KR100443232B1 - Inductively Coupled Plasma Assisted Ion Plating System - Google Patents

Abstract

The present invention relates to an inductively coupled plasma ion plating system for producing a high-speed corrosion and wear protection coating of excellent properties, the vacuum means for forming a vacuum is connected to one side, the source for plasma formation is supplied to the other side A chamber; At least one source supply unit connected to the chamber to supply at least one type of source for plasma formation; Evaporation means installed at one end of the chamber to evaporate the sample; A substrate holder mounted on the opposite side of the evaporation means in the chamber to mount a substrate; A shutter installed between the evaporation means and the substrate to control a flow of a sample evaporated by the evaporation means; It is installed between the substrate and the shutter to form an RF electric field to change the source and the sample evaporated by the evaporation means supplied through the source supply to the plasma state to promote chemical synthesis and to increase the binding force to the substrate RFI coils; An RF supply unit supplying RF power to the RFI coil; A DC anode unit which is separately installed on a rear surface of the substrate and connected to a DC anode to charge the rear surface of the substrate to a negative charge; It comprises a DC supply unit for supplying a DC voltage to the DC anode.

Description

Inductively Coupled Plasma Assisted Ion Plating System

The present invention relates to an ion plating system using an inductively coupled plasma, and more particularly to an inductively coupled plasma ion plating system for producing a high speed corrosion and wear protection coating of excellent properties.

The general evaporation method is used to increase the evaporation rate of the source in order to obtain a high deposition rate, but in this case has a disadvantage that a lot of voids or defects occur in the thin film.

To overcome this drawback, studies have been conducted to apply high negative bias to substrates that produce and deposit ions in the evaporator.

Previous techniques, however, have not been very effective because the ion density in the evaporator is not so high, and applying too much substrate bias results in defects in the thin film and results in Ar atoms being buried in the thin film.

The ion (plasma) generation method, which has been mainly used in the past, uses a thermoelectron generator using tungsten filaments. As described above, it is difficult to obtain a high ion density and has disadvantages such as an influence on process pressure.

Meanwhile, in the conventional ion plating method, when the deposition rate is increased, the reaction between the reactive gas and the source material is not sufficient, so that a high substrate temperature is required. In particular, the corrosion and abrasion resistant coating materials are mainly used nitrides of transition metals, and in these cases, when the deposition rate is increased, nitrides are not formed properly, and metal phases are often reported.

In addition, research has been conducted for a long time to improve the performance and life of tools and mechanical parts by applying a corrosion and wear resistant coating on the surface of the base material, and various manufacturing techniques have been developed along with various kinds of protective coatings. The application of the surface coating technology is very broad and expanding from electronics and optics to mechanical and chemical fields.

In the field of mechanical applications, the most researched and actually commercialized field is the protective coating for improving the life and work performance of cutting tools, dies and dies. In particular, the technology of coating ceramic materials to extend the life and function of various molds and tools is being actively researched around the world as a strategy to increase the added value through advanced tools.

Methods for producing corrosion and abrasion resistant coatings include chemical vapor deposition such as thermal chemical vapor deposition, plasma chemical vapor deposition, and organic chemical vapor deposition, and physical vapor deposition such as evaporation, sputtering, and ion plating.

In addition, wear-resistant hard coating material Ti (C, N) in combination with a combination of materials having different properties, such as nitrides of transition metals (Cr, Ti, Zr), carbides CrN, TiN, TiC, ZrN, HfN Tertiary nitrides, borides, carbides, such as (Cr, Al) N, (Ti, Cr) N, (Ti, Al) N, and (Ti, Al, Zr) N, Ti (C, B, N) Quaternary wear-resistant hard coatings such as are also being studied. Among them, CrN has high hardness, excellent corrosion resistance and oxidation resistance, and is widely used as a corrosion and wear protection coating. CrN is reported to have a hardness around 2000 HK (kgfmm ^-2 ). As a nitride of Cr, there is also a Cr ₂ N phase. In the past, when a thin film is grown at a high speed, a CrN _x thin film in which Cr, Cr ₂ N, and CrN phases coexist rather than a single CrN phase is formed. If Cr ₂ N phase is present, the hardness is slightly higher, but the adhesion is worsened, and thus the function as a protective film is much lowered.

