KR100644219B1 - Method, apparatus and product for formation of nano-sized particulates on a substrate - Google Patents

Abstract

In the deposition apparatus for controlling the size of the nanoparticles deposited on the substrate, the plasma surface treatment unit for forming a hydrophilic plasma polymer on the surface of the substrate, by modifying the polymer formed on the surface of the substrate to increase the nanoparticle nucleation density on the surface of the substrate For the surface modification treatment, a nanomaterial evaporation source for forming nanoparticles on the surface-modified substrate, and a nanomaterial evaporation source for substrates running continuously with a process time t _{2 at} which merging of the nanoparticles deposited on the substrate starts. It is composed of a substrate feed rate control unit for controlling the relationship between the exposure time t ₁ in t ₂ > t ₁ . The present invention is to modify the surface of the substrate material such as metal, ceramic, polymer, etc. with hydrophilicity to increase the surface energy to facilitate adhesion, control the degree of hydrophilic modification, substrate transfer time t ₁ than the process time t ₂ of the nanoparticles By short-forming nanoparticles with controlled size directly on the surface of the substrate, the durability between the substrate and the nanoparticles, the physical and chemical properties of the nanoparticles, and the nano-effects can be maximized.

Nanoparticles, substrate transfer time, surface modification treatment, nanomaterial deposition source, nucleation density, nanoparticle coalescence, surface energy, nano effect

Description

Formation method of nanoparticles, apparatus thereof and application thereof {METHOD, APPARATUS AND PRODUCT FOR FORMATION OF NANO-SIZED PARTICULATES ON A SUBSTRATE}

1 is a view showing an apparatus for forming nanoparticles according to an embodiment of the present invention.

Figure 2 is a schematic diagram showing the change in the size of the stable critical nucleus according to the surface energy of the substrate on the surface treated substrate according to an embodiment of the present invention.

3 is a schematic diagram showing the effect of the change in the surface energy of the substrate on the contact angle between the thin film and the substrate.

4 is a graph showing a change in contact angle and surface energy according to the amount of ion irradiation.

5 is a graph of XPS analysis of the chemical state of the surface according to the presence or absence of surface treatment.

FIG. 6 is a schematic diagram showing the size and density of nanoparticles deposited on a substrate according to positions P1, P2, and P3 of the substrate in the nanoparticle formation region 6.

FIG. 7 is an AFM image of nanoparticles formed on (a) IAR treated surfaces and (b) non IRA treated surfaces. FIG.

8 is a graph analyzing the size and coverage of the nanoparticles by the AES depth profile.

9 is an AFM image showing the size distribution of nanoparticles according to the amount of ion irradiation.

10 is an STM image of the nucleus at an early stage of partial ionization beam (PIB) deposition.

The present invention relates to a method for forming a nanoparticle, a device thereof, and an application thereof, and more particularly, a transfer time from a deposition start position to a deposition end position of a nanomaterial evaporation source that generates nanoparticles on a continuously running substrate. t ₁ is shorter than the process time t ₂ which is the concatenation of the nanoparticles to start deposition on a substrate (t _2> t ₁₎ held by the method of forming the nano-particles to control the size of the nanoparticles deposited on the substrate, his device And its applications.

The present invention is used in air conditioners, textiles, polymer films, medical aids, well-being products, etc., by providing discontinuous and non-uniform nanoparticles on the surface of the substrate to impart antimicrobial and bactericidal properties to the product.

In general, the surface treatment method for increasing the surface energy of the substrate (base metal) is the ion beam assisted reaction method (US Patent No. 5,783,641) for ceramics and polymers, and the plasma condition method (US Patent No. 6,162,513) for metals. . This is briefly described as follows.

1) Ion Assisted Reaction (IAR) exhausts air conditioning to 1x10 ^-6 Torr and adjusts the inflow of reactive gas to adjust the surface of the polymer material in a reactive gas atmosphere of 1x10 ^-5 to 1x10 ^-2 Torr. A method of modifying only the surface of a polymer by irradiating a low energy ion beam of 5.0 keV or less. The ion-assisted reaction method uses a low energy ion beam, thereby hardly damaging the surface of the polymer material by ion beam irradiation, and may impart new functions to the surface while maintaining the inherent properties of the polymer material. Low-energy ion beam irradiation forms radicals on the surface of the polymeric material, and the activated surface then chemically reacts with the surrounding reactive gases to create new polar functional groups. As a result, the surface energy of the polymer material can be increased to 72 erg / cm ² , which is the surface energy of water, and the polymer surface shows strong adhesion to other materials with an increase in hydrophilicity.

2) Optimal Condition Plasma zone method is to form a hydrophilic polymer on a metal material using plasma, and proceeds as follows. After placing the metal material to be surface treated in the vacuum chamber at the anode or cathode and placing the opposite electrode at the other side, the pressure in the chamber is maintained in a predetermined vacuum state, and the polymerizable monomer gas having a predetermined pressure is subjected to a predetermined pressure. Positive and negative ions and radicals resulting from the polymerizable monomer gas and the non-polymerizable gas by DC discharge by mixing with the polymerizable gas of the polymer and injecting the same into a vacuum chamber and applying a voltage to the electrode. Plasma is obtained and a polymer having hydrophilicity is produced on the metal material placed on the electrode by the generated plasma.

