WO2014126388A1

WO2014126388A1 - Polycarbonate blocking ultraviolet rays and having improved hardness and wear resistance

Info

Publication number: WO2014126388A1
Application number: PCT/KR2014/001161
Authority: WO
Inventors: 김영우; 김대철; 유석재; 한승희; 문선우; 김성민
Original assignee: 한국기초과학지원연구원
Priority date: 2013-02-12
Filing date: 2014-02-12
Publication date: 2014-08-21

Abstract

An aluminum-silicon-nitride film deposition apparatus for improving surface hardness and wear resistance of a polycarbonate material, according to the present invention, comprises a vacuum bath for depositing a thin film by using magnetron sputtering; a pulsed direct current power supply for applying direct current or pulsed direct current power to aluminum and silicon sputtering targets mounted on a deposition source of magnetron sputtering; a plasma produced by the sputtering targets mounted on the deposition source; an RF antenna inserted into the inside of the vacuum bath so as to plasmarize a gas; a conductive sample-mounting board for mounting a sample which is deposited on the inside of the vacuum bath; an RF power supply for supplying a power source to the RF antenna; a high vacuum turbo pump for maintaining high vacuum on the inside of the vacuum bath; a vacuum gauge for measuring the degree of vacuum on the inside of the vacuum bath; and a gas flow control unit for controlling the flow rates of argon (Ar) and nitrogen (N₂) gases used for producing the plasma; thus, the apparatus has the effect of improving surface hardness and wear resistance.

Description

Polycarbonate with improved UV protection and hardness and wear resistance

The present invention relates to an aluminum-silicon-nitride deposition method and apparatus for improving the surface hardness and wear resistance of polycarbonate materials, and more particularly, aluminum and silicon sputtering in a magnetron sputtering deposition source that is used as a deposition source for thin film deposition Replacing the vehicle glass by mounting a target and simultaneously injecting argon, which is an inert gas, and nitrogen gas, which is a reactive gas, into the vacuum chamber and depositing an aluminum-silicon-nitride film, which is a high hardness transparent film, on the surface of the polycarbonate by reactive sputtering The present invention relates to an aluminum-silicon nitride film deposition method and apparatus for improving the surface hardness and wear resistance of a polycarbonate material.

Polycarbonate has a high impact resistance and light weight can be used as a replacement for automotive glass, but low hardness, low wear resistance, deterioration and discoloration due to ultraviolet rays are a problem. Therefore, in order to improve hardness and wear resistance, deterioration due to ultraviolet rays and discoloration, it is necessary to form a transparent hard coating layer on the surface thereof.

To this end, a technique of forming a coating layer by attaching an adhesive sheet to the surface of the polycarbonate, a technique of forming a coating layer made of an organic material on the surface of the polycarbonate using a coating method such as dip coating is widely used. .

However, since the coating layer manufactured by the organic coating method has a limitation in improving hardness, wear resistance, and the like, a technique of forming an inorganic coating layer by deposition methods such as PVD and PECVD has recently been studied.

In particular, since the adhesion between the hard coating film and the polycarbonate is not good, an intermediate layer is formed, and a technology of forming a multilayer film by PECVD is used to implement various functions.

[Patent Document 1] (US Patent, 2007026235, Glazing system for behicle tops and windows) is searched as a prior art. This technology is used to form a film for UV protection after the coating of other materials through a wet process, and then to deposit a wear resistant hard coating film by forming a silicon oxide film or aluminum oxide film of ~ 5㎛ thickness on the surface by PECVD method have.

As another technique, [Patent Document 2] (US Pat. No. 2008083186, Polycarbonate glazing system and method for making the same) is searched, but this coating method is difficult to secure economic feasibility because many processes are required for the multilayer structure.

In addition, research on PECVD deposition using microwave plasma is ongoing, but the characteristics are poor. [Non-Patent Document 1] (Thin Solid Films 502 (2006) 270-274, Hard coatings by plasma CVD on polycarbonate for automotive and optical applications).

[Preceding technical literature]

[Patent Documents]

(Patent Document 0001) Republic of Korea Patent Publication No. 10-0337483 (2002.05.08)

Therefore, the present invention is designed to complement the low hardness and weak wear resistance of the polycarbonate material, polycarbonate material by depositing a multi-functional, high hardness transparent three-dimensional thin film of aluminum-silicon nitride film on the surface of the polycarbonate material SUMMARY OF THE INVENTION An object of the present invention is to provide an aluminum-silicon-nitride film deposition method and apparatus for improving the surface hardness and wear resistance of a polycarbonate material which can increase the surface hardness and improve the wear resistance.

