KR101535577B1 - Method and apparatus for forming a nano pattern - Google Patents

Abstract

An apparatus for forming a nano pattern is disclosed. An apparatus for forming a nano-pattern according to an embodiment of the present invention includes: a processing chamber having a processing space therein; A support member disposed in the chamber and supporting a thin film formed substrate including the block copolymer; And a common supply unit connected to the process chamber and supplying the common steam to the process chamber; The coalescer feeder uses a vacuum pressure to induce a phase change of the coalescer and feeds the phase change cooperate vapor to the process chamber.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a nano-

The present invention relates to a substrate processing apparatus, and more particularly, to an apparatus and a method for forming a nanopattern using a block copolymer.

A block copolymer is a kind of polymer material, and it is a form in which two or more polymers are connected to each other through covalent bonds. In a diblock copolymer, which is the simplest structure of the block copolymer, two polymers having different tendencies are connected to each other to form a polymer. The two polymers connected to each other are easily phase-separated due to their different material properties, and finally the block copolymer can self-assemble to form a nanostructure.

In order to broaden the application range of the nanostructure produced using the block copolymer, it is important to form a thin film containing the block copolymer on a substrate, and to induce the formation of a stable nanostructure inside the thin film . However, in the above-mentioned thin film, there is a problem that the block copolymer has a nanostructure different from that of the bulk phase due to the interaction between the self-assembled material and the substrate, or the nanostructure is arranged in a different form from the specific structure .

In order to solve this problem, techniques for controlling the orientation and arrangement of nanostructures in the thin film formed on the substrate have been developed.

In order to control the alignment or orientation of the nanostructures, the solvent (co-solvent) was spontaneously vaporized or a bubbling method using N 2 gas was used. However, the natural vaporization method and the bubble method have limitations in increasing the concentration of the solvent gas There is a problem that the process time is increased, and it is limited to the application of a large-sized substrate.

Embodiments of the present invention are intended to provide an apparatus and a method for forming nanopatterns using a block copolymer.

Embodiments of the present invention are intended to provide an apparatus and method for forming a nanopattern that can be applied to shortening the process time and increasing the area of the process by increasing the solvent concentration.

 The objects of the present invention are not limited thereto, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

According to an aspect of the present invention, there is provided a process chamber comprising: a processing chamber having a processing space therein; A support member disposed in the chamber and supporting a thin film formed substrate including the block copolymer; And a common supply unit connected to the process chamber and supplying the common vapor to the process chamber.

The coalescer feeder may also utilize vacuum pressure to induce a phase change of the coalescer and supply the phase change cooperate steam to the process chamber.

The common supply unit may further include: a storage container in which the common ware is stored; A connection pipe connecting the storage vessel and the process chamber; And a shut-off valve installed in the connection pipe.

The common supply unit may further include a heating member installed in the storage container.

In addition, the heating member may include a heating line installed inside or outside the storage container for heating the co-solvent by an indirect heating method, through which the heating medium flows.

The common supply unit may further include a carrier gas supply unit connected to the connection pipe and mixing and supplying the carrier gas when the common gas is supplied to the process chamber.

The co-solvent may also be selected from the group consisting of carbon tetrachloride, 1,1-dichloroethane, o-xylene, 1,1-dichloroethylene, It is preferable to use an organic solvent such as ethylacetate, methyl acetate, toluene, tetrahydrofuran (THF), trichloroethane, benzene, chloroform or trichlorethylene. And at least one selected from the group consisting of

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a neutral layer on a base substrate; Forming a thin film comprising a block copolymer on the neutral layer; And annealing the thin film using a cosolvent to form a nanostructure; The annealing step is to provide a nanopattern formation method for inducing a phase change of a co-solvent using a vacuum pressure and forming the nanostructure using a phase-change coprecipitate vapor.

The annealing may further include loading a substrate into a process chamber; Forming a vacuum in the process chamber; And introducing the phase change into the co-solvent stored in the storage vessel using vacuum pressure and supplying the phase-change coprecipitate to the process chamber via the connection piping.

