KR100953741B1 - Apparatus for forming thin film using ecr plasma - Google Patents

Abstract

The present invention is a microwave generator having a uniform linear output of more than 1m in width and a magnetic field generator having a corresponding width to generate an ECR (Electron Cyclotron Resonance) plasma having a high energy that can be supplied to a large area at low temperature A device capable of producing a substrate having good electrical conductivity and light transmittance by continuously depositing a metal, a transparent metal oxide, an inorganic material, or the like on a transparent plate, which is a plastic plate and a glass plate by ions, and a film deposition method using the device and the device It relates to a substrate for a touch panel having a transparent conductive film that can be formed by.

Electromagnetic Resonance (ECR), Transparent Conductive Film, Plasma, Chemical Vapor Deposition, Plastic Substrate

Description

Mr. Lee Plasma deposition equipment {APPARATUS FOR FORMING THIN FILM USING ECR PLASMA}

The present invention relates to an apparatus for depositing a film on a substrate, and more particularly, to an apparatus for depositing a film on a substrate by an Electron Cyclotron Resonance (ECR) plasma method.

Development of compact display video devices such as terrestrial digital broadcasting (DMB), personal digital assistant (PDA), Play Station Portable (PSP), and Portable Multimedia Player (PMP) Increasingly, there is an increasing tendency to add a touch function to a display for inputting, outputting and retrieving information through a small terminal. Accordingly, the demand for touch panels is rapidly increasing.

At the same time, it is required to reduce the weight of communication or imaging devices, and thus, development of forming touch panels by providing functionality to plastic substrates or films instead of glass substrates is underway.

Conventionally used touch panels are formed of a dot spacer between a conductive glass substrate and a glass substrate electrode after depositing an indium tin oxide (ITO) layer, a representative transparent conductive material, onto a glass substrate by a sputtering method. There are many.

However, in terms of weight reduction and safety and durability against external impact, the use of a touch panel using a transparent conductive polymer film attached to a glass substrate or a conductive transparent film attached to a plastic substrate is increasing. In addition, a method of forming a high quality transparent conductive film without using expensive indium has been sought.

In order to provide electrical conductivity to a glass substrate, a plastic substrate, or a resin sheet surface, the process of forming a conductive transparent thin film is required. As a method of forming a thin film on a substrate, physical vapor deposition (PVD) such as chemical vapor deposition (CVD) or sputtering may be used.

As a method of forming a transparent conductive thin film in a conventional touch panel, a physical deposition method using sputtering or ion beam assist is most commonly used. These methods do not cause thermal damage or deterioration of the substrate due to heat accumulation when applied to glass substrates, but may cause thermal damage or substrate degradation when coated on plastic substrates.

That is, when the thin film is formed on the plastic substrate by conventional sputtering or physical vapor deposition using ion beam assist, the cooling surface of the coating surface is slow due to the low thermal conductivity of the plastic even when the substrate is cooled, and the substrate is moved for continuous processing. Cooling efficiency is even worse. Due to the energy of the sputtered atoms or molecules at the surface of the coated surface of the substrate, deterioration occurs on the surface of the plastic, which not only loses the uniqueness of the plastic substrate but also discolors due to thermal damage, resulting in high chromaticity. There is a problem that is difficult to apply to the touch panel substrate that must maintain the transmittance.

In addition, since the plastic substrate or the resin sheet is softened or melted at a high temperature of several hundred degrees Celsius or more, unlike the semiconductor wafer, the substrate may be deformed unless the conductive transparent thin film is formed at a low temperature.

On the other hand, depending on the material, it may be difficult to form a thin film by the sputtering method. For example, a soft metal having a low melting point is difficult to form by sputtering techniques. In addition, it may be difficult to form the structure of the shape by the sputtering technique in the material film having a good grain characteristics when the film has a certain grain. For example, tin, zinc, oxides thereof, and the like are difficult to form a film by a sputtering technique, and fluorine-doped tin fluoride tin film (FTO) is also not suitable for forming by sputtering.

In the chemical vapor deposition (CVD) process, a source gas of a deposition film, which forms a thin film to be deposited, is introduced into a process chamber to form and deposit a film by a chemical reaction on a substrate.

