KR100953297B1 - Fabrication method of nano-dots array using Atomic Layer Deposition - Google Patents

Abstract

The present invention relates to a method for manufacturing a nano dot array and a sensor comprising the nano dot array produced thereby. The present invention provides a method of preparing a substrate comprising: (a) providing a substrate on which a porous nano template is disposed in a reaction chamber, wherein the porous nano template includes pores in the form of a cylinder formed using a triblock copolymer; (b) maintaining a first bubbler comprising a first precursor in a preset temperature range; (c) maintaining a second bubbler comprising a second precursor within a preset temperature range; And (d) sequentially supplying the first precursor and the second precursor to the reaction chamber to sequentially react the first precursor and the second precursor on the surface of the substrate exposed inside the pores to form a nano dot array. Steps. According to the present invention, there is an advantage in that a nano-dot array that can be variously utilized by using a nano template and an atomic layer deposition machine using a triblock copolymer.

Nano dots, triblock copolymers, atomic layer evaporators, TiO2, bubblers, templates

Description

Fabrication method of nano-dots array using Atomic Layer Deposition

The present invention relates to a method for producing a nano-dot array using an atomic layer evaporator, and more particularly to a method for producing a nano-dot array of a desired thickness using a triblock copolymer.

The spatial arrangement of nanostructures, such as domains in block copolymer thin films, has a wide application range from block copolymer lithography to catalysts and solar cells.

In the related art, a nano-platelet having pores in the form of cylinders is prepared by using a block copolymer, and thus a nano dot array is manufactured.

A general approach to controlling the orientation of the PS- b- PMMA (styrene-methyl methacrylate block copolymer) system, which is mainly used as a block copolymer in the manufacture of nano-templates, makes the interfacial energy between the substrate and the polymer copolymer neutral. In order to form a pattern through thermal annealing (thermal annealing) using a random polymer copolymer.

However, according to the prior art, when the molecular weight of the polymer copolymer exceeds 100 kg / mol has a disadvantage that the pattern is not formed well. (Ting Xu, Ho-Cheol Kim, Jason DeRouchey, Chevery Seney, Catherine Levesque, Paul Martin, C. M. Stafford, T. P. Russell, Polymer 42, 9091, 2001)

In addition, since a 6 nm-thick random polymer copolymer is present between the substrate and the pattern, an element requiring direct contact with the substrate requires an etching process, thereby making the process complicated and difficult.

Furthermore, the pattern formation method according to the prior art was not suitable when a large area pattern was required because the domain of the pattern was 500 nm or less.

In addition, in PS- b- PEO, PEO is located in the center of the cylindrical domain and PS is located around it. Due to the strong bonding force between PEO and PS, the PEO is hardly removed even after UV and acetic acid treatment. There was a difficulty in preparing nano templates with pores.

Meanwhile, conventional chemical vapor deposition is mainly used to manufacture nano dot arrays through nano-templates, but chemical vapor deposition is not only difficult to manufacture thin nano dot arrays but also has difficulty in controlling.

In the present invention, to solve the problems of the prior art as described above, it is proposed a method for manufacturing a nano-dot array using an atomic layer evaporator capable of uniformly forming a large area nano-dot array.

Another object of the present invention is to provide a method for manufacturing a nano dot array using an atomic layer deposition machine that can improve the miniaturization and sensitivity of the sensor by applying various chemical, physical, electrical and magnetic properties of the nano dot.

According to a preferred embodiment of the present invention to achieve the above object, a method of manufacturing a nano-dot array using an atomic layer deposition machine, the method comprising the steps of: (a) providing a substrate having a porous nano-template disposed inside the reaction chamber The porous nano template comprises pores in the form of cylinders formed using triblock copolymers; (b) maintaining a first bubbler comprising a first precursor in a preset temperature range; (c) maintaining a second bubbler comprising a second precursor within a preset temperature range; And (d) sequentially supplying the first precursor and the second precursor to the reaction chamber to sequentially react the first precursor and the second precursor on the surface of the substrate exposed inside the pores to form a nano dot array. Provided is a method of manufacturing a nanodot array comprising the steps.

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According to the present invention, since the porous nano template formed through the triblock copolymer is used, there is an advantage of uniformly manufacturing the nano dot array.

In addition, according to the present invention, it is possible to manufacture a nano-point array of a fine size, if the miniaturization is possible there is an advantage that can be utilized in the sensor with improved sensitivity.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. Like reference numerals are used for like elements in describing each drawing.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In order to facilitate a thorough understanding of the present invention, the same reference numerals are used for the same means regardless of the number of the drawings.

