TWI615494B - Closed high energy magnetron sputtering device for coating optical hard film and manufacturing method thereof - Google Patents

Description

Closed high energy magnetron sputtering device for coating optical hard film and manufacturing method thereof

The invention relates to a closed high energy magnetron sputtering device for coating an optical hard film and a manufacturing method thereof, in particular to an optical industry, in particular to a transparent hard film without optical absorption.

At present, thin film technology has been widely used in semiconductor, machinery, people's livelihood, optoelectronics, energy, environmental protection, biomedical and nanotechnology industries, in order to provide the required characteristics of components such as scratch resistance, abrasion resistance, corrosion resistance, oxidation resistance, and enhancement. The superior properties of surface hardness and new color, while reducing costs and increasing productivity, make nanometer-scale hard films more important in today's technology industry. In the past, in the research and application of nano-hard films (such as US Patent Nos. 2009173622, 8,540,786 and Republic of China Patent No. 201315830), nitrides and carbides of transition metals are preferred, with ultra-high hardness and surface hardness. Corrosion resistance and anti-wear and anti-oxidation as the orientation, however, considering the different application requirements, such as the booming optical industry, optical film process technology has always been an important basic technology in the optical industry, and the quality requirements are also higher. For example, liquid crystal screens, high-density optical discs, digital camera optical systems, projection technology, optical fiber communication, lithography, and light-emitting diodes all require optical film processing technology, in which fluoride has a wide band of energy, light can be Directly through without being absorbed, it is a very important optical material.

Traditionally, the plating method of fluoride can be divided into thermal evaporation and sputtering, and the starting materials of the two coating methods are usually expensive fluorides, and the films coated by thermal evaporation have small optical absorption. However, due to the low density of vapor deposition, the environmental impact is obviously poor and the mechanical properties are common. Not good; if the process is changed to sputtering, although the film forming energy is higher, the bulk density can be increased, but the optical absorption is greatly increased. Some studies have shown that the addition of fluorine gas in the process can effectively improve the absorption of the film, but it is not respected because of its danger. In addition, if reactive sputtering is carried out with metal as the target, the reactive gas will be poisoned. The target causes the plasma to be unstable, the plating rate to be slow, or the reaction to be incompletely caused by the absorption of the film. Therefore, it is necessary to develop a transparent hard film that can be used in the optical industry without optical absorption. Therefore, the general practitioners cannot meet the needs of the user in actual use.

The main object of the present invention is to overcome the above problems encountered in the prior art and to provide an integration which can increase the coating rate and film reaction ability, and also maintain the stability of the plasma; and can reduce the temperature of the substrate, A closed high-energy magnetron sputtering device and a manufacturing method thereof that improve the density and adhesion of a film and the like.

A secondary object of the present invention is to provide a closed-type high-energy magnetron sputtering apparatus and a method of manufacturing the same, which have high mechanical and optical qualities, which can improve the absorption caused by incomplete reaction in the reaction of sputtering a compound film.

Another object of the present invention is to provide a closed optical high-energy magnetron sputtering device with a high hardness and high visible light transmittance of a touch screen. And its manufacturing method.

10μm之透明硬膜，其中該製鍍出之硬膜消光係數小於1×10^-3且硬度大於莫氏硬度9(13Gpa)。 For the purpose of the above, the present invention is a closed high energy magnetron sputtering apparatus for coating an optical hard film, and a manufacturing method thereof, the closed high energy magnetron sputtering apparatus comprising: a vacuum chamber, which is provided with a vacuum chamber a substrate holder having a substrate disposed on the substrate holder; a closed plasma system comprising at least two sets of sputtering guns disposed in the vacuum chamber, the sputtering guns respectively A high-purity metal target is disposed, and the metal targets respectively correspond to the substrate, wherein each metal target surface is provided with a plurality of magnetic elements arranged in non-parallel magnetic poles to form an unbalanced magnetron splash A gun is sprayed, and the metal target is made of an inexpensive high-purity metal, and is titanium (Ti), aluminum (Al), tantalum (Ta), zirconium (Zr), niobium (Nb), niobium (Hf). a chromium (Cr), zinc (Zn), tin (Sn), bismuth (Si) metal or a combination thereof; and a high power pulsed plasma source system coupled to the vacuum chamber, comprising a gas supply And a pulse controller, the gas supply device is supplied with oxygen or nitrogen or nitrogen and oxygen in different proportions to the true The chamber adjusts the coating parameters through the pulse controller at room temperature or below 600 ° C, provides a high power density pulse power source to the metal target, and ion bombards the deposited film, and the plating is highly transparent. Light, high hardness and thickness

A 10 μm transparent hard film in which the hard film extinction coefficient is less than 1 × 10 ^-3 and the hardness is greater than Mohs hardness of 9 (13 GPa).

