• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    Procedure for transfer of micro- and/or nanostructured motifs to arbitrary surfaces. The present invention relates to a method of transferring high-resolution micro- and/or nanostructured motifs to arbitrary surfaces, from the use and manipulation of a sacrificial sheet. Furthermore, in the method of the present invention, the micro- and/or nanostructured motifs of the sacrificial sheet are transferred in such a way that they are in direct contact with the surface of interest, without the use of an adhesive material as an interface. Therefore, the present invention can be framed in the area of surface processing. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2775649A1
    申请号:ES201830750
    申请日:2018-07-24
    公开日:2020-07-27
    发明作者:Suñé Gemma Rius；López Olga Muntada；Francesc Xavier Pérez-Murano
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    [0002] Procedure for transferring micro- and / or nano-structured motifs to arbitrary surfaces
    [0004] The present invention refers to a process for transferring high resolution micro and / or nanostructured motifs to arbitrary surfaces, based on the use and manipulation of a sacrificial sheet. Furthermore, in the process of the present invention, the micro- and / or nanostructured motifs of the sacrificial sheet are transferred so that they remain in direct contact with the surface of interest, without the use of an adhesive material as an interface.
    [0006] Thus, the present invention can be found in the area of surface processing.
    [0008] BACKGROUND OF THE INVENTION
    [0010] The industrial interest in arranging micro and nano structures on surfaces is multiple. In the first place, the micro / nano-metric texturing allows to provide surfaces with functional properties, such as, for example, hydrophilicity, hydrophobicity, greater adherence, bacteriophobicity, optical or chromatic effects, and therefore , is relevant in a wide variety of applications (anti-fog, antimicrobial, self-cleaning, decoration, etc.). These properties provide added value to a wide variety of products. On the other hand, micro and nano structures, such as micro and nano particles, micro and nano threads, aligned and / or properly positioned, can provide surfaces with advanced functionalities. For example, arrays of semiconductor nanowires can be used as light emitters, or interconnected micro / nano metallic or semiconductor wires can be used as sensors.
    [0012] Conventional lithographic techniques such as optical lithography or electron beam lithography are used to achieve good definition and positioning of micro and nano structures on surfaces, which are very efficient in defining micro and nano patterns on flat surfaces with little roughness. Without However, most lithographic techniques cannot be used or have significant limitations in applying them to curved surfaces or certain types of substrates. Having nanometric motifs on surfaces of arbitrary morphology responds to needs that appear in various fields such as decoration, construction or the automotive industry, given that many objects that are used daily have curved surfaces. Ultimately, a high-resolution, precision, and flexible nanostructuring technology for surfaces would allow the creation of smart surfaces (in English 'smart surfaces') by including complex functionalities (for example, sensors that detect substances and emitters that emit signals).
    [0014] Most of the methods reported to date that do not use lithography to define or transfer motifs on arbitrary surfaces are based on defining the motifs by structuring a mold that is subsequently transported to the surface of interest where post-processing is carried out (WO2017201602A1, US2015202834A1 ). These methods present i) limitations regarding the (production and) transfer of motifs of arbitrary shape and size, understood as the ability to generate any design ( pattem), and ii) restrictions regarding the type of material that allows transfer, by only applying to certain materials or requiring mediating layers to improve adhesion.
    [0016] Consequently, it is necessary to develop new procedures for obtaining micro- and / or nanostructured motifs on surfaces of any morphology and size.
    [0018] DESCRIPTION OF THE INVENTION
    [0020] The present invention refers to a high precision method for obtaining high resolution micro- and / or nanostructured motifs on an arbitrary surface of interest, that is, on a receiving substrate of interest. It is based on defining patterns directly on top of a sacrificial or transfer sheet, which, once said patterns are defined, is separated from the initial substrate and placed on the surface of interest of the receiving substrate. In the process of the present invention, the micro- and / or nanostructured motifs, initially defined on the sacrificial or transfer sheet, are arranged, at the end of the process, in direct contact with the surface of interest of the receiving substrate.
    [0022] The process of the present invention is simple and requires a reduced number of steps. Unlike the methods known in the state of the art and currently used, it does not require the prior manufacture of a mold, and does not consist in structuring the sacrificial or transfer sheet, but in defining solid motifs on its surface and transferring them to the surface of interest of the receiving substrate.
