KR101205826B1 - Fabrication method of new stamps with various pattern shapes or dimensions using one stamp - Google Patents

Abstract

One stamp provides a way to make another stamp with a changed pattern shape or size. In one configuration of the method for manufacturing a stamp according to the present invention, after coating an inorganic resin containing a metal-organic precursor formed by combining an organic ligand decomposed by at least one of light and heat to a metal element on a stamping substrate, a pattern Prepare the first stamp with. After pressing the inorganic resin with the first stamp, the pressurized inorganic resin is irradiated with ultraviolet rays simultaneously with heating or ultraviolet irradiation or heating to form a cured metal oxide thin film pattern. At least any of the shape, line width, and height of the metal oxide thin film pattern for removing the first stamp from the metal oxide thin film pattern, and then manufacturing a second stamp having a metal oxide thin film pattern different from the pattern of the first stamp. The metal oxide thin film pattern is irradiated with ultraviolet rays simultaneously with heating or ultraviolet irradiation or heating so as to change one.

Description

Fabrication method of new stamps with various pattern shapes or dimensions using one stamp}

The present invention relates to a nanoimprint process, and more particularly, to a method of forming a metal oxide thin film pattern on a substrate using ultraviolet irradiation and / or heated nanoimprint and to produce a stamp for nanoimprint using the same.

Nano imprint is a technique proposed to realize nano processing (1-100 nm), which is ultra-fine processing, by applying a photocurable or thermoplastic resin on a substrate for a device, applying pressure with a nano-sized mold and irradiating or heating ultraviolet rays. The technique of transferring a pattern by hardening is said. Nanoimprint technology overcomes the photolithography limitations of current semiconductor processes and enables the fabrication of nanostructures as simple as painting.

In addition, the use of nanoimprint technology will improve the current 100nm fine process to 10nm, facilitating technological development in the next-generation semiconductor field. In particular, the nanoimprint technology has been recognized as a circuit forming technology for the next-generation semiconductor and flat panel display.

Nano imprint technology is a method of curing the resin by transmitting ultraviolet rays through a thermal imprinting technique using an opaque silicon stamp and a transparent quartz stamp (or a transparent quartz substrate when using a silicon stamp), depending on the curing method. It is divided into ultraviolet imprinting technology that adopts the method.

Among them, in ultraviolet imprinting, a master mold is formed by first forming a master pattern on a transparent mold substrate through nanolithography equipment such as an electron beam. After spin coating (or dispensing) the prepolymer resin cured by ultraviolet rays onto the substrate, the prepared master mold is brought into contact with the resin. At this time, the resin is filled into the master pattern by capillary force, so that the pattern is transferred. After filling is complete, ultraviolet light passing through the transparent mold substrate causes curing of the polymer component in the resin and the master mold is removed in the next step.

Currently, imprint stamp fabrication such as a master mold is performed by etching an absorber layer using an electron beam lithography in a photomask process and then etching the mold substrate using a patterned absorber layer as an etching mask through a dry etching process. Thereafter, the patterned absorbing layer is removed. However, in the case of the nano imprint process using such a stamp, there is a problem in that the life of the stamp is shortened due to deformation and breakage of the stamp because the high temperature and high pressure processes are used.

In order to prevent deformation and breakage of the stamp, a method using materials such as sapphire, diamond, etc. having excellent mechanical strength has been studied, but diamond has difficulty in practical use due to high manufacturing cost.

In addition, in the case of a stamp produced once, since the pattern line width, height, and pattern shape cannot be changed, when a pattern different from the pattern line width, height, or pattern shape of the produced stamp needs to be formed, a limitation of having to recreate an expensive stamp There is.

The technical problem to be solved by the present invention is to provide a method for manufacturing a new stamp having a pattern shape or size (line width or height, etc.) different from the stamp using a conventionally produced one stamp. Up to now, there is no way to change the pattern of the already produced stamp.

In one aspect of the method for manufacturing a stamp according to the present invention for solving the above technical problem, an inorganic resin including a metal-organic precursor formed by combining an organic ligand decomposable by at least one of light and heat to a metal element. After coating on the stamp substrate, a first stamp having a pattern is prepared. After pressing the inorganic resin with the first stamp, the pressurized inorganic resin is irradiated with ultraviolet rays simultaneously with heating or ultraviolet irradiation or heating to form a cured metal oxide thin film pattern. At least any of the shape, line width, and height of the metal oxide thin film pattern for removing the first stamp from the metal oxide thin film pattern, and then manufacturing a second stamp having a metal oxide thin film pattern different from the pattern of the first stamp. The metal oxide thin film pattern is irradiated with ultraviolet rays simultaneously with heating or ultraviolet irradiation or heating so as to change one.