The annealing may further include detecting an increase in the thickness of the nanostructure and blocking supply of the vapor to the process chamber when the thickness of the nanostructure reaches a predetermined value.

The annealing may further include a reaction inducing step of waiting for a reaction to be induced for a predetermined time after the supply of the vapor is stopped.

In addition, the step of forming a vacuum in the process chamber may include opening a vacuum valve connected to the pumping unit such that a vacuum pressure is applied to the process chamber; Opening the connection piping so that vacuum pressure provided to the process chamber is also provided to the storage tank; Blocking the connection pipe when the vacuum pressure of the storage tank reaches a set value; And blocking the vacuum valve when the vacuum pressure of the process chamber reaches a set value.

Also, the annealing step may be performed at a pressure of the storage tank between 140 and 160 Torr.

Also, the annealing step may be performed at a temperature of the cosolvent stored in the storage tank between 20 and 25 ° C.

The co-solvent may also be selected from the group consisting of carbon tetrachloride, 1,1-dichloroethane, o-xylene, 1,1-dichloroethylene, It is preferable to use an organic solvent such as ethylacetate, methyl acetate, toluene, tetrahydrofuran (THF), trichloroethane, benzene, chloroform or trichlorethylene. And at least one selected from the group consisting of

In addition, the annealing step may be such that the common vapor is mixed with the carrier gas and supplied to the process chamber.

According to an embodiment of the present invention, nanoblocks can be formed by annealing using a co-solvent.

According to the embodiments of the present invention, it is possible to process a large-area substrate by improving the common steam supply method which was carried out at the existing atmospheric pressure by using a vacuum, and by reaching the point where the co- It is possible to shorten the processing time by increasing the concentration and amount of the steam.

1 is a flowchart illustrating a method of fabricating a nanostructure according to an embodiment of the present invention.
FIGS. 2A to 2C are cross-sectional views illustrating respective steps according to the flowchart of FIG.
3 is a perspective view illustrating the nanostructure of FIG. 2C.
4 is a conceptual cross-sectional view of the nanopatterning apparatus used in the co-annealing process of FIG.
FIG. 5 is a graph showing the temperature change of the co-solvent depending on the pressure.
6 is a flow chart for explaining the annealing process.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout the specification and claims. The description will be omitted.

FIG. 1 is a flow chart for explaining a method of manufacturing a nanostructure according to an embodiment of the present invention, and FIGS. 2A to 2C are sectional views for explaining each step according to the flowchart of FIG.

Referring to FIGS. 1 and 2A, a neutral layer 120 is formed on a base substrate 110 (step S110).

The base substrate 110 may be a glass substrate, a plastic substrate, or the like.

The neutral layer 120 is formed on the base substrate 110 in such a manner that a block copolymer that is a polymer in which different monomers are covalently bonded is perpendicular to the surface of the base substrate 110, To grow steadily. The block copolymer will be described in detail with reference to FIG. 2B.

The neutral layer 120 has a chemically neutral state that is neither hydrophilic nor hydrophobic. The neutral layer 120 is formed on the surface of the base substrate 110 (or the surface of the base substrate 110) using hydroxyl-terminated polystyrene-random-polymethyl methacrylate (HO-PS- By grafting the grains. Quot; A " and "B" for hydroxyl-terminated homopolymers, e.g., polymers, Compounds having -A-OH structure and B-B- The neutral layer 120 can be formed by applying a mixture of compounds having a -B-OH structure on the base substrate 110. [

Alternatively, the neutral layer 120 may include an organic monolayer, including a self-assembled monolayer (SAM), a polymer brush or a cross-linked random copolymer mat (MAT) can do.

Although not shown in the drawing, the surface of the base substrate 110 may be pretreated with an acidic solution before the neutral layer 120 is formed. By the pretreatment, the affinity between the base substrate 110 and the neutral layer 120 can be improved. Examples of the acidic solution include hydrofluoric acid (HF).