Chemical vapor deposition may be a means for forming a deposited film complementary to sputtering physical deposition. To improve chemical reactivity in chemical vapor deposition, the process can be carried out at high temperatures, and source gases can be activated to facilitate chemical reactions even at relatively low temperatures. Thin film formation on plastic substrates at high temperatures has the problems of substrate degradation and deformation already mentioned. Plasma can be formed in the process chamber to make the activated state as low as possible. There are a number of methods for forming a plasma in the process chamber, and one of the methods for forming a high-density plasma may use an electron rotation resonance (hereinafter, referred to as 'ECR') method.

On the other hand, when laminating a thin film on a substrate, it is important to form the thin film in an even thickness and state over the entire effective area of the substrate. In particular, when a thin film is deposited on a substrate for forming a display panel, including a touch panel, the display is often rectangular rather than circular, and since the display is enlarged, it is increasingly difficult to form a thin film evenly on the front of the display panel. have. However, it is very important to deposit the film evenly on the panel substrate in order to increase the yield of the product and to improve the uniformity and reliability of the quality.

However, conventional ECR plasma equipment has a form of inducing microwaves to the plasma formation chamber using a waveguide. The waveguide used for the microwave induction has a problem in that the vertical cross section has a quadrangle based on the direction in which the microwave is transmitted, the microwave is strong in the center in the cross section, and the edge has a weak microwave strength, making it difficult to form a uniform plasma.

Therefore, increasing the vertical cross section or forming it linearly in either direction is undesirable in view of the uniformity of plasma formation. Instead of forming the vertical cross section of the waveguide to one side, it is also possible to divide the waveguide into several parts and arrange the branches in one direction. However, in this case, the induction efficiency and uniformity according to the branch are not good. Connecting the microwave generators one by one can increase the uniformity, but it is complicated and expensive.

If the microwave inputted through the waveguide is not evenly introduced into the plasma forming chamber, the density of charged particles of the thin film forming material introduced into the process chamber with the substrate through the slit of the plasma forming chamber is also not uniform, and eventually forms a film on the substrate. In a process or the like, it becomes difficult to perform a uniform treatment over the entire substrate.

Therefore, it is difficult to form a uniform thin film with high plasma formation efficiency on the square substrate for display through existing ECR plasma equipment.

According to an aspect of the present invention, to solve the problems of the conventional ECR plasma film forming equipment described above, an object of the present invention is to provide an ECR plasma film forming equipment that can form a uniform thin film efficiently on a substrate used for display and the like. .

More specifically, the present invention uses the conventional method of circular electromagnets and simultaneously introduces microwaves through a rectangular waveguide, thereby increasing the intensity of microwaves at the center and lowering them at the edges. ECR plasma film forming equipment that can improve the difference and the problem that the uniformity cannot be secured due to the variation in the thickness of the deposited film on the substrate that may occur due to the change in the concentration of ions (charged particles of the material used as the material of the deposition film). It aims to do it.

In addition, an aspect of the present invention is to provide an ECR plasma film forming equipment that can improve the difficulty of applying to the commercialization process in the research phase according to the difficulty of large area of the existing ECR plasma film forming equipment.

One aspect of the present invention is to provide a substrate for a touch panel having a uniform transparent conductive film formed by the ECR plasma method on a relatively susceptible synthetic resin substrate.

One aspect of the present invention is to provide a method for efficiently forming a film on a substrate in the ECR plasma film forming equipment having a linear antenna and a magnetic field forming means corresponding to the linear antenna.

ECR plasma film forming equipment according to an aspect of the present invention for achieving the above object comprises a plasma forming apparatus and a process chamber in which deposition on the substrate, the plasma forming apparatus is a linear antenna, a plasma generator connected to the linear antenna And a magnetic field forming device for forming a magnetic field in the space between the linear antenna and the substrate of the process chamber.

