CN103376646A - Nanoimprint lithographic method - Google Patents
Nanoimprint lithographic method Download PDFInfo
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- CN103376646A CN103376646A CN2013101255126A CN201310125512A CN103376646A CN 103376646 A CN103376646 A CN 103376646A CN 2013101255126 A CN2013101255126 A CN 2013101255126A CN 201310125512 A CN201310125512 A CN 201310125512A CN 103376646 A CN103376646 A CN 103376646A
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- lithographic plate
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/02—Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/3828—Moulds made of at least two different materials having different thermal conductivities
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides a nanoimprint lithographic method, these methods uses (S10) a mold (100), one side (101) of the mold comprises a topographic pattern (140) formed by structures (130) having nanometer scale dimensions. The nanoscale structures are heated above a decomposition temperature (Td) of a thermally decomposable polymer film (210) such as poly (phthalaldehyde) which is disposed on a substrate (220) facing the mold. The structures are brought into contact (S20) with the polymer film to thermally decompose portions which correspond to the pattern of the structures and the structures are removed (S50) from the polymer film.
Description
Technical field
The present invention mainly relates to the field of nanometer marking lithographic plate printing method and relevant devices.Particularly, it proposes to be used for extensive new technology of making the structure of nano-scale.
Background technology
Nanoscale with high resolving power and while high yield is manufactured with challenge.Nanometer marking offset printing (nanoimprint lithography) (perhaps NIL) is a kind of technology for come the patterning nanoscale structures by molded or embossment (embossing).Utilize NIL, might the low-cost very little feature of patterning (for example showing as down to the 5nm feature or still less, only limited by template) of high yield on principle.This is to point out that this technology is a kind of potential technology for patterning 32nm and 22nm feature why in semi-conductive international route map (ITRS).Have various following methods, the common ground of these methods is that their use moulds (perhaps template) are to shift pattern from mould to substrate.NIL finds to be used for the application of magnetic disk memory, biology sensor microarray, microchannel and photon crystal device.Yet NIL still faces technical matters.Illustrate some problems in these problems by summarizing two kinds of NIL methods commonly used: hot embossment and stepping and the offset printing of the flash of light marking.
In hot embossment NIL method, mould makes thermoplastic polymer films (for example PMMA) distortion with High Voltage and the temperature more than the Glass Transition of polymkeric substance.Even patterned such dot matrix pattern little as 6nm, this technology still has some difficult points.These difficult problems are mainly as follows:
The different heat expansion of-polymkeric substance, substrate and mould causes alignment issues;
-template filling is imperfect when patterning different characteristic size;
-owing to this process length consuming time and need temperature cycles to yield poorly;
-template is degraded owing to High Voltage and temperature;
-be difficult to discharge the minor structure with high aspect ratio.Structure is often broken and owing to the too high mainboard that adheres to of cohesive.
Stepping and flash of light offset printing or S-FIL (Molecular Imprints, the trade mark of Inc.) are developed in 1999 and refer to the low viscosity monomer solution of a kind of use and the technology of transparent template (for example quartzy).Structure in the liquid filling mould and need not High Voltage or temperature.Then monomer is exposed to the UV light through transparent template, and this makes its photopolymerization.The user has pointed out following difficult point:
-this technology is limited to quick photopolymerization and low-viscosity material;
-must make mould by transparent material;
-resist may during curing shrink;
-have a high aspect ratio little feature may avalanche;
-etching selectivity may be low, so the design transfer difficulty;
-need releasing layer to discharge the material of the marking from template and to protect template;
-for the feature with different size, must print with ink-jet printer the optimization droplet pattern of resist at substrate.
One or more problem during the purpose of some embodiments of the present invention is to address the above problem.
Summary of the invention
According to first aspect, realize that the present invention is a kind of nanometer lithographic plate printing method, the method comprises:
Provide: mould, comprise the structure with nanoscale yardstick in a side of mould, structure forms pattern (topographic) pattern; And the thermal decomposition polymer film relative with a described side of mould on the substrate, wherein this structure is heated to more than the decomposition temperature of polymer film;
Make described structure contact part with thermal decomposition itself and described structural correspondence with polymer film; And
Remove structure from polymer film.
In certain embodiments, before making described structure and polymer film contact, keep the temperature of substrate below the glass transformation temperature of polymer film, and described structure is contacted with polymer film preferably include and make described structure approaching to realize with it thermo-contact and cooling structure towards substrate.
In some variants, carry out making described structure contact to unwind with polymer film and/or its molecule of desorb.Preferably, the polymer film that provides is so that can carry out and make described structure contact to come its part of thermal decomposition according to endothermic decomposition with polymer film.