In the formation of hydrophilic polymers using plasma, the reactions and intermediate products in the plasma are both complex and varied to an unknown level. Therefore, even if the external process conditions, ie, the amount and ratio of the raw material gas, voltage, current and pressure are very well controlled, it is difficult to control the degree of hydrophilicity and surface energy of the resulting plasma polymer.

In addition, the method of forming nanoparticles includes liquid phase methods such as solid phase method, gas phase method, hydrolysis, and sol-gel method, which are represented by mechanical grinding methods. When the nanoparticles are made by the above-described method, the size of the nanoparticles, which can be formed according to the above-described method, are not only difficult to control, but are limited. For example, in the liquid phase method, the chemical method requires a solution in which the component elements of the nanoparticles to be formed are dissolved. In the solid phase method, there is a limit to grinding, so it is difficult to make the size below a certain level. There is a problem in the meteorological law that cannot produce much. On the other hand, as a commonly used method for practical use of such nanoparticles are used by mixing or synthesizing with a substrate (base material). For example, silver nano refrigerators and silver nano washing machines are used by mixing silver nanoparticles in plastic injection moldings that form structures. However, when the silver nanoparticles are mixed in the plastic injection molding, how well the silver nanoparticles are dispersed is an important problem, and only a small portion of the silver nanoparticles which face the plastic injection surface even though the dispersion is well disinfected It only plays a role in antibacterial and odor removal. As another example, a catalyst used in a filter, etc., may be used by coating nanoparticles on a substrate (mother system), but in such a case, nanoparticles are sometimes peeled off and disappeared from the substrate (base metal) by the flow of liquid, etc. It is a problem.

That is, in the conventional nanoparticle formation method and its practical method, the nanoparticles are produced by the solid phase method, the liquid phase method, and the vapor phase method, and in order to be practical, they have to go through a two-step process of mixing or synthesizing with the substrate (base material). Depending on the manufacturing method, there are limitations in the type, size, and quantity of nanoparticles, and the dispersion should be good when mixing and synthesizing. If the coating on the surface of the base material, there is a disadvantage that there is no durability due to peeling, loss due to weak adhesion with the base material (base material).

Therefore, the technical problem to be achieved by the present invention is to improve the above-mentioned problems of the prior art, controlling the degree of hydrophilicity and surface energy of the substrate to control the process time t ₂ of the nanoparticles deposited on the substrate nanomaterial evaporation source It is to provide a technique for forming nanoparticles that can control the material deposited on the surface of the substrate to a nano size by greater than the transport time t ₁ of the continuous running substrate in.

An object of the present invention is to provide an application of the nanoparticles formed on the surface of the substrate.

It is an object of the present invention to provide a device in which nanoparticle formation technology is applied to deposit nanoparticles onto a substrate surface.

It is to be understood that both the foregoing general description and the following detailed description are exemplary rather than limiting of the invention.

The present invention is best understood from the following detailed description when understood in conjunction with the accompanying drawings.

In order to achieve the above technical problem, the present invention, a first step of preparing a substrate;

Exposing the substrate to a nanomaterial evaporation source until a process time t ₂ at which merging of nanoparticles deposited on the substrate begins; A third step up to a process time t ₁ for transferring the substrate from the deposition start position of the nanomaterial deposition source to the deposition end position; It provides a method of forming nanoparticles on the surface of the substrate, characterized in that the process time t ₁ of the third step is less than the process time t ₂ of the second step. And the present invention comprises the first step of preparing a substrate; Forming a base film with a DC discharge plasma on the substrate; A third step of surface modifying the underlayer of the substrate to increase nanoparticle nucleation density on the surface of the substrate; Forming a nanoparticle on the surface-modified substrate; Forming an upper film with the DC discharge plasma on the substrate on which the nanoparticles are formed, the nanoparticles are formed on the surface of the substrate characterized in that the nanoparticles are embedded in the base film to the upper film Provides

In the second step, when the substrate is a metal, the following process is performed using an optimal plasma zone method for forming a hydrophilic polymer on a metal material.

In the vacuum chamber, the metal material to be surface treated is placed on the anode or cathode and the electrode on the other side is maintained, the pressure in the chamber is maintained at a predetermined vacuum, and the polymerizable monomer gas at a predetermined pressure is supplied at a predetermined pressure. Positive and negative ions and radicals resulting from the polymerizable monomer gas and the non-polymerizable gas by DC discharge by mixing with the polymerizable gas of the polymer and injecting the same into a vacuum chamber and applying a voltage to the electrode. It is possible to obtain a plasma consisting of a polymer having a hydrophilic property on the metal material placed on the electrode by the generated plasma.

In the third step, the degree of hydrophilicity and surface energy of the surface of the substrate may be adjusted by irradiating an ion beam onto the surface of the substrate.

In the third step, the ion source used for surface modification of the substrate is Kaufman type, cold hallow cathode type, Electron Cyclotron Resonance type, End hole type type. or gridless type and Radio Frequency type can be selected and used.

