KR20180118835A - A freestanding-like membrane structure and a method of manufacturing the same - Google Patents

Abstract

The present invention relates to a free standing membrane structure, in which a carbon thin film is directly coupled and grown on a substrate surface, and to a manufacturing method thereof, and more particularly, to a free standing membrane structure, in which the carbon thin film is directly coupled and grown on the substrate without a separate coupling layer or a linker by using a plasma polymerization method using a monomer containing a benzene compound as a basic structure, and to a manufacturing method thereof. Therefore, the free standing membrane structure of the present invention is excellent in durability and permeability.

Description

 BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a free standing membrane structure and a method of manufacturing the same,

The present invention relates to a free standing membrane structure in which a carbon thin film is directly bonded to and grown on a substrate surface and a method for manufacturing the free standing membrane structure. More particularly, the present invention relates to a free standing membrane structure comprising benzene Free-standing membrane structure in which a carbon thin film is directly bonded and grown on a substrate without a separate bonding layer or a linker, and a method for manufacturing the same .

In the semiconductor process, the original plate of a pattern used for transferring a pattern to a wafer is called a mask. The protective film for protecting the mask from contaminants is called a pellicle. The pellicle forms a protective film with a certain distance from the mask, so that even if contaminants are formed in the protective film or the contaminating particles sit, these types of defective materials do not interfere with pattern formation by the wafer. Since the light transferred to the wafer is focused by the mask and exposes, the contaminant is allowed to sit on the pellicle spaced at a certain distance. However, this is not focused and does not affect the size of the pattern to be created by the user, Which is an expensive product.

These pellicles did not cause problems in fabrication until the present ArF immersion lithography technique. However, when the conventional pellicle is applied to the EUVL exposure process, the EUV light source is absorbed by the pellicle due to the organic material, and the film itself is damaged due to high energy. As a result of these problems, several alternatives to proceed the process without pellicle have been researched but it is believed that it is difficult to completely block the pollutant and it is convinced that the development of pellicle for EUV is necessary.

The use of pellicles in EUV masks has the advantage that they can prevent the formation of defects in the wafer pattern due to contaminants, but EUV pellicles should be made in ultra-thin (<50 nm) structures because the EUV wavelength is easily absorbed by all materials .

However, it is very difficult to fabricate such an ultra-thin membrane with a size of 6 inches. Thus, various support structures are proposed as a reinforcing agent. In order to compensate for the weak strength of the ultra-thin structure pellicle, we are trying to use a honeycomb-type support as a reinforcing agent. This structure can also improve some problems such as deflection and tear of the pellicle membrane. However, There arises a problem that the intensity distribution of the EUV light becomes uneven after passing through the pellicle.

Therefore, there is a need for research on pellicles for EUV lithography that can solve this problem.

As a method for solving such a problem, a method of using graphite (graphite), graphene, and graphene oxide has attracted attention. Graphene is a single flat sheet composed of sp ² bonds of carbon atoms. It can be seen in the form of a hexagonal crystal lattice integrated. It has advantages such as mechanical and electrical properties of carbon nanotube, Because it has unusual physical properties, it is emerging as the most popular material in recent years.

Oxidized graphene is a material that is produced by oxidizing graphite. Various processes have been proposed to obtain graphene oxide with the recent interest of graphene. In the process of forming the graphene oxide through the oxidation treatment of graphite, it takes a long time to synthesize the graphene oxide in the method proposed so far, so that after the oxidation graphene is synthesized, It is difficult to separate the acid from the graphene oxide grains because the amount of acid penetration increases.

Further, the acid used in the synthesis of the graphene oxide is discarded in a large amount, which adversely affects the environment.

Accordingly, the present inventors have found that a process for coating a benzene-based polymer on a surface of a substrate through a plasma polymerization process using a monomer having benzene as a basic structure, and a process for carbonizing the carbon thin film directly, And confirming the effect thereof through the membrane structure.

In addition, the free standing membrane structure according to the present invention has a nano-thick substrate, so that it has a characteristic of a free standing membrane type without a separate support, and it has been confirmed that the membrane has an excellent transmittance.

1. Korean Patent Publication No. 10-2016-0057217 2. Korean Patent Publication No. 10-2014-0135725 3. US Patent No. 9,360,749 B 4. Japanese Laid-Open Patent Application No. 2016-80967 A

SUMMARY OF THE INVENTION It is an object of the present invention to provide a free standing membrane structure in which a carbon thin film is directly bonded and grown on a surface of a substrate and a method for producing the free standing membrane structure, To provide a free standing membrane structure, and to provide a free standing membrane structure having a high nano-thickness transmittance.

In order to achieve the above object,

A free standing membrane structure directly bonded to and grown on the substrate and the surface of the substrate; And a method for producing the same.

The present invention relates to a substrate; And a free-standing membrane structure having a total thickness of 2 to 100 nm including a carbon thin film having a thickness of 1 to 20 nm directly bonded to and growing on the substrate surface.

At this time, the substrate may include at least one selected from the group consisting of graphite, Cr, Zr, Mo, Y, Si, Rb, Sr, Nb and Ru and has a thickness of 1 to 80 nm.

In this case, the substrate may further include at least one substrate.

In this case, the substrate may include a first substrate; And

And a second substrate positioned on the upper portion of the first substrate, the lower portion, or both the upper and lower portions of the first substrate.

In one embodiment of the present invention, the first substrate is Si, and the second substrate is selected from the group consisting of graphite, Cr, Zr, Mo, Y, Rb, Sr, Nb or Ru .

The carbon thin film may include at least one selected from the group consisting of graphite, graphite, graphene, oxide graphene, and carbon nanotube, and in one embodiment may be graphene oxide.

At this time, the carbon thin film may be obtained by carbonizing a polymer thin film composed of a polymer which is a plasma polymer of a monomer containing benzene as a basic structure.