In the present invention, the magnetic field forming apparatus may be configured to have a shape corresponding to the linear antenna so as to limit the plasma to the linear space corresponding to the linear antenna. The magnetic field forming device may be formed by arranging permanent magnets, but a plurality of electromagnets may be used instead of the permanent magnet, and the coil may correspond to a linear antenna such as a track having a long straight line or an ellipse having a long axis. Can be wound into a solenoid coil.

In the equipment of the present invention, the linear antenna may have a form in which both ends are coupled to two microwave generators resonating with each other.

In the equipment of the present invention, it is preferable that the linear antenna is wrapped with a tube of a material which can protect the surface of the antenna without interfering radiation of radio waves such as a crystal tube so that film deposition or the like is not performed by plasma action. .

In the present invention, the linear antennas may be formed in plural numbers arranged in parallel with each other, and each linear antenna may be formed in a form in which both ends are connected to a corresponding microwave generator. In this case, a shield member may be installed between the linear antennas so as to exclude the influence of the adjacent linear antennas between the linear antennas arranged in parallel with each other.

Plasma forming space, which is a space in which the plasma forming apparatus is installed in the equipment of the present invention, may be formed integrally with the space of the process chamber in which the substrate on which the film is formed is formed or may be a space separated by a partition wall. When divided by the partition wall, the partition wall that separates the two spaces are formed of various types of windows such as slits, the two spaces can be connected through the window. In this case, the window is formed so that the source gas particles for forming the deposition film activated in the plasma formation space may reach the substrate surface at a uniform frequency.

A touch panel substrate having a transparent conductive film according to an aspect of the present invention is characterized in that the transparent conductive film formed by ECR plasma CVD on the synthetic resin substrate. In this case, the transparent conductive film may be a tin oxide or a fluorine-doped tin oxide transparent conductive film. The synthetic resin substrate may have a softening point temperature of 200 ° C. or less. The thickness variation in the substrate of the transparent conductive film may be 20 nm or less.

In the method of depositing a film on a substrate by using the plasma film forming equipment according to an aspect of the present invention, a process chamber in which deposition is performed is located in one section of a flow path of the substrate, and a sidewall of the substrate facing the substrate surface on which the deposition film is to be formed is disposed on the process chamber. In the plasma film forming equipment having a linear antenna and a linear plasma forming apparatus having a magnetic field forming apparatus and a window corresponding to the linear antenna,

An activated deposition source source gas is supplied to the substrate through the window while the substrate is continuously or semi-continuously transferred along the substrate flow path perpendicular to the longitudinal direction of the linear antenna. In this case, the substrate is transported semi-continuously in the form of an in-line process where the substrate is deposited in the process chamber after the transfer to the entire position of the process chamber, and then the substrate is discharged from the process chamber to an outlet different from the input direction. Means. On the other hand, in the method of the present invention, the substrate is continuously transferred, which means that the substrate continues to move when film deposition is performed on the substrate.

In the equipment of the present invention, microwaves introduced into the plasma forming space through the linear antenna from the microwave generator are emitted by 360 degrees around the antenna in a direction perpendicular to the length of the linear antenna. In addition, a magnetic field forming apparatus is installed in at least some space between the substrate on which the film is to be deposited and the linear antenna to form a magnetic field. When the plasma source gas flows into the space in which the magnetic field is formed, the plasma source gas is turned into a plasma state by microwaves passing through the space. Charged particles such as electrons and ions in the plasma may remain in a confined space formed by the magnetic field forming apparatus under the influence of the magnetic field, thereby maintaining high density. The source gas for forming a deposition film is injected into a region where a high density plasma is formed and activated, and then moved toward the substrate to form a deposition film on the substrate surface.

In this case, the magnetic field forming apparatus may be configured such that the source gas particles for forming the deposition film activated through the magnetic field forming apparatus are concentrated and discharged in the direction of the substrate, and a process chamber in which a plasma is formed between the plasma forming apparatus and the substrate and the substrate is deposited. If there are partition walls therebetween, the partition walls may have linear windows corresponding to the linear antennas between the plasma formation spaces and the process chambers.

In chemical vapor deposition, metal organic chemical vapor deposition (MOCVD) using an organic metal gas may be used as the deposition film source gas.