According to some embodiment, the polymer film that provides comprises via intermolecular non-covalently cross-linked in fact molecular network, and execution contacts with its molecule of desorb described structure with polymer film.
Preferably, the average molecular mass of the molecule in the polymer film that provides is between 100Da and 2000Da, more preferably from the scope of 150Da to 1000Da, and wherein preferably via the crosslinked described molecule of hydrogen bond.
According to some other embodiment, the polymer film that provides comprises the polymeric material with the polymer chain that can unwind when thermostimulation: carry out in this case the polymer chain make described structure contact to unwind polymeric material with polymer film.
Preferably, the polymer film that provides comprises poly-adjacent benzene (poly (phthalaldehyde)).Polymer film preferably has 125 ℃ ± 20 ℃ glass transformation temperature and 150 ℃ ± 30 ℃ heat decomposition temperature.
In certain embodiments, the mould that provides comprises main body and the material layer between main body and structure, main body preferably includes crystalline silicon, material layer preferably includes monox, and described material layer has than the temperature conductivity of main body obviously lower, preferably low ten times and low fiftyfold at least temperature conductivity more preferably at least.
Preferably, the corresponding thermal linear expansion coefficient of material layer and main body differs and is less than 5 times.
Material layer can have the thickness between 1 and 30 micron, and this thickness is preferably 6 ± 4 microns.
In certain embodiments, one or more structure in the structure of the mould that provides has following height, average thickness such as this aspect ratio polymer film of measuring in the direction vertical with polymer film is larger, and preferably three times than the average thickness of polymer film are larger.
According to some embodiment, keep the temperature of substrate below the glass transformation temperature of polymer film, and before beginning to make described structure and polymer film contacts, at the volatile temperature heating arrangement of the decomposition product of polymer film; Described structure is contacted with polymer film comprise and make described structure approaching to realize with it thermo-contact and cooling substrate on the substrate.
Preferably, before making described structure and polymer film contacts, the temperature difference between the structure of the substrate that heats and heating is at least 100 ℃, preferably is at least 200 ℃.
According on the other hand, the present invention is embodied as a kind of nanometer offset printing device, and this device comprises:
Mould comprises the structure with nanoscale yardstick in a side of mould, and structure forms the pattern pattern; And
Substrate has the thermal decomposition polymer film relative with a described side of mould thereon,
Heating arrangement is arranged to for structure being heated to more than the decomposition temperature of polymer film; And
Actuating device be used for to realize making described structure to contact with polymer film with the part of thermal decomposition itself and described structural correspondence and from polymer film removal structure.
In certain embodiments, this device also comprises the cooling device that is suitable for substrate is maintained at the temperature below the glass transformation temperature of polymer film.
To and describe by the unrestricted example of reference unit of the present invention and the method for realizing with reference to the accompanying drawings now.
Description of drawings
-Fig. 1 schematically illustrates the vertical setting that is suitable for implementing according to the step of the NIL method of some embodiment;
The step of-Fig. 2 A-Fig. 2 D diagram as the NIL method that relates in certain embodiments and as the approximate temperature distribution plan of the appearance at different levels in the parts of the setting of Fig. 1; And
-Fig. 3 is the process flow diagram of describing such as in certain embodiments sequence of steps.
Embodiment
Structure is following as follows describes.Main embodiment and H variety (chapters and sections 1) are at first described.Ensuing chapters and sections solve specific embodiment (chapters and sections 2 and chapters and sections 3).
1. main embodiment and H variety
With reference to Fig. 1-Fig. 3, main aspect of the present invention is at first described, this main aspect relates to the nanometer lithographic plate printing method.
At first, these methods are used the mould 100 that is also referred to as Tu Yin or template.As seen in Figure 1, the latter comprises pattern pattern 140 in one side 101.The structure 130 that has one or more nanoscale yardstick by the marking forms this pattern.Should heat these structures to produce the pattern of the described pattern pattern 140 of reflection at marking resist.Structure 130 can correspondingly be connected to heating arrangement 104, thereby allows heating arrangement 130 and preferably control the temperature of heating arrangement 130.
Secondly, on another part 200, at structure in opposite directions the polymer film 210 (anticorrosive additive material) of substrate 220 placements with mould.This polymer film thermal decomposition, namely it can decompose the composition hydrolysis products when suitable thermostimulation.Correspondingly at the decomposition temperature T of polymer film
dAbove heating arrangement 130, thus when making described structure contact S20 with polymer film, its part that reflects described structure 130 and pattern 140 usually thermal decomposition S30 becomes volatile decomposition products.
