METHOD OF FORMING MICRO- OR NANOWIRES AT PREDETERMINED POSITIONS OF AN OBJECT USING A MICRO- OR NANOPIPETTE
20220250344 · 2022-08-11
Inventors
- Jung Ho JE (Pohang-si, KR)
- Un YANG (Pohang-si, KR)
- Seung Soo OH (Pohang-si, KR)
- Moon Jung YONG (Incheon, KR)
- Byung Hwa KANG (Pohang-si, KR)
Cpc classification
B82Y30/00
PERFORMING OPERATIONS; TRANSPORTING
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
Provided is a method of forming a micro/nanowire having a nanometer- to micrometer-sized diameter at predetermined positions of an object. The method includes: preparing a micro/nanopipette having a tip with an inner diameter which is substantially the same as the diameter of the micro/nanowire to be formed; filling the micro/nanopipette with a solution containing a micro/nanowire-forming material; brining the solution into contact with the object through the tip of the micro/nanopipette; and pulling the micro/nanopipette from the object at a pulling speed lower than or equal to a predetermined critical speed (ν.sub.c) to obtain a micro/nanowire having substantially the same diameter as the inner diameter of the micro/nanopipette tip.
Claims
1. A method of forming a micro/nanowire having a nanometer- to micrometer-sized diameter at predetermined positions of an object, the method comprising: preparing a micro/nanopipette having a tip with an inner diameter which is substantially the same as the diameter of the micro/nanowire to be formed; filling the micro/nanopipette with a solution containing a micro/nanowire-forming material; brining the solution into contact with the object through the tip of the micro/nanopipette; and pulling the micro/nanopipette apart from the object at a pulling speed lower than or equal to a predetermined critical speed (ν.sub.c) to obtain a micro/nanowire having substantially the same diameter as the inner diameter of the micro/nanopipette tip, wherein the critical speed (ν.sub.c) is a maximum limit of the pulling speed at which the micro/nanowire to be formed has the same diameter as the inner diameter of the micro/nanopipette tip, and when the pulling speed is lower than the critical speed, a micro/nanowire having the same diameter as the inner diameter of the micro/nanopipette tip is formed, and when the pulling speed is higher than the critical speed, a micro/nanowire having a diameter different from the inner diameter of the micro/nanopipette tip is formed.
2. The method of claim 1, wherein the critical speed (ν.sub.c) is inversely proportional to the inner diameter of the micro/nanopipette tip.
3. The method of claim 1, wherein the critical speed (ν.sub.c) is determined by the following equation:
4. The method of claim 1, further comprising separating the micro/nanowire from the micro/nanopipette tip by increasing the pulling speed of the micro/nanopipette.
5. The method of claim 1, wherein the object is a silicon substrate, an optical fiber, or any nanometer- to micrometer-sized device or structure, and the micro/nanowire is formed at a flat or curved surface, edge, corner, vertex, or horn-shaped tip of the object.
6. The method of claim 1, wherein the micro/nanowire-forming material comprises at least one of: a hydrophobic polymer selected from the group consisting of polystyrene, poly(lactic acid) (PLA), poly(caprolactone) (PCA), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), polystyrene-co-maleic acid, poly(methyl methacrylate), polycarbonate, polyurethane, polyvinylpyrrolidone (PVP), and polyvinylidene fluoride (PVDF); or a hydrophilic polymer selected from the group consisting of poly(acrylic acid) (PAA), polyacrylamide (PAM), polystyrene sulfonate (PSS), poly(vinyl alcohol) (PVA), alginate, and dextran; or an organic conductive polymer (π-conjugated polymer); or a nucleic acid selected from the group consisting of DNA and RNA; or a protein selected from the group consisting of bovine serum albumin (BSA), gelatin, and collagen; or a polysaccharide selected from the group consisting of dextran and glycogen.
7. The method of claim 1, wherein a solvent for dissolving the micro/nanowire-forming material comprises: at least one of DI water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), toluene, xylene, tetrahydrofuran (THF), ethanol, and chloroform; or any material capable of dissolving the micro/nanowire-forming material.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0024]
[0025]
[0026]
[0027]
[0028]
[0029]
[0030]
[0031]
[0032]
[0033]
[0034]
DETAILED DESCRIPTION
[0035] Hereinafter, preferred embodiments of a method of forming a micro/nanowire at predetermined positions of an object using a micro/nanopipette according to the present disclosure will be described with reference to the accompanying drawings. For reference, the terms referring to each component in the present disclosure are terms defined in consideration of the functions of the components, and thus it should not be understood that the technical content of the present disclosure is predicted and limited by the terms themselves. In addition, in the present disclosure, singular expressions include plural expressions unless specified otherwise in the context thereof.