When the metal oxide thin film pattern is heated, a heating temperature is 50 ° C. to 800 ° C., and a heating time may be 15 seconds to 5 hours. Irradiation time when the ultraviolet irradiation to the metal oxide thin film pattern may be 1 second to 5 hours. Here, the first stamp may be a master mold made of silicon or quartz or an organic mold replicating the master mold.

In particular, the organic mold may be a deformation after replicating the master mold, coating the organic resin on the replica substrate; Preparing a master mold made of silicon or quartz; Pressing the organic resin into the master mold; Preparing an organic mold having a pattern in which the master mold is replicated by heating or irradiating ultraviolet light to the pressurized organic resin or simultaneously with heating; Removing the master mold from the organic mold; And in order to modify the pattern of the organic mold, it may be prepared by a method comprising the step of irradiating the organic mold with ultraviolet light at the same time heating or ultraviolet irradiation or heating.

In order to solve the above technical problem, another configuration of the stamp manufacturing method according to the present invention comprises the steps of coating an organic resin on a replica substrate; Preparing a master mold made of silicon or quartz; Pressing the organic resin into the master mold; Preparing an organic mold having a pattern in which the master mold is replicated by heating or irradiating ultraviolet light to the pressurized organic resin or simultaneously with heating; Removing the master mold from the organic mold; Irradiating the organic mold with ultraviolet rays simultaneously with heating or ultraviolet irradiation or heating in order to deform the pattern of the organic mold to use as the first stamp; Coating an inorganic resin including a metal-organic precursor formed by binding an organic ligand decomposed by at least one of light and heat to a metal element on a stamping substrate; Pressing the inorganic resin with the first stamp; Forming a cured metal oxide thin film pattern on the pressurized inorganic resin by heating or ultraviolet irradiation or heating at the same time; And manufacturing a second stamp made of the metal oxide thin film pattern on the stamp substrate by removing the first stamp from the metal oxide thin film pattern.

In the above methods, the organic resin is polytetrafluoroethylene (PTFE), polyurethane acrylate (polyurethane acrylate (PUA), ethylene tetrafluoroethylene (ETFE), polydimethylsiloxane (polydimethylsiloxane, PDMS) ) And perfluoroalkyl acrylate (PFA). Heating temperature of the organic mold heating is 30 ℃ to 300 ℃, the heating time may be 1 second to 5 hours. The irradiation time when the UV irradiation to the organic mold may be 1 second to 5 hours.

In the stamp manufacturing method according to the present invention, the metal element constituting the metal-organic precursor is lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium (Mg), aluminum (Al) ), Silicon (Si), indium (In), sulfur (S), potassium (K), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn) ), Iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), rubidium ( Rb), Strontium (Sr), Yttrium (Y), Zirconium (Zr), Niobium (Nb), Molybdenum (Mo), Ruthenium (Ru), Rhodium (Rh), Indium (In), Tin (Sn), Tel Rulium (Te), Antimony (Sb), Barium (Ba), Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Gadolinium (Gd), Hafnium (Hf), At least one selected from the group consisting of tantalum (Ta), tungsten (W), iridium (Ir), lead (Pb), bismuth (Bi), polonium (Po), and uranium (U).

The organic ligand constituting the metal-organic precursor is ethylhexanoate, acetylacetonate, dialkyldithiocarbamates, carboxylic acids, carboxylates , Pyridine, diamines, arsines, diarsines, phosphines, diphosphines, butoxide, isopropoxide, ethoxylate Ethoxide, chloride, acetate, carbonyl, carbonate, hydroxide, arene, beta-diketonate , 2-nitrobenzaldehyde (2-nitrobenzaldehyde), acetate dihydrate (acetate dihydrate) may be selected from the group comprising a mixture thereof. The inorganic resin is hexane, 4-methyl-2-pentanone, ketone, methyl isobutyl ketone, methyl ethyl ketone, water, methanol, ethanol, propanol, isopropanol, butanol and pentane as solvents. Allol, hexanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran (THF), tecan, nonane, octane It may include at least one selected from the group consisting of, heptane, pentane and 2-methoxyethanol (e-methoxyethanol).

According to the present invention, after the stamp is duplicated through an imprinting method using an inorganic resin or an inorganic resin and an organic resin, the pattern shape of a previously produced stamp may be changed by heating, UV irradiation, or UV irradiation simultaneously with heating. It is easy to change the size. Accordingly, by using a single stamp produced, it is possible to manufacture a new stamp having various shapes and sizes by changing the shape or line width of the pattern without a complicated method such as lithography.

For example, replicating a stamp with a 50 nm line width pattern and irradiating UV light simultaneously with heating, ultraviolet irradiation or heating reduces the pattern line width, thus making it possible to produce a 20 nm stamp. In general, it is expensive to produce a 20nm stamp because it requires expensive equipment such as electron beam lithography equipment.However, in the case of this technology, a 20nm stamp can be produced at a low cost by duplicating a 50nm stamp that is already manufactured. . As the method of the present invention, which consists of stamp replication and heating, ultraviolet irradiation or heating, and pattern reduction using ultraviolet irradiation, is repeated, stamps of smaller and smaller line widths can be obtained.