In the above embodiment of the invention, the magnetic lines of force of the magnetic element extend outwardly to the closed curve of the substrate.

In the above embodiment of the present invention, the high power pulse plasma source system uses a DC power, a Radio Frequency (RF), and a High Power Impulse Magnetron Sputtering. , HIPIMS), or a medium frequency (MF) combined with a high power pulsed magnetron sputtering source to provide a high power density pulsed power supply to the metal target.

In the above embodiment of the present invention, the pulse controller adjusts the coating parameter, wherein the off time of the regulated pulse power source accounts for less than 10% of the duty cycle range and the pulse frequency range is lower than the pulse frequency range. 10kHz.

In the above embodiment of the present invention, a heat source is disposed on the back surface of the substrate, and the heat source is disposed in the vacuum chamber to provide heating from the back surface of the substrate and to control it in a desired temperature range.

In the above embodiment of the invention, the heating source is a halogen lamp or a resistance heater.

X

1))、氮化鋁(AlN)、氮氧化鋁(Al_3-xO_3xN_3(1-x)(0

X

1))、氮化矽鋁(AlSiN)、氮氧化矽鋁(AlSiON)、氧化矽(SiO₂)、氧化鈦(TiO₂)、氧化鋯(ZrO₂)、氧化鋁(Al₂O₃)、或氧化鉭(Ta₂O₅)。 In the above embodiment of the invention, the transparent hard _{film is tantalum} nitride (Si ₃ N ₄ ), _yttrium oxynitride (Si _{3-2 x} O _{2 x} N _{4 (1-x)} (0

X

1)), aluminum nitride (AlN), aluminum oxynitride (Al _3-x O _3x N _3(1-x) (0

X

1)), lanthanum aluminum nitride (AlSiN), lanthanum aluminum oxynitride (AlSiON), yttrium oxide (SiO ₂ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), aluminum oxide (Al ₂ O ₃ ), Or yttrium oxide (Ta ₂ O ₅ ).

In the above embodiment of the present invention, the transparent hard film may be further plated into an anti-reflection film, a band pass filter, a cut filter, a narrow band filter, or a high reflection mirror by optical film theory. In the above embodiment of the present invention, the closed plasma system is provided with a gas barrier plate around the metal targets to isolate the sputtering region from the reaction region.

1‧‧‧vacuum chamber

11‧‧‧Substrate mount

12‧‧‧heat source

2‧‧‧Closed plasma system

21‧‧‧Spray gun

22‧‧‧Metal target

23‧‧‧ Magnetic components

24‧‧‧ gas barrier

3‧‧‧High Power Pulse Plasma Source System

31‧‧‧ gas supply

32‧‧‧pulse controller

33‧‧‧DC power supply

34‧‧‧RF

35‧‧‧High power pulsed magnetron sputtering source

4‧‧‧Substrate

5‧‧‧Quality monitor

Figure 1 is a schematic view of the unbalanced magnetic lines of force of the present invention.

Fig. 2 is a schematic view showing the isolation of the sputtering region and the reaction region of the present invention.

Figure 3 is a schematic view of the enclosed high energy magnetron sputtering apparatus of the present invention.

Fig. 4 is a schematic diagram showing the configuration of a pulse power supply of the high power pulse plasma source system of the present invention.

Figure 5 is a graph of the transmittance test of the present invention.

Figure 6 is a hardness test chart of the present invention.

Fig. 7 is a graph showing the transmittance of the multilayer antireflection film of the present invention.