Referring to FIGS. 1 and 2B, a thin film 130 including a block copolymer is formed on the base substrate 100 on which the neutral layer 120 is formed (step S120).

The monomers constituting the block copolymer have different physical properties and chemical properties. Any one of the first monomers is relatively hydrophilic relative to the other second monomer, and the second monomer has a relatively hydrophobic property as compared with the first monomer. The block copolymer is a compound in which a first polymer comprising the first monomer and a second polymer comprising the second monomer are blocked. In the present invention, the volume ratio of the first monomer and the second monomer to the total volume of the block copolymer is about 1: 1. When the volume ratio is greater than or equal to about 1: 1, the block copolymer has a cylinder, gyroid, or spherical shape other than a lamellar structure, so that the unit block according to the present invention forms a stripe- It is difficult to do.

When the weight average molecular weight of the block copolymer is about 100,000 or less, it can take a long time, but it can be easily phase separated even through thermal annealing conventionally known. However, as the weight average molecular weight of the block copolymer increases or the area of the base substrate 110 increases, it is difficult to form a nanostructure using the block copolymer. Therefore, a block copolymer having a weight average molecular weight of less than about 150,000 is usually used to form a nanostructure.

On the other hand, in the production of the nanostructure according to the present invention using the co-annealing to be described in detail below, the block copolymer may have a weight average molecular weight of about 150,000 or more. Specifically, even if the weight average molecular weight of the block copolymer is 150,000 to 300,000, the nanostructure can be easily formed.

The block copolymer may comprise polystyrene-block-poly (n-alkyl) methacrylate. Here, "n-alkyl" represents an alkyl group having 1 to 10 carbon atoms. For example, the block copolymer can be selected from the group consisting of polystyrene-block-poly (methyl methacrylate), PS-b-PMMA, polystyrene-block-poly (ethyl methacrylate) poly (ethyl methacrylate), PSb-PEMA], polystyrene-block-poly (propyl methacrylate), polystyrene-block-poly (butyl methacrylate) (polystyrene-block-poly (butyl methacrylate)], polystyrene-block-poly (normal-pentyl methacrylate), polystyrene- Polystyrene-block-poly (normal-hexyl methacrylate)].

Alternatively, the block copolymer may be selected from the group consisting of polystyrene-block-poly (ethylene oxide), PS-b-PEO, polystyrene-block-poly vinyl pyridine, PS-b-PVP, polystyrene-block-poly (ethylene-alt-propylene), PS-b-PEP, polystyrene- [polystyrene-block-polyisoprene, PS-b-PI].

Referring to FIGS. 1 and 2C, the base substrate 110 on which the thin film 130 is formed is subjected to cosolvent annealing to form a nanostructure NS.

The co-solvent is a solvent having affinity for both the first and second monomers of the block copolymer. That is, when the co-solvent is the first monomer as "A, " -A, and when the second monomer is referred to as "B, " The second polymer having a structure such as -B can be dissolved.

Specific examples of the co-solvent include carbon tetrachloride, 1,1-dichloroethane, o-xylene, 1,1-dichloroethylene ), Ethyl acetate, methyl acetate, toluene, tetrahydrofuran (THF), trichloroethane, benzene, chloroform, or trichlorethylene trichlorethylene) and the like.

All of the first and second polymers constituting the block copolymer of the lamellar structure have an affinity equivalent to that of the surface of the base substrate 110, specifically, the surface of the neutral layer 120 Each of the first and second polymers is brought into contact with the neutral layer 120 at a substantially equal ratio with respect to a predetermined area. That is, the first and second polymers may be aligned in the horizontal direction with respect to the surface of the neutral layer 120.