According to the present invention, it is possible to efficiently and uniformly form a film on a substrate constituting a rectangular display panel, particularly a large area substrate.

According to the present invention, an ECR plasma is formed by using a linear microwave generator and an ellipse or track trajectory field forming device that forms a long magnetic field on one side, and thus, on a resin sheet or plate type substrate at a relatively low temperature similar to room temperature conditions. The film can be deposited. Therefore, the ECR room temperature chemical vapor deposition system with high ionization rate and energy, after ionizing the deposited film precursor in the gas phase, reacts the ions produced by the surface chemical reaction on the surface of the substrate to reduce the degradation of the surface of the substrate, while maintaining a large area continuous coating. It becomes possible.

In addition, according to an aspect of the present invention, by adjusting the residence time of the deposit in the process chamber by chemical vapor deposition of a conductive material film having excellent transparency, low electrical resistance and excellent adhesion, the surface resistance of the deposited film is tens of Ω / □ ~ hundreds Ω / □ A range of high quality transparent conductive substrates that can be easily controlled in a range and satisfies the total visible light transmittance of 86% or more including the deposited film and the transparent resin substrate, and the chromaticity a = + 2.0 ~ -2.0, b = 2.0 ~ -2.0 Formation is possible.

Hereinafter, the configuration of the present invention will be described in more detail with reference to the accompanying drawings.

Figure 1 is a perspective view schematically showing the configuration of the main part of the ECR plasma film forming equipment according to an embodiment of the present invention, Figure 2 is a cross-sectional view taken along line AA of Figure 1 an embodiment of the present invention device 3 is a cross-sectional view taken along the line BB of the part shown in FIG. 2 of an embodiment of the present invention apparatus. However, the gas supply line and the vacuum line were replaced with a simple wiring display.

1 to 3, a process chamber 10 serving as a work space in which deposition is performed on the surface of the substrate 13 is provided below. Four unit plasma forming apparatuses 20 are installed above the process chamber 13. Then, a microwave generator is provided above each unit plasma forming apparatus 20.

The microwave generator includes a linear antenna 23 made of metal and a microwave generator 21 coupled to both ends of the linear antenna 23. Two microwave generators 21 connected to one linear antenna 23 are adjusted to resonate with each other.

The magnetic field forming apparatus generates a uniform magnetic field in a direction perpendicular to the linear metal antenna in the plasma formation space. In the present embodiment, the magnetic field forming apparatus is composed of an electromagnet 27 in the form of a solenoid coil.

In each unit plasma forming apparatus 20, one linear antenna 23 coupled with two resonant microwave generators 21 is paired with one magnetic field forming apparatus. In another aspect, a microwave generator for generating a 2.45 GHz microwave output to satisfy an ECR plasma condition in which the plasma particles are confined and confined in a space defined by a magnetic field forming device for rotational resonance of electrons and ions in the plasma. (21) and an ellipse or long track-shaped electromagnet having a large eccentricity capable of forming a magnetic field having a corresponding 875 Gauss are combined.

Electrons and ions in the plasma formed from the plasma source gas introduced into the plasma forming apparatus rotate and resonate to maintain a high density plasma. As the deposited film source gas is introduced into the plasma region 28, activated ions and radicals are generated. These activated ions, radicals, enter the substrate with a slit effect through long, narrow windows into the process chamber region. Chemical vapor deposition at room temperature enables the deposition of metals or metal oxides on the base material without thermal damage or deformation. In this case, the deposition film source gas may be an organic gas having a metal element included in the deposition film, and various organic gases may be used as a source of one metal element. Organic gas having a metal element is well known for each element, so specific examples thereof will be omitted.

The substrate may include both plastic and metal plates and inorganic plates such as transparent or opaque glass, silicon, stainless steel, aluminum, alumina, Teflon, PE, PP, PC, PMMA, PEEK, etc. in the form of plates or sheets. .