According to the present invention, if a new type of stamp fabrication capable of pattern modification is implemented at low cost, a display (LED, LCD, OLED, etc.), a MEMS application device (bio device, biochip, cell chip, DNA chip), nano memory device (ReRAM) And the use of nanoimprint devices such as flash memories, which enables scaled-down patterning to achieve device miniaturization.

1 is a flow chart of the stamp manufacturing method according to an embodiment of the present invention,
2 is a process chart according to the flowchart of FIG.
3 is a flowchart of a stamp manufacturing method according to another embodiment of the present invention;
4 is a process chart according to the flowchart of FIG.
5 is a flowchart of a stamp manufacturing method according to another embodiment of the present invention;
6 is a SEM image of a ZnO stamp using a nano imprint formed according to Example 1 of the present invention,
7 is an SEM and AFM image of a ZrO ₂ stamp using nanoimprint formed according to Example 2 of the present invention,
8 is an SEM and AFM image of a TiO ₂ stamp using a nanoimprint formed according to Example 3 of the present invention, and
9 is an SEM image of an unaligned ZnO stamp using nanoimprint formed in accordance with Example 4 of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention and to those skilled in the art to fully understand the scope of the invention. It is provided to inform you. The shape and the like of the elements in the drawings are exaggerated in order to emphasize a more clear description, elements denoted by the same reference numerals in the drawings means the same elements.

1 is a flowchart of a stamp manufacturing method according to an embodiment of the present invention, Figure 2 is a process diagram accordingly. Referring to Figures 1 and 2 will be described in the stamp manufacturing method according to an embodiment of the present invention.

First, as shown in (a) of FIG. 2, a stamp substrate 10 is prepared and an inorganic resin 20 including a metal-organic precursor is coated thereon (step S1 of FIG. 1).

Here, the stamp substrate 10 is an inorganic material such as silicon, gallium arsenide, gallium phosphide, gallium arsenide, silicon oxide, sapphire, quartz, glass, or polycarbonate, polyethylene naphthalate, polynorbornene, polyacrylate, It may be made of a transparent polymer such as polyvinyl alcohol, polyimide, polyethylene terephthalate, polyether cell phone.

In order to prepare the inorganic resin 20, a metal-organic precursor formed by combining an organic ligand decomposable by at least one of light and heat to a metal element is first synthesized.

Metal elements constituting the metal-organic precursor are lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium (Mg), aluminum (Al), silicon (Si), phosphorus (P) , Sulfur (S), potassium (K), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co) , Nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), rubidium (Rb), strontium (Sr), yttrium (Y ), Zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), indium (In), tin (Sn), tellurium (Te), antimony (Sb), barium (Ba), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), gadolinium (Gd), hafnium (Hf), tantalum (Ta), tungsten (W), iridium It may be made of at least one metal selected from the group consisting of (Ir), lead (Pb), bismuth (Bi), polonium (Po), and uranium (U).

The metal-organic precursor includes about 5 to 95% by weight of an organic ligand and a metal element added to 100% by weight in total, and the metal-organic precursor may be prepared by combining the metal element with an organic ligand. The metal-organic precursor may be dissolved in a solvent to prepare an inorganic resin. At this time, the solvent may be included in about 5 to 95% by weight based on the total content of the inorganic resin.

The organic ligand is ethylhexanoate, acetylacetonate, dialkyldithiocarbamate, carboxylic acid, carboxylate, pyridine, diamine, arsine, diarcin, phosphine, diphosphine, butoxide, isopropac To be used in the group comprising the side, ethoxide, chloride, acetate, carbonyl, carbonate, hydroxide, arene, beta-diketonate, 2-nitrobenzaldihydrate, acetate dihydrate and mixtures thereof Can be.

And the solvent is hexane, 4-methyl-2-pentanone, ketone, methyl isobutyl ketone, methyl ethyl ketone, water, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, dimethylsulfoxide, dimethylform At least one selected from the group consisting of amide, N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran, tecan, nonane, octane, heptane, pentane and 2-methoxyethanol can be used.

The inorganic resin 20 manufactured as described above is decomposed in the organic matter when ultraviolet rays are irradiated, thermally cured or heated and irradiated with ultraviolet rays. Accordingly, the metal element can react with oxygen in the atmosphere to form a metal oxide thin film. . The inorganic resin 20 may be selected from among spin coating, dip coating, spray coating, solution dropping, and dispensing. Can be coated on. The inorganic resin 20 coated on the stamp substrate 10 may be heat dried to remove residual solvent.

Next, as shown in FIG. 2B, the first stamp 30 having the pattern 31 having the uneven structure is formed (step S2 of FIG. 1).