1 is a diagram showing the configuration of an atomic layer deposition machine used in the present invention.

Atomic layer evaporator is a nano thin film evaporator using the principle that monoatomic layer is formed on the surface of the substrate during the manufacturing process of devices such as semiconductors. It is possible. Such atomic layer evaporators can form thin films even at low temperatures.

As shown in FIG. 1, an atomic layer depositor may include a reaction chamber 100 and one or more bubblers 102.

According to the present invention, a substrate on which a porous nano-template is disposed is provided on the inside of the reaction chamber 100 and a precursor is injected through the bubbler 102 on the surface of the substrate exposed through the pores of the porous nano-template. This results in an array of nanodots of desired atomic layer thickness.

2 is a flow chart of a nano dot array manufacturing process according to a preferred embodiment of the present invention, Figure 3 is a schematic diagram of a nano dot array manufacturing process according to the present invention.

2 to 3, first, a substrate 302 having a porous nano template 300 disposed inside a reaction chamber is provided (step 200).

In the present invention, the pressure of the reaction chamber is maintained at 10 ⁻³ torr and the temperature at 100 ° C.

As described above, the porous nano-template 300 applied to the present invention is formed using a triblock copolymer, preferably PS- b- PMMA- b- PEO (poly (styrene- b- methyl methacrylate- b) -ethylene oxide)) is used.

4 is a view schematically showing a process for producing a porous nano-template through the triblock copolymer applied to the present invention.

Referring to FIG. 4, PS- b- PMMA- b- PEO 400 is coated on a substrate and solvent annealed under predetermined temperature and benzene vapor conditions to vertically align the cylindrical domains on the substrate.

At this time, the PEO 310 is arranged at the center of the cylindrical domain, and the PSMA 314 is arranged at the periphery of the PMMA 312 and the frame.

Thereafter, the vertically oriented PEO domain and PMMA are removed through UV irradiation and acetic acid treatment to form the porous nano template 300 (see FIGS. 3-4). When forming the nano template through the triblock copolymer, PMMA is disposed between PEO and PS to facilitate removal of the PEO domain.

Preparation of porous nano templates using triblock copolymers is described in Joona Bang. et al. Defect-Free Nanoporous Thin Films from ABC Triblock Copolymers (J. AM. CHEM. SOC. 9 VOL. 128, NO. 23, 2006).

According to the present invention, a first bubbler 102-1 and a second bubbler 102-2 for injecting a first precursor into the reaction chamber 100 may be provided.

While placing the substrate 302 on which the porous nano template 300 formed through the triblock copolymer is disposed in the reaction chamber 100 as described above, the first bubbler 102-1 including the first precursor is The temperature is maintained at the preset temperature range (step 202), and the second bubbler 102-2 including the second precursor is maintained at the preset temperature range (step 204).

According to the invention, the first precursor is H ₂ O, the second precursor is a Ti source, preferably, the Ti source may be Ti (OCH (CH ₃ ) ₂ ) ₄ (Titanium (IV) isopropoxide). This makes it possible to produce a nano-dot array consisting of a TiO ₂ layer on the substrate.

In the following, the case where the precursors are H ₂ O and Ti sources will be described.

When the first precursor is H ₂ O and the second precursor is a Ti source, the first bubbler and the second bubbler may be maintained in the range of 50 to 70 ° C., preferably the first bubbler is 60 ° C., The 2 bubbler can be maintained at 63 ° C.

H ₂ O of the first bubbler 102-1 is supplied to the reaction chamber 100 to react with the substrate exposed inside the pores in a gaseous state to form an end group (OH) as shown in FIG. 206).

Thereafter, high concentration nitrogen (N ₂ , 99.999%) is injected into the reaction chamber 100 to remove the reaction residue (step 208).

After removing the residue, nitrogen is injected into the second bubbler 102-2 (step 210), and the mixed nitrogen and Ti source in the second bubbler 102-2 is supplied to the reaction chamber 100 ( Step 212).

In step 212, the nitrogen and Ti sources react with end groups formed on the substrate in a gaseous state to form a layer as shown in FIG. 5C, and nitrogen is injected into the reaction chamber 100 to remove reaction residues (step 214). .

Thereafter, H ₂ O is again supplied to the reaction chamber 100 through the first bubbler 102-1 to form TiO ₂ on the substrate 302. Form a layer (step 216, see FIG. 5D).

Through the above process, the TiO ₂ layer of the monoatomic layer is formed, and the nanopoint array 304 having the desired thickness is formed by repeating the above steps 206 to 216 (step 218).