At last, can remove the S50 structure from polymer film.If essential, as then can to use any suitable transfer method to obtain owing to above-mentioned thermal decomposition to another layer transfer pattern.
As other NIL technology, said method has the potentiality with high yield patterning high-resolution features.Yet present technique can be faster, i.e. the basic decomposable process work that (namely is less than 10 microseconds) in the microsecond scope; It is not the speed restriction factor.Need not High Voltage, and can depend on the relative low temperature degree.
In addition, said method does not bring the incomplete problem of template filling when patterning different characteristic size.Also need not to make anticorrosive additive material to distribute and adapt to die plate pattern (as the S-FIL needs of ink jet printing resist).
Can be for example simply the spin-coating erosion resistant agent material be the thin flat film.In addition, can imagine various templates and resist combination with present technique.This process guarantees when withdrawal figure prints without bonding appearance, because the polymeric material that volatilization contacts with formwork structure.Therefore avoid adhesion problem, shift and the corresponding templates pollution such as partial pattern.
In the preferred embodiment of in such as following chapters and sections 3, describing, before making described structure and polymer film contacts S20, keep substrate at the glass transformation temperature T of polymer film
gBelow the temperature of (and preferably in much lower temperature).This is limited in the expansion of the material of period of contact decomposition.
In addition, step S20 can comprise make described structure towards the approaching S40 of substrate to realize with its thermo-contact and to cool off this structure.As long as mould structure 130 does not touch substrate (perhaps at least fully away to prevent a large amount of heat interchange with substrate), print structure keeps enough heat, thereby namely allows the decomposition resist more than decomposition temperature.Then, if make Tu Yin and for example show high heat conducting substrate (for example silicon) close contact, then heat interchange appearance and substrate 220 are cooled to print structure 130 at T
gFollowing temperature.Flowing that the further decomposition that prevents polymkeric substance or melting cause falls in the temperature of structure, and wherein this process is from restriction.This allows to obtain very clean pattern.
Corresponding with said method, the device (10) that is suitable for implementing this method comprises described above: mould 100 has structure 130; And substrate 220, have thermal decomposition polymer film 210 thereon.Such device also comprises for the decomposition temperature T that structure is heated to polymer film
dAbove suitable heating arrangement 104 and the actuating device 102,240,250 that is used for realizing contact.In certain embodiments, device also comprises for advancing the glass transformation temperature T that substrate is maintained in the template polymer film offseting with resist 210
gThe suitable cooling device 230 of following temperature.
The example that is suitable for best the anticorrosive additive material of this method is molecular glass (perhaps referred to as MG) or poly-adjacent benzene (hereinafter being PPA).The inventor has realized that and can remove exactly a small amount of these materials when contacting with sharp NIL structure 130.Up to now, have down to the feature of half pitch of 8nm with this method success marking.Almost do not remove the more material of the shape that occupies than structure 130, for example PPA.This means that patterning resolution only is subjected to the structural limitations that contacts with the thermal decomposition material.
More specifically, preferably the selective polymer film so that its molecule can when the thermostimulation of structure 130, unwind and/or desorb.The polymkeric substance that unwinds allows rapid stimulation and decomposition.The decomposition product of desorbing polymer also is like this.The temperature that attention needs for the polymkeric substance that will unwind the unwinds gained decomposition product that is enough to volatilize is because monomeric unit volatilizees in lower temperature.Also preferably design polymer film to realize the endothermic decomposition process.Can recognize that such process should prevent the further heat expansion in the material inherently, therefore improves marking resolution.
Therefore, except poly-adjacent benzene, can use other polymkeric substance that unwinds, namely comprise the material of the polymer chain that can when suitable thermostimulation, unwind.Thereby can be via the solution chain reaction of structure 130 thermostimulation films 210 for the trigger polymers chain.Usually, the some or all of effect of unwinding of the first degraded Event triggered.
In the situation of poly-adjacent benzene, preferred a kind of organic catalysis mode for polymerization, this mode are for example used dimerization 1-tert-butyl-2,2,4,4,4-five (dimethyl)-2 Λ when having pure initiating agent
5, 4 Λ
5-catenadi (phosphonitrile) (P
2-t-Bu) the phosphonitrile base material is as anionic catalyst.For example resulting polymers (comprise molecular wt with 27kDa is equal to～200 monomeric units) has low ceiling temperature and further helps for the ability that produces permanent pattern by the selectivity pyrolysis with the structure that heats.Utilize such material, can write degree of depth pattern and do not apply indentation (indentation) power or apply a small amount of indentation power to structure in fact.This makes owing to indentation or the pattern distortion that produces of displacement material are minimum.In addition, polymeric chain can be comprised of random length, and this gives a large amount of dirigibilities when regulating material character (such as glass temperature and anti-dissolubility).Attendant advantages is to need not to finely tune intermolecular force, this from need to be different from the stable material of secondary structure (such as hydrogen bond).Be that 125 ℃ ± 20 ℃ and heat decomposition temperature are that 150 ℃ ± 30 ℃ polymer film obtains the particularly preferred marking for glass transformation temperature.