At the same time, a portion of the neutral layer (120) in contact with the first polymer has the property of the first polymer that is not neutral by contacting with the first polymer. That is, since the affinity of the first polymer in contact with the neutral layer 120 to the first polymer is much stronger than that of the second polymer in the thin film 130, The first polymer attracts another first polymer and the second polymer, which is in contact with the neutral layer 120, attracts another second polymer, and in such a chain direction, the first and second polymers interact with the neutral layer And accumulates in the vertical direction with respect to the surface of the substrate 120. Accordingly, the first and second polymers are phase-separated by the co-solvent.

The co-solvent promotes the above-described chain direction to form the second nanoblocks NB1 disposed between the first nanoblocks NB1 and the adjacent first nanoblocks NB1 in a direction perpendicular to the surface of the neutral layer 120, By growing the nano blocks NB2, the unit block can form the nanostructure NS having a stripe shape.

3 is a perspective view illustrating the nanostructure of FIG. 2C.

Referring to FIGS. 2C and 3, the first nanoblocks NB1 and the second nanoblocks NB2, which are unit blocks of the nanostructure NS, extend in a first direction D1. . The first and second nano blocks NB1 and NB2 may be arranged in a line in a second direction D2 that intersects the first direction D1. Since the block copolymer has a lamellar structure, the first and second nano blocks NB1 and NB2 may have a structure extending in the first direction D1.

The first polymer is annealed in the third direction D3 perpendicular to the first and second directions D1 and D2 on the surface of the neutral layer 120 by annealing the thin film 130 using the co- The first nanoblocks NB1 are formed. In the same manner, the thin film 130 is annealed using the co-solvent to form the second nanoblocks NB2 while the second polymer is gathered in the third direction D3 from the surface of the neutral layer 120, .

The annealing process of the thin film 130 using the co-solvent is phase-separated using the chemical properties of the co-solvent and the block copolymer, and therefore, when inducing phase separation of the first and second polymers by heat, Lt; RTI ID = 0.0 > C, < / RTI > As an example, the annealing process of the thin film 130 using the co-solvent may be performed at about 10 ° C to about 20 ° C.

Hereinafter, the annealing process of the thin film 130 using the co-solvent will be described in detail with the production apparatus shown in FIG.

4 is a conceptual cross-sectional view of the nanopatterning apparatus used in the co-annealing process of FIG. In FIG. 4, the base substrate 110 on which the thin film 130 is formed is briefly shown and referred to as a "process substrate S ".

4, the nano-pattern forming apparatus 200 includes a process chamber 210, a support member 220, a common supply unit 240, a temperature control unit 232, a temperature sensing unit 234, 280).

The nano-pattern forming apparatus 200 is for an annealing process for forming the nanostructure NS using the thin film 130.

The process chamber 210 provides a space for performing the annealing process. The support member 220 is installed in the inner space of the process chamber 210. A showerhead 218 is installed on the upper part of the process chamber 210.

The substrate S on which the thin film 130 shown in FIG. 2B is formed is disposed on the support member 220. The supporting member 220 may be provided with a heating member 224 for heating the base substrate 110 and a cooling member 228 for cooling the base substrate.

 The inner space of the chamber 210 may be provided in a vacuum state at atmospheric pressure by the pumping portion 280.

On the bottom surface of the process chamber 110, exhaust holes are provided. The exhaust holes are connected to the pumping portion 280. The pumping portion 280 includes a pumping line 282 and a vacuum pump 284. Within this pumping line, a vacuum valve 286 is provided to turn on / off the supply of vacuum pressure to the process chamber 110. That is, the vacuum valve 286 is installed in the pumping line 282 between the process chamber 210 and the vacuum pump 284 and functions to transfer or block the suction force of the vacuum pump 284 to the process chamber 210 . Generally, the vacuum valve 286 turns on / off the vacuum pressure while blocking or opening the flow path inside the pumping line 282.

The temperature inside the process chamber 210 may be between about 10 ° C and about 20 ° C.

