阅读说明：本技术 具有印模结构的印模及其制造装置和方法 (Stamp having stamp structure and manufacturing apparatus and method thereof ) 是由 D.特赖布尔迈尔 于 2013-06-20 设计创作，主要内容包括：本发明涉及制造用于在基底或软印模上施加微-和/或纳米结构的具有印模结构的结构印模的方法,其中所述印模结构至少部分地用涂层涂覆。另外,本发明涉及相应的结构印模以及制造用于在基底或软印模上施加微-和/或纳米结构的具有印模结构的结构印模的装置,其中所述装置具有用于涂覆所述印模结构的涂覆工具。(The invention relates to a method for producing a structured stamp with a stamp structure for applying micro-and/or nanostructures on a substrate or a soft stamp, wherein the stamp structure is at least partially coated with a coating. In addition, the invention relates to a corresponding structural stamp and to a device for producing a structural stamp having a stamp structure for applying micro-and/or nanostructures on a substrate or a soft stamp, wherein the device has a coating tool for coating the stamp structure.)

1. Method for manufacturing a structure stamp with a stamp structure for applying microstructures and/or nanostructures on a substrate or a soft stamp, wherein the stamp structure is at least partially coated with a coating, wherein the coating is:

-is electrically conductive and is electrically conductive,

-is grounded, and

transparent to UV light.

2. Stamp with stamp structure for applying nanostructures on a substrate or a soft stamp, wherein the stamp structure is at least partially coated with a coating, wherein the coating is:

-is electrically conductive and is electrically conductive,

-is grounded, and

Transparent to UV light.

3. Device for producing a structured stamp with a stamp structure for applying microstructures and/or nanostructures on a substrate or a soft stamp, wherein the device has a coating means for coating the stamp structure, wherein the coating is:

-is electrically conductive and is electrically conductive,

-is grounded, and

transparent to UV light.

Technical Field

the present invention relates to a method of manufacturing a stamp with a stamp structure for applying nanostructures on a substrate or a soft stamp, a corresponding device and a structure stamp manufactured by the method.

Background

In the semiconductor industry, materials have to be subjected to structuring processes in order to be able to produce corresponding functional elements. One of the most important structuring processes in the last decades has so far been photolithography.

in recent years, however, in addition to lithography, imprint technology has become recognized as a new alternative structuring technology, which is not only, but is still currently used primarily for structuring highly symmetrical, in particular repetitive, structural elements. By means of imprint techniques, the surface structure can be built up directly in the imprint material by means of a stamping process. The advantages resulting therefrom are apparent. The chemicals for development and etching that are still required for the lithographic process can be omitted. In addition, it is now possible to imprint structures in the nanometer range in size, but with conventional lithography they can only be produced by means of extremely complex and particularly expensive apparatuses.

In imprint technology, two types of stamps are distinguished, namely a hard stamp and a soft stamp, theoretically various stamping methods can be performed using either a hard stamp or a soft stamp, however, there are many technical and economic reasons for using only a hard stamp as a so-called master stamp per se and for each time necessary a soft stamp is formed from the master stamp, which is subsequently used as the actual structural stamp.

Although a hard stamp has the advantage that it can be directly manufactured from a component of a material having high strength and high stiffness by a suitable method, such as e-beam lithography or laser beam lithography. Such a hard printing tool has a very high hardness and is therefore more or less wear-resistant. However, this high strength and wear resistance is especially faced with the high cost required to make hard stamps. Even if the hard stamp can be used for several hundred embossing steps, it no longer has reliable wear resistance over time. In addition, it is technically difficult to release the hard stamp from the impression compound. The hard printing mold has a relatively high bending strength. They do not deform particularly well and therefore ideally have to be lifted in the normal direction (normarichtung). In the demolding of the hard stamp after the imprinting process, damage to the imprinted nano-and/or microstructure usually results here, since the hard stamp has a very high rigidity and can therefore damage the micro-and/or nanostructure of the imprinted imprint material that has just been formed. In addition, the substrate may have defects that may subsequently lead to damage or destruction of the hard stamp. However, if a hard stamp is used only as the master stamp, the process of forming a soft stamp from this master stamp is very well controllable and is accompanied by very little wear of the master stamp.