In the variant of the polymkeric substance that unwinds, can use molecular glass, namely material 210 comprises in this case via intermolecular (non-in fact covalency) the crosslinked molecule of key.Such molecule can easily desorb when using heating arrangement 130 patterning polymeric material.The average molecular mass of described molecule is preferably between 100Da and 2000Da, and more preferably from the scope of 150Da to 1000Da, this gives the desorb character of enhancing.Can be via intermolecular linkage (such as Van der Waals for or hydrogen bond) cross linking membrane.Offset on the surface of the structure 130 of suitably heating and film 210 and to be pushed into and when interacting with it, interacting may one or more molecule of desorb.Can adjust detector temperature and structure 130 and be exposed to the time on surface to optimize the analysis desorb.
In all cases, be favourable at the volatile temperature heating arrangement 130 of the decomposition product of polymer film.In practice, the high-temperature of seeking between structure and substrate is poor, for example more than 100 ℃, 200 ℃, possible 300 ℃ or even more.
Then, particularly preferred solution utilization such as bed die, this mould comprise such as visible main body 110 and material layer 120, for example monox of being made by crystalline silicon better among Fig. 1.Layer 120 is between main body 110 and structure 130.Material layer 120 has than the significantly lower temperature conductivity of the temperature conductivity of main body, for example low ten times or more (preferably low 50 or even 100 times).
In addition, the corresponding thermal linear expansion coefficient of material layer 120 and main body 110 can be close to each other as far as possible ideally.In practice, if differing, they are less than 5 times then obtain gratifying result.
On the other hand, preferably make this material layer 120 for thin, namely thinner than body layer 110, for example between 1 and 30 micron.Use in practice 6 ± 4 microns thickness to realize very well results.In this regard, preferably imagine with lower thickness:
-main body 110: between 100 and 800 μ m, preferably be about 400 μ m;
-cushion 120: between 1 and 30 μ m;
-structure 130: greater than the thickness of polymkeric substance 210;
-polymer film 210: between 20nm and 1 μ m; And
-substrate 220: between 100 and 800 μ m, preferably be about 400 μ m.
Consider an example.The second layer 120 (for example monox) has low heat conductivity and low thermal coefficient of expansion.Because the high thermal resistance of layer 120 is seen Fig. 2 A-Fig. 2 D, temperature difference T
1-T
2Will be when mould and substrate contact mainly at the level of this one deck descend (seeing Fig. 2 B-Fig. 2 C).This prevents the heat expansion in the substrate and allows the thermal decomposition material layer stay below Glass Transition/melt temperature.Low-thermal-expansion falls the minimizing misalignment by temperature.Also can reduce misalignment by the layer that for example only is about 10 micron thickness, so lateral expansion is limited to layer 110.
What also impliedly relate to as mentioned is such, and it is favourable providing the structure 130 with such aspect ratio to provide: namely the height of structure (as vertically measuring with polymer film 210) should be greater than the average thickness of polymer film.This is preferably greater than the twice of average polymer film thickness or three times.As shown in Fig. 2 B, have such structure and allow for thermal decomposition material 210a volatilization and stay sufficient space.
Indirectly describe above-described embodiment with reference to accompanying drawing, and above-described embodiment can adapt to a plurality of variants.In a preferred embodiment, it is contemplated that some combinations of above-mentioned feature.In ensuing chapters and sections, provide object lesson.
2.DRIL the specific embodiment of method
This chapters and sections are described hereinafter referred to as " contaminate and melt (dip and run) marking offset printing " or referred to as the specific embodiment of " DRIL ".Described above such, use the thermal decomposition material film that is brought on the substrate.Can use the material such as molecular glass (MG) or poly-adjacent benzene (PPA).
Only need a single step that is used for making at wafer scale feature.Can make template for DRIL with conventional nanometer manufacturing technology.It can be made by the various materials of for example going up to about 250 ℃ of mechanically stables.For example silicon is suitable material.