The temperature control unit 232 and the temperature sensing unit 234 are connected to the process chamber 210 to maintain a constant temperature in the process chamber 210. The temperature control unit 232 and the temperature sensing unit 234 are also connected to each other. For example, when the temperature sensing unit 234 detects that the temperature of the process chamber 210 is lowered or increased, the temperature sensing unit 234 transmits a signal to the temperature control unit 232, 210 may be increased or decreased.

The substrate (S) is provided with the co-solvent vapor, thereby annealing the thin film (130). That is, the thin film 130 is co-annealed by the common vapor.

The coalescer feeder 240 is connected to the showerhead 218 installed in the process chamber 210 to provide the process chamber 210 with a common vapor. The coalescer feeder 220 phase-changes the coalescer to the gaseous state to provide the coalescer vapor to the chamber 210. The coalescer feeder 240 uses the vacuum pressure to induce a phase change of the coalescer and feeds the phase change cooperate steam to the process chamber.

As shown in FIG. 5, when the pressure of the storage container is changed from 140 to 160 Torr at normal pressure, the coalescence starts to be broken at about room temperature (20-25 DEG C) Vapor pressure generation can be increased.

The common supply portion 240 includes a storage vessel 242 in which a co-solvent is stored, a connection piping 244 connecting the storage vessel 242 and the showerhead 218 of the process chamber 210, And a heating member 260 installed inside or outside to heat the co-solvent by indirect heating. The heating member 260 may include a heating line 262 through which the heating medium flows and the heating line 262 may be installed inside or outside the storage container 242.

The connection piping 244 may be provided with a shutoff valve 246 that functions to supply or shut off the common steam to the process chamber 210. The connection pipe 244 may be connected to a carrier gas supply unit 250 capable of supplying N 2 gas or air gas to the process chamber 210.

6 is a flow chart for explaining the annealing process.

6, the annealing process in the nano-pattern forming apparatus 200 includes steps S110 and S110 of disposing a substrate S including a thin film 130 on a supporting member 220 of the process chamber 210, (S120) forming the inner space of the process chamber 210 at a predetermined vacuum pressure (S120), supplying the phase-changed coprecipitated steam in the storage tank 242 to the process chamber (S130), measuring the thickness of the nanostructure on the substrate (S160), a reaction inducing step (S170), a process chamber pumping step (S180), and a step (S180) of determining whether the thickness of the nanostructure is a set value Unloading step (S190).

Step S120 of forming the inner space of the process chamber 210 with a predetermined pressure of vacuum opens the vacuum valve 286 connected to the pumping unit 280 so that vacuum is supplied to the process chamber 210. The connection piping 244 is then opened so that the vacuum pressure provided to the interior of the process chamber 210 is also provided to the storage vessel 242. When the vacuum pressure of the storage tank 242 reaches the set value (140-160 Torr), the connection pipe 244 is shut off. In the storage tank 242, the phase change of the co-solvent is caused by the vacuum pressure. On the other hand, when the process chamber 210 reaches the set vacuum pressure, the vacuum valve 286 is shut off. Because the storage tank 242 is smaller in volume than the process chamber 210, it will reach the desired vacuum pressure faster than the process chamber 210.

The step of supplying the phase-change coprecipitated steam to the process chamber in the storage tank 242 (S130) may be performed by opening the shutoff valve 246 provided in the connection pipe 244 and storing the pressure by the pressure difference between the process chamber and the storage tank In vessel 242, the phase-change coproduct vapor is supplied to process chamber 210 via connection piping 244. In the process chamber 210, the thin film 130 annealing process is performed while the common vapor is supplied. For reference, the common vapor can mix and supply the carrier gas from the carrier gas supply unit.