A soft stamp can very easily be manufactured from a master stamp (hard stamp) by a replication method. In this case, the master stamp is a negative type corresponding to the soft stamp. The soft stamp is thus imprinted on the master stamp, after which it is released from the mold and subsequently used as a structure stamp to imprint the stamp structure on the substrate. Compared to hard stamps, soft stamps can be removed from the imprint material significantly more easily, milder and less problematically. In addition, any number of soft stamps can be molded from the master stamp. After the soft stamp has a certain degree of wear, the soft stamp is discarded and a new soft stamp is formed from the master stamp.

A problem of the current state of the art is that soft stamps, due to their chemical structure, have a very high absorption capacity, especially for other molecular compounds. They are therefore permeable to other molecular compounds than hard stamps consisting essentially of metal, ceramic or glass. In the case of metal and ceramic microstructures, the absorption of molecular species is in most cases excluded, however in the case of special hard stamps it can also lead to absorption of molecular species.

During an imprint process that utilizes imprint material, the soft stamp typically absorbs a portion of the imprint material. This absorption leads to a number of undesirable effects.

The soft stamp expands due to absorption of imprint material molecules first. This swelling is particularly problematic in the micro-and/or nanostructured regions on the surface of the soft stamp, since a small number of imprint material molecules is already sufficient to deform the micro-and/or nanostructures. As the soft stamp is used multiple times, it absorbs more and more molecules of the imprint material during use. The absorption of imprint material molecules decisively reduces the service life of the soft stamp. The expansion can be measured directly by different probes, such as Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM), etc., or indirectly via volume and/or weight gain. However, the measurement of volume and/or weight gain requires a measuring device with very high resolution. For example, it is conceivable to measure this weight gain by micro-and/or nano-gravimetric method.

In addition, the impression compound is cured thermally or by electromagnetic radiation. In particular in curing by electromagnetic radiation, molecules of the imprint material that have partially penetrated into the stamp have an adverse effect on the exposure time of the entire imprint material. The reason for this is the solidification of the imprint material molecules that have penetrated into the soft stamp. The imprint material molecules in the soft stamp solidify and thus become less transparent and thus reduce the intensity of the electromagnetic radiation that propagates into the actual imprint material. This problem is equally important for soft and hard stamps.

adhesion of the soft stamp is a third problem. The soft stamp is mainly composed of a polymer having similar physical and/or chemical properties as the imprint material. Thus causing the surface of the soft stamp to adhere to the imprint material, which has a detrimental effect on the release properties of the soft stamp.

Disclosure of Invention

It is therefore an object of the present invention to improve the manufacture of a structural stamp for imprint techniques, thereby improving the performance of the structural stamp in terms of lifetime and quality of formation.

this object is achieved by the method and the imprint stamp of the present invention. All combinations of at least two of the features of the invention are also encompassed within the scope of the invention. In the case of the value ranges given, values lying within the abovementioned limits should also be regarded as being disclosed as limit values and claimed in any combination.

The present invention relates to a stamp, preferably a soft stamp, which allows an extremely easy release of the stamp from an imprint material, preventing its swelling and protecting it from contamination by the actual imprint material, by means of a coating of the stamp structure of the present invention, according to the present invention, the coating is thus especially impermeable with respect to the imprint material, this is a particular advantage of the present invention when the hydrophilicity and hydrophobicity alternate between the imprint material and the coating of the structure stamp of the present invention, if the imprint material is hydrophobic, the coating of the structure stamp of the present invention should be hydrophilic and vice versa, however, in very particular, when the structure stamp and the imprint material are both hydrophobic, this may be particularly advantageous, since the coating of the structure stamp of the present invention may be selected with always a material having a small adhesion property with respect to the imprint material, if the imprint material is hydrophobic, this is therefore advantageous according to the present invention, also when the coating of the present invention is impermeable to molecules of the imprint material, this may be additionally advantageous according to the present invention, when the coating of the present invention is as thin as possible, to minimize damage in the use of the soft stamp, especially when the surface of the imprint material is not permeable to imprint material, it may be less than a smooth or more preferably less than a smooth surface, and thus may be more effectively connected to a smooth surface, preferably a smooth surface, such as a less than a smooth surface, as a smooth surface, preferably a smooth surface, as a smooth surface, more effectively as a smooth surface, more effectively as a surface, preferably a surface, more effectively as a surface, preferably a surface, more effectively as less than a smooth as a smooth surface under the present invention, preferably a smooth surface under the present invention, more effectively under the present invention, a smooth surface under the average roughness of a smooth surface under the present invention, a less than a smooth, a smooth surface under the present invention, a more effectively under the.