The free standing membrane structure may be used as an EUV pellicle.

The present invention also provides a method of manufacturing a free standing membrane structure, comprising the steps of:

(a) coating a polymer thin film composed of a benzene-based polymer on a substrate by performing a plasma polymerization process using a monomer containing benzene as a basic structure; And

(b) carbonizing the coated substrate.

 At this time, the monomer containing benzene as a basic structure

Benzene, aniline, phenol, dopamine, benzylamine, phenethylamine, pyrocatechol, 2-hydroxypyridine, 3 Hydroxypyridine, hydroxypyridine, anthracene, naphthalene, 2-naphthol, 9-anthracenol, 2-anthracenol, And 1-anthracenol. &Lt; / RTI &gt;

At this time, the plasma polymerization method may be a dry plasma polymerization method. In the dry plasma polymerization method, argon gas is used as a carrier gas; As the active gas, at least one gas selected from the group consisting of hydrogen, nitrogen, oxygen, water vapor, ammonia, and mixed air thereof is used. Preferably, an oxygen gas can be used.

In one embodiment of the present invention, a polymer was synthesized in the form of a polydodamine-like compound through plasma polymerization using dopamine as a monomer containing benzene as a basic structure, and the polymer was obtained in the form of a coating on a substrate.

That is, the synthesized polydopamine-like compound can be obtained in the form of a film, which is synthesized into a film and simultaneously coats the object solids.

The carbonization may be performed at 700 to 2000 ° C in a hydrogen atmosphere through e-beam heating or laser hauling, preferably at 1000 ° C.

The present invention can provide various uses of a free standing membrane structure in which a carbon thin film is directly bonded and grown on a substrate surface.

As a specific example, an EUV pellicle including a free standing membrane structure in which graphene grains are directly bonded and grown, and an EUV mask including the EUV pellicle may be utilized.

The free-standing membrane structure of the present invention has a form in which a carbon thin film having a thickness of 1 to 20 nm is directly bonded on a substrate. Therefore, compared to a form in which a binder is bonded between a conventional substrate and a carbon thin film, And the chemical characteristics are not reduced.

The method of manufacturing a free standing membrane structure according to the present invention is a method of manufacturing a free standing membrane structure in which a polymer is coated on a substrate through a plasma polymerization method using a monomer having benzene as a basic structure, By manufacturing the EUV pellicle, the carbon thin film can be grown directly on the substrate uniformly without a catalyst.

In addition, by coating a nano-thick benzene-based polymer on a substrate through a plasma polymerization method, a membrane structure of a free standing membrane type thin film that does not require a separate support can be provided.

1 is a schematic view of a structure of a free standing membrane structure as an example of the present invention.
Fig. 2 shows the results of measurement by Raman spectroscopy for identifying the graphene oxide of Example 3-1. Fig.
Fig. 3 shows the results of the determination of the presence or absence of crystallinity by XRD in order to confirm the crystallinity of the graphene oxide of Example 3-2.
Fig. 4 shows the result of functional group measurement by FTIR to confirm the chemical structure of the graphene oxide of Example 3-3. Fig.
5 is an image of the surface roughness of the graphene oxide of Example 3-4 (1) measured by AFM.
6 shows the topographical image of the surface roughness of the graphene oxide of Example 3-4 (1) measured by AFM and the magnification of the graphene oxide deposited on the silicon substrate.
7 is a current image by i-AFM for identifying the graphene oxide of Example 3-4 (2).
8 is a graph showing current values at respective voltages by i-AFM for identifying the graphene oxide of Example 3-4 (2).
9 is an image and FFT pattern diffraction pattern image by TEM measurement for confirming the crystal structure of the graphene oxide of Example 3-5.
Fig. 10 shows the results of EELS measurement for analyzing the electronic structure of the graphene oxide.

The definitions of the terms used in the present invention are as follows.

The term " free standing membrane structure "of the present invention means a membrane having a free standing type layer structure in which there is no supporting structure, and has a nano thickness, It has one thing to have.

The term " EUV pellicle " of the present invention refers to a substance adhering to the edge of the photosensitive drum in the absence of particles or extraneous defects when EUV (Extreme Ultra Violet) is used as a light source to protect the MASK.

In the present invention, the term "pellicle" can be used as a concept including a pellicle membrane or a pellicle membrane and a pellicle frame (pellicle membrane support structure).

The "mask" of the present invention is a glass plate on which a fine electronic circuit used in a photolithography process is formed during a process of manufacturing a semiconductor integrated circuit in a semiconductor / display process, and a mask is formed by drawing a circuit pattern designed using an electron beam apparatus on a glass plate it means.

The term "graphene" in the present invention means a material in which carbon atoms form a honeycomb structure in a planar shape, and includes graphite, which is used as a pencil lead, and a suffix, -ene, which means a molecule having a carbon double bond It is a term made by combining. Graphene is very thin and transparent with a thickness of 0.34 nm and is excellent in chemical safety and electrical conductivity. In particular, because it does not lose its electrical conductivity even when stretched or folded due to its excellent stretchability, graphene can be used for wristwatch-like mobile phones, bendable display screens and solar cells.

"Monomer" of the present invention means a monomolecular compound that forms a polymer as a plasma polymer, which is a low molecular weight material that is a unit constituting a polymer compound or the like. In the present invention, the term &quot; benzene-based polymer &quot; means a compound having a low molecular weight substance and a benzene compound as a basic structure.

"Polymer" of the present invention is a high molecular weight compound containing a large number of repeating units, and is a plasma polymer of a monomer compound containing a benzene compound as a basic structure, and contains monomers as repeating units. In the present invention, benzene-based polymers may also be used interchangeably.