In the third step, flame treatment, laser treatment, corona discharge, plasma treatment (DC plasma, RF plasma), chemical treatment, and similar treatment other than the above-described ion beam Techniques and the like can be used to control the degree of hydrophilicity and surface energy of the surface of the substrate.

In the fourth step, the nanoparticles may be used to select any one of inorganic and organic materials, such as all elements, alloys, ceramics, oxides on the periodic table of the elements.

In the third step, the surface modification conditions are accelerated voltage 50 eV ~ 5.0 keV, ion dose 1x10 ¹⁴ ~ 5x10 ¹⁸ ions / cm ² , flow rate of reactive gas 0 ~ 1000 ml / min, and Working Pressure It is desirable to proceed at 1x10 ^-5 to 1x10 ^-2 Torr.

In the fourth step, the method for forming nanoparticles may include ion beam sputtering, thermal evaporation, e-beam evaporation, ion plating, alf or lf. One of RF or RF Magnetron Sputtering, MF or MF Magnetron Sputtering, and DC or DC Magnetron Sputtering, and Dual Magnetron Sputtering You can choose to use it.

Hereinafter, a method of forming nanoparticles, an apparatus thereof, and an application thereof according to embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a view showing an apparatus for forming nanoparticles according to an embodiment of the present invention.

The vacuum chamber of the nanoparticle forming apparatus is composed of seven regions. Loading area 1 on which base material 8 for forming nanoparticles is mounted, plasma surface treatment area 2 for forming hydrophilic plasma polymer on the surface of base material 8 made of metal material, plasma surface treatment A first buffer region 3 for preventing the mixing of heterogeneous gases used in the region and the ion beam surface treatment region and maintaining different vacuum degrees, and an ion beam surface treatment region for controlling the degree of hydrophilicity and controlling the surface energy (4) ), A second buffer region (5) for preventing the incorporation of heterogeneous gases used in the ion beam surface treatment region and the nanoparticle formation region, and maintaining different vacuum degrees, the size of which is controlled on the surface-treated substrate (8) It is divided into a nanoparticle forming region 6 for forming nanoparticles, and an unloading region 7 for unloading the base material 8 on which the nanoparticles are formed. In addition, the plasma surface treatment region 2, the first buffer region 3, the ion beam surface treatment region 4, and the second buffer to prevent sagging due to the weight of the base metal due to the length of the treatment are increased. ) A tension adjusting roll (not shown) is provided at an appropriate position of the connecting portion of the region 5 and the nanoparticle forming region 6.

The loading area 1 and the unloading area 7 include a base material 8 having a roll shape, a plasma surface treatment area 2, and a first buffer area 3. , Unwinding, winding or tensioning the transfer device 9 for transferring the ion beam surface treatment region 4, the second buffer region 5, and the nanoparticle forming region 6. ).

The plasma surface treatment region 2 which forms a hydrophilic plasma polymer on the surface of the base material 8 formed in a roll form allows a polymerizable monomer gas of a predetermined pressure to be mixed with a polymerizable gas of a predetermined pressure and introduced into the vacuum chamber. The first gas supply port 10 and the second gas supply port 11, a metal material and the first plasma surface treatment electrode 12 and the second plasma surface treatment electrode 13 that can cause a DC discharge do.

Amounts derived from the polymerizable polymerizable monomer gas and the non-polymerizable gas by DC discharge by applying a voltage to the base material 8, the first plasma surface treatment electrode 12 and the second plasma surface treatment electrode 13. A plasma consisting of (+) and negative (-) ions and radicals is obtained, and the generated plasma produces a polymer having hydrophilicity on the metal base material placed on the electrode.

However, the plasma polymer obtained by the plasma surface treatment has a limitation that it is not easy to control the degree of hydrophilicity and the surface energy level. Such a restriction cannot achieve the size control of the nanoparticles to be achieved in the present invention, for this purpose, it is necessary to control the degree of hydrophilicity and the control of surface energy through ion beam surface treatment. The ion beam surface treatment region 4 for controlling the degree of hydrophilicity and controlling the surface energy is supplied to an ion source separately from the third gas supply port 14 and the fourth gas supply port 15 for introducing a reactive gas therein. A first surface treatment ion source 16 and a second surface treatment comprising an ionization portion for ionizing an inert gas supplied to an ion source separately from an inert or reactive gas, and an acceleration portion for accelerating the ionized gas ions to be extracted as ions. It consists of the ion source 17 for a dragon.

The ion beam of 5.0 keV or less generated from the first surface treatment ion source 16 and the second surface treatment ion source 17 activates the surface without damaging the surface of the base material 8 having a roll shape. . The surface of the activated base material 8 is formed with new polar functional groups on the surface of the base material 8 through chemical reaction with the incoming reactive gas so that the surface is controlled in the degree of hydrophilicity and the surface energy. To control the nano-size.

The base material 8 formed in a roll form uses one of polymers and metals, including natural fibers, textiles, plastic vinyl, polymer films, artificial fibers, aluminum roll materials, and stainless roll materials. In the case of a model, ceramic base materials, such as nitride and an oxide, can also be used.