In a previous study to solve the above problems, Y. Murayama of Japan devised an RF Reactive Ion-Plating (RF-RIP) device, which introduced a plasma generation method by an RF coil in a system using an evaporation source. There is a bar.

However, the microstructure control was possible due to the inability to use inductively coupled plasma generation characteristics by the RF coil, but the result was not obtained in the dense thin film structure or the reactivity improvement.

The present invention has been made in view of the above-described problems of the prior art, and its object is to increase the reactivity through plasma formation, to form a high ion (plasma) density, to increase the deposition rate, and to enter the density of the plasma and the substrate The present invention provides an ion plating system using an inductively coupled plasma capable of precisely controlling and forming fine tissues by independently controlling ion energy and forming dense tissues.

1 is a block diagram illustrating an ion plating system using an inductively coupled plasma according to the present invention.

2 is a graph showing the relationship between ion density according to RF power and process pressure.

Figure 3 is a graph showing the XRD diffraction pattern of the Cr-N thin film prepared by RF-RIP.

Figure 4 is a graph showing the XRD diffraction pattern of the Cr-N thin film prepared according to the present invention.

5 is a graph showing the hardness of the Cr-N thin film prepared by RF-RIP.

6 is a graph showing the hardness of the Cr-N thin film according to the RF power.

7 is a SEM surface photograph according to the RF power.

8 is a SEM cross-sectional view of the RF power.

In order to achieve the above object, the present invention is a vacuum means for forming a vacuum is connected to one side, the chamber is supplied with a source for plasma formation on the other side; At least one source supply unit connected to the chamber to supply at least one type of source for plasma formation; Evaporation means installed at one end of the chamber to evaporate the sample; A substrate holder mounted on the opposite side of the evaporation means in the chamber to mount a substrate; A shutter installed between the evaporation means and the substrate to control a flow of a sample evaporated by the evaporation means; It is installed between the substrate and the shutter to form an RF electric field to change the source and the sample evaporated by the evaporation means supplied through the source supply to the plasma state to promote chemical synthesis and to increase the binding force to the substrate RFI coils; An RF supply unit supplying RF power to the RFI coil; A DC anode unit which is separately installed on a rear surface of the substrate and connected to a DC anode to charge the rear surface of the substrate to a negative charge; It provides an ion plating system using an inductively coupled plasma comprising a DC supply for supplying a DC voltage to the DC anode.

In order to minimize the influence of the residual gas, the chamber has an initial pressure of 1 × 10 ⁻⁶ Torr or less, and then supplies an inert gas and a reactive gas using the source supply unit, thereby reducing the process pressure from 1 × 10 ⁻² Torr to 1 × It is maintained at 10 ^-3 Torr.

The sample placed on the evaporation means is a metal material chemically bonded to the reaction gas supplied through the source supply unit, and the reaction gas supplied through the source supply unit is a gaseous substance chemically coupled to the sample, and the metal Is chromium and the gas is nitrogen.

The chamber and the substrate are electrically grounded, and the deposition rate of the substrate using the sample and the source is 16 kW / s.

A distance between the substrate and the RFI coil and the RFI coil and the evaporation means is maintained at 3 cm or more, respectively, and the evaporation means is heated by AC power, and the RFI coil is formed of a tube through which a refrigerant for cooling passes. It further comprises a refrigerant supply means for supplying.

As described above, in the present invention, the deposition performance of the substrate may be increased, and the deposition may be performed in a dense structure, the deposition speed may be high, and the deposition may be performed at low temperature.

(Example)

Hereinafter, with reference to the accompanying drawings showing a preferred embodiment of the present invention described above in more detail.