The term " plasma " of the present invention means a state in which charged particles of yin and yang which are freely moving are mixed with a neutral gas to be electrically neutral as a whole. Plasma used in the plasma polymerization has a high ionization degree and thermodynamically equilibrium "Low temperature plasma" or "cold plasma" with an average temperature of several tens of thousands.

The term &quot; plasma polymerization &quot; of the present invention means a process in which molecules of gases and organic vapors repeatedly undergo a consecutive activation-deactivation step in a plasma state, and a benzene- Based polymer is converted into a polymer thin film.

"Analogous compounds" of the present invention refer to compounds having similar chemical structures in relation to their use, for example, derivatives (e.g., compounds having approximate chemical structures included in the same superordinate concept), homologs, Isomers and the like.

The term &quot; carbonization &quot; in the present invention refers to all processes in which only carbon remains by heating at a high temperature, which means that an organic compound changes into carbon by thermal decomposition or chemical change, or a substance combines with carbon.

The term &quot; growth &quot; of the present invention means an increase in amount not accompanied by a change in form, which means that the carbon material is increased in the course of carbonization of the polymer thin film coated on the substrate to the carbon thin film.

&Quot; Recrystallization &quot; of the present invention means that a crystalline solid is crystallized again by heat, which means that reorganization of the carbon skeleton occurs and the bond between carbon and carbon is reorganized by the bond between two sp ² hybrid carbons .

The term "coating" of the present invention means that the surface of an object is coated with a thin film such as a resin. In the present invention, the benzene-based polymer can be coated on a substrate to form a thin film.

By "about" is meant a reference quantity, level, value, number, frequency, percentage, dimension, size, quantity, weight or length of 30, 25, 20, 25, 10, 9, 8, 7, 6, 5, 4 , Level, value, number, frequency, percent, dimension, size, quantity, weight, or length that varies from one to three, two, or one percent.

Throughout this specification, the words &quot; comprise &quot; and &quot; comprise &quot;, unless the context otherwise requires, includes the stated step or element, or group of steps or elements, but not to any other step or element, It is to be understood that the group is not excluded.

Hereinafter, the present invention will be described in detail.

Free standing Membrane  Structure

The present invention relates to a novel free-standing material which can be used in various fields such as a transparent electrode for a display, a high-speed semiconductor device, a heat-radiating material, an ultra lightweight material, A membrane structure, a method for producing the membrane structure, and a use thereof.

The free standing membrane structure of the present invention is a structure having characteristics similar to those of a membrane type in which there is no supporting structure, and is characterized by a very thin thickness of nano thickness.

The free standing membrane structure comprises a thin substrate and a carbon thin film directly bonded to and grown on the substrate surface. In one embodiment, the free standing membrane structure can be used, for example, as a pellicle, and can be used, for example, as an EUV pellicle.

The free standing membrane may have a thickness of several to several tens of nanometers. The thinner the membrane, the lower the physical durability. On the contrary, the thicker the membrane, the lower the transmittance of light and the lower the productivity.

Unlike conventional membranes, the free standing membrane structure of the present invention has very thin nano-thickness and is excellent in durability and excellent in transmittance.

The free standing membrane structure is characterized by having a total thickness of 2 to 100 nm including a carbon body having a thickness of 1 to 20 nm bonded and grown directly on the substrate surface.

The free standing membrane structure has a total thickness of 2 to 100 nm and is very thin.

In other embodiments, the free standing membrane structure may be about 50 nm or less, about 70 nm or less, about 90 nm or less, or about 100 nm or less, but is not limited thereto.

The free standing membrane structure comprising: a substrate; And a 1 to 20 nm thick carbon thin film directly bonded to and growing on the substrate surface.

Hereinafter, the constituent elements of the free standing membrane structure will be described in detail.

The substrate that can be used in the present invention can be used without limitation as long as it is a substrate made of a material suitably selected and used by a person skilled in the art.

May be one or more selected from the group consisting of Cr, Zr, Mo, Y, Si, Rb, Sr, Nb and Ru, have.

The substrate may comprise an insulating material or a conductive material. When the height of the pellicle is insufficient with the base substrate alone, the pellicle frame may be further bonded to the outside of the base substrate with a silicon single crystal or the like. The substrate may be a flexible substrate.

If the thickness of the substrate is large, the free standing membrane structure can not have the property of a free standing type having no support, and therefore, the substrate has a thickness of 1 to 80 nm .

The substrate may further include at least one substrate.

Also, in one embodiment of the present invention, the substrate includes a first substrate; And a second substrate disposed on an upper portion of the first substrate, a lower portion of the first substrate, or both upper and lower portions of the first substrate.

In one embodiment of the present invention, the first substrate is silicon (Si), and the second substrate is selected from the group consisting of graphite, Cr, Zr, Mo, Y, Rb, Sr, can do.

The first substrate and the second substrate may have a thickness of about 80 nm or less, and the first substrate and the second substrate may each have a thickness of about 20 nm or less, about 15 nm or less, about 10 nm or less, and about 5 nm or less But may not be limited.

The free standing membrane structure is also characterized in that the membrane is formed by directly bonding the carbon thin film to the substrate surface without a bonding layer or a linker.

On the other hand, the carbon thin film to be directly grown on the substrate may be graphite, graphite thin film, graphene, oxidized graphene, or carbon nanotube, but may not be limited thereto.

The carbon thin film may have a thickness of 1 to 20 nm.

The carbon thin film may have a thickness of about 20 nm or less, about 15 nm or less, about 10 nm or less, or about 5 nm or less, but may not be limited thereto.

Since the carbon thin film can be grown directly on the nano-thick substrate with no bonding layer or linker, the carbon thin film can be grown on a nano-thick substrate. Therefore, the carbon thin film has a characteristic of free standing type Respectively.