    [0024] The process of the present invention allows the design of a great variety of micro- and nanostructured motifs. It can be carried out with a wide variety of materials of different nature such as metals, ceramics, etc., and is compatible with most standard micro- and nano-manufacturing processes, including microelectronics processes and is especially suitable to complement the replication processes, such as roll-to-roll printing or injection molding of plastics.
    [0026] The process of the present invention is of special interest in the structuring of molds for plastic injection and the structuring of printing rollers (roll-to-roll).
    [0028] He is also interested in structuring the target surfaces of receiving substrates to include functional properties such as color, hydrophobicity, hydrophilicity, self-washing or bacteriophobicity.
    [0030] The process of the present invention is also of interest in the manufacture of electronic, magnetic and / or optical devices where an electronic, magnetic and / or optical functionality is of interest. Other functionalities related, for example, to plasmonics and / or phonics are derived from the nanometric dimensions of the micro- and / or nano-structured motifs and are also of interest in the manufacture of electronic, magnetic and / or optical devices.
    [0032] In particular, the application of the transfer procedure of the present invention applied to complex, functional and / or active structures that allow adding intelligence to the surface (in English smart surfaces ).
    [0033] Finally, the method of the present invention is of interest in the transfer of motifs to surfaces of interest of reception substrates so that said motifs serve as a mask for a selective attack of said substrate,
    [0035] Therefore, in a first aspect, the present invention refers to a process for transferring micro- and / or nano-structured motifs onto a surface of interest (hereinafter the "process of the invention") characterized in that it comprises the following stages:
    [0036] a) depositing a sacrificial polymeric foil on a substrate to form a sacrificial foil-substrate system,
    [0037] b) generating micro- and / or nano-structured motifs on the surface of the sacrificial sheet of the system obtained in step (a) by lithography or deposition methods with or without a mask,
    [0038] c) separating the sacrificial sheet with the micro- and / or nanostructured motifs obtained in step (b) from the substrate by technically non-demanding mechanical means,
    [0039] d) place the sacrificial sheet on the surface of interest, leaving the micro- and / or nano-structured motifs of the sacrificial sheet obtained in step (c) in direct contact with the surface of interest, while the whole sacrificial sheet -surface of interest is immersed in water,
    [0040] e) drying the assembly obtained in step (d), and
    [0041] f) removing the sacrificial sheet from the assembly obtained in step (e) by physical, chemical methods or a combination thereof.
    [0043] In the process of the present invention, the term "micro- and / or nanostructured motifs" is understood to mean solid structures with lateral dimensions between 10 nm and 10 pm, and thickness less than 1 pm. The composition of said solid structures is metallic; the micro- and / or nanostructured motifs are composed of at least one metal or a metallic alloy. The composition of the micro- and / or nanostructured motifs can be layered
    [0045] By the term "surface of interest" is understood, in the present invention, as that surface of a receptor substrate where it is desired to generate micro- and nanostructured motifs.
    [0046] The target surface of the receptor substrate can be curved, machined, or prestructured. By "pre-structured surface" is understood, in the present invention, as that surface that has been processed prior to the transfer of the micro- and / or nanostructured motifs to define therein, for example, a set of structures, a certain relief, a certain roughness or texture, or a certain composition.
    [0048] The surface of interest is not limited to a single surface within the receptor substrate; It can contemplate different surfaces within the same receptor substrate that are physically separated from each other.
    [0050] Step (a) of the process of the invention relates to the deposition of a sacrificial or transfer polymeric sheet on a substrate to form a sacrificial sheet-substrate system.
    [0052] By the term "polymeric sacrificial or transfer sheet" refers to a sheet, usually composed mainly of a polymer, that is used to transfer the micro- and / or nanostructured motifs onto the surface of interest. The transfer or sacrifice foil is not part of the final piece with micro and / or nano-structured motifs.
    [0054] By the term "substrate" is understood in the present invention, as a stable and flexible substrate, to be able to be transferred without being damaged and to be able to conform to any surface of interest, that is to say, to any surface of the receiving substrate.
    [0056] The surface of the substrate can be curved, flat or structured. In a preferred embodiment of the present invention, the substrate of step (a) is a flat substrate.