[0036] The present disclosure discloses a method of forming a micro/nanowire having a nanometer- to micrometer-sized diameter at predetermined positions of an object. The method includes: preparing a micro/nanopipette having a tip with a nanometer- to micrometer-sized diameter, particularly an inner diameter which is substantially the same as the diameter of the micro/nanowire to be formed; filling the micro/nanopipette with a solution containing a micro/nanowire-forming material; brining the solution into contact with the object through the tip of the micro/nanopipette; and pulling one or both of the micro/nanopipette and the object at a speed lower than or equal to a predetermined critical speed to form a micro/nanowire having a diameter which is substantially the same diameter as the inner diameter of the tip of the micro/nanopipette and is uniform during growth. The method further includes separating the formed micro/nanowire from the tip of the micro/nanopipette by increasing the pulling speed of the micro/nanopipette when the micro/nanowire is formed up to a predetermined length.
[0037] Here, the critical speed (νc) is the maximum limit of the pulling speed at which the micro/nanowire to be formed has the same diameter as the inner diameter of the tip of the micro/nanopipette, and when the pulling speed is lower than the critical speed, a micro/nanowire having the same diameter as the inner diameter of the tip of the micro/nanopipette is formed, and when the pulling speed is higher than the critical speed, a micro/nanowire having a diameter different from the inner diameter of the tip of the micro/nanopipette, particularly a diameter smaller than the inner diameter of the tip, is formed.
[0038] As used herein, the expression “pulling one or both of the micro/nanopipette and the object” includes moving both the micro/nanopipette and the object closer to each other or away from each other; moving the object in a state in which the micro/nanopipette is fixed; or moving the micro/nanopipette in a state in which the object is fixed. In particular, the present disclosure describes that the micro/nanopipette is moved upward in a state in which the object is fixed at the lower side. In particular, the present disclosure describes that the tip of the micro/nanopipette is brought into contact with the object by moving the micro/nanopipette downward in a vertical direction in a state in which the object is fixed at the lower side, and the micro/nanowire extending from the object in the vertical direction is formed by moving the micro/nanopipette upward in the vertical direction.
[0039] As used herein, the term “object” may include any/all objects. For example, the term “object” may include a substrate formed of silicon and other materials, an optical fiber, or any nanometer- to micrometer-sized device or structure.
[0040] In addition, the micro/nanowire may be formed at any predetermined positions of the object. For example, the micro/nanowire may be formed at any predetermined position such as on a flat or curved surface, an edge, a corner, a vertex, or a horn-shaped tip. In addition, the micro/nanowire may be formed not only in a linear (straight) shape, but also in any three-dimensional curved shape.
1. PRINCIPLE AND PROBLEM OF CONVENTIONAL MENISCUS-GUIDED METHOD
[0041] A micro/nanowire is produced while a solution is drawn and solidified when a micro/nanopipette filled with the solution is pulled upward (v.sub.1 in
[0042] In the process of fabricating the micro/nanowire, the transition region greatly affects the growth behavior of the micro/nanowire. Where the pulling speed (v.sub.1) of the micro/nanopipette is sufficiently fast so that the evaporation rate of the solution that is drawn from the micro/nanopipette is lower than the drawing rate, a transition region occurs in which the liquid phase and the solid phase coexist. In this transition region, a meniscus is formed by the surface tension of the solution (
[0043] Then, as the solvent evaporates from the surface of the stretched meniscus, a completely solid micro/nanowire is formed from the wet solid region while the proportion of the solute significantly increases. When the micro/nanopipette is continuously pulled at a constant speed, the diameter of the micro/nanowire reaches the equilibrium value while the shape of the stretched meniscus is maintained. At this time, a problem arises in that the stretching degree of the meniscus varies depending on the type of material or the surrounding environment, and thus the diameter value of the micro/nanowire also changes. In addition, it is inevitable that the diameter of the micro/nanowire decreases gradually until it reaches the equilibrium value.