The free standing membrane structure of the present invention is produced by a method of directly bonding and growing a carbon thin film on a substrate surface. A monomer containing benzene as a basic structure is coated on a substrate by a plasma polymerization method Coating is another feature.

In one embodiment, the method of manufacturing a free standing membrane structure of the present invention comprises:

(a) coating a thin film of a polymer supported on a benzene-based polymer on a substrate by performing a plasma polymerization process using a monomer containing benzene as a basic structure; And

(b) carbonizing the coated substrate.

Hereinafter, the main structure used for manufacturing the free standing membrane structure of the present invention will be described in detail.

Substrates and monomeric materials that contain benzene compound base structure

In the present invention, a substrate coated with a benzene-based polymer is prepared by coating a polymer, which is a plasma polymer of a monomer containing benzene as a basic structure, on a substrate.

At this time, as a starting material for coating a polymer as a plasma polymer, a monomer containing a benzene compound as a basic structure is used.

Benzene compound as a basic structure, the following materials which can be easily synthesized or obtained by those skilled in the art can be used without limitation.

For example, the most basic structure is benzene, aniline, phenol, dopamine, benzylamine, phenethylamine, pyrocatechol, Hydroxypyridine, hydroxypyridine, anthracene, naphthalene, 2-naphthol, 9-anthracenol, and the like. ), 2-anthracenol, 1-anthracenol, and the like can be used. Most preferably, benzene, aniline or dopamine can be used.

In addition, analogues or derivatives of the above-mentioned other monomer materials can be appropriately selected and used.

For example, benzene, or pyrocatechol with a hydroxyl function (-OH) attached to the benzene ring, benzylamine with one and two methylene bridges and one amine group attached to the benzene ring, respectively, benzylamine, phenethylamine, 2,3-dihydroxynaphthalene, which is a structure attached to naphthalene in which two hydroxyl functional groups are sublimable, 1-naphthyl which has an amine functional group in naphthalene A derivative compound such as naphthylmethylamine may be used as the monomer.

Then, a polymer thin film composed of a benzene-based polymer is coated on the surface of the substrate by plasma polymerization using a monomer containing the benzene compound as a basic structure.

plasma  Polymerization Coatings

As a starting material, "plasma polymerization" is used in one specific method. In particular, a dry plasma polymerization method can be used.

Plasma is a gas that is ionized and electrically neutral as a whole. Plasma used in the plasma polymerization is a "low temperature plasma" plasma having a high degree of ionization, a thermodynamically equilibrium component and an average temperature of several tens of thousands cold plasma ". This can be easily achieved by electrically discharging gas or organic vapor at low pressure.

The gas used in the present invention can be classified into an active / inactive gas, a carrier gas, and the like depending on its function, which includes an inert gas such as argon; Hydrogen, nitrogen, oxygen, water vapor, ammonia, or a gas mixture thereof may be used. Preferably argon gas as a carrier gas; As the active gas, at least one gas selected from the group consisting of air, hydrogen, oxygen, water vapor and ammonia is used. More preferably, oxygen or ammonia is used, and oxygen is most preferably used.

The plasma polymerization process in the present invention can be carried out under a pressure condition of a low pressure of 1 torr or less close to a vacuum, preferably 1 ^-3 to 5 ^-1 Torr, and when gases and vapors are converted into plasma at low pressure As the polymer material is produced, it is coated in the form of a thin film on the surface of the surrounding solid. Thus, the plasma polymer of the present invention is directly bonded to the solid surface to grow as a thin film.

The polymer material may be, for example, dopamine.

In addition, the plasma polymer of the monomer is a benzene-based polymer, and may be, for example, a polydopamine-like compound.

Polydopamine (pDA) is a substance produced by spontaneous polymerisation of dopamine (C8H11NO2) under basic and oxidative conditions, and is a substance that mimics mussel adhesive proteins.

Also, the term "polypodamine-like compound" refers to a compound similar in chemical composition to polydodamine in relation to its use as a similar compound. For example, a compound having a chemical structure similar to that contained in the same superordinate concept Compounds having the same or different substituents), homologs, structural isomers and the like.

 As an example of the present invention, the term &quot; polypodamine-like compound &quot; means a polymer material obtained by polymerization using a compound having a benzene compound as a basic structure, preferably by plasma polymerization.

Plasma Polymerization has been used to synthesize polypodamine, which has been produced mainly by liquid phase method, by dry plasma polymerization, making it possible to apply and mass-produce in various fields where aqueous solution can not be used. I have.

A benzene-based polymer is produced by such a plasma polymerization method, whereby a benzene-based polymer coating layer or a polymer thin film is formed on the substrate surface.

The polymer thin film may have a thickness of 10 to 60 nm, 10 to 50 nm, 10 to 40 nm, 10 to 30 nm, 10 to 20 nm, 20 to 50 nm, 30 to 50 nm, and 40 to 50 nm. Preferably, the polymer thin film may be 40 to 50 nm, but the present invention is not limited thereto. In one embodiment of the present invention, the polymer thin film has a thickness of about 50 nm.

A thin film of benzene-based polymer can be coated on the surface of the substrate by the plasma polymerization method, and then a very thin carbon thin film can be obtained through a carbonization process.

Carbonization process

Next, a benzene-based polymer coated on the surface of the substrate is produced as a carbon thin film directly grown on a substrate through a carbonization process.

As an example of the present invention, a polydopamine-like compound coated on the surface of a substrate can be produced as a graphene oxide through a carbonization process.

Carbonization refers to a chemical change that pyrolysis of various organic materials into other materials. When organic materials are shut off from the supply of air in a container with a gas outlet and heated, they are not burnt. And they are converted into combustible gas by bonding or decomposition. Therefore, they are used as a heat source of the carbonization process, and finally, only the carbide is left. Through this carbonization process, benzene-based polymers can form carbon bodies such as graphite, graphene, graphene grains, and carbon nanotubes.