In a very particular embodiment, the coating of the invention is electrically conductive. Thereby preferably preventing or at least reducing electrostatic charging. Still more preferably, the conductive coating of the present invention can be made grounded so as to conduct out the electric charges generated on the surface thereof. By means of the electrically neutral surface, the attraction of particles, in particular the electrostatic attraction, is hindered or completely eliminated and thus the longer time-consuming cleaning of the stamp is increased. Preferably, the ground contact contacts the edge of the coating of the present invention.

Hydrophilic is understood as the high ability of the surface of a substance to interact with water. Hydrophilic surfaces are predominantly polar and interact reasonably well with the permanent dipoles of the fluid molecules, preferably with water. Surface hydrophilicity was quantified by contact angle measurement. Here, the hydrophilic surface has a very small contact angle. If the coating according to the invention must have a hydrophilic surface in order to be able to be released from the impression compound as easily as possible, the following value ranges should be applied according to the invention: the hydrophilic surface of the present invention particularly has a contact angle of less than 90 °, preferably less than 60 °, more preferably less than 40 °, still more preferably less than 20 °, most preferably less than 1 °.

hydrophobicity is understood as the low ability of the surface of a substance to interact with water. Hydrophobic surfaces are predominantly non-polar and have little permanent dipolar interaction with fluid molecules. If the coating according to the invention in one embodiment of the invention has a hydrophobic surface in order to be able to be removed as easily as possible from the impression compound, the following value ranges should be applied according to the invention: the hydrophobic surfaces of the present invention particularly have a contact angle of more than 90 °, preferably more than 100 °, more preferably more than 120 °, still more preferably more than 140 °, most preferably more than 160 °.

The stamp of the present invention is particularly an imprint stamp for use in imprint techniques. The stamp is designed as a hard stamp for making a soft stamp or preferably as a soft stamp for imprinting a substrate. It is also conceivable to use the inventive coating directly for imprinting the imprint material and not only as a hard stamp for the master stamp.

By means of the coating according to the invention, release of the stamp from the imprint material can be achieved by making the coating preferably have a small adhesion to the imprint material, without damaging and/or (partially) destroying the structure. The ability to adhere between two surfaces can be best described by energy per unit surface, i.e. the energy surface density. Which is understood to be the energy required to separate two interengaging surfaces from one another again along a unit surface. The adhesion between the inventive imprint material and the structural stamp is in particular less than 2.5J/m²Preferably less than 1J/m²More preferably less than 0.1J/m²And still more preferably less than 0.01J/m²Most preferably less than 0.001J/m²the maximum possible is preferably less than 0.0001J/m²Most preferably less than 0.00001J/m². Demolding is thus easier, faster, more efficient and more economical than a stamp or a hard stamp without a coating. More economical, inter alia, because the increased demolding speed can increase the number of embossing steps per time unit. In addition, the service life of the stamp is drastically increased, thereby also reducing the manufacturing costs.

In addition, because of the sealing properties of the coating, swelling of the structural stamp, in particular of the soft stamp, is prevented by the coating, since no impression compound can penetrate into the soft stamp. Accordingly, deformation of the stamp structure is avoided to the greatest extent.

In addition, if the coating blocks absorption of the imprint material into the stamp structure, the exposure time of the imprint material is reduced by the stamp coating. This is particularly advantageous according to the invention if the imprint material is exposed through the structured stamp. The coating according to the invention is therefore preferably predominantly transparent to the electromagnetic radiation used. Since most imprinting materials are cured by UV light, the coatings of the present invention are preferably transparent to UV light. The coating according to the invention is therefore transparent in particular in the wavelength range from 5000 nm to 10 nm, preferably from 1000nm to 100nm, more preferably from 700 nm to 200 nm, most preferably from 500 nm to 400 nm.