2. FEATURE OF THE PRESENT DISCLOSURE: CONFINED GROWTH METHOD
[0044] When the pulling speed (v.sub.2) of the pipette is sufficiently low so that the evaporation rate of the solution is higher than the flow rate of the solution, the transition region may be negligibly small and no meniscus may be formed (
[0045] In summary, when the pulling speed of the pipette is high, non-confined growth occurs. On the other hand, when the pulling speed is low, confined growth is expected to occur. Thereby, it can be considered that there may be a critical speed (v.sub.c) that defines a boundary between confined and non-confined growth.
[0046] The present disclosure has advantages in that the diameter of the micro/nanowire is easily controlled during the growth thereof under the confined growth condition, and in that the diameter thereof does not change depending on the type of solution material or the surrounding environment, as long as the confined growth condition is satisfied.
3. MATERIALS USABLE IN MICRO/NANOWIRE FABRICATION
[0047] In the present disclosure, the solution containing the material consists of a micro/nanowire-forming material and a solvent. Examples of the micro/nanowire-forming materials include most organic materials. In particular, the micro/nanowire-forming material that may be used in the present disclosure may be a hydrophobic polymer selected from the group consisting of polystyrene, poly(lactic acid) (PLA), poly(caprolactone) (PCA), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), polystyrene-co-maleic acid, poly(methyl methacrylate), polycarbonate, polyurethane, polyvinylpyrrolidone (PVP), and polyvinylidene fluoride (PVDF); or a hydrophilic polymer selected from the group consisting of poly(acrylic acid) (PAA), polyacrylamide (PAM), polystyrene sulfonate (PSS), poly(vinyl alcohol) (PVA), alginate, and dextran. In addition, as the micro/nanowire-forming material, an organic conductive polymer (π-conjugated polymer) may be also used, which is characterized in that the electrical and optical properties thereof may be freely controlled through chemical doping. A biopolymer may be also used as the micro/nanowire-forming material. The biopolymer may be a nucleic acid selected from the group consisting of DNA and RNA; or a protein selected from the group consisting of bovine serum albumin (BSA), gelatin, and collagen; or a polysaccharide selected from the group consisting of dextran and glycogen.
[0048] Meanwhile, as the solvent, a liquid capable of dissolving the micro/nanowire-forming material may be used, and examples thereof include DI water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), toluene, xylene, tetrahydrofuran (THF), ethanol, chloroform, and the like.
4. SIMULATION OF CONFINED GROWTH METHOD
[0049] (1) Calculation of Critical Speed (v.sub.c) of Pipette
[0050] As suggested in the feature of the present disclosure, it is expected that the growth behavior of a micro/nanowire will show confined growth when the pulling speed of the pipette is sufficiently low, and will show non-confined growth when the pulling speed of the pipette is high. Accordingly, it is necessary to calculate the critical speed (v.sub.c) of the pipette that determines the growth behavior of the micro/nanowire.
[0051] In general, a transition region exists between the liquid phase of the solution and the wet solid region, but it appears that the transition region is very small near the critical speed. When the solvent evaporates from the wet solid surface, the concentration of the solvent vapor at the surface is as follows by Fick's 2nd law:
[0052] wherein c represents the vapor concentration of the solvent, and D is the diffusion coefficient and is affected by the type of solvent, temperature, humidity, and the like.
[0053] Here, assuming that the solvent evaporates rapidly from the surface of the wet solid forming the micro/nanowire and that the vapor concentration (c) of the solvent rapidly reaches a steady state in a gas area adjacent to the surface, the following equation is obtained:
∇.sup.2c=O (2)
[0054] In fact, on the surface of the wet solid forming the micro/nanowire, the solvent evaporates rapidly because of the large specific surface area of the wet solid. Thus, it is reasonable to assume that the vapor concentration of the solvent rapidly reaches a steady state in the gas area adjacent to the surface.