Process conditions for modifying the surface of the base material 8 are accelerated voltage 50 eV to 5.0 keV, ion dose 1x10 ¹⁴ to 5x10 ¹⁸ ions / cm ² , flow rate of reactive gas 0 to 1000 ml / min, Working Pressure Use 1 x 10 ^-5 to 1x10 ^-2 Torr.

The ion sources used to modify the surface of the base material 8 are Kaufman, cold hallow cathode, Electron Cyclotron Resonance, End hole type or gridless type. Any ion source can be used as long as the ion source can control the energy of ions such as radio frequency and the number of ions.

Flame treatment, laser treatment, corona discharge, plasma treatment (DC plasma, RF plasma), chemical treatment, and similar treatment techniques other than the ion beam using the above-described ion source Etc. can be used to adjust the degree of hydrophilicity and surface energy of the surface of the substrate.

4 is a graph showing a change in contact angle and surface energy according to the amount of ion irradiation.

As the amount of ion irradiation increased, the contact angle with water decreased from 77 ° to 10 °, and the surface energy increased in inverse proportion. At this time, the surface energy can be largely divided into polar force and dispersion force, and it can be seen that the surface energy increase due to the ion assist reaction treatment is almost due to the increase in the polar force. This increase in polar force is caused by polar functional groups containing oxygen generated on the surface of the polymer by ion assist reaction, and can be detected by using x-ray photoelectron spectroscopy (XPS) that can analyze the chemical state of the surface. For example, FIG. 5 is a graph illustrating the chemical state of the surface of the polymer substrate with XPS according to the presence or absence of surface treatment of the polymer substrate PC by the ion assisted reaction method (IAR). Referring to Figure 5 showing the C 1s peak of the high-resolution XPS spectrum, the C 1s peak of the untreated pristine PC can be represented by five Gaussian functions, each of the binding form and binding energy is as follows; aromatic CH (286.4 eV), aliphatic CH (285.1 eV), C-0 (286.1 eV), CO ₃ (290.3 eV) and π-π * shake-up peak (291.8 eV). The biggest changes after the ion assisted reaction were the formation of new C═O bonds and the disappearance of CO ₃ and π-π * shake-up peaks. That is, it can be seen that the benzene ring on the surface of the PC is broken by the irradiation of Ar ions, and reactive oxygen is bonded to the portion to form a C = O bond, which is a polar functional group. Therefore, it can be confirmed that the increase in the polar force is due to the increase in the polar functional group.

The nanoparticle forming region 6 that forms nanoparticles on the surface-modified base material 8 accelerates the ionization portion that ionizes the inert or reactive gas that is separately supplied to the ion source and accelerates the ionized gas ions to be taken out as ions. First sputter deposition ion source 18 and second sputter deposition ion source 19 comprising a portion, and a first sputter target 20 providing a material for forming nanoparticles. ) And a second sputter target 21.

The ion source is an ECR (Electron Cyclotron Resonance) type using a microwave discharge (Microwave Discharge) of 2.45GHz, three 200mm modules can be combined to process a width of 600mm in total length. The maximum acceleration energy is 2 keV and current density of 2 mA / cm2 or more is obtained, and the uniform zone within 5% is 400 mm or more.

As shown in the nanoparticle formation region 6, the ion beams with energy in the ion source 18 for the first sputter deposition and the ion source 19 for the second sputter deposition are the first sputter targets. Atoms of the first and second sputter targets 18 and 19 irradiated to the 20 and the second sputter target 21 and to be energized by collision with the incident ions are emitted from the first and second sputter targets to sputter Particles.

The sputter particles have energy to reach the surface of the polymer material to form nanoparticles, and help improve adhesion, uniformity, and crystallinity. This method is called an ion beam sputtering method. The ion beam sputtering method is a very effective method of polymer material that can be formed at room temperature and is highly affected by thermal damage in a manner suitable for low temperature processes.

The nanomaterial deposition source for forming nanoparticles deposited on the substrate is not only ion beam sputtering, but also thermal evaporation and electron beam evaporation that do not thermally damage the polymer base material. , Ion Plating, RF or RF Magnetron Sputtering, MF or MF Magnetron Sputtering, and D.C. or D. Magnetron Sputtering Dual Magnetron Sputtering is also available.

In order to continuously coat the substrate (substrate), the substrate is continuously moved in the longitudinal direction to form nano-sized particles on the surface of the substrate. At this time, the moving speed of the base material is controlled by the substrate (substrate) feed rate adjusting unit (not shown). The base material movement speed adjusting unit includes a system control means for controlling the feed speed in the feed direction of the base material, and is applied to improve operability and reliability in a thin film coating apparatus such as a roll coater.

Assuming that it is time t _{2 at} which the coalescense of nanoparticles deposited on the base material starts to occur in the nanoparticle formation region 6 by ion beam sputtering, which is a source of nanomaterial deposition, The exposure time of the base material at the nanomaterial evaporation source of the nanoparticle formation region 6 is less than t ₂ to form nanoparticles whose size is controlled with little coalescense phenomena on the base material. That is, the transfer time t ₁ (t ₁ <t ₂ ) from the deposition start position to the deposition end position can be used as the substrate (base material) feed rate control unit.