In general, ion density is a very important process parameter in a plasma deposition process. It is known from previous studies that a high ion density can form a thin film due to the ion collision effect on the substrate, and to form a stoichiometric thin film by improving the reactivity due to excitation of reaction source atoms. .

In the case of plasma generation by the RF coil, there are two plasma generation modes, Capacitively Coupled Plasma (CCP) and Inductively Coupled Plasma (ICP). Compared to the CCP mode, the ICP mode has a high ion density, which is required for the deposition process for producing a thin film.

In the present invention, in the ion plating apparatus using the inductively coupled plasma by the ion density measurement using the L-probe to find the process conditions that can generate the plasma in the ICP mode of high ion density and to produce a thin film of excellent characteristics, the process An impedance matching system was designed to generate plasma stably under the conditions.

The inductively coupled plasma ion plating according to the present invention activates the plasma inside the chamber 10 by mounting the RFI coil 34, which is a new plasma assisting device, to the existing evaporator in a circular or spiral manner and mounting it directly in the chamber 10. It is a technique to let.

Applying RF (Radio Frequency) power to the RFI coil 34 mounted inside the chamber 10 causes a sudden electric field change, and a magnetic field is formed in the axial direction of the RFI coil 34, which changes over time. Under the influence of the magnetic field, the secondary electric field is induced around the RFI coil 34, and the induced electric field is then evaporated by a circular acceleration along the RFI coil 34 around the RFI coil 34. Particles and reactant gases of the sample are then ionized.

Therefore, it is possible to further activate the plasma in the chamber 10 and to increase the ionization rate of the particles to be larger than the conventional ion plating apparatus. In general, the ion density is very low in the evaporation method used, whereas in the case of inductively coupled plasma evaporation (ICP-Evaporation) according to the present invention, a very high ion density of ˜10 ¹¹ # / cm ³ was obtained.

As shown in FIG. 1, the ion plating system using the inductively coupled plasma according to the present invention is installed at the bottom of the chamber 10 and the chamber 10 in which the ion plating reaction is performed to melt the sample 40 to evaporate. A substrate holder 20 on which the substrate 44 on which the deposit is deposited is mounted, and installed between the evaporation table 16 and the substrate 44. RF I coil 34 to form an RF electric field, a source supply unit 42 connected to one side of the chamber 10 to supply a reaction gas, and connected to the other side of the chamber 10 of the chamber 10. Vacuum pump 15 for adjusting the pressure, RF supply unit for supplying RF power to the RFI coil 34 through the matching unit 32 which is an electrical matching means, the chamber on the back of the substrate 38 DC anode portion 38 that is electrically insulated from (10) and installed, DC voltage to the DC anode portion 38 It consists of a DC supply unit 36 for supply.

In the present invention, the metal melted on the evaporation zone 16 uses chromium (Cr), and the gas supplied through the source supply part 42 is argon (Ar) and nitrogen (N ₂ ) gas, which is a reaction gas. Chromium nitride (CrN) by a compound of chromium (Cr) and nitrogen gas was deposited on the substrate 44.

The chromium (Cr) is 99.95% pure, the argon (Ar) is 99.999% pure, and the nitrogen gas (N ₂ ) is 99.999% pure.

The substrate 44 and the chamber 10 are electrically grounded, and maintain a distance of approximately 10 cm between the evaporation zone 16 and the substrate 44 and between the substrate 44 and the RFI coil 34. The distance is about 4 cm and the pitch distance of the RFI coil 34 itself is about 3 cm. On the other hand, the evaporator 16 is generated by receiving an alternating current power to evaporate the chromium sample by melting.

The distance between the substrate 44 and the RFI coil 34 and the distance between the RFI coil 34 and the evaporation zone 16 is 3 cm or more, respectively.

An inductively coupled plasma is formed between the evaporation zone 44 and the substrate 44 and is obtained by applying a high frequency voltage of 13.56 MHz to the RFI coil 34 through an impedance matching system by the matching section 32.