The principle of DRIL can be described with reference to Fig. 1.Heated die plate 100, and with substrate side 200 parallel alignment templates 100.Template is contacted with polymer film 210 on the substrate 220.No matter where the thermal decomposition material 210 on the substrate obtains heating from the structure 130 on the hot-die plate, and it all will volatilize.The gas molecule that produces needs the space to volatilize.This space can be provided by opened areas or the cavity that for example may produce owing to the pattern 140 that structure 130 and they form in the template.When operating in a vacuum, improve this process, because the gas that more spaces can be used for decomposing.
Can movable platen until via the definition position of piezo-electric motor 102 controls or until template is touched underlying substrate 220.
After reaching the target location, again mention template.The structure of template is replicated in the thermal decomposition material layer and can be further processed or be directly used in application.Thermal decomposition material mentioned above is well suited for further processing, such as reactive ion etching (RIE).
More specifically, in case the decomposition reaction of thermal decomposition material it reach remarkable decomposition temperature T
dJust occur.In the situation of PPA as the thermal decomposition material, the heat absorption of the decomposable process of polymkeric substance.This causes the certainly restriction of decomposable process, because decomposition itself absorbs heat.This reduces temperature, therefore prevents thermal diffusion.Follow-up volatilization is also absorbed heat.Therefore only directly touch molecular breakdown and the volatilization of the heated structure 130 on the template.Gas flows out along the gap that produces by heat structure.This gap with width d is preferably as far as possible little in order to realize high resolving power.Ideally, remove only molecular layer.Vacuum will reduce the heat conduction by this gap, and it is little therefore will helping to keep gap width d.
Possible damage or pollute the fact (expensive) marking mainboard by the patterning process such as the critical defect in the prior art of mentioning in the background technology.Just the opposite, in this situation, the pollution of thermal decomposition resist should be a problem.In fact, be heated to 215 ℃ or when more at the wafer that will have the PPA film, stay on the silicon wafer without the PPA residue.Carry out the sensitive surface analysis of having confirmed this point, such as ToF-SIMS (the flight time secondary ion mass spectrometry (SIMS) is analyzed) (not shown).To in follow-up article, announce experimental result.Attention is in the equipment of Fig. 1, and optional layer (between layer 210 and 220 or 220 and 230) can be used for adjusting the heat conduction.Similarly, other parameter may need for example to use (further) of trial and error to optimize.
3. certainly limit hot nanometer marking embodiment (substrate of cooling)
These chapters and sections are described some other specific embodiment, wherein further keep substrate at the glass transformation temperature T of polymer film before contact
gFollowing temperature.Use in addition the figure seal/mainboard that is configured to vertically low and high thermal conductivity zone.
Therefore use the mainboard of heating and the substrate of cooling.As hereinafter will specifically discussing, resulting structures is the optimization Temperature Distribution in the permission system during marking step: an important plan seal does not touch substrate, thereby print characteristics just keeps heat to allow the clean decomposition of resist.If Tu Yin and substrate close contact, then print characteristics is cooled to temperature below the glass transformation temperature of polymkeric substance by substrate.
This one-level that temperature is fallen at layer 120 is in the Tu Yinnei appearance, sees Fig. 1-Fig. 2.If only a feature 130 is touched substrate 220, then this also local appearance.Therefore, arranging of Fig. 1 can be used with the vertical power of height, thereby realizes mainboard and the good contact of substrate on whole printing zone.Because the great majority of mainboard remain in high-temperature, so thermal shrinkage is not a problem.
Fig. 2 A diagram allows mould 100 place in substrate initial conditions of (as in addition also as shown in Fig. 1) more than 200.With the decomposition temperature T of mold heated to thermal decomposition material 210
dMore than, and substrate is cooled to its glass transformation temperature T
gBelow (if perhaps applicable then at least below its melt temperature).
Fig. 2 B: mould approaches substrate.When the structure of heating was touched thermal decomposition material 210, it evaporated into volatile decomposition product, for example monomer 210a.The temperature of mould structure only slightly reduces and still at T
dMore than.The thermal decomposition material membrane remains in T
gBelow, because very little by the heat conduction of air/vacuum gap.In addition, film 210 is cooled off efficiently by substrate and is further benefited from endothermic decomposition and volatilization process.
Fig. 2 C: mould touches substrate.Structure 130 is by substrate 220 cooling and owing to their high expansion coefficient shrinks (seeing 130a).The temperature of mould in layer 120 and above layer (layer 110 etc.) thereof only at T
gAnd T
dMore than, therefore prevent the further decomposition of thermal decomposition material 210.The final film 210b that obtains the patterning of cleaning.
Fig. 2 D: remove mould from substrate.