At this time, the line speed of the base material is precisely a predetermined length l ₁ base material (length corresponding to the distance of the nanoparticle forming region) is processed in the nanoparticle forming region and the nanoparticles are processed. The time taken before passing through the formation region and transferred to the next space is less than the time required for the particles (nuclei) formed in the nanoparticle formation region to grow and coalesce in the length l ₁ substrate. It controls the formation of size controlled nanoparticles with little coalescense phenomena.

10 is an STM image of the nucleus at an early stage of partial ionization beam (PIB) deposition.

10, as the exposure time in the nanomaterial deposition source of the nanoparticle forming region 6 increases (nucleus size is 0.6 ms at 1.5 seconds, nucleus size is 1.0 ms at 2.5 seconds, nuclei at 10 seconds). The size of the nucleus is 4.0 ms and the nucleus size is 8.0 ms at 20 sec.) It can be seen that adjacent particles (nuclei) grow and coalesce.

FIG. 6 shows nanoparticles deposited on a substrate according to positions P1, P2, and P3 of the substrate in the nanoparticle forming region 6 with and without a substrate (base metal) treated by an ion assist reaction method (IAR). It is a schematic diagram showing the size and density of.

At position P1 of the substrate,

The substrates treated with the ion assisted reaction method (IAR) and the substrates not subjected to the ion assisted reaction method (IAR) have the same nucleus size and density. This state is a state before the evaporated particles reach the substrate to form a stable critical nucleus.

At position P2 of the substrate,

In the substrates treated with the ion assisted reaction method (IAR), the nucleus size does not increase but the density increases, whereas the substrate growth without the ion assisted reaction method (IAR) takes precedence.

At position P3 of the substrate,

In the substrate treated with the ion assisted reaction method (IAR) just before the merger, a large number of small nanoparticles were formed, whereas on the substrate not subjected to the ion assisted reaction method (IAR), only a few large particles were present. Is formed.

And depending on whether the nanoparticles formed are insulators, oxides, or conductive materials, or according to the required properties of the resulting nanoparticles, a suitable method is selected and used.

In the nanoparticle forming apparatus, the plasma surface treatment region 2, the ion beam surface treatment region 4, and the nanoparticle forming region 6 are subsequently added to the plasma surface treatment region 2A, the ion beam surface treatment region 4A, The nanoparticles formed on the substrate by adding the nanoparticle forming region 6A,,, are embedded in the underlying film or the upper film formed in the above-described plasma surface treatment region 2 and plasma surface treatment region 2A. do. In the nanoparticle forming apparatus, the substrate (substrate) is continuously moved to form nano-sized particles on the substrate surface. At this time, the moving speed of the base material is controlled by the substrate (substrate) feed rate adjusting unit (not shown). Suppose that the time t _{2 at} which coalescense starts to occur on the base material by ion beam sputtering, which is a source of nanomaterial deposition in the nanoparticle formation regions 6 and 6A, is continuously The running substrate is shorter than t ₂ at the nanomaterial deposition source of the nanoparticle forming regions 6 and 6A to form nanoparticles whose size is controlled so that there is little merging on the surface of the substrate.

That is, the transfer time t ₁ (t ₁ <t ₂ ) from the deposition start position to the deposition end position can be used as the substrate (base material) feed rate control unit. The particles (nuclei) formed in the nanoparticle formation region 6 with the length l ₁ base material floating in the nanoparticle formation region 6 before being transferred to the next region, the plasma surface treatment region 2A. They control the formation of size-controlled nanoparticles with less time to grow and coalesce so that there is little coalescence in the base material.

In order to process a product having a difficult roll type, the loading area 1 and the unloading area 7 are improved to a batch type or an in-line type device. It can be converted and processed, and simultaneous processing of one side or both sides is possible if necessary.

Figure 2 is a schematic diagram showing the change in the size of the stable critical nucleus according to the surface energy of the substrate on the surface treated substrate according to an embodiment of the present invention.

2, it can be seen that as the surface energy of the substrate increases for the deposition material having a predetermined energy, the contact angle θ decreases, and as a result, the size of the critical nucleus decreases. Here, the critical nucleus means a nucleus in which a particle becomes a stable nucleus when one particle is added. Of course, it is conceivable that only the contact angle decreases while the critical r size is fixed, and that the size of the nucleus itself decreases and the number increases because the free energy change for nucleation decreases.

At this time, the size r of the critical nucleus has a relationship between the radius r ₀ and r = r ₀ sin θ of the exact hemisphere as shown in FIG. 2, and has the following relationship with the height h and the contact angle θ of the critical nucleus.

The size of the critical nucleus is related to the free energy for nucleation as follows.