Between each of the electromagnets 27 corresponding to the four linear antennas 23 formed in parallel with each other, the magnetic field generated by each electromagnet interferes with the microwave output and the ECR plasma generation in the surrounding unit plasma forming apparatus 20. The shield or separator 26 is installed in a metal material such as aluminum so as not to cause it. The installation of the separating plate 26 to prevent the interference of the magnetic field between each electromagnet 27, it is possible to generate a linear, large-area ECR plasma having a width of 1m or more in one direction with little influence on uniformity.

In order to increase the processing efficiency and productivity of the substrate glass or the resin substrate, in the exemplary embodiment of the present invention, a plurality of linear unit plasma forming apparatuses 20 are arranged side by side with respect to the linear antenna 23.

Since the linear antenna 23 is located in the plasma forming space occupied by the plasma forming apparatus 20 and is not spatially separated from the plasma forming space, the linear antenna 23 may receive an etching operation due to plasma formation. In addition, some active particles in the plasma may be deposited on their surface, reducing the efficiency of microwave generation. Therefore, the linear antenna 23 is installed in the quartz tube 25 to protect the linear antenna 23 from etching and deposition. The quartz tube 25 may be used after being separated, replaced, and cleaned with the linear antenna 23 and the microwave generator 21 through a regular maintenance and repair process, thereby facilitating maintenance and repair.

The spatial division of the process chamber 10 and each plasma forming apparatus 20 may be formed as though the entirety is not clear, but a separate partition or partition 29 is preferably formed between the two spaces. However, as shown, a window 291 connecting the two spaces to each other is required for the passage of the plasma-formed deposited film forming particles. The window 291 is of a width at which linear microwaves emitted from the linear antenna 23 are induced, i.e. roughly the same as the linear antenna 23 to introduce a uniformly activated deposition source gas into the substrate 13 to be processed. It may be formed in the form of a linear slit of length.

The window 291 has a length corresponding to the width or length of the substrate used in a conventional quadrangular display panel, and is a long track-shaped slit having a constant width small enough to produce a slit effect compared to the length. Can be done. The window 291 may be formed to be opened and closed.

An electrode capable of applying a DC bias may be provided in the middle of the ECR plasma region 28 and the process chamber 10 in which the deposition takes place, and is generated in the plasma generating region by applying a positive or negative DC power to the electrode. The deposited film source gas ions may be efficiently accelerated or induced to a substrate to form a metal, a metal oxide, an inorganic material, an inorganic oxide, or a composite film thereof.

As the transparent conductive material coated on a substrate such as an optical film or a plastic substrate, tin oxide (SnO 2), indium tin oxide (ITO), In 2 O 3, ZnO, CdSnO 4, or the like may be used.

The process chamber 10 is installed to occupy a part of the space forming the horizontal flow of the substrate 13. The process chamber 10 maintains a vacuum during processing to maintain deposition of plasma treated deposition film forming particles in a practical range. In order to apply a vacuum, a vacuum line 50 is connected to the process chamber 10, and a vacuum pump 51 is connected to the vacuum line 50. Meanwhile, a separate vacuum application pipe may be connected to the plasma forming chamber constituting the plasma forming space or the spaces forming the horizontal flow of the substrate 13 before and after the process chamber 10.

In order to generate an ECR plasma and induce active particles to the substrate, the initial process chamber 10 has a high vacuum of 1 × 10 −6 Torr and a pressure of several mTorr to several tens of mTorr to perform the deposition process simultaneously with the introduction of the process gas. In order to maintain the vacuum line 50 has a vacuum pump 51, the vacuum pump 51 is a rotary pump 511 and mechanical booster pump 513 for the first roughing, to maintain a high vacuum state The turbo molecular pump 515 is formed by sequentially connecting. The vacuum line 50 may also be of other conventional forms, and other piping elements, such as throttle valves and gate valves, may be installed on the vacuum line 50. Then, the state of the vacuum pump 51 is designed to be automatically controlled according to the difference between the pressure measured by the pressure gauge (not shown) and the input value for the preset pressure.

A plurality of gas supply lines 30 and 40 are connected to the plasma forming apparatus 20 to supply the deposition film source gas and the plasma source gas into the plasma forming space and the process chamber. Mass flow controllers 33 and 43 are installed in each of the deposition source gas supply line 30 and the plasma source gas supply line 40 together with piping elements such as valves 31 and 41 to control the gas supply. . The deposition source gas supply line is typically composed of a plurality of lines instead of one single line. Since the deposition source gas may serve as a plasma source gas, a deposition source gas supply line and a separate plasma source gas supply line are not installed. It may not.