    [0058] The choice of the sacrificial polymeric sheet and the substrate is key in the process of the present invention, since it must meet the condition that the sacrificial polymeric sheet has sufficient adhesion with the substrate but at the same time is easily removable from it, that is, the polymeric sheet must be easily detached from the substrate.
    [0059] The sacrificial polymeric sheet must be mechanically stable in order to be transported to another substrate / surface of interest. It is further advantageous that the sacrificial polymeric sheet is flexible to be able to conform to curved end substrates.
    [0061] Step (b) of the process of the invention refers to the generation of micro- and / or nano-structured motifs on the surface of the sacrificial sheet or transfer of the sacrificial sheet-substrate system obtained in step (a) by means of High resolution lithography or deposition methods with or without a mask.
    [0063] The micro- and / or nanostructured motifs are generated on the sacrificial or transfer sheet by consolidated techniques based on lithography, or deposition methods with or without a mask. These methods allow a good adherence of the micro- and / or nanostructured motifs to the sacrificial or transfer sheet. The micro- and / or nanostructured motifs printed on the sacrificial sheet will remain until the end of the procedure and will be printed on the surface of interest of the receiving substrate.
    [0065] The micro- and / or nanostructured motifs are composed of at least one metal or one metal alloy.
    [0067] In a preferred embodiment of the method of the present invention, the composition of the micro- and / or nanostructured motifs is layered, that is, the composition varies along its thickness.
    [0069] Examples of types of lithography are optical lithography, electron beam lithography, nano-printing lithography, atomic force microscopy based lithography, block copolymer based lithography, deposition methods with or without mask such as ion beam deposition focused, by focused electron beam, or shading mask deposition.
    [0071] Step (c) of the process of the present invention refers to separating the micro- and / or nano-structured sacrificial sheet obtained in step (b) from the substrate by mechanical means, for example, peeling off the polymeric layer manually by means of the help of tweezers.
    [0072] Step d) of the process of the invention refers to placing the sacrificial sheet on the surface of interest so that the micro- and / or nanostructured motifs of the sacrificial sheet obtained in step (c) are in direct contact with the surface of interest, the whole sacrificial sheet-surface of interest being immersed in water.
    [0074] As mentioned previously, the surface of interest of the receiving substrate can have any morphology: for example, the surface can be curved or it can be prestructured or machined. Examples of surfaces of interest are metal molds for plastic injection processes, printing rollers or curved pieces for decoration.
    [0076] In a specific implementation, the surface of interest may be previously immersed in a container with water and the sacrificial sheet is placed on it so that the micro- and / or nano-structured motifs of the sacrificial sheet are in direct contact with the surface of interest.
    [0078] The sacrificial sheet-surface of interest assembly must be immersed in water to promote adhesion. Simply placing the layer of polymeric patterns on the chosen substrate would not provide sufficient mechanical adhesion and this would possibly be non-uniform, that is, there would only be local contact between the sheet and the substrate. Adhesion is the bonding force at the contact interface between two materials (in this case, between the micro- and nano-motifs and the polymer), and is described as van der Waals forces. Sufficient adhesion is necessary to i) enable removal of the polymeric layer, while still maintaining the patterns on the desired arbitrary substrate, and
    [0079] ii) to favor the adhesion of the motifs to the substrate, that is, to enable their use, for example, in injection molding processes, to guarantee a certain durability and robustness of the mold.
    [0081] Adhesion at the microscopic level depends, on the one hand, on the roughness of both surfaces, but also on the degree of wetting of the intermolecular contact. In the transfer method of the present invention, adhesion is emphasized and facilitated by
    [0082] i) surface tension metal / water / polymer motifs, and
    [0083] ii) by the use of a flexible transfer foil.
    [0085] As mentioned above, the surface of interest where the motifs are transferred can have any morphology, for example the surface can be curved or it can be pre-structured or machined.
    [0087] Slow drying, i.e. evaporation of water under proper conditions, is also key to achieving the desired adhesion. Step (e) of the process of the invention refers to the drying of the sacrificial sheet-surface of interest assembly. For this step (e) to be effective, it is sufficient to allow the surface of interest-sacrificial sheet system to rest for a few hours under ambient conditions so that the remaining water is gradually and uniformly eliminated. Other alternatives such as drying at high temperature and / or in a low humidity environment may be equally convenient.