[0055] The concentration of the solvent at the surface of the wet solid is taken as the saturated vapor concentration, and at this time, the evaporation flux (E) is as follows:
E=−D∇c (3)
[0056] Here, given the type of solvent, temperature, and humidity, the evaporation flux has a constant value, and the evaporation flux of the solvent per unit time at the surface of the wet solid is as follows:
πd.sub.wetxE (4)
[0057] wherein d.sub.wet represents the diameter of the wet solid region (which may be replaced by the inner diameter of the pipette tip), and x represents the axial length of the wet solid region. When the solvent evaporates from the surface of the wet solid, the solution in the pipette moves in the direction of the micro/nanowire by capillary flow. In the present disclosure, the diameter of the wet solid region, the diameter of the micro/nanowire to be formed, and the inner diameter of the tip of the micro/nanopipette are considered substantially the same as one another. At this time, since the amount of the moved solution is the same as the amount of the evaporated solvent, the following equation is established:
[0058] wherein u represents the moving speed of the solution that moves from the pipette in the direction of the micro/nanowire by capillary flow. In addition, assuming that the growth rate of the wet solid region is ν.sub.wet, the following relationship is established (see Langmuir, 26, 9269-9275 (2010)):
[0059] wherein φ.sub.wet represents the volume fraction of the solute in the wet solid region, and φ.sub.0 represents the volume fraction of the solute in the solution filled in the micro/nanopipette. When equation (6) is substituted into equation (5), the following equation is established:
[0060] Here, when the pulling speed (ν) of the pipette is higher than the growth speed (ν.sub.wet) of the wet solid region, a transition region is formed between the tip of the pipette and the wet solid region to some extent, thereby forming a meniscus, and the diameter of the micro/nanowire varies depending on the stretching degree of the meniscus. On the other hand, when the pulling speed (ν) of the pipette is lower than the growth speed (ν.sub.wet) of the wet solid region, the transition region may be neglectable, so that the wet solid region reaches the tip of the pipette, and thus the micro/nanowire is fabricated at the pulling speed (ν), and the diameter (d.sub.wet) of the wet solid region is the same as the inner diameter (d.sub.pt) of the pipette tip. As a result, the critical speed (ν.sub.c) that determines the growth behavior of the micro/nanowire can be found from the growth rate (ν.sub.wet) of the wet solid region, and the following equation is established:
[0061] Equation (8) above can be simply expressed as follows from d.sub.pt (which is a major variable related to micro/nanowire fabrication) and the coefficient (a) which is determined by the other factors:
[0062] In Equation (9) above, d.sub.pt (=the inner diameter or diameter of the pipette tip) becomes an important variable that determines the critical speed (ν.sub.c). “a” in Equation (9) is determined by the surrounding environment, the type and concentration of material, and the like.
[0063] Here,
is only taken as an example of the most basic model, and may be modified depending on the external environmental factors (e.g., temperature, humidity, electric field, atmospheric pressure, etc.) of the micro/nanowire fabrication process.
[0064] (2) Simulation of Critical Speed
[0065]
[0066] When the pulling speed of the pipette is higher than the critical speed (ν>ν.sub.c), a transition region is formed as described above, and as a result, a stretched meniscus is formed and non-confined growth occurs. In the case of non-confined growth, the diameter of the stretched meniscus determines the diameter of the micro/nanowire, and hence the diameter of the stretched meniscus varies depending on the pulling speed of the pipette, so that the diameter of the micro/nanowire will continue to change depending on the pulling speed.
[0067] On the other hand, when the pulling speed of the pipette is lower than the critical speed (ν<ν.sub.c), confined growth will occur, and a micro/nanowire having a constant diameter (which is the same as the inner diameter of the pipette tip) will grow regardless of the pulling speed of the pipette. The present disclosure relates to the growth of micro/nanowires by confined growth in which the diameter of the micro/nanowires is easily controlled.
5. EXAMPLES OF THE PRESENT DISCLOSURE
(1) Example 1. Non-Confined Growth and Confined Growth Depending on Pipette Pulling Speed
[0068]
[0069] First,
[0070] On the other hand,
(2) Example 2. BSA Protein Micro/Nanowire Depending on Pipette Diameter and Pipette Pulling Speed
[0071]
[0072]
[0073] The diameter of the BSA protein micro/nanowire has a constant value equal to the diameter of the pipette tip in the confined growth region (dark background), but decreases in the non-confined growth region (bright background) as the pulling speed increases.