As a preferred example of the present invention, the carbonization step may be performed by electron beam heating or laser heating.

The carbonization step, which is carried out by heating with photons such as UV light or photons from a laser, or by heating with electrons such as electron beams, may be carried out at a temperature in the range of 700 to 1500 ° C.

In the present invention, by controlling the temperature of the carbonization step to 700 to 1500 ° C, the yield of the carbon body, in particular, the yield of the graphene oxide and the sp ² hybridization degree (recrystallization) of the carbon skeleton can be controlled within a preferable range.

If the temperature of the carbonization step is less than 700 ° C., recrystallization may not occur. If the temperature is higher than 1500 ° C., carbon may be vaporized due to bonding with residual oxygen, resulting in loss of the carbon body.

In one specific embodiment of the carbonization step of the present invention, carbonization can proceed at 1000 占 폚.

The carbonization can be carried out under high pressure (typically 1 to 1000 Torr) or under ultra-vacuum (typically 10 ^-6 to 1 Torr).

In one specific embodiment of the carbonization step, the reaction can proceed at a pressure of 10 mTorr or less, but the present invention is not limited thereto.

The carbonization step may be carried out in an inert gas such as N 2, a rare gas atmosphere such as He, Ar, Ne, Cr, Xe, or in a reducing gas atmosphere (for example, in the presence of hydrogen).

In a specific embodiment of the present invention, the carbonization step may be carried out in a hydrogen environment, but is not limited thereto.

In one embodiment of the present invention, the benzene-based polymer can be carbonized by laser heating to produce a free standing membrane structure.

The laser heating method uses infrared rays, for example, and is often used for surface treatment.

The laser heating method may take the form of a laser pulse with a frequency in the range of 1 Hz to 10 kHz for a wavelength in the range of 200 nm to 600 nm and an energy form in the range of 0.1 J / cm 2 to 100 J / cm 2 for a time of 1 minute to 12 hours.

 However, the scope of the present invention is not limited to the kind and condition of the laser beam, and a solid laser or the like can also be used. As the laser beam is irradiated, the temperature of the substrate coated with the benzene-based polymer to which the laser beam is irradiated rises, whereby the benzene-based polymer undergoes a carbonization process.

In one embodiment of the present invention, the benzene-based polymer may be carbonized by electron beam heating to produce a free standing membrane structure.

Electron beam heating (electron beam heating) is a process in which electrons are radiated into heated materials by collision of electrons and heated materials. It is easy to process very small parts, and the heating range is narrow. .

The electron beam irradiating device uses a thermoelectrical driving method in which a cathode material is heated to a suitable temperature of a high temperature by heating a filament to obtain an electron beam, or a method using an electron source using a property of generating a strong electric field around the cathode electrode to emit electrons or plasma May be used.

In one embodiment of the present invention, the electron beam heating method may be performed with an acceleration voltage of 10 kV or less and a current of 1 to 50 mA. In addition, the heating time can be performed for 1 minute to 2 hours, but is not limited thereto.

As an example of the present invention, the carbonization step may be performed by a thermal heating method using a plasma.

The plasma is composed of gaseous atoms, gaseous ions and electrons as a high temperature luminous gas which is ionized at least partially (1 to 100%). The thermal plasma can be generated by passing the gas through an electric arc. The electric arc will rapidly heat the gas passing through the arc within a microsecond to a very high temperature by resistive and radiant heating. Often, the plasma emits at temperatures above 9,000 K.

Therefore, as a specific example of the present invention, a benzene-based polymer can be carbonized by a thermal heating method using a plasma to produce a free standing membrane structure in which a carbon thin film is directly grown on a substrate.

The carbon thin film may be 1 to 20 nm, 5 to 20 nm, 10 to 20 nm, 15 to 20 nm, 1 to 15 nm, 1 to 10 nm, 1 to 5 nm, but is not limited thereto.

The present invention can produce a free standing membrane structure in which a carbon thin film is directly grown on a substrate using the carbonization process of a benzene-based polymer.

The free standing membrane structure manufactured by the above method can be used in various fields as a novel nanocomposite material that can be used in various fields such as a transparent electrode for display, a super high-speed semiconductor device, a heat dissipation material, and an ultra lightweight material.

According to another aspect of the present invention, a carbon thin film carbonized with a benzene-based polymer may be separated from a membrane structure.

As the carbon thin film is closer to a region directly contacting the plasma, more carbon material components such as graphite, graphite, graphene, oxide graphene, and carbon nanotube may be present. With this property, a partially carbonized benzene-based polymer can be partially included in the portion adjacent to the substrate, and a solvent can be used to separate the carbon thin film from the substrate depending on the nature of the benzene-based polymer.

In order to separate the carbon thin film, the thickness of the benzene-based polymer thin film may be at least a predetermined thickness, preferably at least 50 nm, but is not limited thereto. This is because the benzene-based polymer thin film or carbon thin film is lost through the carbonization process.

The partially carbonized benzene-based polymer during the carbonization process may have properties such that it is dissolved in an aqueous solution or in an alcohol having not more than 4 equivalents. The carbonized thin film can be separated from the membrane structure by dissolving the benzene-based polymer by putting the carbonized membrane structure into an aqueous solution of a solvent or an alcohol having a valence of four or less.

The carbon thin film separated from the membrane structure by the above method can be applied to various fields as a novel nanocomposite material.

EUV Pellicle

As an example of the present invention, the free standing membrane structure manufactured by the above method can be used as an EUV pellicle.

A pellicle is a substance that adheres to the edge of a photosensitive disk in the absence of a shape for the purpose of protecting the photosensitive disk (MASK) from particles or external defects.