Please refer to FIG. 1 to FIG. 7 , which are schematic diagrams of the unbalanced magnetic lines of force of the present invention, the isolation of the sputtering region and the reaction region of the present invention, and the schematic diagram of the closed high energy magnetron sputtering device of the present invention. A schematic diagram of a pulse power supply configuration of the high power pulsed plasma source system of the present invention, a transmittance test chart of the present invention, a hardness test chart of the present invention, and a multilayer antireflection film transmittance test chart of the present invention. As shown: the invention is a plating optics A hard-film closed high-energy magnetron sputtering device for manufacturing an optical hard film comprising a vacuum chamber 1 and a closed plasma system 2 And a high power pulse plasma source system 3 is constructed.

A substrate holder 11 is disposed in the vacuum chamber 1 , and a substrate 4 is disposed on the substrate holder 11 , and a heating source 12 is further disposed on the back surface of the substrate 4 . It is disposed in the vacuum chamber 1 to provide heating from the back surface of the substrate 4 and to control it in a desired temperature range, wherein the heating source 12 is a halogen tube or a resistance heater.

The closed plasma system 2 includes at least two sets of sputter guns 21 disposed in the vacuum chamber 1 , and the sputter guns 21 are respectively provided with high-purity metal targets 22 , the metals The targets 22 respectively correspond to the substrate 4, wherein each of the surfaces of the metal targets 22 is provided with a plurality of magnetic elements 23 arranged in non-parallel magnetic poles to form an unbalanced magnetron sputtering gun.

The high-power pulse plasma source system 3 is connected to the vacuum chamber 1 and includes a gas supplier 31 and a pulse controller 32, and uses a DC power source 33 and a radio frequency (Radio Frequency, RF). 34 and a High Power Impulse Magnetron Sputtering (HIPIMS) 35 (as shown in Figure 3), or a DC power supply 33, a Medium Frequency (MF) and a high power The pulsed magnetron sputtering source 35 is combined as a sputtering power supply to provide high power density pulses to the metal target 22. If so, a new closed high-energy magnetron sputtering device is constructed by the above disclosed process.

The apparatus further includes a mass monitor 5 coupled to the vacuum chamber 1 adjacent to the substrate 4 being sputtered. The quality monitor 5, such as a Quartz Crystal Microbalance (QCM), can be used to measure the quality of a sputtered film on a substrate.

The magnetic elements 23 (e.g., magnets) of each of the sputtering guns 21 in the closed plasma system 2 are unbalanced systems, and the magnetic lines of force can extend outwardly, and the magnetic lines of force are extended outward by a suitable combination of the sputtering guns. One of the substrates closes the curve. As shown in Fig. 1, the device can generate four plasma regions a, b, c and d, so that the substrate, the sputtered target particles and the reaction gas are all in the plasma envelope. Increasing the coating rate and the ability of the film to combine with the reactive gas can also maintain the stability of the plasma. In addition, the device can also be as shown in FIG. 2, the closed plasma system 2 can be provided with a gas barrier baffle 24 around the metal targets to isolate the sputtering region from the reaction region, so that the system has a high Sputter rate and high plasma stability.

The high-power pulse plasma source 3 is as shown in Figures 3 and 4, and the pulse controller 32 is added to the DC power supply 33 of the original DC sputtering system to provide a high power density pulse power supply in hundreds of microseconds ( kW/cm ² ) on the metal target 22, the ionic current density generated on the substrate 4 can be two orders of magnitude higher than the direct current magnetron sputtering (dcMS), which is adjusted by the pulse controller 32. Coating parameters, including the off time of the regulated pulse power supply, operating at low duty cycle (<10%) and low pulse frequency (<10kHz) make the average power density much lower than the peak power density, approximate In general dcMS (~W/cm ² ), the plasma density is increased to above 10 ¹⁸ /m ³ , which is about 100~10000 times higher than the plasma density of dcMS (10 ¹⁴ ~ 10 ¹⁶ /m ³ ). The detachment rate of the metal target 22 is as high as 70% or more. By ion bombardment of the deposited film by the high power density pulse power supply, in addition to lowering the temperature of the substrate 4, the film density and adhesion can be improved, and the device is very suitable for application to high quality optical film and hard. membrane.