Aluminum-silicon-nitride film deposition method for improving the surface hardness and wear resistance of the polycarbonate material according to the present invention for achieving the above object (a) a conductive sample mount located inside the vacuum chamber for thin film deposition using magnetron sputtering Mounting a silicon wafer or polycarbonate substrate as a sample on the sample; (b) evacuating the vacuum in the vacuum chamber to a high vacuum region with a high vacuum turbopump and a low vacuum pump to assist the turbopump, and (c) magnetron deposition. In order to operate the aluminum and silicon sputtering targets mounted in a circle, argon (Ar), which is an inert gas, and nitrogen (N2), which is a reactive gas, are introduced into the vacuum chamber by a gas flow rate adjusting device to control the pressure inside the vacuum chamber. step; RF power is applied to the RF antenna inside the vacuum chamber to form a plasma of the gas introduced in step (c), and (e) after the plasma formation, to a magnetron sputtering deposition source equipped with an aluminum metal target and a silicon target. And applying a pulsed DC power by a direct current or pulsed DC power supply to generate a plasma for thin film deposition.

Aluminum-silicon-nitride film deposition apparatus for improving the surface hardness and wear resistance of the polycarbonate material according to the present invention for achieving the above object is a vacuum chamber for thin film deposition using magnetron sputtering, aluminum mounted on the deposition source of magnetron sputtering Pulsed DC power supply for applying DC or pulsed DC power to the target and silicon sputtering target, plasma generated by the sputtering target mounted on the deposition source, RF antenna for entering gas into the vacuum chamber, and inside the vacuum chamber Conductive sample mount for mounting the sample deposited in the, RF power supply for supplying power to the RF antenna, high-vacuum turbopump for maintaining the high vacuum inside the vacuum chamber, vacuum gauge for measuring the degree of vacuum inside the vacuum chamber, And oils of argon (Ar) and nitrogen (N 2) gases used for plasma generation It characterized in that it comprises a gas flow rate adjusting unit for adjusting the amount.

On the other hand, the present inventors have recognized the above problems, and through the present invention, to provide a multi-functional thin film deposition technology for implementing a high hardness, wear resistance, UV protection properties with a double thin film.

Accordingly, the present invention is to deposit a hydrogenated silicon nitride film for blocking UV rays on the surface of the polycarbonate, for the purpose of compensating the polycarbonate material is low in hardness, high wear, deterioration and discoloration by ultraviolet light, The present invention relates to a thin film deposition method and apparatus for depositing a high hardness transparent aluminum-silicon-nitride film to increase hardness and reduce wear.

In one aspect, the present invention, the hydrogenated silicon nitride (SiN: H) deposited on one side or both sides in order to improve the high hardness, wear resistance and UV protection characteristics; And an aluminum-silicon nitride film deposited on the hydrogenated silicon nitride film.

The hydrogenated silicon nitride film improves UV blocking properties, and the aluminum-silicon nitride film improves hardness and wear resistance.

The hydrogenated silicon nitride film is formed by a reactive sputtering method by introducing an inert gas, nitrogen, and hydrogen in a plasma reactive magnetron sputtering thin film deposition apparatus including a silicon sputtering target.

The aluminum silicon nitride film is formed by a reactive sputtering method by introducing an inert gas and nitrogen in a plasma reactive magnetron sputtering thin film deposition apparatus including a silicon sputtering target and an aluminum sputtering target.

The pressure inside the deposition apparatus is characterized in that 0.5 mTorr to 20 mTorr.

The inert gas is characterized in that the argon.

In another aspect, the present invention provides a method of depositing nitride on a polycarbonate surface to improve high hardness, abrasion resistance and sun protection properties.

The method includes the steps of: mounting a polycarbonate substrate having a polycarbonate substrate or a silicon oxide film formed on a plasma reactive magnetron sputtering thin film deposition apparatus; Depositing a silicon hydride nitride film on the polycarbonate substrate by sputtering from a silicon sputtering target; And depositing an aluminum silicon nitride film on the hydrogenated silicon nitride film from the silicon sputtering target and the aluminum sputtering target.

The hydrogenated silicon nitride film deposition is characterized by a reactive sputtering method by introducing an inert gas, nitrogen and hydrogen into the deposition apparatus.

The aluminum silicon nitride film deposition is characterized by the reactive sputtering method by introducing an inert gas and nitrogen in the plasma reactive magnetron sputtering thin film deposition apparatus including a silicon sputtering target and an aluminum sputtering target.

The inert gas is characterized in that the argon.