In particular in addition to the coating, the stamp surface is preferably designed to have low adhesion properties to the imprint material.

according to another aspect of the invention is based on coating the surface of the stamp, preferably a soft stamp, with a coating, preferably a metal coating, by the coating method of the invention.

The stamp structure and/or the structural stamp itself is in particular at least predominantly, preferably completely, composed of at least one of the following materials:

● polymers, in particular

o Polydimethylsiloxane (PDMS)

O perfluoropolyether (PFPE)

O polyhedral oligomeric silsesquioxanes (POSS)

o Polydimethylsiloxane (PDMS)

O tetraethyl orthosilicate (TEOS)

O poly (organo) siloxanes (silicones)

Thermoplastic O

O thermosetting plastic

● Metal

● ceramic

● glass.

in the case of the soft stamp of the present invention, the stamp structure is preferably composed of Polydimethylsiloxane (PDMS). Furthermore, it is conceivable according to the invention to manufacture the stamp, in particular the stamp structure, from a material combination of the above-mentioned materials. It is also conceivable to use a stamp and a back plate in a kit, wherein the stamp and the back plate consist in particular of different materials. The use of a plurality of different materials results in a single or combined stamp being an advantageous hybrid stamp of the present invention. Here, the back plate may be used to reinforce the stamp. However, a back plate which is extremely flexible and serves only as a carrier for the stamp is also conceivable. In this case, the backsheet has in particular a thickness of less than 2000 μm, preferably less than 1000 μm, more preferably less than 500 μm, most preferably less than 100 μm.

The coating according to the invention is, however, particularly effective when the structural stamp or at least the material of the structural stamp is at least partly composed of a material capable of absorbing the imprint material. Thus, stamp structures of the following materials are particularly protected by the coating of the present invention:

● Polydimethylsiloxane (PDMS)

● Polymer

● perfluoropolyether (PFPE)

● ceramics.

The coating method of the present invention is preferably one of the following methods:

● Chemical Vapor Deposition (CVD)

● Physical Vapor Deposition (PVD)

● PE-CVD

● electrochemical deposition

● Atomic Layer Deposition (ALD)

● Molecular Layer Deposition (MLD).

according to the invention, preference is given to a CVD process, which is used in particular for depositing chromium.

According to the invention, the following material/material classes are used in particular as coating materials for at least partially coating the stamp structure:

● Metal

○ Cr、Be、Wi、Cd、Ga、In、Ir、Mg、Mn、Mo、Os、Pa、Rh、Ru、Ta、Ti、V、Zn、Sn、Zr、Cu、Ni、Co、Fe、Pt、Ag、Au、Pb、W、Al

● semiconductor material

O Si, Ge, alpha-Sn, Se, Te, B, GaP, GaAs, InP, InSb, InAs, GaSb, GaN, AlN, InN, AlxGa1-xAs, InxGal-xN or oxides of the above materials

● ceramic

O non-oxide ceramics (carbides, nitrides, borides, silicides)

○ Si₃N₄、BN、SiC

● oxide ceramic

○ Al₂O₃、MgO、ZrO₂、TiO、Ti₂O₃、TiO₂

O suboxide

● glass

O borosilicate glass, Quartz (SiO)₂）

● Polymer

● organic molecules.

for the coating according to the invention, it is preferable to select materials with low adhesion to the impression compound, in particular the following materials:

● metal, especially

○ Cr、Be、Wi、Cd、Ga、In、Ir、Mg、Mn、Mo、Os、Pa、Rh、Ru、Ta、Ti、V、Zn、Sn、Zr、Cu、Ni、Co、Fe、Pt、Ag、Au、Pb、W、Al。

The present invention relates to:

1. Method for manufacturing a structure stamp with a stamp structure for applying microstructures and/or nanostructures on a substrate or a soft stamp, wherein the stamp structure is at least partially coated with a coating, wherein the coating is:

-is electrically conductive and is electrically conductive,

-is grounded, and

Transparent to UV light.

The method of claim 1, wherein the stamp structure and/or the structure stamp is formed predominantly of at least one of the following materials:

● Polymer

● Metal

● ceramic

● glass.

The method of claim 1, wherein the stamp structure and/or the structure stamp is formed entirely of at least one of the following materials:

● Polymer

● Metal

● ceramic

● glass.