As the volume of the process chamber 10 increases, the cost of applying and maintaining the vacuum and the cost of equipment increase, so it is preferable to design the minimum volume in the range where the continuous process is possible.

A roller 15 for moving the substrate 13 in a horizontal flow space of the substrate 13 including the process chamber 10 is installed. The transfer roller 15 is designed to control the substrate transport speed to 0.1 ~ 10m / min. A substrate 11 is provided with a cooling plate 11 for cooling thermal energy generated by ions or radicals having high energy in the process chamber 10 region in which deposition is performed. A coolant circulation pipe may be installed on the rear surface of the cooling plate 11 so that the coolant may take heat from the substrate. The refrigerant may be a liquid or gas such as water.

In the process chamber 10, a film is deposited on a substrate through a continuous or semi-continuous process. In the continuous process, the deposition film source gas activated through the window 291 of the partition wall 29 of the plasma forming apparatus is transported while the substrate 13 continues to be transported by the roller 15 even in the process chamber 10. 13) is supplied. By reducing the moving speed of the substrate 13, a single plasma forming apparatus may also form a transparent conductive film having a predetermined thickness on the substrate 13, but in this case, the process time increases, and when the process time increases, the thermal accumulation of the substrate deteriorates. The chances are high. Therefore, it is possible to shorten the time required for film deposition on one substrate by increasing the number of unit plasma forming apparatuses connected to the process chamber.

In a continuous process method, a roll-to-roll is applied in which the substrate is rolled into the process chamber in order to reduce the volume of the process chamber, while the roll is released on the other hand, the roll is wound on the other side, and the substrate is flattened in the middle. You can use the roll to roll method. The roll-to-roll method can be applied to a relatively thin and flexible plastic substrate capable of winding the substrate. By such a roll-to-roll method, continuous large area deposition of the substrate can be facilitated.

In a semi-continuous process, the process chamber 10 in the horizontal flow space of the substrate 13 may be isolated through other horizontal flow spaces and valves (not shown) such as gate valves. For example, the substrate 13 is moved through the roller 15 in another horizontal flow space, and then the gate valve at the inlet of the process chamber 10 is opened and the robot arm or the vacuum chuck (not shown) in the process chamber 10. It is mounted on the cooling plate 11. In this case, the substrate often does not move in the process chamber, and the activated deposition source source gas is supplied to the substrate through the partition window 291 of the plasma forming apparatus 20. In order to cover a large area at once, a plurality of unit plasma forming apparatuses 20 having linear partition wall windows 291 are provided side by side. The number of unit plasma forming apparatuses 20 may be operated in different numbers according to the substrate area. After the film deposition process is completed, the film is transferred from the cooling plate 11 to the conveying roller 15 and conveyed by the conveying roller 15 for the next treatment.

In addition, a halogen lamp or an infrared lamp 17 may be installed in the horizontal flow space of the substrate so as to heat the surface of the substrate during an inorganic or metal plate treatment such as a relatively thermally stable glass substrate.

On the other hand, if the length of the barrier window corresponds to the long side (horizontal) of the substrate, and the speed is maintained while moving the substrate (substrate in the vertical direction) perpendicular to the longitudinal direction of the window (continuous process), the plasma of the present invention in the horizontal direction By the uniformity of the longitudinal direction of the plasma by the forming apparatus, the uniformity of the deposited film can be easily ensured on the entire surface of the substrate by controlling the uniformity of the movement speed of the substrate in the longitudinal direction, and the formation of the deposited film on the quadrilateral substrate can be efficiently performed. It becomes possible. In the semi-continuous process, the deposition film uniformity in the horizontal direction may be secured by adjusting the interval and slit width for forming a plurality of unit plasma forming apparatuses instead of the horizontal movement speed of the substrate.