Aluminum-silicon nitride film deposition method and apparatus for improving the surface hardness and wear resistance of the polycarbonate material according to the present invention is a multi-functional high hardness transparent aluminum-silicon-nitride film deposited by a reactive magnetron sputter deposition method on the surface of the polycarbonate material Thereby, there exists an effect which improves surface hardness and abrasion resistance.

In addition, the aluminum-silicon-nitride film deposition method for improving the surface hardness and wear resistance of the polycarbonate material according to the present invention and the polycarbonate material by the apparatus can be used as a windshield of a vehicle, and also has a light skylight, It can be used in various fields such as skylights for buildings, living rooms, factories, safety glass, roofs and windows of public facilities, bulletproof and soundproof walls, public telephone boxes, indoor partitions, indoor and outdoor sign boards.

On the other hand, according to the present invention, by depositing a hydrogenated silicon nitride film on the surface of the polycarbonate substrate can be obtained the effect of improving the UV protection properties, and by depositing a high hardness transparent aluminum-silicon-nitride film thereon to improve the hardness and wear resistance You can get the effect. This makes it possible to use polycarbonate as a vehicle's windshield, and also includes light skylights, skylights for buildings and living rooms, factories, safety glass, roofs and windows of public facilities, soundproof walls, public telephone boxes, and interior partitions. It can be used in various fields such as indoor and outdoor sign boards.

1 is a block diagram of an aluminum-silicon-nitride film deposition apparatus for improving the surface hardness and wear resistance of the polycarbonate material according to the present invention,

Figure 2 is an aluminum nitride film, a seal deposited on the silicon wafer of Example 1 of the present invention

The hardness measurement result of a lycon-nitride film and an aluminum-silicon-nitride film,

Figure 3 (a) is also a wear test result of the sample of the aluminum-silicon nitride film deposited on the polycarbonate substrate material of Example 2 of the present invention,

3 (b) is also a wear test result of the polycarbonate substrate material,

4 (a) to (e) is a UV-visible region measurement result of the glass substrate (Eagle 2000) sample of the aluminum-silicon-nitride film of Example 3 of the present invention,

4 (f) is a UV-visible region transmittance measurement result diagram of a glass substrate (Eagle 2000) sample without a film deposited, and

5 is a flowchart illustrating a method of depositing an aluminum-silicon nitride film for improving surface hardness and wear resistance of a polycarbonate material according to the present invention.

6 illustrates a plasma reactive magnetron sputtering thin film deposition apparatus for the deposition of the aluminum-silicon-nitride film and the hydrogenated silicon nitride film of the present invention.

7 is a hardness measurement result of the sample deposited with a hydrogenated silicon nitride film on the silicon wafer of Example 4 of the present invention, the hardness measurement results of the sample deposited with an aluminum-silicon nitride film on the silicon wafer of Example 5 and Example 6 The hydrogenated silicon nitride film is deposited on the silicon wafer of, and the hardness measurement results of the sample on which the aluminum-silicon-nitride film is deposited are shown.

8 is a light transmittance measurement result of a sample deposited with a hydrogenated silicon nitride film on the Eagle 2000 glass substrate of Example 4 of the present invention, the light transmittance of a sample deposited aluminum-silicon-nitride film on the Eagle 2000 glass substrate of Example 5 The measurement results and the light transmittance measurement results of the sample deposited with the hydrogenated silicon nitride film and the aluminum-silicon nitride film deposited on the Eagle 2000 glass substrate of Example 6 are shown.

Figure 9a is a result of measuring the light transmittance before and after the taber abrasion test of the polycarbonate substrate, Figure 9b is before and after the taber wear test of the sample deposited with a hydrogenated silicon nitride film on the polycarbonate substrate and deposited on the silicon-silicon nitride film It is the result of the light transmittance measurement later.

Hereinafter, with reference to the accompanying drawings will be described in detail an embodiment of the present invention. Prior to this, terms or words used in the present specification and claims should not be construed as being limited to the ordinary or dictionary meanings, and the inventors should properly explain the concept of terms in order to best explain their own inventions. Based on the principle that it can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.

Therefore, the embodiments described in the specification and the drawings shown in the drawings are only the most preferred embodiment of the present invention and do not represent all of the technical idea of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

Aluminum-silicon-nitride deposition apparatus for improving the surface hardness and wear resistance of the polycarbonate material according to the present invention is a vacuum chamber (1), pulsed DC power supply (2), sputtering target (3), plasma (4), RF antenna (5), sample (6), sample mounting table (7), matching box (8), RF power supply (9), gas used (10), gas flow rate control unit (11), vacuum gauge (12) Common turbo pump 13 and low vacuum pump 14 are included.