The method of claim 2 or 3, wherein the polymer is selected from the group consisting of polydimethylsiloxane, perfluoropolyether, thermoplastics, and thermosets.

the method of any of claims 1-3, wherein the coating is applied by at least one of the following methods:

● chemical vapor deposition

● physical vapor deposition

● plasma enhanced chemical vapor deposition

● electrochemical deposition

● atomic layer deposition

● molecular layer deposition.

Method according to one of claims 1 to 3, wherein at least one of the following material/material classes is used as coating material for coating the stamp structure:

● Metal

● semiconductor material

● ceramic

● glass

● Polymer

● organic molecules.

The method of claim 6, wherein the metal is selected from the group consisting of Cr, Be, Wi, Cd, Ga, In, Ir, Mg, Mn, Mo, Os, Pa, Rh, Ru, Ta, Ti, V, Zn, Sn, Zr, Cu, Ni, Co, Fe, Pt, Ag, Au, Pb, W, and Al.

The method of claim 6, wherein the semiconductor material is selected from the group consisting of Si, Ge, α -Sn, Se, Te, B, GaP, GaAs, InP, InSb, InAs, GaSb, GaN, AlN, InN, AlxGa1-xAs, and InxGal-xN.

The method of claim 6, wherein the ceramic is selected from the group consisting of non-oxide ceramics and oxide ceramics.

The method of claim 9, wherein the non-oxide ceramic is selected from the group consisting of carbides, nitrides, borides, and silicides.

The method of claim 10, wherein the non-oxide ceramic is selected from Si₃N₄、BN、SiC。

the method of claim 9, wherein the oxide ceramic is selected from Al₂O₃、MgO、ZrO₂、TiO₂、SiO₂And suboxides.

The method of claim 12, wherein the suboxide ceramic is selected from the group consisting of TiO and Ti₂O₃。

The method of any one of claims 1-3, wherein the coating comprises a metal.

The method according to any of claims 1 to 3, wherein the structural stamp or the soft stamp is releasable from the imprint material by bending thereof.

The method according to any of claims 1-3, wherein the structural or soft stamp is impermeable to imprint material molecules.

The invention also relates to:

17. Stamp with stamp structure for applying nanostructures on a substrate or a soft stamp, wherein the stamp structure is at least partially coated with a coating, wherein the coating is:

-is electrically conductive and is electrically conductive,

-is grounded, and

Transparent to UV light.

The stamp of claim 17 wherein the stamp structure is comprised of a cured polymer.

The stamp of claim 18 wherein the cured polymer is an elastomer.

The stamp of claim 18, wherein the cured polymer is a siloxane.

the stamp of claim 18, wherein the cured polymer is polydimethylsiloxane.

A stamp as claimed in any one of the claims 17-21, wherein the coating comprises a metal.

Stamp according to one of claims 17-21, wherein the structural stamp or the soft stamp is releasable from the imprint material by bending thereof.

stamp according to one of claims 17-21, wherein the structural stamp or the soft stamp is impermeable for imprint material molecules.

The invention also relates to:

25. Device for producing a structured stamp with a stamp structure for applying microstructures and/or nanostructures on a substrate or a soft stamp, wherein the device has a coating means for coating the stamp structure, wherein the coating is:

-is electrically conductive and is electrically conductive,

-is grounded, and

Transparent to UV light.

Drawings

Figure 1 shows a schematic cross-sectional view of a stamp in a first manufacturing step according to the invention,

FIG. 2 shows a schematic cross-sectional view of a stamp in a second manufacturing step of the invention, an

fig. 3 shows a schematic cross-sectional view of the stamp in a third manufacturing step of the invention.

Detailed Description

In a particularly preferred embodiment, the stamp is first coated with the coating material according to the invention and then additionally coated with an anti-adhesion layer in order to additionally reduce the adhesion between the coating material and the impression compound. The anti-adhesion layer is preferably an organic molecule with rather low adhesion properties to the imprint material. If the stamp is already impermeable to the imprint material molecules, as is usually the case for e.g. metal, ceramic or glass stamps, the coating according to the invention as a diffusion barrier can be dispensed with and the stamp can be coated directly with an anti-adhesion layer (in this case as the coating according to the invention). At least one advantageous effect in terms of release properties on the basis of adhesion is thus obtained.