The first stamp 30 may be a master mold made of silicon or quartz manufactured by a conventional manufacturing method, or may be an organic mold obtained by replicating the master mold. Accordingly, the main material of the first stamp 30 may be silicon, quartz, or an organic material. Examples of the organic material may include polytetrafluoroethylene, polyurethane acrylate, ethylene tetrafluoroethylene, polydimethylsiloxane, and perfluoroalkyl. Acrylates and the like.

The first stamp 30 has a pattern 31 corresponding to the pattern to be formed on the stamp substrate 10. For example, the pattern 31 is composed of pillars 311 having a predetermined line width, and the spacing between the pillars 311 is as indicated by "312". The pillars 311 of the pattern 31 are patterned into recesses (holes) in the metal oxide thin film on the stamping substrate 10 in a subsequent process, and the gap 312 between the pillars 311 is a stamping substrate 10. The metal oxide thin film is patterned with convex portions.

Next, the inorganic resin 20 is pressurized with the first stamp 30 as shown in FIG. 2C (step S3 of FIG. 1). When pressing the first stamp 30 on the inorganic resin 20, it may be pressed at a pressure of 1 to 100 bar (bar) or under vacuum.

Next, the inorganic resin 20 pressurized with the first stamp 30 is heated or irradiated with ultraviolet rays or heated and simultaneously irradiated with ultraviolet rays to cure the inorganic resin 20 and accordingly the metal oxide thin film pattern 21. (Step S4 of FIG. 1) is formed. Here, in order to irradiate or heat ultraviolet rays and irradiate ultraviolet rays, the first stamp 30 is preferably made of a transparent material, and in the case of heating only, the first stamp 30 may be made of an opaque material. .

When heating the pressurized inorganic resin 20, it heats to the temperature of 30 degreeC-350 degreeC using predetermined | prescribed heating means, such as a heater or a furnace or an electric oven. Here, the heating time can adjust the time within the range of 15 seconds to 2 hours. When the pressurized inorganic resin 20 is heated, organic matters attached to the metals are thermally decomposed to leave only the metals, and combine with oxygen in the air to form the metal oxide thin film pattern 21. In this case, in order to create an oxygen atmosphere when the metal oxide thin film pattern 21 is formed, an oxygen atmosphere may be formed in a predetermined chamber and then heated through a predetermined heating means.

The metal oxide thin film pattern 21 may have a gap between a recess (hole) 212 corresponding to the pillar 311 of the pattern 31 of the first stamp 30 and the pillar 311 of the first stamp 30. A convex portion 211 corresponding to 312 is provided. Each line width is copied as it is, without change. That is, the concave portion (hole) 212 of the metal oxide thin film pattern 21 and the pillar 311 of the first stamp 30 have the same line width, and the convex portion 211 and the first portion of the metal oxide thin film pattern 21 are formed. The spacing 312 between the pillars 311 of one stamp 30 has the same line width.

On the other hand, in the case of irradiating ultraviolet rays while irradiating ultraviolet rays or heating the pressurized inorganic resin 20 simultaneously, KrF (248 nm), ArF (193 nm), F ₂ (157 nm) as an exposure apparatus for ultraviolet irradiation. It is possible to use a laser-based exposure apparatus composed of a laser-based exposure apparatus consisting of a G-line (436 nm), I-line (365 nm). Here, the ultraviolet irradiation time may be irradiated by adjusting the time within the range of 1 second to 10 hours, such ultraviolet irradiation may be performed at room temperature. When the ultraviolet light is irradiated onto the pressurized inorganic resin 20, organic substances attached to the metal may undergo a photolysis reaction, leaving only the metal, and combining with oxygen in the air to form the metal oxide thin film pattern 21. As such, when the ultraviolet rays are irradiated simultaneously with the heating, the process time for forming the metal oxide thin film pattern 21 can be reduced.

Next, after the cured metal oxide thin film pattern 21 is formed, the first stamp 30 is removed from the metal oxide thin film pattern 21 as shown in FIG. 2 (d) (step S5 of FIG. 1). After releasing and removing the first stamp 30 from the metal oxide thin film pattern 21, as shown in FIG. 2D, the metal oxide thin film pattern 21 is formed on the stamp substrate 10. Are exposed as a condition.

Then, further processing for changing the line width, height, or pattern shape of the metal oxide thin film pattern 21 is performed with reference to FIG. 2E (step S6 in FIG. 1). This treatment is heating at the same time as ultraviolet irradiation, heating or ultraviolet irradiation. The line width, height, or shape of the metal oxide thin film pattern 21 can be changed as desired by adjusting the time, temperature, heating time, and the like of ultraviolet irradiation.

The inorganic resin including the metal-organic precursor constituting the metal oxide thin film pattern 21 may be deformed in the form of a pattern during heat treatment and / or ultraviolet irradiation, and densification of the inorganic resin during ultraviolet irradiation or heat treatment due to the characteristics of the inorganic resin. And the line width and thickness (pattern height) of the patterned film by the formation of crystallinity phase. In the present invention, these changes are used to produce stamps of various types.

