described full wafer nano impression, comprises the steps:
1), make master mold: take silicon as master mold base material, according to semicon industry standard technology flow process, adopt micro-nano graph method, and manufacture master mold in conjunction with etching technics;
2), process anti-stick company of master mold: the method for using plasma polymerization, self assembly, make on silica-based master mold surface assisted demoulding agent reduce master mold surface can, realize processing anti-stick company of master mold surface;
3), on master mold, apply feature structure layer: connect spin coating precuring feature structure layer on the master mold workplace of processing anti-stick, feature structure layer adopts hard PDMS(H-PDMS), control 50～80 microns of thickness, and precuring;
4), on precuring feature structure layer, apply elastic cord breaker: on precuring feature structure layer, apply liquid PDMS, 400～500 microns of elastic buffer layer thicknesses;
5), compound rigid support layer and liquid PDMS: rigid support layer adopts AF45 or AF32 glass, and concrete composite steps is: 5.1) AF45 or AF32 glass are carried out to physics and help adhesion process; 5.2) rigid support layer is installed on stamping and photoetching machine, vacuum suction is fixed; 5.3) master mold of the liquid PDMS of spin coating is installed on stamping and photoetching machine sample stage, and vacuum suction; 5.4) gas circuit state switches, and starts one by one vacuum state to be switched to pressure state to two side directions from impression center, impels AF45 or AF32 glass to produce gradually Bending Deformation to both sides from center, contacts compound with liquid PDMS; Then, all pressure channel normal pressures keep uniformity, and room temperature keeps, the H-PDMS layer of the liquid PDMS of primary solidification and precuring;
6), the primary solidification demoulding: start gradually to center from master mold both sides, closing presure pipeline, open vacuum line, open the nozzle that the demoulding is used simultaneously, produce under horizontal force acting in conjunction in pull of vacuum and nozzle pressurized air, the transparent soft mold of three-layer composite structure is separated from each other with master mold gradually from two side direction centers, completes the demoulding, take out, obtain the transparent soft mold of the three-layer composite structure of primary solidification;
7), completely curing: the transparent soft mold of three-layer composite structure to be carried out to normal temperature or isothermal curing, obtain the transparent soft mold of spendable three-layer composite structure.
Described assisted demoulding agent is fluorochemicals, comprises C
4f
8.
Described precuring refers to the isoperibol that is placed in 50 ℃, solidifies 10～15 minutes, takes out.
It is to adopt oxygen gas plasma bombardment or corona that described physics helps adhesion process.
The present invention is except the transparent soft mold of the three-layer composite structure series of advantages that (especially to non-smooth substrate moulding process) has in moulding process, and remarkable advantage of the present invention also comprises:
1, the manufacture method of the transparent soft mold of three-layer composite structure, do not need to set up any special purpose device mechanism, in imprint lithography process conventional spin coating and thermostatic equipment, on stamping and photoetching machine patent " a kind of Full wafer photo nanoimprint lithography machine " (publication number: 202205025U) Suo Shu, can complete whole making flow processs of the transparent soft mold of three-layer composite structure.
2, the manufacture method of the transparent soft mold of three-layer composite structure, every step manufacture process does not all rely on operating personnel's individual functipnal capability and operating experience, and all can robotization carry out, and has reduced the stochastic error of manufacturing process, increase the consistance that mould is manufactured, guaranteed making quality.
3, the feature structure layer H-PDMS in the transparent soft mold of three-layer composite structure and resiliency supported layer PDMS all belong to silicone rubber kinds, the H-PDMS of precuring and liquid PDMS can realize without interphase in solidification process and adhering in follow-up primary solidification and completely, and adhesiving effect is good and do not change the self attributes of each composite bed; The AF45 of physical method processing or AF32 glass, can realize high-intensity bonding with liquid PDMS, greatly improved the combined strength bination of composite die and used durability degree.
4, the recombination process of the AF45 of the transparent soft mold of three-layer composite structure or AF32 glass and liquid PDMS, utilizes the vacuum-pressure switching gradually to both sides from centre, has realized " spreading out attached " formula compound, has eliminated " bubble " defect of recombination process.