According to a further advantageous embodiment of the present invention, only the stamp surface of the stamp structure, i.e. in particular the protrusions of the stamp structure which are in contact with the imprint material, are coated. This is especially interesting for nano-contact imprinting.

In a particular embodiment, the entire surface of the stamp structure of the stamp is coated with the coating according to the invention.

The layer thickness of the coating according to the invention is in particular less than 1 mm, preferably less than 100 μm, more preferably less than 10 μm, most preferably less than 1 μm, most probably preferably less than 100nm, most preferably less than 10 nm.

The extremely small layer thickness also has a favourable effect on the transparency of the electromagnetic radiation used. A solid can absorb only photons that interact with particles (e.g., electrons) or quasiparticles (particularly optical phonons) in the solid. This effect is well known to every physicist. Although this interaction cannot now be avoided, the number of photons can be increased by the intensity of the electromagnetic radiation or the number of particles (or quasiparticles) in the solid can be reduced according to the invention by reducing the layer thickness, so that the first, i.e. photons, dominates the second, i.e. particles and quasiparticles. Thus, the solid no longer participates in the excitation with the particles (or quasiparticles) and, according to the invention, photons are enabled to penetrate the practically non-transparent solid by reducing the layer thickness of the coating. The solid is at least partially transparent due to the layer thickness. It is thus disclosed that the small thickness of the coating of the invention has a favourable effect on the number of photons penetrating the coating. This in turn has a favourable effect on the curing of the impression compound covered by the coating.

In the UV curing of the impression compound, the coating material according to the invention is preferably at least partially transparent in the wavelength range of the electromagnetic radiation which crosslinks the impression compound. Herein, the transparency is more than 0%, preferably more than 20%, more preferably more than 50%, most preferably more than 80%, most probably preferably more than 95%. The wavelength range for the optical transparency is in particular from 100nm to 1000nm, preferably from 150 nm to 500 nm, more preferably from 200 nm to 400 nm, most preferably from 250 nm to 350 nm.

The stamp, in particular the inventive coating, has a thermal conductivity as high as possible if the imprint material is thermally cured. The thermal conductivity here is greater than 0.1W/(m × K), preferably greater than 1W/(m × K), preferably greater than 10W/(m × K), most preferably greater than 100W/(m × K), most preferably greater than 1000W/(m × K).

the structure stamp with the coating is especially designed to be temperature stable. The structured stamp may in particular be used at a temperature above 25 ℃, preferably above 100 ℃, more preferably above 500 ℃, most preferably above 1000 ℃, most probably preferably above 1500 ℃.

The ratio between the coefficient of thermal expansion of the coating material and the coefficient of thermal expansion of the impression material is less than 10000, preferably less than 1000, more preferably less than 100, still more preferably less than 10, most preferably less than 5, most preferably exactly 1.

In other embodiments, the manufacture of a stamp 1 provided with a ground 4 and coated with a layer 5 according to the invention is disclosed.

In a first manufacturing step of fig. 1, a stamp 1 having a stamp surface 1o and structures 2 is fixed to a back plate 3.

In the second manufacturing step of fig. 2, a conductive layer, in particular a ring-shaped grounding member 4, is deposited on the back plate surface 3o of the back plate 3, preferably only laterally alongside the stamp 1, preferably only on the side edges.

In a third manufacturing step of fig. 3, the stamp 1 is coated with a coating 5 according to the invention, so that the coating 5 also contacts, and in particular covers at least predominantly, preferably completely, the ground 4 and thus creates an electrically conductive contact between the coating surface 5o and the ground 4.

The ground 4 preferably completely surrounds the die 2. The charge can be removed, for example, on the side 4s of the ground 4 through the lead line L1. Alternatively or additionally, it is also conceivable to make a bore 6 through the back plate 3 to remove the charge through the lead L2.

It is especially conceivable to deposit the grounding member 4 directly on the edge of the stamp 1 if the back plate 3 can be omitted.

reference numerals

1 impression

1o impression surface

2 structure

3 Back plate

3o surface of backboard

4 ground connection part

5 coating layer

5o coating surface

6 drilling

l1, L2 conductor.