When heating for deformation of the metal oxide thin film pattern 21, the heating temperature may be 50 ° C to 800 ° C, and the heating time may be 15 seconds to 5 hours. When irradiating an ultraviolet-ray, irradiation time can be made into 1 second-5 hours.

FIG. 2 (f) shows a metal oxide thin film pattern 22 having a concave portion 222 having a line width increased and a convex portion 221 having a reduced line width on the stamp substrate 10 through this process. Shows that it is formed. The stamp substrate 10 on which the metal oxide thin film pattern 22 is formed can now be used as a new second stamp 25.

Through treatment such as ultraviolet irradiation and heating, the line width of the convex portion 221 is smaller and the line width of the concave portion (222) is increased in the metal oxide thin film pattern 22 than the metal oxide thin film pattern 21 before the treatment. It was. The recesses (holes) 212 and the convex portions 211 of the metal oxide thin film pattern 21 before the treatment are spaced 312 between the pillars 311 and the pillars 311 of the first stamp 30 pattern 31. ), Respectively. Therefore, the second stamp 25 has been changed so that the convex portion 211 has a small line width while having a reverse phase structure with the first stamp 30.

When the newly manufactured second stamp 25 is used as the first stamp again, the second stamp 25 is reproduced according to the method of the present invention to reduce the pattern, thereby obtaining a stamp having a finer pattern. Therefore, by performing this method once or several times, it is possible to produce a new stamp having a reduced line width. For example, a 20nm-class new stamp can be produced using an initial stamp with a 50nm-class linewidth pattern. It is simple and inexpensive to manufacture a 20 nm-class stamp like the present invention without using a method such as electron beam lithography.

On the other hand, in the above embodiment, the first stamp 30 has a pillar 311, whereas the second stamp 25 has a concave portion (hole) 212 is a case of having a reversed structure with each other. Hereinafter, with reference to FIGS. 3 and 4, when the initial stamp has a pillar, a case in which the newly created stamp has the same structure as the pillar will be described.

This embodiment also manufactures a new stamp according to the method of the description with reference to FIGS. 1 and 2. However, there is a difference in the process of preparing the first stamp. In the description with reference to FIGS. 1 and 2, a case in which the first stamp is a master mold made of silicon or quartz is exemplified. In this embodiment, an organic mold obtained by replicating such a master mold is used as the first stamp. Therefore, there is a difference in preparing the first stamp.

Figure 3 is a flow chart of a stamp manufacturing method according to another embodiment of the present invention, Figure 4 is a process diagram accordingly. In FIG. 3, the same step numbers as in FIG. 1 are the same process, and thus repeated descriptions thereof will be omitted.

First, an inorganic resin including a metal-organic precursor is coated on a stamp substrate (step S1 of FIG. 3). For example, an inorganic resin containing Ti-organic precursor containing Ti as a metal element is prepared and coated so as to form TiO ₂ by subsequent treatment.

Then, a first stamp having a pattern is prepared (step S2 'in Fig. 3). In this embodiment, the first stamp is prepared as follows.

First, the organic resin is coated on the replica substrate (step S2-1 of FIG. 3). To coat the organic resin, a method of spin coating, solution dropping, or dispensing may be used. The replica substrate may be a transparent polymer such as polycarbonate, polyethylene naphthalate, polynorbornene, polyacrylate, polyvinyl alcohol, polyimide, polyethylene terephthalate, polyethercellone. The organic resin may be a commonly used photocurable resin or thermosetting resin, for example, polytetrafluoroethylene, polyurethane acrylate, ethylene tetrafluoroethylene, polydimethylsiloxane, perfluoroalkyl acrylate, and the like. In a direct embodiment of this embodiment, polytetrafluoroethylene was coated on a polycarbonate substrate by spin coating, solution dropping or dispensing.

Next, a master mold made of silicon or quartz is prepared (step S2-2 in FIG. 3). In a direct embodiment of the present embodiment, a silicon master mold 26 having a hole pattern having a line width of 265 nm is prepared as shown in FIG.

Next, the organic resin is pressurized with the master mold 26 (step S2-3 in FIG. 3). An organic mold 30 'having a pattern in which the master mold 26 is replicated by heating or irradiating ultraviolet light or heating at the same time with the pressurized organic resin is manufactured as shown in FIG. S2-4). In other words, the master mold 26 is imprinted on the replica substrate coated with the organic resin to prepare an organic mold 30 'having a pillar pattern having a line width of 265 nm as shown in FIG. This organic mold is used as the first stamp 30 as described above in the subsequent process.

After removing the master mold 26 from the organic mold 30 '(step S2-5 of FIG. 3), the first stamp 30 in the method described with reference to FIGS. 1 and 2 3, the rest of the stamp manufacturing method in the method described with reference to FIGS. 1 and 2 is performed (steps S3 to S6 of FIG. 3).