More specifically consider the thermal decomposition material, can consider following main points:
1) preferably has the material of high Glass Transition/melt temperature, thereby do not have non-required distortion to occur;
2) decomposition product preferably volatilizees in order to allow immediately in that these temperature are volatile;
3) the endothermic decomposition process prevents the further thermal diffusion in the material, therefore realizes the high resolving power marking;
4) suitable material is that glass transformation temperature is that～125 ℃ ± 20 ℃ and decomposition temperature are～150 ℃ ± 30 ℃ poly-adjacent benzene;
5) on substrate 220, apply thermal decomposition material 210.For example this can finish with spin coating.
Consider now mold feature:
1) as shown in fig. 1, can on well heater 104 and motor 102, place mold component 110-130.The design motor is to allow to/accurately approaching and remove mould from mould 210.Motor can be to have the seldom piezo-electric motor of transverse shifting.
2) with mold heated to the temperature more than the decomposition temperature of thermal decomposition material, this temperature in practice can be usually high or more as 300 ℃;
3) mould comprises the layer with different thermal conductivity.Especially:
-have a ground floor 110 (for example crystalline silicon) of high thermal conductivity.This ensures that the smoothed temperature in the mould distributes.
-have the second layer a 120 (silicon oxide sio for example of low heat conductivity and low-thermal-expansion
2).As more early pointing out, since the high thermal resistance of this one deck, temperature difference T
1-T
2Will be when mould and substrate contact mainly at layer 120 this one-level descend (seen in Fig. 2 C).This prevents the heat expansion in the substrate, and allows thermal decomposition material layer 210 stay below Glass Transition/melt temperature.Cool off caused misalignment by reducing substrate with the thick layer of≤10 μ m, therefore by the leading lateral expansion of ground floor; And
-have the 3rd layer (for example crystalline silicon) of high thermal conductivity.This one deck comprises structure 130.High thermal conductivity ensures that the feature of nano-scale also obtains to be heated to more than the decomposition temperature of thermal decomposition material.In case structure and substrate joint, high thermal conductivity also is reduced to substrate temperature with the temperature of structure.Structure 130a shrinks along with their coolings, and this helps prevent removes too many material (seeing Fig. 2 C).
4) structure 130 in the 3rd layer can at random be shaped.Some do not touch then unimportant if some structures are touched substrate (Fig. 2 C), because the second layer 120 prevents more than the cooling that touches structure.
5) structure advantageously have even as big as for the aspect ratio of the thermal decomposition material slot milling of volatilization (at least～2: 1, usually～3: 1);
6) be SOI (silicon-on-insulator) wafer for the suitable material of making mould.These wafers commercially available and be included in above have the silicon wafer (the 1st layer) of silicon oxide layer (the 2nd layer) and another silicon layer (the 3rd layer).Silicon has very high thermal conductivity (k=149Wm
-1K
-1); Its thermal linear expansion coefficient is α=2.610
-6K
-1The respective value that is used for monox is lower k=1.4Wm to being enough to be fit to this purpose
-1K
-1And α=8.410
-7K
-1
Consider now substrate feature:
1) can be to cooling unit 230 and the upper stationary substrate 220 (as shown in fig. 1) of parallel aligning guide 240-250;
2) can use vacuum exhaust device (not shown) to fix substrate;
3) preferably with substrate active cooling (for example water cooling) to the glass transformation temperature of thermal decomposition material;
4) preferably, the conduction of substrate height underground heat, this improves cooling; The same silicon that is fit to;
5) in order to cool off, Peltier's element or water cooling can be used for substrate is cooled to usually～5 ℃.
6) the possible mechanism that is used for parallel alignment substrate and mould uses a ball bearing 240-250 under substrate.When mould began to touch substrate, it obtained until 3 of mould touch substrate.It is then parallel ideally.This also can finish before utilizing the marking process of cold die tool.Then with the parallel mould of aiming at of solid thermal decomposition material layer.Position that can stationary substrate can be mentioned again and heating mould is used for follow-up marking step.
Comment at last:
1) poor the helping prevent of the high-temperature between mould and substrate removed too many material.
2) if reduce the duration of contact of substrate and mould, thereby then Glass Transition is shifted to higher temperature and is made more robust of this process;
3) the very short contacting time corresponding with the frequency below the transverse resonance frequency helps to reduce because the distortion due to the transverse vibration;
4) low atmospheric pressure or vacuum can help to reach the resolution of raising, because eliminate the heat conduction by air fully.
5) the alternative of ball bearing parallel alignment 240-250 can be to use piezoelectric tilt motor and bulk of optical feedback;
6) parallel alignment mechanism and motor can all be in substrate or mould.