    [0089] The last step (f) of the procedure refers to the removal of the sacrificial sheet from the surface of interest by physical or chemical methods or a combination thereof. The removal method will depend on the material of the surface of interest, and you should selectively remove the transfer or sacrifice sheet without damaging the motifs to be transferred or the surface of interest.
    [0091] Examples of physical methods for removing the sacrificial foil include attack by argon ions or by oxygen plasma.
    [0093] In a preferred embodiment of the process of the present invention, chemical dissolution methods are used using solvents for organic materials such as acetone since the sacrificial or transfer sheet is of the polymeric type, and the motifs to be transferred to the surface of interest are composed of a metal or an alloy.
    [0095] Throughout the description and claims the word "comprise" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the invention will emerge partly from the description and partly from the practice of the invention. invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0097] BRIEF DESCRIPTION OF THE FIGURES
    [0099] FIG. 1. General sequence of the procedure of the invention
    [0101] FIG. 2. Specific description of an implementation of the method of the invention
    [0103] FIG. 3. Electron microscopy (SEM) images of motifs transferred to a flat and optically polished substrate (silicon substrate) using the method described in Figure 2 (A-I1).
    [0105] FIG. 4. (A) Photograph of a polished and curved steel sheet where micrometric and nanometric motifs have been transferred using the procedure described in figure 2. (BD) SEM images of the motifs transferred to the steel sheet in figure A using the method described in figure 2 (A-I2). The SEM image in figure D corresponds to a small area of the area shown in figure C.
    [0107] EXAMPLES
    [0109] The invention will be illustrated below by means of tests carried out by the inventors, which demonstrate the effectiveness of the product of the invention.
    [0111] In figure 1 the following differentiated stages of the process of the present invention can be observed:
    [0113] (A) Deposition of a sheet (1) (transfer or sacrifice sheet) on a flat substrate (2).
    [0114] The fact that the flat substrate is flat facilitates the use of lithography methods to produce the micro / nano structured motifs to be transferred.
    [0116] (B) The second step consists of generating the motifs (3) on the layer (1). The shape and positioning of the structures generated in this sacrificial sheet will be maintained at the end of the process on the receiving substrate.
    [0117] (C) The third step consists of separating the substrate from the sacrificial sheet (1) with the micro / nano structured motifs (3).
    [0119] (D) (E) The fourth step consists of transferring the inverted sheet (1) with the micro / nano structured motifs (3) to the receiving / interest substrate (4). The transfer or sacrifice sheet is transferred turned upside down, so that the micro-nano structured motifs (3) are in direct contact with the receiving substrate (4).
    [0121] (F) In the last step, the transfer sheet (1) is removed by physical or chemical methods, or a combination of both, obtaining the original motifs (3) on the surface of interest (4)
    [0123] In the following sequence of steps, see figure 2, the materials used experimentally are specified in parentheses.
    [0125] (A) First, a polymer sheet (1) (polyimide) is deposited on a very low roughness silicon substrate (optical polishing) so as not to limit the maximum resolution obtainable (2). Transfer foil:
    [0126] • allows the creation of a thin film on a flat substrate by spin coating (deposition by rotation)
    [0127] • It is compatible with nano-manufacturing processes based on lithography (and specifically electron beam lithography, metal deposition and lift-off), which allows the definition of structures on its surface
    [0128] • It is easily removable from the initial flat substrate • It is mechanically stable to be transported to another substrate
    [0129] • Is flexible enough to conform to curved, pre-structured or machined end surfaces
    [0130] • Can be removed by selective etching without damaging the motifs to be transferred or the surface of interest, for example by etching with oxygen plasma.
    [0131] (B) The second step consists of an electron beam lithography process to define the motifs with high precision on the micro / nano scale. This process includes: the deposition of the layer of a sensitive resin (3) (PMMA), its irradiation with an electron beam and its development (MIBK: IPA), leaving areas of the covered polyimide and areas of the polyimide uncovered
    [0133] (C) It is desirable to deposit an additional layer of conductive material to avoid the accumulation of electrical charges in the polyimide and PMMA during the process of exposure to the electron beam. This additional layer can be easily removed later by immersion in water.