That is, the inorganic resin coated in step S1 of FIG. 3 is pressurized with the first stamp 30 which is the organic mold 30 '. Then, the pressurized inorganic resin is heated or irradiated with ultraviolet rays or heated and irradiated with ultraviolet rays. Then, when the first stamp 30 is removed, a mold 23 having a TiO ₂ pattern having a hole having a line width of 265 nm is manufactured as shown in FIG. 4 (c). Then, a treatment for heating at the same time as ultraviolet irradiation, heating or ultraviolet irradiation is performed to change the line width, height or pattern shape of the TiO ₂ pattern. For example, when the heat treatment is performed at 300 ° C. for 1 hour, as shown in FIG. 4 (d), the line width of the hole formed in the TiO ₂ pattern is increased to 365 nm to manufacture the second stamp 25 ′.

In the present embodiment, the initial stamp has a hole as the master mold 26, and newly made by performing the staff manufacturing method according to the present invention using the duplicated organic mold 30 'as the first stamp 30. The second stamp 25 'can be manufactured in a structure having a hole like the initial stamp.

Meanwhile, in the present embodiment, the master mold 26 is duplicated once to manufacture an organic mold 30 'and used to manufacture a stamp, and another organic mold which duplicates the organic mold 30' is made to make a stamp. In this case, a new stamp can be obtained that is inverse to the master mold 26.

On the other hand, the above embodiments have been described mainly in the case of changing the line width of the pattern, according to the present invention, it is also possible to manufacture a stamp in which the aligned pattern is changed to an unaligned pattern.

5 is a flowchart of a stamp manufacturing method according to another embodiment of the present invention. In FIG. 5, the same step numbers as those of FIG. 1 or 3 are the same processes, and thus repeated descriptions thereof will be omitted.

First, an inorganic resin including a metal-organic precursor is coated on a stamp substrate (step S1 of FIG. 5). Then, a first stamp having a pattern is prepared (step S2 " in FIG. 5). In this embodiment, the first stamp is the same from steps S2-1 to S2-5 in the method described with reference to FIG. The organic mold is first obtained, and then the step of irradiating the organic mold with heating or ultraviolet irradiation or simultaneously with heating is further performed to deform the pattern of the organic mold to use as the first stamp (FIG. 5). Steps of S2-6 ').

The heating temperature at the time of heating the organic mold is 30 ℃ to 300 ℃, the heating time may be 1 second to 5 hours. The irradiation time when the organic material is irradiated with ultraviolet rays may be 1 second to 5 hours. When the organic mold is irradiated with ultraviolet rays simultaneously with heating or ultraviolet irradiation or heating, the pattern of the aligned state is transformed into the pattern of the unaligned state. Using the pattern-modified organic mold as the first stamp 30 in the method described with reference to FIGS. 1 and 2, the rest of the stamp manufacturing method is performed (steps S3 to S6 of FIG. 5). In this case, step S6 of modifying the metal oxide thin film pattern is an optional step that may or may not be performed.

As described above, when the organic mold is deformed, a stamp having an unaligned pattern may be manufactured.

Hereinafter, specific embodiments of the embodiments of the present invention described above will be described.

Example 1

6 is an SEM image of a ZnO stamp using a nano imprint formed according to Example 1 of the present invention.

Initial stamps were prepared according to the general manufacturing method to have holes (hole-patterned stamp). The line width of the hole was 265 nm. In this embodiment, in order to produce a ZnO stamp having a reverse phase structure with a initial stamp, that is, a pillar-patterned stamp, a polyethylene terephthalate (PET) is used as a substrate for replicating polyurethane acrylate (PUA) as an organic resin. ) Dropped on top of the substrate, the initial stamp was pressed to irradiate UV light for 3 minutes and then separated to prepare a PUA stamp having a pillar width of 265 nm first by imprint method. After that, polytetrafluoroethylene (PTFE) was added dropwise onto the new PET substrate as an organic resin, and then a PUA stamp having a pillar prepared as described above was pressed and irradiated with ultraviolet rays for 3 minutes to obtain a PTFE stamp having a hole having a line width of 265 nm. Prepared.

To synthesize the photosensitive ZnO resin as an inorganic resin, zinc acetate dihydrate, 2-methoxyethanol, 2-aminoethanol and 2-nitrobenzaldihydr were mixed in a predetermined amount. After spin-coating a photosensitive ZnO resin on a silicon substrate as a stamp substrate, a PTFE stamp having a hole manufactured as described above was used as the first stamp, and after pressing it for 3 minutes to irradiate ultraviolet rays, the PTFE stamp having a hole was separated, A ZnO stamp having a pillar having a line width of 265 nm was prepared first, and the result is shown in FIG. 6 (a).