The step of sensing the thickness of the nanostructure on the substrate S140 and the step S150 of determining whether the thickness of the nanostructure is a set value are performed in such a manner that the thickness measuring sensor 290 provided in the process chamber 210 measures the increment of the nanostructure on the substrate S When the nanostructure is formed to have an appropriate thickness, the supply of the common vapor is blocked (S160). Then, a reaction inducing step (S170) for waiting for reaction for a predetermined time after the supply of the common vapor is blocked is performed. Finally, the substrate S is unloaded from the process chamber 210 (S180, S190) after the common vapor in the process chamber is completely removed through the pumping unit 280.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

210: process chamber 220: support member
240: Solvent supply unit 250: Carrier gas supply unit
280:

Claims (16)

A nano-pattern forming apparatus comprising:
A process chamber having a processing space therein;
A pumping unit providing vacuum pressure into the process chamber;
A support member disposed in the chamber and supporting a thin film formed substrate including the block copolymer; And
A coalescer connected to the process chamber to induce a phase change of the coalescer using vacuum pressure and to supply the phase change cooperate steam to the process chamber;
The co-
A storage vessel in which the co-solvent is stored and a phase change of the co-solvent is made using the vacuum pressure of the process chamber;
A connection pipe connecting the storage vessel and the process chamber; And
Opening the connection pipe so that a vacuum pressure provided in the connection pipe is provided to the storage container, and when the storage container reaches a set vacuum pressure, And a shut-off valve for shutting off the connection piping so that a phase change of the wafer occurs. delete delete The method according to claim 1,
The co-
And a heating member installed in the storage container. 5. The method of claim 4,
The heating member
And a heating line installed inside or outside the storage container for heating the co-solvent by an indirect heating method, the heating line through which the heating medium flows. The method according to claim 1,
The co-
And a carrier gas supply unit connected to the connection pipe and mixing and supplying the carrier gas when the co-solvent is supplied to the process chamber. The method according to claim 1,
The co-solvent is selected from the group consisting of carbon tetrachloride, 1,1-dichloroethane, o-xylene, 1,1-dichloroethylene, ethyl acetate (s) selected from the group consisting of ethylacetate, methyl acetate, toluene, tetrahydrofuran (THF), trichloroethane, benzene, chloroform or trichlorethylene Lt; RTI ID = 0.0 > 1, < / RTI > A method for forming a nano pattern, comprising:
Forming a neutral layer on the base substrate;
Forming a thin film comprising a block copolymer on the neutral layer; And
And annealing the thin film using a cosolvent to form a nanostructure;
The annealing step
Loading a substrate into a process chamber;
Forming a vacuum in the process chamber; And
Introducing the co-solvent stored in the storage vessel to a phase change using vacuum pressure, and supplying the phase-change coprecipitate to the process chamber via a connecting line,
The step of forming a vacuum in the process chamber
Opening a vacuum valve connected to the pumping unit such that vacuum pressure is provided to the process chamber;
Opening the connection piping so that vacuum pressure provided to the process chamber is also provided to the storage tank;
Blocking the connection pipe when the vacuum pressure of the storage tank reaches a set value;
And blocking the vacuum valve when the vacuum pressure of the process chamber reaches a set value. delete 9. The method of claim 8,
The annealing step
Detecting a thickness increment of the nanostructure and blocking supply of the vapor to the process chamber when the thickness of the nanostructure reaches a predetermined value. 11. The method of claim 10,
The annealing step
And a reaction inducing step of waiting for the reaction induction to be performed for a predetermined time after the supply of the common vapor is blocked. delete 9. The method of claim 8,
The annealing step
Wherein the pressure of the storage tank is between 140 and 160 Torr. 14. The method of claim 13,
The annealing step
Wherein the temperature of the cosolvent stored in the storage tank is between 20 and 25 < 0 > C. 9. The method of claim 8,
The co-solvent is selected from the group consisting of carbon tetrachloride, 1,1-dichloroethane, o-xylene, 1,1-dichloroethylene, ethyl acetate (s) selected from the group consisting of ethylacetate, methyl acetate, toluene, tetrahydrofuran (THF), trichloroethane, benzene, chloroform or trichlorethylene Lt; RTI ID = 0.0 > 1, < / RTI > 9. The method of claim 8,
The annealing step
Wherein said common vapor is mixed with a carrier gas and supplied to said process chamber.

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