(3) Example 3. DNA Micro/Nanowire Depending on Pipette Diameter and Pipette Pulling Speed
[0074]
[0075] Under the condition of confined growth, it becomes easy to control the diameter of the micro/nanowire. The following Examples all relate to the growth of micro/nanowires under the condition of confined growth.
(4) Example 4. Growth of Polymer Micro/Nanowire on Si Substrate or at Tip of Optical Fiber by Confined Growth
[0076]
[0077] First, a pipette is prepared, which contains therein a solution containing a micro/nanowire-forming material and may discharge the solution through the tip thereof. At this time, the inner diameter of the pipette tip (or the outer diameter of the pipette tip; the inner and the outer diameters of the pipette tip may be considered substantially the same) may be set to substantially the same value as the diameter of the micro/nanowire to be fabricated. Subsequently, the pipette is filled with the solution containing the material, and then the pipette is moved and positioned at a desired position (positioning).
[0078] Next, the pipette tip is brought into contact with the surface of an object on which or at which the micro/nanowire is to be fabricated. For example, it can be seen that the pipette is brought into contact with the surface of a silicon substrate (
[0079] Then, a micro/nanowire is formed by moving the tip of the pipette away from the object. At this time, the upward moving speed of the tip is preferably maintained so that the discharged material solution is not cut off or the diameter thereof does not change. When the pipette is moved upward as described above, the material-containing solution in the pipette is extended in the form of a micro/nanowire in a state connected to the target object, and a micro/nanowire having substantially the same diameter as the inner diameter (or outer diameter) of the pipette tip is formed while the solvent of the material-containing solution evaporates (pulling).
[0080] In addition, in another example, the pipette may be moved in a desired direction in order to control the shape of the micro/nanowire and the direction in which the micro/nanowire extends.
[0081] Finally, when the micro/nanowire has grown to a desired length, the produced micro/nanowire may be separated from the pipette tip by removing the pipette at a very high speed (pipette removal).
(5) Example 5. Light Transmission Through Optical Fiber to Micro/Nanofiber Grown Under Confined Growth Condition
[0082]
[0083] The optical coupling efficiency is defined as the ratio between the optical power at the tip of a micro/nanowire and the optical power at the tip of an optical fiber with no micro/nanowire grown, under the same condition.
[0084] The dark stars in
[0085] The pale stars in
[0086] In addition, the optical coupling efficiency calculated as the ratio of the laser power between before and after the light is transmitted to the micro/nanowire is indicated as hollow dots at the top of the graph.
[0087] It is confirmed that the optical coupling efficiency of the micro/nanowire fabricated under the confined growth condition according to the present disclosure is 92% or higher of the total power of the input laser. This high optical coupling efficiency demonstrates that the micro/nanowire fabricated under the confined growth condition is sufficient to be utilized as an optical interconnection.
[0088] The micro/nanowire fabricated on the tip of the tapered optical fiber according to the present disclosure has optical coupling efficiency of 90% or higher. Thus, the micro/nanowire thus fabricated is suitable for use as an optical interconnection for transmitting light from an optical fiber to the micro/nanowire or receiving light from the micro/nanowire to the optical fiber. In addition, the micro/nanowire may be used in an optical sensor that receives light from an optical fiber to the micro/nanowire and transmits the reflected light from the tip of the micro/nanowire or any light generated back to the optical fiber.
[0089] As described above, the method of fabricating micro/nanowires (microwires or nanowires) according to the present disclosure enables precise control of the position and geometry of the micro/nanowires within a three-dimensional space. In addition, the method omits the meniscus formation step which is essential in the conventional method, so that the process is simplified, thus greatly increasing the utility of the method. Furthermore, according to the method of the present disclosure, it is easy to control the diameter (d.sub.w) of the micro/nanowire. Specifically, the diameter of the micro/nanowire may be controlled to be constant (d.sub.w≈d.sub.pt) regardless of the type of material or external environmental factors, as long as the condition of confined growth is satisfied.
[0090] The above-described embodiments of the present disclosure are merely illustrative of the technical spirit of the present disclosure, and the scope of protection of the present disclosure should be interpreted by the appended claims. In addition, any person skilled in the art to which the present disclosure pertains will appreciate that various modifications and variations are possible without departing from the essential characteristics of the present disclosure. Thus, all technical ideas within the scope equivalent to the present disclosure should be construed as being included in the scope of the present disclosure.