The ZnO stamp was heat-treated at 300 ° C. for 1 hour using a predetermined heating means, here, a furnace, in order to control the pillar line width and the gap between the pillars of the prepared ZnO stamp, thereby producing a ZnO stamp as a second stamp. In 6 (b). As shown in Figure 6 (b), it can be seen that the line width of the pillar is reduced from 265nm to 127nm through the heat treatment process, it can be seen that the pattern line width of the ZnO stamp can be reduced by adjusting the heat treatment process conditions.

Example 2

7 is an SEM and AFM image of a ZrO ₂ stamp using nano imprint formed in accordance with Example 2 of the present invention.

In order to produce a ZrO ₂ stamp (hole-patterned stamp) of the same type as the prepared initial stamp (hole-patterned stamp), PTFE was added dropwise onto the PET substrate as a replica substrate, and then the initial stamp was used. A PTFE stamp having a pillar was prepared in a printing manner. Subsequently, zirconyl 2-ethylhexanoate and hexane were mixed in a predetermined amount to synthesize a photosensitive ZrO ₂ resin. After spin-coating a photosensitive ZrO ₂ resin on a silicon substrate, the PTFE stamp having a pillar was pressed and irradiated with ultraviolet rays for 20 minutes, and then the PTFE stamp having a pillar was separated to prepare a ZrO ₂ stamp having a hole. The results are in FIGS. 7 (a) and 7 (c).

, First the prepared ZrO ₂ Stamp predetermined heating means, the ZrO ₂ Stamp was thermally treated for 1 hour at 400 ℃ modified using a Fig. 7 (b) to adjust the hole width of the produced ZrO ₂ stamped and In 7 (d). As shown in FIG. 7, it can be seen that the line width of the hole increases from 265 nm to 450 nm through the heat treatment process, and the pattern line width of the ZrO ₂ stamp can be increased by adjusting the heat treatment process conditions.

Example 3

FIG. 8 is an SEM and AFM image of a TiO ₂ stamp using nano imprint formed according to Example 3 of the present invention.

A PTFE stamp having a pillar was prepared in the same manner as in Example 2, and titanium (n-butoxide) ₂ (2-ethylhexanoenite) ₂ [Titanium (n-butoxide) ₂ was used to synthesize a photosensitive TiO ₂ resin. (2-ethylhexanoate) ₂ ] and hexane were mixed in a certain amount. After spin-coating a photosensitive TiO ₂ resin on a silicon substrate, the prepared PTFE stamp was pressed, irradiated with ultraviolet rays for 20 minutes, and the PTFE stamp was separated to prepare a TiO ₂ stamp having holes. The result is in Figs. 8 (a) and 8 (c).

Using a TiO ₂ as a stamp producing to adjust the line width of the prepared hole stamp TiO ₂ was heat-treated for 1 hour at 400 ℃. The results are shown in FIGS. 8 (b) and 8 (d). As shown in FIG. 8, it can be seen that the line width of the hole increases from 265 nm to 370 nm through the heat treatment process, and the pattern line width of the TiO ₂ stamp can be changed by adjusting the heat treatment process.

In addition, although the same heat treatment process conditions were performed in FIGS. 7 and 8, it can be seen that the diameters and shapes of the increased holes are different from each other. That is, it can be confirmed that the diameter and shape of the hole can be changed by changing the type of the inorganic resin.

Example 4

9 is an SEM image of an unaligned ZnO stamp using nanoimprint formed in accordance with Example 4 of the present invention.

After the PTFE was added dropwise to the PET substrate, the prepared initial stamp (hole-patterned stamp) was pressed and irradiated with ultraviolet rays for 3 minutes and separated to prepare a PTFE stamp having a pillar. Initially manufactured pillars are vertically aligned on a PET substrate, and in order to deform the vertically aligned pillars into a misaligned form, additionally irradiate the PTFE stamp with the manufactured pillars to warp the pillar shape. It was transformed into a misaligned form.

In the case of (a) of FIG. 9, a ZnO stamp having holes manufactured using the photosensitive ZnO resin as in Example 1 using a PTFE stamp having a pillar initially prepared without additional ultraviolet irradiation. In the case of Figure 9 (b), after the ultraviolet irradiation to the PTFE stamp having the initially prepared pillar for 5 minutes to prepare a stamp having a modified pillar, ZnO stamp prepared using this. In addition, in the case of Figure 9 (c) is a ZnO stamp prepared by using a PTFE stamp having a modified pillar by further irradiating the PTFE stamp having an initially prepared pillar for 10 minutes further ultraviolet rays.

That is, as shown in Figure 9 it can be confirmed that by additionally irradiating the ultraviolet-ray to the PTFE stamp having the initially prepared pillar, it is possible to transform the ZnO stamp from alignment to misaligned form.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation in the embodiment in which said invention is directed. It will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the appended claims.