In the production of a semiconductor device or a liquid crystal display panel, a method called photolithography is used for patterning a semiconductor wafer or a liquid crystal substrate. In photolithography, a mask is used as an original plate for patterning, and a pattern on the mask is transferred to a wafer or liquid crystal substrate. If the dust adheres to the mask, light is absorbed or reflected by the dust, so that the transferred pattern is damaged, resulting in a problem that the performance and the yield of the semiconductor device, the liquid crystal display panel, and the like are lowered. Therefore, although these operations are usually performed in a clean room, there is dust in the clean room, so that a method of attaching a pellicle to prevent dust from adhering to the surface of the mask is performed. In this case, the dust does not directly adhere to the surface of the mask but sticks to the pellicle film. At the time of lithography, the focal point matches the pattern of the mask, so that the dust on the pellicle is not focused and transferred to the pattern.

Gradually, the required resolution of an exposure apparatus for semiconductor manufacturing is getting higher, and the wavelength of the light source is getting shorter to realize the resolution. Specifically, the UV light source is gradually shortened in ultraviolet light (EUV, extreme ultra violet, 13.5 nm) in the ultraviolet light g line 436, the I line 365, the KrF excimer laser 248 and the ArF excimer laser 193 ought.

EUV was absorbed by all substances in the natural world. The internal structure of the conventional ArF immersion apparatus, in which the light source passes through the large lens through a straight line and touches the mask, has a limitation in increasing the output. This is because the lens absorbs most of the light. For this reason, EUV equipment is designed with a structure in which a multilayer thin film special mirror is placed inside and the light source is reflected several times to touch the wafer. The development of EUV pellicles is slow because of this reflective structure. In the conventional lens system, the light is transmitted only once through the pellicle. However, in the EUV system, which is a reflection structure, the light must enter once and then be reflected again. Loss of light source is large. Therefore, development of a new light source, a resist, a mask, and a pellicle is indispensable for realizing an exposure technique using such an ultraviolet ray.

As an example of the present invention, an EUV pellicle using a free standing membrane structure has a form in which a carbon thin film is directly bonded to a substrate, and a binder or the like is bonded between a conventional substrate and a carbon thin film And the electrochemical characteristics are not reduced more than the shape.

Also, it has a characteristic of good permeability due to its nano-thickness.

Pellicle  frame

As an example of the present invention, an EUV pellicle using a free standing membrane structure can attach a frame.

The finished pellicle is generally used in a state of being fixed to the pellicle frame in order to prevent deformation, distortion and damage.

In the pellicle frame, it is advantageous to use a light material because the pattern of the mask of the extreme ultraviolet exposure machine is directed downward.

Therefore, the material of the pellicle frame used in the present invention may be a metal such as plastic, ceramic, or aluminum. Preferably, aluminum can be used. More preferably, an aluminum alloy such as A7075, A6061, A5052 or the like can be used as the pellicle frame.

In addition, since the pellicle frame is expected to suffer damage to the pellicle and the space surrounded by the mask and the pressure difference between the outside and the outside, an open structure with a fine filter can be used.

Also, the shape of the pellicle frame can be octagon, rectangular, circle, truncate, LCD pellicle frame.

Attachment of the pellicle and the pellicle frame can be done by heat treatment or plasma treatment, and it is possible to use an adhesive which is not reactive with the solvent dissolving the soluble coating material.

This is because, when the pellicle frame and the adhesive are organic materials, there is a risk of contamination caused by carbon generated from the organic material during the exposure process, so it is necessary to use it when the carbon contamination prevention technology is stably applied in a hydrogen atmosphere.

The pellicle is attached to the pellicle frame which is coated with an adhesive such as acrylic resin, epoxy resin, or fluorine resin by pulling the separated pellicle to the pellicle frame, and after cutting unnecessary film outside the frame, it is fixed to the pellicle frame do.

The release liner for protecting the pressure-sensitive adhesive for protecting the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer made of polybutene resin, polyvinyl acetate resin, acrylic resin or silicone resin can be provided.

In addition, the pellicle frame can form an oxide film to prevent contamination by aluminum during the lithography process.

The oxidation film of the pellicle frame is formed in black. When the exposure is incident on the pellicle frame and reflected, the transferred pattern is damaged, so that the reflection of the exposure light incident on the pellicle frame must be minimized. This is because the surface of the pellicle frame must be black so that it is easy to identify impurities and dust adhering to the surface.

As an example of the present invention, a large pellicle frame can also be provided.

The large pellicle frame is used for repeatedly etching the thin film of ARRAY, semiconductor, metal, transparency, insulator and so on in order and repeating the etching process in the proper pattern. It corresponds to FRAME for pattern.

In one example of the present invention, the size of the frame for a large pellicle may be about 850 mm x 1200 mm to 1500 mm x 1500 mm, and the size of the pellicle frame is not constant, but may be a constant amount of exposure depending on the size of the pattern formed on the mask It is obvious that it can be changed depending on the size of the pattern.

The present invention can also provide a pellicle case for protecting the pellicle during transportation of the pellicle.

After the pellicle is attached to the mask, there is an effect of preventing the intrusion of foreign matter into the inside of the closed space formed by the pellicle from the outside, but when foreign matter is attached to the pellicle itself and the inside thereof is inside the closed space, It is difficult to prevent adhesion.

If foreign matter is adhered to the pellicle frame cavity or to the inner surface of the pellicle foil facing the inner wall of the metal frame during manufacture or transportation of the pellicle, foreign matter may fall onto the mask during use and, as a result, Lt; / RTI &gt; Therefore, not only pellicle itself is required to have high cleanliness, but also a pellicle storage container used for storage and transportation is strongly required to maintain its cleanliness.

The present invention can also provide a pellicle case for storing and transporting the pellicle. The pellicle storage container may be made of ABS, acrylic, or synthetic resin. The pellicle storage container may be manufactured by injection molding or vacuum molding a material.