는 각각 기상과 박막 (

_VF), 박막과 기판 (

_FS), 그리고 기판과 기상 (

_SV) 사이의 계면 에너지를 나타낸다. 이때, a₁, a₂, a₃는 각각의 경우에 있어서 비례 상수로 박막과 기판이 이루는 각θ에 따라 결정되는 값으로 a₁ = 2π(1-cosθ), a₂ =πsin²θ, a₃ =π(2-3cosθ+cos³θ)/3이다. 위 식 1로부터 새로운 핵이 생성될 때, 새로운 표면 형성에 의한 자유에너지 증가와 박막의 기판 표면에서의 성장에 따른 기상과 기판 사이의 계면 감소에 의한 에너지가 서로 상쇄하여 핵의 임계 크기가 결정되게 된다. 이때, 기판의 표면 에너지 변화는 박막과 기판 사이의 접촉각θ를(도 3a 의 모식도 참조) 변화시켜 결과적으로 임계핵의 크기를 변화시킨다. 접촉각 의 계면 에너지와의 관계는 아래와 같다.Here, ΔGv is the change in free energy according to the phase change from the gas phase to the condensation phase,

Are vapor and thin film, respectively

_VF ), thin films and substrates (

_FS ), and substrate and vapor phase (

_SV ) is the interfacial energy between. In this case, a ₁ , a ₂ , and a ₃ are proportional constants in each case and are determined by the angle θ formed by the thin film and the substrate, and a ₁ = 2π (1-cosθ), a ₂ = πsin ² θ, a ₃ = π a ^{(2-3cosθ + cos 3 θ) /} 3. When a new nucleus is generated from Equation 1 above, the free energy due to the formation of a new surface and the energy due to the reduction of the interface between the vapor phase and the substrate due to growth on the substrate surface of the thin film cancel each other so that the critical size of the nucleus is determined. do. At this time, the surface energy change of the substrate changes the contact angle θ (see the schematic diagram in FIG. 3A) between the thin film and the substrate, and consequently changes the size of the critical nucleus. The relationship between the contact angle and the interfacial energy is as follows.

This change in the size of the critical nucleus results in a change in the size of the nanoparticles.

3B is a schematic showing a nucleation deposition mechanism reaching a surface treated substrate in accordance with an embodiment of the present invention.

Referring to FIG. 3, when the deposition material forms a cap (cone) shaped critical nucleus at the initial deposition, the volume of the nucleus is calculated as follows for the contact angle θ and the size r of the critical nucleus.

Where r is also a function of the contact angle, so r is _equal to the radius r ₀ of the hemisphere

To be displayed.

Suppose that the contact angles θ are 60 ° and 20 °, respectively, for particles reaching a certain amount of particles (a certain number of particles). At this time, assuming that all other process conditions are constant (if only a change in contact angle due to the surface energy viewpoint occurs), the volume of the critical nucleus is proportional to the contact angle θ. Accordingly, if the contact angle θ is 60 °, assuming that the volume is V ₁ , when the contact angle θ is 60 °, it has a volume of about 1/58 of V ₁ . That is, when the deposition material reaching the substrate reaches V ₁ , one critical nucleus is generated when the contact angle is 60 °, but when the contact angle is 20 °, 58 critical nuclei having a size of 1/58 are generated. Will be. At this time, since the size of the critical nucleus has a relationship of r = r _o sin θ, when θ is 60 °, the critical nucleus will be as small as sin20 ° / sin60 °.

Next, let's consider phenomenologically the effect of substrate surface change on the kinematic side of the atom. Factors affecting the generation and growth of nuclei in kinematics are largely the adsorption and desorption of clusters and the mobility of atoms on the substrate. In fact, in the case of the surface treated by the ion assist reaction, defects caused by ion irradiation on the surface or many functional groups having polarity are generated. These defects are very likely to act as nucleation sites first in the nucleation of nanoparticles, so that adsorption of particles reaching the substrate will occur very well. In other words, the sticking coefficient, which represents the fraction of particles adsorbed to the substrate relative to the total number of particles reaching the substrate surface, will gradually increase so that nuclear growth occurs first, and the nucleation density will increase rapidly. In particular, the increase of C = 0 (carbonyl bond) has a greater effect on the movement of the deposited particles on the substrate since this bond has a relatively higher dipole moment than other functional groups.

In view of the above-described theory of nucleation deposition mechanism and critical nucleus size change, the nanoparticle formation technique of the present invention can change the shape of thin film growth by increasing the hydrophilicity (surface energy increase) of the surface by ion assist reaction. It can be seen that the size of the particles generated on the surface can be arbitrarily adjusted.

Figure 7 (a) IAR-treated surfaces, (b) IAR surface with no surface look at additional information in AFM images of the nanoparticles are not ion-assisted reaction process PC and ion dose ² x 10 ¹⁷ / cm 2 formed in the non-treated The ITO thin film deposited on the treated PC substrate with a thickness of 5 nm was observed using the atomic force microscope (AFM) in the surface shape of the 100 × 100 nm ² region. The untreated surface of Figure 7 (a) shows that about 40 nm of ITO nanoparticles are formed, but in the case of FIG. Able to know. In fact, the surface energy of the ITO thin film is more than one order larger than that of the PC polymer substrate, and thus, in the case of ITO deposited under general conditions, three-dimensional growth occurs, thereby forming large nanoparticles as shown in FIG. 7 (a). However, on the PC subjected to the ion assisted reaction [Fig. 7 (b)], many functional groups having polarity are formed to trap particles reaching the substrate, thereby interfering with movement and acting as a nucleation site, thereby increasing the nucleation density. The size of the critical nucleus and nanoparticles will be reduced. In addition, since the generated functional groups serve to increase the surface energy of the substrate, relatively two-dimensional thin film growth will occur because a driving force is generated to reduce the thermodynamically high surface energy. That is, when the ion-assisted reaction is treated, the above two things happen at the same time, it is thought that very small and thin ITO nanoparticles were formed. These changes can be observed using auger electron spectroscopy (AES).