5, the recombination process of the AF45 of the transparent soft mold of three-layer composite structure or AF32 glass and liquid PDMS, identical with the moulding process workflow of stamping and photoetching machine patent " a kind of Full wafer photo nanoimprint lithography machine " (publication number: 202205025U) Suo Shu, be a kind of original position manufacture method.And utilize the mobility of PDMS, make up the depth of parallelism regulating error of plane machining error, wafer-supporting platform and the impressing mould workplace of shuttering work platform, can effectively reduce on the one hand the impact of uneven error on impression effect, guarantee to greatest extent the impression quality of non-smooth substrate, design, processing request to wafer-supporting platform be can reduce on the other hand, mechanism design, processing cost and fabrication cycle greatly reduced.
6, the PDMS material that the H-PDMS that the transparent soft mold feature structure layer of three-layer composite structure is selected and resiliency supported layer are selected is the conventional material that uses in nano-imprint lithography technique, the AF45(that rigidity limiting layer is selected or AF32) glass is the thin plate packaged glass that semiconductor industry is general, these materials have met the functional requirement of NIL on the one hand separately, with low cost on the other hand, be suitable for large-scale production.
Figure of description
Fig. 1 is the transparent soft mold schematic diagram of three-layer composite structure.
Fig. 2 is low-surface-energy master mold schematic diagram after treatment.
Fig. 3 is master mold schematic diagram after spin coating H-PDMS semi-solid preparation.
Fig. 4 is master mold schematic diagram after coating PDMS.
Fig. 5 is rigid support layer and PDMS recombination process schematic diagram.
Embodiment
Describe the present invention below in conjunction with drawings and Examples.
The transparent soft mold of three-layer composite structure for full wafer nano impression, as shown in Figure 1, comprise rigid support layer 7, rigid support layer 7 adopts borate glass AF45 or AF32,200 microns of thickness, on rigid support layer 7, be followed successively by feature structure layer 2 and elastic cord breaker 3, feature structure layer 2 adopts hard PDMS(H-PDMS), 50～80 microns of thickness; Elastic cord breaker 3 adopts PDMS, 400～500 microns of thickness; The transparent soft mold of three-layer composite structure utilizes Full wafer photo nanoimprint lithography machine to realize original position manufacture.
The transparent soft mold original position of three-layer composite structure manufacture method for described full wafer nano impression, comprises the steps:
1), make master mold: take silicon as master mold base material, according to semicon industry standard technology flow process, adopt the micro-nano graph methods such as optical lithography, electron-beam direct writing, laser interference lithography, and manufacture master mold in conjunction with etching technics;
2), anti-stick company of master mold processes: the method for using plasma polymerization, self assembly, make assisted demoulding agent on silica-based master mold surface, for example silicon fluoride compounds fluorosilane(1H, 1H, 2H, 2H-perfluorodecyl-trichlorosilane), the surface that reduces master mold can, complete processing anti-stick company of master mold surface, obtain the master mold 1 shown in Fig. 2;
3), on master mold, apply feature structure layer: connect spin coating precuring feature structure layer 2 on master mold 1 workplace of processing anti-stick, concrete steps are: 3.1) according to standard proportioning, the hard silicon rubber of configuration H-PDMS(); 3.2) liquid H-PDMS is watered and casts from master mold 1 picture surface, spread out the whole graph area of attached area covering, under vacuum environment, keep 5 minutes; 3.3) method of employing spin coating (spin coating), controls elementary, senior rotating speed, makes feature structure layer 2,50～80 microns of thickness on master mold 1; 3.4) scraping is removed the H-PDMS of master mold 1 lateral wall and back side redundancy; 3.5) master mold of spin coating H-PDMS 1 is placed in to the isoperibol of 50 ℃, precuring 10～15 minutes, takes out, and prepares on master mold 1 and covers one deck H-PDMS as feature structure layer 2, as shown in Figure 3;