Looking at the embodiment of the touch panel substrate of the present invention formed by the present invention ECR plasma film forming equipment with reference to the drawings while having sufficient transparency and color balance when film deposition is made using a variety of synthetic resin substrate in the ECR plasma film forming equipment Check that the conductive substrate can be formed.

(Example 1)

In Example 1, PC (Poly Carbonate), a kind of synthetic resin, was used as a substrate for film deposition. Initially, before the coating of tin oxide, it was confirmed that the optical properties of the PC sheet (sheet) as a substrate were visible light transmittance of 92%, chromaticity a = -0.31, and b = 0.25.

Microwave generators and elliptical electromagnets were installed in the ECR plasma film forming equipment to generate plasma having a uniform thickness and state up to 1.5 m in width and to process substrates. Using this film forming apparatus, an attempt was made to deposit a transparent conductive film on a PC substrate.

That is, fluorine (F) is doped by supplying a tin (Sn) source gas, an oxygen gas, and a fluorine gas that are processed through a plasma region of a plasma forming apparatus to a PC (poly carbonate) substrate having a thickness of 1 mm having excellent heat resistance and abrasion resistance. Transparent tin oxide (Tin Oxide: SiO 2) film was deposited to a thickness of 250nm. A transparent conductive sheet having a surface resistance of 450? / ?, visible light transmittance of about 87.02%, chromaticity a = -0.02, and b = 3.05, which was reduced by 5% on the original substrate, was obtained.

This result can be confirmed through the visible light transmittance graph for each wavelength of FIG. 4, the brightness coordinates and the color coordinates of FIG. 5. At this time, the brightness coordinates and the color coordinates were in accordance with the CIELAB system. The CIELAB system is one of the standard color-difference formulas published by the CIE in 1976. Brightness coordinates are the numerical values representing the brightness (L) of the lightness vertical line divided into 100 grades, and D65 is the statistical representation of average daylight with a correlation color temperature of 6500K. It is a value normalized to 100 at 560 nm wavelength. The horizontal axis (a axis) of the color coordinates of the brightness coordinates is displayed by dividing red (+)-green (-) into 128 grades, and the vertical axis (b axis) is displayed by dividing yellow (+)-blue (-) by 128 grades. It is.

(Examples 2 and 3)

In Example 2 and Example 3, poly methyl methacrylate (PMMA) was used as a substrate for film deposition. As a substrate to be coated, fluorine-doped tin oxide was deposited under the same experimental conditions as Example 1 using a thermoplastic resin, poly methyl methacrylate (PMMA). PMMA is a material with excellent light transmittance with a softening point of 80 to 100 ° C and a wavelength range of 400 nm to 760 nm and a visible light transmittance of 90 to 99% when the thickness of the PMMA is 400 nm to 800 nm, depending on the forming conditions. to be.

In order to confirm the characteristics of the transparent conductive film according to the material of the substrate, the film was carried out under the same experimental conditions using a PMMA sheet having an initial visible light transmittance and a thickness similar to that of Example 1, but with different times. Was carried out.

That is, the characteristics of the PMMA substrate used for film deposition were 91.9% of visible light transmittance, chromaticity a = 0.1, b = 0.34 and thickness of 1 mm, and tin oxides doped with fluorine were deposited to 250 nm thickness and 270 nm thickness for each implementation.

The surface resistivity of the deposited film was 480 Ω / □ and 520 Ω / □ for short and long treatment times, respectively, with a short treatment time of 88.86% visible light transmittance, a = -2.4, b = 3.17, and a long treatment time for visible light. The transmittance was 86.8%, the chromaticity was a = 0.62, and b = 6.37. As a result of the treatment time, the chromaticity was increased due to heat damage due to heat accumulation on the surface. In the short wavelength range, the transmittance of the sample with long treatment time was relatively lower than that of the short sample, and the transmittance was high in the long wavelength range of 550 nm or more.

6 and 7 are graphs of visible light transmittance, brightness coordinates, and color coordinates of respective wavelengths showing the results of this embodiment.