The frequency of the RF power supplied to the RFI coil 34 uses 13.56 MHz, which can easily float an inductively coupled plasma and commercially obtain an RF power generator, and the RF power applied to the RFI coil 34. Since the voltage of the RF coil 34 varies depending on the shape of the chamber, the structure of the chamber, and the matching part, voltage and power having optimal conditions are selected and applied according to each component.

The RFI coil 34 is inserted into the chamber 10 by winding a copper tube having excellent electrical conductivity and thermal conductivity twice to a diameter of approximately 17 cm. The cooling water is supplied into the RFI coil 34 during deposition and cooled.

In order to minimize the influence of the residual gas, the pressure in the chamber 10 is set to 1 × 10 ^-6 Torr or less, and then, argon and nitrogen gas, which is a reactive gas, are supplied to process the pressure from 1 × 10 ^-2 Torr to 1 × 10. ^{At -3} Torr, if the pressure is too low, the number of particles is too small and the ionization rate due to electron collision is low. If the pressure is too high, the number of particles is too large to allow ionization only to a part of the entire source. When the pressure is high, the deposition rate of the thin film is reduced with respect to the source evaporation amount due to scattering due to disordered collision of particles.

In the embodiment of the present invention, the process was carried out at a process pressure of 2 x 10 ^-2 Torr, and the deposition rate was constant at about 16 mW / s.

2 shows the ion density according to RF power and process pressure of the inductively coupled plasma ion plating apparatus. The ion density tends to increase with increasing RF power, and it can be seen that the ion density rapidly increases between 100W and 300W. In general, it is known that at low power in the plasma generation by the RF coil 34, the influence of the Capacitively Coupled Plasma (CCP) method is not sufficient to transfer power to the plasma sufficiently. When the RF power is 300 W or 400 W or more, the plasma is converted into an ICP (Inductively Coupled Plasma) method, and the power is sufficiently transferred to the plasma, thereby obtaining a high ion density.

It can be seen from FIG. 2 that the relation between the process pressure and the ion density holds. When the RF power is 300W, it shows a high ion density of 10 ¹¹ / cm 3 and above at a process pressure of 10 ^-2 Torr or more. This shows that excellent thin films can be obtained under process conditions in which a pressure of 10 ^-2 Torr or more and sufficient RF power for plasma can be formed by ICP method are supplied.

Figure 3 shows the XRD diffraction pattern according to the deposition rate of the Cr-N thin film deposited by K. Kasiwagi, Japan, using an RF-RIP device. As can be seen in Figure 2, when the deposition rate is high, such as 12 Å / s, 18 Å / s, the thin film is almost composed of a Cr phase, when the deposition rate is lowered to about 4 Å / s, 8 Å / s Cr ₂ N phase is mainly To achieve.

In this study, the deposition was performed at a low process pressure of 10 ^-4 Torr, indicating that the plasma could not be sufficiently activated and sufficient reactivity could not be obtained to obtain a thin film of CrN.

Figure 4 shows the XRD diffraction pattern of the Cr-N thin film according to the RF power in a high pressure process of about 20mTorr deposited according to the present invention. As shown in the previous plasma analysis results, it can be seen that the phase is almost made of CrN at 400W or more when the plasma is converted to ICP and sufficiently activated. Since the above results are obtained at a high deposition rate of 16 kW / s, this is a great result compared to other deposition processes to date.

Figure 5 shows the hardness of the Cr-N thin film prepared using a conventional RF-RIP device. When the deposition rate is low, the value is about 2000kg / mm ² , and when it is high, the phase is almost composed of Cr phase, and thus the value is about 1200-1400 kg / mm ² .

Figure 6 shows the change in hardness of the Cr-N thin film according to the RF power applied to the RF coil 34 in accordance with the present invention. The hardness of Cr-N increases with increasing RF power, and the hardness rapidly increases between 1000kg / mm ² and 3500kg / mm ² between 200W and 400W. The hardness of 3500 kg / mm ² or more is very high compared to the hardness of CrN reported in the literature, especially given the very high deposition rate of 16 kW / s and without the substrate 44 heating, It is a very good value.