4), on precuring feature structure layer, apply elastic cord breaker: liquid PDMS is watered on the H-PDMS layer that casts from semi-solid preparation, adopt the method for spin coating, control elementary, senior rotating speed, make elastic cord breaker 3,400～500 microns of thickness, scraping is removed master mold 1 lateral wall and back side redundancy PDMS, prepares the PDMS on master mold 1 and H-PDMS, as elastic cord breaker 3, as shown in Figure 4;
5), compound rigid support layer and elastic cord breaker: rigid support layer 7 adopts borate glass AF45 or AF32, composite steps as shown in Figure 5, be specially: 5.1) adopt the method for oxygen gas plasma bombardment or corona, one side is processed clean AF45 or AF32 glass, 200 microns of thickness; 5.2) AF45 or AF32 glass treatment are faced down, untreated towards being above installed on the stamping and photoetching machine described in patent " a kind of Full wafer photo nanoimprint lithography machine " (publication number: 202205025U); 5.3) master mold of the liquid PDMS of spin coating is installed on the described sample stage of patent " a kind of Full wafer photo nanoimprint lithography machine " (publication number: 202205025U), and vacuum suction; 5.4) the valve plate auxiliary rigidity limiting layer of 4 gas circuits switching and elastic cord breaker are compound, and concrete steps are: a, the described eindruckwerk of patent " a kind of Full wafer photo nanoimprint lithography machine " (publication number: 202205025U) drop to stamp work position; B, from impression center, vacuum line 6 is closed, pressure piping 5 is opened, initial vacuum state is switched to normal pressure state by valve plate 4, impel AF45 or AF32 center of glass position to produce Bending Deformation, contact with liquid PDMS, as shown in Fig. 5 (a); C, from impression center close successively to two side direction vacuum lines 6, pressure piping 5 is opened successively, one by one valve plate 4 vacuum states are switched to pressure state, AF45 or AF32 glass and liquid PDMS contact area increase gradually, until whole liquid PDMS layers contact completely with AF45 glass, as shown in Fig. 5 (b); D, all pressure channel normal pressures keep uniformity, and room temperature keeps eight hours, and the H-PDMS primary solidification of liquid PDMS and semi-solid preparation, as shown in Fig. 5 (c);
6), the primary solidification demoulding: master mold two side positions are opened vacuum line 6, closing presure pipeline 5, positive and negative pressure switching is realized in valve plate 4 both sides, and the transparent soft mold and the master mold that make outermost start three-layer composite structure start to be separated from each other, as shown in Fig. 5 (d); Subsequently, open one by one vacuum line 6 from master mold two side direction centers, closing presure pipeline 5, valve plate 4 converts back vacuum state by pressure gradually, realize transparent soft mold demoulding of " opening " formula continuously from center, master mold lateral of three-layer composite structure, as shown in Figure 5 (e) shows; Finally, transparent soft mold center and the master mold of three-layer composite structure are separated, and complete the demoulding, obtain the transparent soft mold of the three-layer composite structure of primary solidification, as shown in Fig. 5 (f);
7), completely curing: the transparent soft mold of three-layer composite structure is placed in to 80 ℃ of isoperibols, keep half an hour, feature structure layer H-PDMS and elastic cord breaker PDMS are completely curing, scraping is removed the solid-state PDMS of redundancy lightly subsequently, obtains the transparent soft mold of spendable three-layer composite structure.
Claims (5)
1. the transparent soft mold of three-layer composite structure for full wafer nano impression, it is characterized in that: comprise rigid support layer, adopt borate glass AF45 or AF32,200 microns of thickness, on rigid support layer, be followed successively by feature structure layer and elastic cord breaker, feature structure layer adopts hard PDMS(H-PDMS), 50～80 microns of thickness; Elastic cord breaker adopts PDMS, 400～500 microns of thickness; The transparent soft mold of three-layer composite structure utilizes Full wafer photo nanoimprint lithography machine to realize original position manufacture.