As an example of the present invention, the side length of the outer shape of the storage container of the pellicle may be 200 to 300 mm. As another example of the present invention, the storage container of the pellicle may have a side length of 300 to 500 mm. Further, as the large pellicle storage container, the side length of the outer shape may exceed 500 mm.

The cleanliness of the pellicle can be maintained during storage or transportation through the pellicle case.

Accordingly, the present invention relates to a pellicle manufactured as described above; Or a pellicle attached to a pellicle frame that is not deformed or distorted; And can provide all of these uses.

EUV  Mask

As an example of the present invention, it is possible to provide a mask using an EUV pellicle including a free standing membrane structure.

The mask of the present invention means a glass plate on which a minute electronic circuit used in a photolithography process is drawn during a process of manufacturing a semiconductor integrated circuit in a semiconductor and display process, and a mask is formed by drawing a circuit pattern designed using an electron beam facility on a glass plate .

The photolithography is a process of drawing electronic circuits on a wafer, and drawing billions of electronic components on a semiconductor chip and circuit lines connecting them. A mask is placed in the equipment, and light is transmitted so that a fine electronic circuit picture is formed on the wafer coated with the sensitizing solution.

As an example of the present invention, the manufactured pellicle may be provided with a pellicle frame having a sufficient size to surround the mask pattern and a mask in the form of being attached to one end face of the pellicle frame at predetermined intervals from the mask surface.

As a more specific example,

A substrate on which a mask pattern is formed;

A pellicle disposed on the upper surface of the substrate at a predetermined distance, the pellicle protecting the mask pattern;

A frame attached to the upper surface of the photomask and supporting the pellicle;

A mask which is spaced apart from the pellicle film and the substrate by a predetermined distance and which can be opened and closed in both directions can be provided.

In the mask, the pellicle may consist of a pellicle frame and a transparent pellicle attached to one end face thereof.

The pellicle of the mask may be configured such that the pellicle and the surface of the mask substrate are properly spaced apart by the pellicle frame.

At this time, the pellicle may be adhered to the mask by applying an adhesive to the other end surface of the pellicle frame or by using an adhesive tape on the other end surface. That is, when the pellicle, that is, the mask protecting member is adhered to the mask using, for example, an adhesive, it can be manufactured so that there is no gap between the mask and the protecting member. For example, the entire periphery of the pellicle frame and the entire bottom surface are adhered to the substrate with no gaps and sealed to prevent formation of a gap, which is a passage for dust or the like.

In order to prevent deformation of the mask protecting member during the pressing and adhering of the mask protecting member and to avoid the problem that a double photographing or a partial enlargement of the pattern occurs during transferring the mask pattern to the semiconductor wafer by exposing the mask, A specific adhesive can be used and the pellicle can be pressed onto the substrate at a specific pressure.

As such, the present invention will be useful as a novel standing material structure by providing a free standing membrane structure including a carbon thin film directly bonded to a substrate surface and its various uses.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.

Example  One. plasma  Polymerization method Polydopamine  Similar compound coating

(1) Selection of monomers containing benzene compounds as basic structure

In order to synthesize a polydodamine analog through plasma polymerization, two catechol (OH) functional groups and an amine (NH2) functional group should be polymerized in the benzene ring, which is the basic structure of dopamine. In the plasma polymerization of the present invention, Benzene structure can be formed.

Of the various monomers that can be vaporized at a temperature within 100 ° C, which can be controlled by circulation, and have a basic structure of dopamine, aniline liquid monomers having an amine group attached to the benzene structure are used.

(2) Plasma Polymerization Process Conditions

The bubbling conditions of the aniline were such that the vacuum of the plasma reactor was pumped sufficiently low and then the valve 3 was opened at a circulating bath temperature of 40 캜 so that the liquid monomer was injected into the chamber at a vapor pressure of 40 캜.

Next, the valve 1 is opened and 5 sccm of argon gas is injected into the plasma reactor to make a pressure condition of about 3.2 ^-2 Torr. When the valve 2 is opened and argon gas is simultaneously injected into the chamber and the bubbler, Was closed so that the argon carrier gas was only allowed to flow into the plasma reactor through the interior of the bubbler

This process sequence is to avoid the instantaneous rise of the pressure in the chamber.

Next, the active gas such as air, O 2, and NH 3 was mixed through a gas pipe supplied into the chamber, the working pressure was fixed at 1.5 ^-1 Torr, and the RF power was coated while synthesizing to a desired deposition thickness at 0 to 200 W . A polymer thin film of polypodamine-like compound was obtained with a thickness of about 50 nm by the above method.

Example  2. Polydopamine  Carbonization of similar compounds

The polypodamine-like compound film coated on the silicon substrate was heated to 1000 ° C using e-beam heating in a hydrogen atmosphere, and the carbonization process was performed. As a result, the surface of the substrate was exposed to free standing free standing membrane structure.

Example  3. Oxidized graphene  Verification of creation

3-1. Identification by Raman spectroscopy

Three main bands shown in the Raman spectrum is a 2D band in the G band, 2700cm ^-1 in the D band at 1350cm ^-1, 1580cm ^-1 is generated, oxidation yes we can see the edited of the pin (2) The D-peak appears as one peak, which is distinct from the graphite D-band consisting of two peaks.

3-2. XRD  (X-ray diffraction)

The XRD was measured to measure the crystallinity, and the result was as shown in Fig. Referring to FIG. 3, it was confirmed that graphene oxide was confirmed through crystallization.

3-3. FTIR  (Fourier Transform-infrared Spectrometer)

As a result of measuring a FTIR to analyze the chemical structure of the sample is out of the peak 1044㎝ ^-1, 1730㎝ ^-1, 3340㎝ ^-1 respectively, CO, C = O, it was found that the OH bond is present. (Fig. 4). Therefore, it was found that the film satisfied the graphene oxide (GO).