In the case of CrN deposited by general evaporation or other methods, hardness is reported to be less than 3000kg / mm ² .

Figure 7 shows the surface photograph of the Cr-N thin film prepared by ICP ion plating according to the present invention. It can be seen that the microstructure of the thin film changes as the RF power increases. Particular changes in tissue were observed, particularly between 200W and 400W.

8 shows a cross-sectional photograph of a Cr-N thin film prepared by ICP ion plating according to the present invention. As a result of observation of the cross-sectional structure photograph of the thin film, the structure of the thin film can be seen to be dense and finely changed as the RF power increases. In particular, at 400W, the columnar tissue disappeared and the tissue was changed drastically, unlike at powers lower than that. This aspect is considered to be the result of the stable activation of the plasma above 400W as shown in FIG.

According to the present invention made as described above, a thin film of Cr-N, which is widely used as an anticorrosion and abrasion protection coating, was prepared by using an ion plating system using an inductively coupled plasma. Even at a high deposition rate of / s, higher hardness and chemical reactivity than 3500kg / mm ² can be obtained compared to Cr-N thin films manufactured using conventional processes. Deposition of corrosion and abrasion resistant coatings to tools, molds, dies, etc. using the above process will provide a prolonged product productivity and lifespan.

In the above, the present invention has been illustrated and described with reference to specific preferred embodiments, but the present invention is not limited to the above-described embodiments and the general knowledge in the technical field to which the present invention pertains without departing from the spirit of the present invention. Various changes and modifications will be made by those who possess.

Claims (10)

A chamber to which a vacuum means for vacuum formation is connected at one side and a source for plasma formation is supplied to the other side; At least one source supply unit connected to the chamber to supply at least one type of source for plasma formation; Evaporation means installed at one end of the chamber to evaporate the sample; A substrate holder mounted on the opposite side of the evaporation means in the chamber to mount a substrate; A shutter installed between the evaporation means and the substrate to control a flow of a sample evaporated by the evaporation means; It is installed between the substrate and the shutter to form an RF electric field to change the source and the sample evaporated by the evaporation means supplied through the source supply to the plasma state to promote chemical synthesis and to increase the binding force to the substrate RFI coils; An RF supply unit supplying RF power to the RFI coil; A DC anode unit which is separately installed on a rear surface of the substrate and connected to a DC anode to charge the rear surface of the substrate to a negative charge; And a DC supply unit for supplying a DC voltage to the DC anode unit. The method of claim 1, wherein the chamber is set to an initial pressure of 1 × 10 ^-6 Torr or less in order to minimize the influence of residual gas, and then the inert gas and the reactive gas are supplied using the source supply unit so that the process pressure is 1 × 10. Ion plating system using an inductively coupled plasma, characterized in that it is maintained at ^-2 Torr ~ 1 × 10 ^-3 Torr. The ion plating system using an inductively coupled plasma according to claim 1, wherein the sample placed on the evaporation means is a metal chemically bonded to the reaction gas supplied through the source supply unit. The ion plating system of claim 1, wherein the reaction gas supplied through the source supply unit is a gas chemically bonded to the sample. 5. The ion plating system according to claim 3 or 4, wherein the metal is chromium and the gas is nitrogen. The ion plating system of claim 1, wherein the chamber and the substrate are electrically grounded. The ion plating system of claim 1, wherein the deposition rate of the substrate using the sample and the source is 16 μs / s. The ion plating system of claim 1, wherein a distance between the substrate and the RFI coil and the RFI coil and the evaporation means is maintained at 3 cm or more, respectively. The ion plating system using inductively coupled plasma according to claim 1, wherein the evaporation means generates heat by applying AC power. The ion plating system of claim 1, wherein the RFI coil is formed of a tube through which a refrigerant for cooling passes, and further includes refrigerant supply means for supplying the refrigerant.