10μm之透明硬膜，如氮化矽(Si₃N₄)、氮氧化矽(Si_3-2xO_2xN_4(1-x)(0

X

1))、氮化鋁(AlN)、氮氧化鋁(Al_3-xO_3xN_3(1-x)(0

X

1))、氮化矽鋁(AlSiN)、氮氧化矽鋁(AlSiON)、氧化矽(SiO₂)、氧化鈦(TiO₂)、氧化鋯(ZrO₂)、氧化鋁(Al₂O₃)、或氧化鉭(Ta₂O₅)等，其中該製鍍出之硬膜消光係數小於1×10^-3且硬度大於莫氏硬度9(13Gpa)。最後，該可應用光學薄膜理論，製鍍多層膜高透光硬膜，以應用於各種光學元件，如抗反射膜、帶通濾光片、截止濾光片、窄帶濾光片、或高反射鏡等。 The invention integrates the two technologies of the closed plasma system 2 and the high-power pulse plasma source system 3, and uses a relatively inexpensive high-purity metal as a starting material, such as titanium (Ti), aluminum (Al), bismuth ( Ta), zirconium (Zr), niobium (Nb), hafnium (Hf), chromium (Cr), zinc (Zn), tin (Sn), bismuth (Si) metal or a combination thereof, etc., are passed through the gas supply 31 A gas of different proportions of oxygen or nitrogen or nitrogen and oxygen is introduced into the vacuum chamber 1, and the coating parameters are adjusted via the pulse controller 32 at room temperature or below 600 ° C to provide a high power density pulse power source to the metal target. 22, ion bombardment of the film in the deposition, 俾 plating to achieve high light transmission, high hardness and thickness

10μm transparent hard _film , such as _tantalum nitride (Si ₃ N ₄ ), _niobium oxynitride (Si _3-2x O _2x N _4(1-x) (0

X

1)), aluminum nitride (AlN), aluminum oxynitride (Al _3-x O _3x N _3(1-x) (0

X

1)), lanthanum aluminum nitride (AlSiN), lanthanum aluminum oxynitride (AlSiON), yttrium oxide (SiO ₂ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), aluminum oxide (Al ₂ O ₃ ), Or yttrium oxide (Ta ₂ O ₅ ) or the like, wherein the hard film extinction coefficient of the system is less than 1×10 ^-3 and the hardness is greater than Mohs hardness of 9 (13 GPa). Finally, the optical film theory can be applied to produce a multilayer high-transparent hard film for use in various optical components such as anti-reflection films, band pass filters, cut-off filters, narrow-band filters, or high reflections. Mirror and so on.

The invention integrates the closed unbalanced magnetron sputtering system and the high-power pulse sputtering technology, in addition to lowering the reaction temperature, the film density and adhesion can also be improved, so that the device can be applied to high transmittance of plating. Sexual and high hardness transparent hard film. As shown in Figures 5-7 and Table 1, it has been experimentally proved that the refractive index of the transparent hard film is the highest among all the plating systems, and the hardness is also the highest among all the plating systems. By doping other elements to improve the transmittance, and finally introducing the theory of optical films, a multi-layer film high-transmission hard film is applied to various optical components.

Thereby, the present invention has the following two advancements:

1. This device can increase the coating rate and film reaction ability, and also maintain the stability of the plasma.

2. The device can reduce the temperature of the substrate and increase the density and adhesion of the film.

In summary, the present invention is a closed high-energy magnetron sputtering device for coating an optical hard film and a manufacturing method thereof, which can effectively improve various disadvantages of the conventional use, and the device can improve the reaction by integrating the above two advance points. The device can also increase the film forming energy to increase the density of the film when the compound film is sputtered. The novel sputtering device with high mechanical and optical quality and its manufacturing method are proposed, and the new type is applied. Sputtering technology to plate transparent hard film materials, and finally introducing optical film theory to design multilayer film filters to make touch screens It has high hardness and high visible light transmittance, which makes the invention more progressive, more practical and more suitable for users. It has indeed met the requirements of the invention patent application and has filed a patent application according to law.

However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto; therefore, the simple equivalent changes and modifications made in accordance with the scope of the present invention and the contents of the invention are modified. All should remain within the scope of the invention patent.