Although describe the present invention with reference to some embodiment, it will be appreciated by those skilled in the art that and to carry out various changes and can replace to equivalent and do not depart from the scope of the present invention.In addition, the scope that can carry out many modifications and do not break away from it so that particular condition or material adapt to instruction of the present invention.Therefore be intended to the invention is not restricted to disclosed specific embodiment, but the present invention will comprise all embodiment in the scope that falls into claims.In this regard, the embodiment according to selecting need not to relate to all components/steps of describing in the accompanying drawing.In addition, it is contemplated that many other variations except the variation that above refers explicitly to.For example can relate in the device of Fig. 1 unshowned be used to regulating heat conducting other material layer.Those skilled in the art are also with clear, use the feature of describing among the embodiment that can describe and vice versa in the 1st chapters and sections in the 2nd chapters and sections.More generally, can be combined in the feature of describing in the 1st chapters and sections with different modes.
Label list
100 moulds
101 mould structure sides
110 die main bodies
120 low thermal conductivity material layers
130 mould structures
140 mould structure patterns
200 receiver main bodys
210 thermal decomposition polymer films
210 polymer resist films
220 substrates
T
dThe decomposition temperature of polymer film
T
gThe Glass Transition of polymer film or melt temperature.
Claims (15)
1. nanometer lithographic plate printing method comprises:
(S10) is provided:
Mould (100) comprises the structure (130) with nanoscale yardstick in the side (101) of described mould, and described structure forms pattern pattern (140); And
Thermal decomposition polymer film (210) on the substrate (220), relative with a described side of described mould,
Wherein said structure is heated to the decomposition temperature (T of described polymer film
d) more than;
Make described structure contact (S20) with described polymer film with the part of thermal decomposition (S30) itself and described structural correspondence; And
Remove (S50) described structure from described polymer film.
2. nanometer lithographic plate printing method according to claim 1 wherein, making described structure contact (S20) before with described polymer film, further maintains described substrate the glass transformation temperature (T of described polymer film
g) following temperature, and wherein preferably, described structure is contacted with described polymer film comprise to make described structure approach (S40) to realize with it thermo-contact and to cool off described structure towards described substrate (220).
3. according to claim 1 or 2 described nanometer lithographic plate printing methods, wherein carrying out makes described structure contact (S20) with described polymer film to unwind and/or its molecule of desorb (S30), and the described polymer film that wherein preferably, provides is so that can carry out and make described structure contact (S20) with described polymer film to come its part of thermal decomposition according to endothermic decomposition.
4. nanometer lithographic plate printing method according to claim 3, the described polymer film that wherein provides comprises via intermolecular non-covalently cross-linked in fact molecular network, and wherein execution makes described structure contact (S20) with described polymer film with its molecule of desorb (S30).
5. nanometer lithographic plate printing method according to claim 4, the average molecular mass of the molecule in the described polymer film that wherein provides is between 100Da and 2000Da, preferably from the scope of 150Da to 1000Da, and wherein more preferably via the crosslinked described molecule of hydrogen bond.
6. nanometer lithographic plate printing method according to claim 3, the described polymer film that wherein provides comprises the polymeric material with the polymer chain that can unwind when thermostimulation, and wherein execution makes described structure contact (S20) with described polymer film with the polymer chain of (S30) the described polymeric material that unwinds.
7. nanometer lithographic plate printing method according to claim 6, the described polymer film that wherein provides comprise poly-adjacent benzene, and wherein preferably, described polymer film has 125 ℃ ± 20 ℃ glass transformation temperature and 150 ℃ ± 30 ℃ heat decomposition temperature.
8. the described nanometer lithographic plate printing method of arbitrary claim in 7 according to claim 1, wherein said mould comprises main body (110) and material layer (120), described main body (110) preferably includes crystalline silicon, described material layer (120) preferably includes monox, and described material layer (120) is between described main body and described structure and have, preferably low at least ten times and a more preferably low at least fiftyfold temperature conductivity more significantly lower than the temperature conductivity of described main body.
9. nanometer lithographic plate printing method according to claim 8, the corresponding thermal linear expansion coefficient of described material layer (120) and described main body (110) differs and is less than 5 times.
10. according to claim 8 or 9 described nanometer lithographic plate printing methods, wherein said material layer (120) have between 1 and 30 micron, be preferably 6 ± 4 microns thickness.
11. the described nanometer lithographic plate printing method of arbitrary claim in 11 according to claim 1, one or more structure in the described structure (130) of the described mould that wherein provides has following height in the direction vertical with described polymer film, and the average thickness of the described polymer film of this aspect ratio is larger, preferably larger than three times of the average thickness of described polymer film.