3-4. AFM  Measurement result

(1) AFM measurement

Atomic force microscopy (AFM) images were measured to measure the surface roughness of the generated graphene grains. As a result of the AFM measurement, the roughness before plasma carbonization was found to be 0.185 to 0.2 nm, and the roughness after carbonization was found to be 0.165 to 0.375 nm. (Figures 5 and 6)

(2) Atomic Force Microscopy (i-AFM) measurement

In order to measure the conductivity of the sample of the present invention, the bias current was measured in the I-AFM mode to confirm the current flowing on the surface when the bias was applied.

A 10 μm × 10 μm area was measured at the center of each sample, and a current image was obtained when sample bias was not applied (0 V) and +1 V was applied. (Fig. 7)

 AFM was measured by I-AFM mode using Parkes XE-100, Cantilever was measured with CONTSCPt, sample size was 10 μm × 10 μm, and sample bias was +1 V.

A sample of the present invention is a case where dopamine 50 nm is coated on a Si substrate and plasma treatment is performed. A comparative sample is a case where a single layer of graphene is deposited on a Si substrate by a CVD (Chemical Vapor Deposition) method (CVD graphene).

As a result, the sample of the present invention showed a uniform current flow on the surface when a bias of +1 V was applied to the sample when the bias was not applied (0 V). (-0.182 pA at 0 V, 7.422 μA at +1 V) (Figure 8)

[Table 1]

From +1 V Max current of CVD Graphene sample is greater than 42.346μA (42.346 × 10 ⁶ ㎀) of the specimen (sample) of the present invention to ^{53.140μA (53.140 × 10 6 ㎀)} , the average value 7.422μA (7.422 × 10 ㎀ to ⁶⁾ at a much greater than 0.233μA (0.233 × 10 ⁶ ㎀) of CVD Graphene sample it was confirmed that the current flowing through the sample is more uniform surface of the present invention.

From these results, it can be confirmed that the oxidized graphene according to the present invention has better conductivity than the chemically deposited graphene (CVD Graphene).

3-5. TEM  (transmission electron microscope) analysis result

The TEM was measured to confirm the crystal structure of the resulting graphene oxide.

Samples were sampled using Nova FIB instrument and high magnification image and FFT pattern were observed.

Observation of the FFT pattern to observe the SAD (selected area diffraction) pattern revealed that the diffraction pattern shows a considerable graphite lattice pattern (FIG. 9).

As a result, the graphitization by carbonization can be confirmed.

3-6. EELS (electron energy loss spectrometer) analysis result

A sample can be used to analyze the electronic structure of the pellicle film generated from the electron energy loss spectrum and the results are shown in FIG. From the result of the sp ² / sp ³ (π * / σ *) binding ratio in FIG. 10, it was found that graphene was generated.

3-7. Energy Dispersive Spectrometry (EDS) analysis results

EDS analysis was carried out for the analysis of the sample elements. The results are as follows.

[Table 2]

As shown in the table above, C: O = 80: 20 atomic percent. N was not observed in the EDS. From the above results, it is possible to confirm the formation of graphene oxide.

Claims (15)

Board; And a carbon thin film having a thickness of 1 to 20 nm directly bonded to and growing on the surface of the substrate.
A free standing membrane structure with a total thickness of 2 to 100 nm.
The substrate according to claim 1, wherein the substrate comprises at least one selected from the group consisting of graphite, Cr, Zr, Mo, Y, Si, Rb, Sr, Nb or Ru, Free standing membrane structure.
The free standing membrane structure of claim 1, wherein the substrate further comprises at least one substrate.
4. The apparatus of claim 3, wherein the substrate comprises: a first substrate; And
And a second substrate disposed on an upper portion of the first substrate, a lower portion of the first substrate, or both upper and lower portions of the first substrate.
The free standing membrane structure according to claim 4, wherein the first substrate is Si and the second substrate is selected from the group consisting of graphite, Cr, Zr, Mo, Y, Rb, Sr, .
The free standing membrane structure according to claim 1, wherein the carbon thin film comprises at least one selected from the group consisting of graphite, graphite, graphene, graphene oxide, and carbon nanotubes.
The free standing membrane structure according to claim 6, wherein the carbon thin film is graphene oxide.
The carbon thin film according to claim 1,
Wherein the polymer film is obtained by carbonizing a polymer thin film composed of a polymer as a plasma polymer of a monomer containing benzene as a basic structure.
An EUV pellicle comprising the free standing membrane structure of any one of claims 1 to 8.
A method of manufacturing a free standing membrane structure comprising the steps of:
Coating a polymer thin film composed of a benzene-based polymer on a substrate by performing a plasma polymerization process using a monomer containing benzene as a basic structure; And
Carbonizing the coated substrate.
11. The method according to claim 10, wherein the monomer containing benzene as a basic structure is
Benzene, aniline, phenol, dopamine, benzylamine, phenethylamine, pyrocatechol, 2-hydroxypyridine, 3 Hydroxypyridine, hydroxypyridine, anthracene, naphthalene, 2-naphthol, 9-anthracenol, 2-anthracenol, And 1-anthracenol. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
11. The method of claim 10, wherein the substrate comprises at least one selected from the group consisting of graphite, Cr, Zr, Mo, Y, Si, Rb, Sr, Nb and Ru.
11. The method of claim 10, wherein the plasma polymerization process is a dry plasma polymerization process.
11. The method of claim 10, wherein the carbonizing step comprises, in a hydrogen atmosphere,
Wherein the heat treatment is performed by using e-beam heating or laser haaring at 700 to 1500 ° C.
15. The method of claim 14, wherein the carbonizing step is performed at 1000 &lt; 0 &gt; C.

Images