In this experiment, steps 206-216 were repeated four times to deposit a 20 nm TiO ₂ layer.

Next, after removing the substrate from the reaction chamber 100 to remove the porous nano-template (step 220, see Figure 5d).

In step 220, in order to remove the porous nano-template, the substrate on which the nano-dot array is formed is immersed in a toluene solution for a predetermined time, preferably for 10 minutes, and vibrated using an ultrasonic vibration device.

In the above description, the nanopoint array is manufactured by using two precursors. However, the present invention is not limited thereto, and the number of precursors may be variously applied according to components of a desired metal nanopoint.

According to the present invention, since the porous nano-template oriented using the triblock copolymer has a high uniformity, the nano dot array manufactured through the triblock copolymer may also have excellent uniformity.

And by adjusting the amount of each of the components of the PS- b -PMMA- b -PEO triblock copolymer it is possible to control the pore size.

In general, TiO ₂ forms electrons (e-) and holes (h +) when exposed to ultraviolet rays such as sunlight or fluorescent light, and holes (h +) form hydroxides (OH Radicals) that have particularly strong oxidation effects. It has stronger oxidizing power than ozone hypochlorite. In addition, electrons generate oxygen ions adsorbed on the photocatalyst into oxygen ions, which produce intermediates and peroxides in the oxidation reaction or water reaction through hydrogen peroxide. According to the above reaction, TiO ₂ has an antifouling effect, an air purification effect, a water purification effect, a bactericidal effect, and an odor removing effect.

Therefore, the sensor may be manufactured by surface-treating the nanopoint array according to the present invention with various functionalities.

The various chemical, physical, electrical and magnetic properties of these nanodots can be used as electrochemical sensors that detect many toxic gases such as CO, NO _x , SO _x , O ₃ and Dioxin. The present invention is expected to improve the miniaturization and sensitivity of the sensor, it is also expected to be developed as a bio-catalyst if the surface treatment is possible with a material that reacts to a specific bio-material or enzyme.

Preferred embodiments of the present invention described above are disclosed for purposes of illustration, and those skilled in the art will be able to make various modifications, changes, and additions within the spirit and scope of the present invention. Additions should be considered to be within the scope of the following claims.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the configuration of an atomic layer evaporator used in the present invention.

2 is a flow chart of a nano dot array manufacturing process according to an embodiment of the present invention.

Figure 3 is a schematic diagram of a nano dot array manufacturing process according to the present invention.

Figure 4 schematically shows a process for producing a porous nano-template through the triblock copolymer applied to the present invention.

5 shows a reaction process on the surface of a substrate according to the invention.

Claims (11)

A method of manufacturing a nanopoint array using an atomic layer deposition machine, (a) providing a substrate having a porous nano template disposed therein into the reaction chamber, wherein the porous nano template comprises pores in the form of cylinders formed using a triblock copolymer; (b) maintaining a first bubbler comprising a first precursor in a preset temperature range; (c) maintaining a second bubbler comprising a second precursor within a preset temperature range; (d) sequentially supplying the first precursor and the second precursor to the reaction chamber to react the first precursor on the surface of the substrate exposed inside the pores to form terminal groups, and then the terminal group and the second precursor. Reacting a precursor to form an array of nanodots on the exposed substrate surface; And (e) removing the porous nano template using an ultrasonic vibration device. The method of claim 1, The porous nano template is a nano dot array manufacturing method formed using a PS- b -PMMA- b -PEO triblock copolymer. The method of claim 1, The method of (b) and (c) step is a nano dot array manufacturing method in the range of 50 to 70 ℃. The method of claim 1, Wherein the first precursor is H ₂ O, the second precursor is a Ti source, and the step (d) forms a layer of TiO ₂ on the substrate. The method of claim 4, wherein The Ti source is Ti (OCH (CH ₃ ) ₂ ) ₄ Nano dot array manufacturing method. The method of claim 1, In step (d), Supplying H ₂ O of the first bubbler to the reaction chamber to react with the substrate exposed in the pores in a gaseous state to form an end group (-OH); Supplying a Ti source of the second bubbler to the reaction chamber to react with the end group to form a TiO ₂ layer on the substrate. delete The method of claim 6, And supplying nitrogen to the second bubbler, and supplying the nitrogen and Ti sources of the second bubbler to the reaction chamber. The method of claim 6, Step (d) is TiO ₂ of the desired thickness A method of making a nanodot array, repeated over a predetermined number of times to form a layer. The method of claim 1, Wherein (e) step is carried out in the state in which the substrate is placed in a toluene solution. delete

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