12. the described nanometer lithographic plate printing method of arbitrary claim in 12 according to claim 1 wherein maintains described substrate temperature the glass transformation temperature (T of described polymer film
g) below, and wherein make described structure contact (S20) before with described polymer film, heat described structure in the volatile temperature of the decomposition product of described polymer film, and wherein make described structure contact with described polymer film (S20) comprise make described structure on the described substrate approaching (S40) to realize with it thermo-contact and to cool off described substrate.
13. nanometer lithographic plate printing method according to claim 12, wherein the temperature difference between the structure (130) of described substrate (220) and described heating is at least before 100 ℃, preferably is at least 200 ℃ making described structure contact (S20) with described polymer film.
14. a nanometer offset printing device (10) comprising:
Mould (100) comprises the structure (130) with nanoscale yardstick in the side (101) of described mould, and described structure forms pattern pattern (140); And
Substrate (220) has the thermal decomposition polymer film (210) relative with a described side (101) of described mould thereon;
Heating arrangement (104) is arranged to the decomposition temperature (T that described structure is heated to described polymer film
d) more than; And
Actuating device (102,240,250) is used for making described structure to contact (S20) with described polymer film with the part of thermal decomposition itself and described structural correspondence and from described polymer film removal (S50) described structure.
15. nanometer offset printing device according to claim 14 also comprises the glass transformation temperature (T that is suitable for described substrate is maintained at described polymer film
g) cooling device (230) of following temperature.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1207464.7 | 2012-04-30 | ||
| GB1207464.7A GB2501681A (en) | 2012-04-30 | 2012-04-30 | Nanoimprint lithographic methods |
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| Publication Number | Publication Date |
|---|---|
| CN103376646A true CN103376646A (en) | 2013-10-30 |
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ID=46330508
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
| CN (1) | CN103376646A (en) |
| DE (1) | DE102013206755B4 (en) |
| GB (1) | GB2501681A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107827076A (en) * | 2015-12-31 | 2018-03-23 | 陶氏环球技术有限责任公司 | Nano structural material structures and methods |
| WO2018119897A1 (en) * | 2016-12-29 | 2018-07-05 | 苏州中科纳福材料科技有限公司 | Transfer film having photonic crystal structure and manufacturing method for transfer film |
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| US10955599B2 (en) | 2016-04-01 | 2021-03-23 | Infineon Technologies Ag | Light emitter devices, photoacoustic gas sensors and methods for forming light emitter devices |
| US10347814B2 (en) | 2016-04-01 | 2019-07-09 | Infineon Technologies Ag | MEMS heater or emitter structure for fast heating and cooling cycles |
| US10681777B2 (en) | 2016-04-01 | 2020-06-09 | Infineon Technologies Ag | Light emitter devices, optical filter structures and methods for forming light emitter devices and optical filter structures |
| US10895806B2 (en) | 2017-09-29 | 2021-01-19 | Canon Kabushiki Kaisha | Imprinting method and apparatus |
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| US20060173125A1 (en) * | 2004-08-18 | 2006-08-03 | Lawson L R | Nanoimprint lithography method and product |
| US7491049B2 (en) * | 2005-09-30 | 2009-02-17 | Hon Hai Precision Industry Co., Ltd. | Apparatus for hot embossing lithography |
| KR100868300B1 (en) * | 2007-03-20 | 2008-11-11 | 한국생산기술연구원 | Rapid thermal pressing rtp apparatus for nanoimprint lithography |
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- 2012-04-30 GB GB1207464.7A patent/GB2501681A/en not_active Withdrawn
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- 2013-04-11 CN CN2013101255126A patent/CN103376646A/en active Pending
- 2013-04-16 DE DE102013206755.0A patent/DE102013206755B4/en not_active Expired - Fee Related
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| US3984253A (en) * | 1974-04-22 | 1976-10-05 | Eastman Kodak Company | Imaging processes and elements therefor |
| EP0126214A2 (en) * | 1983-05-16 | 1984-11-28 | International Business Machines Corporation | Process for making a lithographic mask |
| CN102265218A (en) * | 2009-01-30 | 2011-11-30 | 国际商业机器公司 | Method for patterning nano-scale patterns of molecules on surface of material |
| CN101963758A (en) * | 2009-07-23 | 2011-02-02 | 国际商业机器公司 | Calixarenes mixed molecules glass photoresist and using method |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE102013206755B4 (en) | 2015-08-27 |
| GB2501681A (en) | 2013-11-06 |
| DE102013206755A1 (en) | 2013-10-31 |
| GB201207464D0 (en) | 2012-06-13 |
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