2. the transparent soft mold original position of three-layer composite structure manufacture method for full wafer nano impression according to claim 1, is characterized in that, comprises the steps:
1), make master mold: take silicon as master mold base material, according to semicon industry standard technology flow process, adopt micro-nano graph method, and manufacture master mold in conjunction with etching technics;
2), process anti-stick company of master mold: the method for using plasma polymerization, self assembly, make on silica-based master mold surface assisted demoulding agent reduce master mold surface can, realize processing anti-stick company of master mold surface;
3), on master mold, apply feature structure layer: connect spin coating precuring feature structure layer on the master mold workplace of processing anti-stick, feature structure layer adopts hard PDMS(H-PDMS), control 50～80 microns of thickness, and precuring;
4), on precuring feature structure layer, apply elastic cord breaker: on precuring feature structure layer, apply liquid PDMS, 400～500 microns of elastic buffer layer thicknesses;
5), compound rigid support layer and liquid PDMS: rigid support layer adopts AF45 or AF32 glass, and concrete composite steps is: 5.1) AF45 or AF32 glass are carried out to physics and help adhesion process; 5.2) rigid support layer is installed on stamping and photoetching machine, vacuum suction is fixed; 5.3) master mold of the liquid PDMS of spin coating is installed on stamping and photoetching machine sample stage, and vacuum suction; 5.4) gas circuit state switches, and starts one by one vacuum state to be switched to pressure state to two side directions from impression center, impels AF45 or AF32 glass to produce gradually Bending Deformation to both sides from center, contacts compound with liquid PDMS; Then, all pressure channel normal pressures keep uniformity, and room temperature keeps, the H-PDMS layer of the liquid PDMS of primary solidification and precuring;
6), the primary solidification demoulding: start gradually to center from master mold both sides, closing presure pipeline, open vacuum line, open the nozzle that the demoulding is used simultaneously, produce under horizontal force acting in conjunction in pull of vacuum and nozzle pressurized air, the transparent soft mold of three-layer composite structure is separated from each other with master mold gradually from two side direction centers, completes the demoulding, take out, obtain the transparent soft mold of the three-layer composite structure of primary solidification;
7), completely curing: the transparent soft mold of three-layer composite structure to be carried out to normal temperature or isothermal curing, obtain the transparent soft mold of spendable three-layer composite structure.
3. the transparent soft mold original position of three-layer composite structure manufacture method for full wafer nano impression according to claim 2, is characterized in that: described assisted demoulding agent is fluorochemicals, comprises C
4f
8.
4. the transparent soft mold original position of three-layer composite structure manufacture method for full wafer nano impression according to claim 2, is characterized in that: described precuring refers to the isoperibol that is placed in 50 ℃, solidifies 10～15 minutes, takes out.
5. the transparent soft mold original position of three-layer composite structure manufacture method for full wafer nano impression according to claim 2, is characterized in that: it is to adopt oxygen gas plasma bombardment or corona that described physics helps adhesion process.
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| CN105093824A (en) * | 2015-08-31 | 2015-11-25 | 西安交通大学 | Gas-electricity cooperative large-area nano-imprinting photo-etching method |
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| CN105093824A (en) * | 2015-08-31 | 2015-11-25 | 西安交通大学 | Gas-electricity cooperative large-area nano-imprinting photo-etching method |
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| CN108162425A (en) * | 2017-12-22 | 2018-06-15 | 青岛理工大学 | A kind of large scale is without splicing micro-nano soft mold manufacturing method |
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| CN109111089A (en) * | 2018-07-30 | 2019-01-01 | 东莞市轩驰智能科技有限公司 | Molding machine and forming method |
| CN109111089B (en) * | 2018-07-30 | 2021-08-13 | 东莞市轩驰智能科技有限公司 | Molding apparatus and molding method |
| CN110361930A (en) * | 2019-07-16 | 2019-10-22 | 京东方科技集团股份有限公司 | A kind of nano-imprint stamp and preparation method thereof |
| CN113618090A (en) * | 2021-08-11 | 2021-11-09 | 吉林大学 | Micro-nano structure roller mold machining and impression forming machine tool and control method thereof |
| CN113618090B (en) * | 2021-08-11 | 2022-06-07 | 吉林大学 | Micro-nano structure roller mold machining and impression forming machine tool and control method thereof |
| CN113866170A (en) * | 2021-12-01 | 2021-12-31 | 聚时科技(江苏)有限公司 | Surface defect detection vision system |
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