FIG. 8 shows ITO thin films on (a) 2 nm, (b) 3 nm, (c) 4 nm, and (d) on PC-treated specimens treated with ion assisted reaction (irradiation: 2 x 10 ¹⁷ / cm ² ) and untreated PC specimens, respectively. AES depth analysis after 6nm deposition. The thin film on the substrate before the ion assisted reaction will grow more three-dimensional in the form of a hat, and after the ion assisted reaction, it will have a two-dimensional growth, so the amount of carbon, the substrate element, is measured more. That is, the size and coverage of the critical nucleus are also determined when the thin film is grown by the ion assist reaction treatment on the substrate surface.

9 shows the surface shape change observed by AFM of the ITO thin film according to the ion irradiation amount of the ion assisted reaction treatment. In FIG. 9, before the ion assisted reaction (a), columnar particles were formed, and as the amount of ion irradiation increased, the columnar particles gradually decreased and exhibit very flat surface shapes (FIGS. 9D and 9E). The change in ion dose actually changes the amount (density) of functional groups generated on the substrate surface, thereby sticking to the movement of the deposited particles on the substrate or changing the surface energy. Accordingly, FIG. 9 indirectly shows that the size of the critical nucleus or nanoparticles of the thin film on the substrate and the coverage on the substrate can be controlled.

And nano-size particles (ultrafine particles) exhibit electronic, optical, magnetic, and photocatalytic properties that are significantly different from those of bulk solids.

The characteristics of the nanoparticles

1) increase in mechanical properties such as strength, hardness

2) specific optical characteristics when the domain size is smaller than the wavelength of visible light

3) Specific electrical and electrochemical properties when the domain dimension is less than the average free path of electrons

4) specific electronic properties such as coulomb blockade

5) Unique thermal characteristics when the domain dimension is less than the phonon length

6) Specific magnetic properties when the material's domain dimension is less than the magnetic domain size

7) It has lower temperature and unique manufacturing characteristics such as faster sintering process.

Sputtering technology is described as a nanomaterial deposition source of the nanoparticle formation region 6 as a deposition technology for forming nanoparticles on a substrate (base material), but as the nanomaterial deposition source, a substrate is formed in a vapor phase in a vacuum. Ion Beam Sputtering, Thermal Evaporation, Electron Beam Evaporation (E-Beam) described above, which can form nanoparticles (e.g., nanoparticles having an average particle size of about 4 nm to 100 nm). Evaporation, Ion Plating, RF or RF Magnetron Sputtering, MF or MF Magnetron Sputtering, and DC or DC Magnetron Sputtering Similar methods other than sputtering, dual magnetron sputtering are also included. The nanoparticles may be formed of one or more kinds of metals such as Ag (silver), Cu (copper), Zn (zinc), Sb (tin) Cr (chromium), Ti (titanium), Ni (nickel), and Fe (iron). from ceramics, such as one metal compound, Al ₂ O3, SiO _2, TiO _2, ZrO _2, a single oxide such as _{and, SiO 2 · Al 2 O 3} , TiO 2 · ZrO 2 such as a composite oxide, nitride-based, carbide-based of Select one or consist of two or more types of complexes.

Example

Patents and utility models have been disclosed in which silver is coated on a substrate (base material, substrate) using silver bactericidal properties to provide antimicrobial and bactericidal properties. Korean Patent Publication No. 20020011310 (published date: February 8, 2002) describes a technique of impregnating and fixing silver nitrate on a fiber to have antibacterial properties. The silver nitrate reduction method has a risk that unexpected heavy metals such as human body may be added when the silver is immersed in the fiber by a wet method, and the treatment process is not environmentally friendly.

Example 1.

Surface treatment of substrates such as woven fabrics, nonwoven fabrics, polymer films, etc. by ion assist method using ion beam is used to control the degree of hydrophilicity and surface energy of the surface of the substrate, and then antibacterial metals such as Ag (silver), Cu (copper) , Cr (chromium), Ti (titanium), Ni (nickel), Fe (iron) and the like by using a method such as sputtering, which is a nanoparticle forming technique described above for antimicrobial ceramics such as nitride, carbide, oxide, etc. Particles of size are attached to and adhered to the substrate to impart a bactericidal and antimicrobial effect to the substrate.

In this case, in order to maximize the effect of the nanoparticles, the nanoparticles are deposited discontinuously and non-uniformly on the surface of a continuous substrate such as a fabric or a nonwoven fabric.

To deposit nanoparticles non-uniformly and discontinuously on the surface of the continuous substrate, the substrate is continuously moved in the longitudinal direction to form nano-sized particles on the surface of the substrate. At this time, the line speed of the substrate is precisely a predetermined length l ₁ base material (length corresponding to the distance of the nanoparticle forming region) is processed in the nanoparticle forming region and the nanoparticles are processed. The time taken before passing through the formation region and transferred to the next space is less than the time required for the particles (nuclei) formed in the nanoparticle formation region to grow and coalesce in the length l ₁ substrate. It controls the formation of size controlled nanoparticles with little merging.