    [0135] The next phase is the transfer of the patterns defined in resin to the silicon substrate or to the curved steel sheet, which consists of:
    [0137] (D) The deposition of a thin layer of metal (4) (Ti + Au) followed by (E) the removal of the electron sensitive resin.
    [0139] (F) The separation of the initial substrate from the flexible polymeric layer with the metal micro / nano motifs is very simple. It is done mechanically, and can simply consist of peeling off the layer manually, for example, with the help of tweezers.
    [0141] (G) The separated layer is placed flipped over pure water in a container.
    [0143] (H1) The transfer to the surface of interest of the receiving substrate has been carried out manually. It is based simply on picking up the polymeric layer decorated with the metal motifs and placing it in contact with the surface of interest of the receiving substrate. When turned upside down, the metal motifs are in direct contact with the target surface of the receiving substrate. Transfers have been made to a flat substrate (H1) (silicon substrate) and to a curved substrate (H2), steel sheet.
    [0145] (I) Once it has dried, the polymeric layer used in the transfer is removed, by a conventional etching method, that is, a reactive ion attack.
    [0146] As can be seen in Figures 3 and 4, the method allows the reliable transfer of motifs, with sub-micrometric resolution (it has been demonstrated for motifs with lateral dimensions slightly less than 300 nm) on both flat and curved surfaces. The maximum transfer area so far has been approximately 25 cm2, although the method is expandable both in resolution (below 50 nm) and in maximum area (700 cm2).
    权利要求:
    Claims (5)
    [1]
    1. A process for transferring micro- and / or nanostructured motifs onto a surface of interest characterized in that it comprises the following steps:
    a) depositing a sacrificial polymeric foil on a substrate to form a sacrificial foil-substrate system,
    b) generating micro- and / or nano-structured motifs on the surface of the sacrificial sheet of the system obtained in step (b) by lithography or deposition methods with or without a mask,
    c) separating the micro- and / or nanostructured sacrificial sheet obtained in step (b) from the substrate by mechanical means,
    d) place the sacrificial sheet on the surface of interest leaving the micro- and / or nano-structured motifs of the sacrificial sheet obtained in step (c) in direct contact with the surface of interest, where the whole sacrificial sheet -surface of interest is immersed in water,
    e) drying the assembly obtained in step (d), and
    f) removing the sacrificial sheet from the assembly obtained in step (e) by physical, chemical methods or a combination thereof.
    [2]
    2. The method according to claim 1, wherein the substrate of step (a) is a flat substrate.
    [3]
    3. The method according to any of claims 1 or 2, wherein the micro- and / or nanostructured motifs are composed of at least one metal or an alloy.
    [4]
    4. The method according to claim 3, wherein the composition of the micro- and / or nanostructured motifs is layered.
    [5]
    5. The process according to any of claims 1 to 4, wherein, in step (f), chemical dissolution methods are used.
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    同族专利:
    公开号 | 公开日
    ES2775649B2|2020-12-01|
    WO2020021142A1|2020-01-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20060048885A1|2002-11-08|2006-03-09|Commissariat A L'energie Atomique|Method for reproduction of a compnent with a micro-joint and component produced by said method|
    US20080283269A1|2005-06-17|2008-11-20|Georgia Tech Research Corporation|Systems and methods for nanomaterial transfer|
    US20090095412A1|2007-05-30|2009-04-16|Ramot At Tel Aviv University Ltd.|Nanotube network and method of fabricating the same|
    US20110229667A1|2008-08-18|2011-09-22|The Regents Of The University Of California|Nanostructured superhydrophobic, superoleophobic and/or superomniphobic coatings, methods for fabrication, and applications thereof|
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    申请号 | 申请日 | 专利标题
    ES201830750A|ES2775649B2|2018-07-24|2018-07-24|PROCEDURE FOR THE TRANSFER OF MICRO- AND / OR NANO- STRUCTURED GROUNDS TO ARBITRARY SURFACES|ES201830750A| ES2775649B2|2018-07-24|2018-07-24|PROCEDURE FOR THE TRANSFER OF MICRO- AND / OR NANO- STRUCTURED GROUNDS TO ARBITRARY SURFACES|
    PCT/ES2019/070513| WO2020021142A1|2018-07-24|2019-07-23|Method for transferring micro- and/or nano-structured patterns to arbitrary surfaces|
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