(Examples 3-6)

Surface resistance, chromaticity, and transparency (visible light transmittance) according to residence time in the process chamber were compared using a sheet having a thickness of 1 mm having a PC material in Table 1 below. Item NO. 1 and 2 were made to be different (longer) the time required for deposition under the same conditions as in Example 1.

As the residence time in the process chamber, which is the area where plasma chemical vapor deposition takes place under the same experimental conditions, surface degradation progressed and surface resistance increased. According to the color coordinates, the a value represents a color coordinate in the range of -2 to -3, which is blue (green), and the b value is 4 to 5, indicating a yellow chromaticity.

The residence time in the process chamber is NO. NO shorter than 1 and 2. In the case of 3 and 4, the deposition thickness is thinner, but it can be confirmed that a deposition film having a low surface resistance value is formed. Accordingly, the chromaticity was similar to the blue (green) series, showing a similar tendency (about -2). The b value was -0.8 to 1.5, and an excellent coating film having a neutral chromaticity was formed. In other words, it can be seen that an appropriate residence time in the reactor can obtain a high-quality deposition film while reducing the thickness of the coating film without any surface deterioration on surface resistance, transparency, and chromaticity.

NO./GK Surface resistance (Ω / □) transparency(%) Chromaticity a Chromaticity b Film thickness (nm) One 520 88.4 -2.6 4.6 270 ± 20nm 2 550 88.0 -2.3 5.0 270 ± 20nm 3 480 86.8 -2.0 -0.8 250 ± 20nm 4 480 88.2 -2.1 1.4 250 ± 20nm

1 is a perspective view schematically showing a main part configuration of an ECR plasma film forming equipment according to an embodiment of the present invention;

Figure 2 is a cross-sectional view showing a cross section taken along line AA of Figure 1 of an embodiment of the present invention device;

3 is a cross-sectional view taken along line BB of the portion shown in FIG. 2 of an embodiment of the present invention;

4 is a graph showing visible light transmittance in one embodiment of the present invention substrate;

FIG. 5 is a graph showing brightness coordinates and color coordinates of the embodiment of FIG. 4; FIG.

Figure 6 is a graph showing the visible light transmittance for other embodiments of the substrate of the present invention.

7 is a graph illustrating brightness coordinates and color coordinates of the embodiment of FIG. 6.

-Explanation of symbols for the main parts of the drawings

10: process chamber 11: cold plate

13: substrate 15: roller

17: infrared lamp

20: plasma forming apparatus 21: microwave generator

23: linear antenna 25: quartz tube

26: separation plate 27: electromagnet (solenoid coil)

29: bulkhead 291: window

30: deposited film source gas supply line 40: plasma source gas supply line

50: vacuum line 51: vacuum pump

Claims (12)

A plasma forming apparatus and a process chamber in which deposition is performed on a substrate, wherein the plasma forming apparatus includes a linear antenna, a plasma generator connected to the linear antenna, and a magnetic field forming a magnetic field in a space between the linear antenna and a substrate of the process chamber. Having a forming apparatus, The linear antenna ECR plasma film forming equipment is formed in the form of the two ends are coupled to two microwave generators (microwave generator) each resonating with each other. 2. The magnetic field forming apparatus of claim 1, wherein the magnetic field forming apparatus has a shape corresponding to the linear antenna and wound the coil in a track shape with a long straight line or an ellipse with a long axis so as to limit the plasma to a space having a shape corresponding to the linear antenna. ECR plasma film forming equipment formed of a solenoid coil. delete The ECR plasma deposition apparatus of claim 1, wherein the linear antenna is wrapped with a crystal tube. The ECR plasma film forming apparatus according to claim 1, wherein the plasma forming apparatus comprises a plurality of unit plasma forming apparatuses arranged side by side such that the linear antennas inside are installed side by side. The ECR plasma film forming apparatus of claim 5, wherein a shield is provided between the plurality of unit plasma generators to shield a magnetic field. The method of claim 1, wherein the partition wall is formed between the plasma forming apparatus and the process chamber, the partition wall has a window connecting the space of the plasma forming apparatus and the space of the process chamber, And the window is formed in a form corresponding to the linear antenna and the magnetic field forming apparatus. delete delete delete delete delete

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