1‧‧‧vacuum chamber

11‧‧‧Substrate mount

12‧‧‧heat source

2‧‧‧Closed plasma system

21‧‧‧Spray gun

22‧‧‧Metal target

23‧‧‧ Magnetic components

3‧‧‧High Power Pulse Plasma Source System

31‧‧‧ gas supply

32‧‧‧pulse controller

33‧‧‧DC power supply

34‧‧‧RF

35‧‧‧High power pulsed magnetron sputtering source

4‧‧‧Substrate

5‧‧‧Quality monitor

Claims (8)

A closed high-energy magnetron sputtering device for coating an optical hard film, comprising: a vacuum chamber, wherein a substrate holder is disposed, the substrate holder is provided with a substrate; The plasma system comprises at least two sets of sputtering guns disposed in the vacuum chamber, and the sputtering guns are respectively provided with high-purity metal targets, and the metal targets respectively correspond to the base a material, wherein each metal target surface is provided with a plurality of magnetic elements arranged in non-parallel magnetic poles to form an unbalanced magnetron sputtering gun, the magnetic lines of force of the magnetic element extending outward to a closed curve of the substrate, and the material The metal target is made of inexpensive high-purity metal, and is titanium (Ti), aluminum (Al), tantalum (Ta), zirconium (Zr), niobium (Nb), hafnium (Hf), chromium (Cr). a zinc (Zn), tin (Sn), bismuth (Si) metal or a combination thereof; and a high power pulsed plasma source system coupled to the vacuum chamber, comprising a gas supply and a pulse controller , the gas supply device is supplied with oxygen or nitrogen or nitrogen and oxygen in different proportions of the gas to the vacuum chamber, in the chamber Or lower than 600 ° C, through the pulse controller to adjust the coating parameters, provide a high power density pulse power supply to the metal target, ion bombardment of the deposited film, 制 plating high transmittance, high hardness and thickness 10μm of a transparent hard film, wherein the dura mater manufactured by plating an extinction coefficient of less than 1 × 10 ^-3 and a hardness greater than the Mohs hardness 9 (13Gpa). The closed high-energy magnetron sputtering device for coating an optical hard film according to the first aspect of the patent application, wherein the high-power pulse plasma source system uses a DC power source and a radio frequency (Radio Frequency). , RF) and a High Power Impulse Magnetron Sputtering (HIPIMS), or A DC power supply, a Medium Frequency (MF), and a high power pulsed magnetron sputtering source are combined to provide a high power density pulsed power supply to the metal target. The closed high-energy magnetron sputtering device for coating an optical hard film according to the first aspect of the patent application, wherein the pulse controller adjusts the coating parameter to include an off-time of the regulated pulse power supply. The duty cycle range is below 10% and the pulse frequency range is below 10 kHz. The closed high-energy magnetron sputtering device of the optical hard film according to the first aspect of the invention, wherein the back surface of the substrate is provided with a heating source, and the heating source is disposed in the vacuum chamber. The back side of the substrate provides heating and controls it over the desired temperature range. A closed high-energy magnetron sputtering apparatus for coating an optical hard film according to claim 4, wherein the heating source is a halogen lamp or a resistance heater. A closed high-energy magnetron sputtering device for coating an optical hard film according to claim 1, wherein the transparent hard film is tantalum nitride (Si ₃ N ₄ ) or bismuth oxynitride (Si _{3- 2x} O _2x N _4(1-x) (0 X 1)), aluminum nitride (AlN), aluminum oxynitride _{(Al 3x O 3x N 3 (} 1-x) (0 X 1)), lanthanum aluminum nitride (AlSiN), lanthanum aluminum oxynitride (AlSiON), yttrium oxide (SiO ₂ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), aluminum oxide (Al ₂ O ₃ ), Or yttrium oxide (Ta ₂ O ₅ ). The closed high-energy magnetron sputtering device for coating an optical hard film according to the first aspect of the patent application, wherein the transparent hard film can be further coated with an optical film to form an anti-reflection film, a band pass filter, Cut-off filter, narrow band filter, or high mirror. A closed high-energy magnetron sputtering device for coating an optical hard film according to claim 1, wherein the closed plasma system is provided with a gas barrier plate around the metal targets for sputtering The area is isolated from the reaction area.