Claims (12)

Coating an inorganic resin including a metal-organic precursor formed by binding an organic ligand decomposed by at least one of light and heat to a metal element on a stamping substrate;
Preparing a first stamp having a pattern;
Pressing the inorganic resin with the first stamp;
Forming a cured metal oxide thin film pattern on the pressurized inorganic resin by heating or ultraviolet irradiation or heating at the same time;
Removing the first stamp from the metal oxide thin film pattern; And
In order to manufacture a second stamp having a metal oxide thin film pattern different from the pattern of the first stamp, the metal oxide thin film pattern may be heated or ultraviolet ray to change at least one of the shape, line width, and height of the metal oxide thin film pattern. Stamp production method comprising the step of irradiating with ultraviolet rays simultaneously with the irradiation or heating. The method of claim 1, wherein a heating temperature of the metal oxide thin film pattern is 50 ° C. to 800 ° C., and a heating time is 15 seconds to 5 hours. The method of claim 1, wherein the irradiation time of ultraviolet irradiation to the metal oxide thin film pattern is 1 second to 5 hours. The method of claim 1, wherein the first stamp is a master mold made of silicon or quartz or an organic mold formed by duplicating the master mold. The method of claim 1, wherein preparing a first stamp having the pattern includes:
Coating an organic resin on a replica substrate;
Preparing a master mold made of silicon or quartz;
Pressing the organic resin into the master mold;
Preparing an organic mold having a pattern in which the master mold is replicated by heating or irradiating ultraviolet light to the pressurized organic resin or simultaneously with heating;
Removing the master mold from the organic mold; And
In order to modify the pattern of the organic mold to be used as the first stamp, the stamp manufacturing method comprising the step of irradiating the organic mold with ultraviolet rays simultaneously with heating or ultraviolet irradiation or heating. Coating an organic resin on a replica substrate;
Preparing a master mold made of silicon or quartz;
Pressing the organic resin into the master mold;
Preparing an organic mold having a pattern in which the master mold is replicated by heating or irradiating ultraviolet light to the pressurized organic resin or simultaneously with heating;
Removing the master mold from the organic mold;
Irradiating the organic mold with ultraviolet rays simultaneously with heating or ultraviolet irradiation or heating in order to deform the pattern of the organic mold to use as the first stamp;
Coating an inorganic resin including a metal-organic precursor formed by binding an organic ligand decomposed by at least one of light and heat to a metal element on a stamping substrate;
Pressing the inorganic resin with the first stamp;
Forming a cured metal oxide thin film pattern on the pressurized inorganic resin by heating or ultraviolet irradiation or heating at the same time; And
And manufacturing a second stamp made of the metal oxide thin film pattern on the stamp substrate by removing the first stamp from the metal oxide thin film pattern. The method of claim 5 or 6, wherein the organic resin is polytetrafluoroethylene (PTFE), polyurethane acrylate (polyurethane acrylate (PUA), ethylene tetrafluoroethylene (ETFE), polydimethyl Stamp production method, characterized in that any one of siloxane (polydimethylsiloxane, PDMS) and perfluoroalkyl acrylate (PFA). The method of claim 5 or 6, wherein the heating temperature during the heating of the organic mold is 30 ° C to 300 ° C, and the heating time is 1 second to 5 hours. The method of claim 5 or 6, wherein the irradiation time when the organic mold is irradiated with ultraviolet rays is 1 second to 5 hours. The metal element constituting the metal-organic precursor according to claim 1 or 6 is lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium (Mg), aluminum (Al). , Silicon (Si), indium (In), sulfur (S), potassium (K), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn) , Iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), rubidium (Rb) ), Strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), indium (In), tin (Sn), tellurium (Te), antimony (Sb), barium (Ba), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), gadolinium (Gd), hafnium (Hf), tantalum It is at least one selected from the group consisting of (Ta), tungsten (W), iridium (Ir), lead (Pb), bismuth (Bi), polonium (Po) and uranium (U). . The organic ligand of claim 1 or 6, wherein the organic ligand constituting the metal-organic precursor is ethylhexanoate, acetylacetonate, dialkyldithiocarbamates, carboxylic acid ( carboxylic acids, carboxylates, pyridine, diamines, arsines, diarsines, phosphines, diphosphines, butoxide Isopropoxide, ethoxide, chloride, acetate, carbonyl, carbonate, hydroxide, arenes , Beta-diketonate (beta-diketonate), 2-nitrobenzaldehyde (2-nitrobenzaldehyde), acetate dihydrate (acetate dihydrate) and a mixture thereof. The method of claim 1 or 6, wherein the inorganic resin is hexane, 4-methyl-2-pentanone, ketone, methyl isobutyl ketone, methyl ethyl ketone, water, methanol as a solvent , Ethanol, propanol, isopropanol, butanol, pentanol, hexanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMMF), N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran ( tetrahydrofuran, THF), tecan, nonane, octane, heptane, pentane and 2-methoxyethanol (e-methoxyethanol) at least one selected from the group consisting of.

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