The continuous substrate is cut to fit various products.

It is applied to masks that release silver ions and sterilize when breathing, and disposable band-aids that maintain hygienic conditions by suppressing the propagation of bacteria and other germs with metal ions in skin wounds.

Example 2.

The hydrophilicity is increased by forming a polymer film on the evaporator surface of the heat exchanger.

But this hydrophilic polymer membrane creates a good atmosphere for bacteria to grow.

The aluminum sheet (coated with a hydrophilic polymer membrane) used as a material of the evaporator is surface treated by an ion assist reaction method using an ion beam to control the degree of hydrophilicity and surface energy of the surface of the aluminum sheet, and then use the nanoparticle forming technique described above. Thereby depositing antimicrobial nanoparticles non-uniformly and discontinuously on the surface of the aluminum sheet.

In order to deposit nanoparticles non-uniformly and discontinuously on the surface of the aluminum sheet, the aluminum sheet is continuously moved in the longitudinal direction to form nano-sized particles on the surface of the aluminum sheet. At this time, the line speed of the aluminum sheet is precisely a predetermined length l ₁ base material (length corresponding to the distance of the nano particle formation region) is processed in the nano particle formation region and the nano The time required to pass through the particle formation region and transfer to the next space is less than the time required for the particles (nuclei) formed in the nanoparticle formation region to grow to merge in the length l ₁ substrate and merge into the substrate. This little control of the formation of size controlled nanoparticles.

The nanoparticles are antimicrobial metals such as Ag (silver), Cu (copper), Zn (zinc), Sb (tin) Cr (chromium), Ti (titanium), Ni (nickel), Fe (iron), and nitride , Carbide-based, oxide-based nano ceramics are formed on an aluminum sheet (coated with a hydrophilic polymer film) by sputtering or the like. The nanoparticles are continuously exposed to moisture or moisture when the air conditioner is used, and the bacteria generated on the hydrophilic polymer membrane are suppressed by the bactericidal effect of the nanoparticles to extinguish the bacteria and destroy the bacteria.

While many details are set forth in the foregoing description, they should be construed as illustrative of preferred embodiments, rather than to limit the scope of the invention.

For example, one of ordinary skill in the art to which the present invention pertains may provide nanoparticles of various sizes and types by using various nanoparticle manufacturing methods according to the technical idea of the present invention. Therefore, the scope of the present invention should not be defined by the described embodiments, but should be determined by the technical spirit described in the claims.

As described above, according to the method of forming the nanoparticles of the present invention, a device thereof, and an application product thereof, the surface of a substrate such as metal, ceramic, polymer, and the like is modified to be hydrophilic to increase surface energy for adhesion, and to control the degree of hydrophilic modification. The process time t ₂ of the nanoparticles deposited on the substrate is greater than the transfer time t ₁ of the continuous running substrate in the nanomaterial deposition source, thereby forming the nanoparticles directly and uniformly on the surface of the substrate, thereby forming Durability, the physical and chemical properties of the nanoparticles and the nano-effects can be maximized.

Claims (27)

delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete In the nanoparticle deposition apparatus for controlling the size of the nanoparticles deposited on the base material surface, A loading area into which a roll-shaped base material is loaded, A plasma surface treatment region for plasma treating a surface of the base material loaded in the loading region; An ion beam surface treatment region for ionizing the surface of the base material, including an ion supply gas supply port and a surface treatment ion source for controlling the degree of hydrophilicity and surface energy of the surface of the base material treated with plasma; A process of growing nanoparticles on the surface of the ion beam surface-treated base material and incorporating the nanoparticles deposited on the base material with a transfer time t ₁ from the deposition start position to the deposition end position of the continuously moving base material. A nanoparticle formation region maintained for less than the time t ₂ (t ₂ > t ₁ ), An unloading area in which the base material is unloaded, Nanoparticle deposition apparatus having a transfer device for continuously moving the base material from the loading region to the unloading region. The method of claim 23, wherein The base material is a nanoparticle deposition apparatus, characterized in that used to select one of a metal, a polymer film, a fabric or a ceramic. The method of claim 23, wherein Nanoparticle deposition apparatus using an optimal condition plasma zone method which is a DC discharge plasma method as a treatment method of the plasma surface treatment region. The method of claim 23, wherein The nanoparticle formation method of the nanoparticle formation region is ion beam sputtering, thermal vapor deposition, electron beam deposition, ion plating, RF sputtering, RF magnetron sputtering, FM sputtering, FM magnetron sputtering, dish sputtering, dish magnetron sputtering and dual Nanoparticle deposition apparatus characterized in that it is one method arbitrarily selected from the group consisting of magnetron sputtering. The method of claim 23, wherein The nanoparticles are at least one arbitrarily selected from the group consisting of Ag (silver), Cu (copper), Cr (chromium), Ti (titanium), Ni (nickel), Fe (iron), nitrides, carbides, and oxides Nanoparticle deposition apparatus characterized in that the above particles.

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