More specifically, the vacuum chamber (1) is a vacuum chamber for thin film deposition using magnetron sputtering, the pulsed DC power supply (2) is a direct current or to the aluminum and silicon sputtering target (3) mounted on the magnetron sputtering deposition source It is a power supply device for applying pulsed DC power.

The plasma 4 represents a plasma generated by the sputtering target 3 mounted on the magnetron deposition source, and the RF antenna 5 is a radio frequency (RF) for plasmalizing the gas introduced into the vacuum chamber. ) Antenna.

The sample 6 represents a sample mounted on the conductive sample holder 7, and the matching box 8 is an RF power matching system generated by the RF power supply 9.

The gas flow rate adjusting unit 12 is a gas flow rate adjusting device for controlling the flow rate of the use gas 10 used for plasma generation.

The vacuum gauge 12 is a vacuum gauge for measuring the degree of vacuum, the high vacuum turbo pump 13 is a pump for maintaining a high vacuum of the vacuum chamber 1, the low vacuum pump 14 is a high vacuum pump It is a pump to help the operation.

A method of plasma magnetron aluminum-silicon-nitride film deposition by an aluminum-silicon-nitride film deposition apparatus for improving surface hardness and wear resistance of a polycarbonate material including the above-described configuration will be described with reference to FIG. 5.

For reference, FIG. 5 is a flowchart of a method of plasma magnetron aluminum-silicon-nitride film deposition according to the present invention.

Mounting the sample (6) to the conductive sample mount (7) located inside the vacuum chamber (1) (S10).

Thereafter, using the high vacuum turbo pump 13 and the low vacuum pump 14 to perform the step of evacuating the vacuum degree inside the vacuum chamber to the high vacuum region (S20).

In order to operate the aluminum and silicon sputtering targets 3 mounted on the magnetron deposition source, argon (Ar), which is an inert gas, and nitrogen (N2), which is a reactive gas, are formed by the gas flow adjusting device 11. 1) the step of adjusting the pressure inside the vacuum chamber 1 is drawn into the inside (S30).

At this time, it is preferable to adjust the pressure inside the vacuum chamber 1 to a pressure of 0.5 mTorr to 30 mTorr.

For this reason, plasma generation is difficult at low pressures below 0.5 mTorr, whereas at higher pressures above 30 mTorr, the plasma density increases during deposition, increasing the sputtering rate, but also increasing the extent to which sputtered atoms are scattered by high pressure. This is because the actual thin film deposition rate is reduced.

In addition, at this time, the flow rate ratio of the argon and nitrogen gas is preferably drawn to be about 10: 1 ~ 1: 1.

This is because, in the case of 10: 1 or less, the nitride film may be deposited untransparently, and in the case of 1: 1 or more, the nitride speed may be faster than the sputtering speed of the silicon and aluminum sputtering target 3 so that the deposition rate may be lowered.

After the step S30, when the pressure inside the vacuum chamber 1 is stabilized, RF power is applied to the RF antenna 5 inside the vacuum chamber 1 to form a plasma of the introduced gas. Perform (S40).

The power applied in step S40 is preferably a value of 0 to 300 W, more preferably 50 W of power.

In the absence of RF power, the nitride film may not be formed well, and the film may be opaquely raised. If the RF power is too high, the temperature of the sample may increase, causing cracks in the deposited thin film. It can be weakened to form a transparent, crack-free film.

After the plasma is formed in the 'S40' step, generating plasma for thin film deposition by applying pulsed direct current power by a direct current or pulsed direct current power supply device 2 to a magnetron sputtering deposition source equipped with an aluminum metal target and a silicon target. Perform (S50).

Direct current or pulsed direct current power can be deposited with a voltage of -200 to -1000 V and a current value of 0 to 1.6 A. In this manner, the composite target or the two targets are simultaneously sputtered (co-sputtering) to deposit the ternary nitride film.

At this time, the average power density of the direct current or pulsed direct current used in the thin film deposition process preferably has a value of 1 W / cm ² to 20 W / cm ² .

For this reason, since the sputtering from the sputter deposition source mounted on the magnetron deposition source is very slow with a DC power of 1 W / cm ² or less, it takes a lot of processing time, and thus the economic value of the present technology is reduced, and 20 W / This is because it is difficult to cool the magnetron deposition source to use a value of cm ² or more.

Example 1

In step S10, the silicon wafer is mounted on the sample holder 7 in the vacuum chamber according to the method of the present invention, and in step S20, after evacuating the inside of the vacuum chamber to 10 ^-6 Torr, In step S30, 24 sccm of argon gas and 6 sccm of nitrogen gas are introduced to adjust the pressure of the vacuum chamber to 10 mTorr, and in step S40, 200 W power is supplied to the RF antenna to form a plasma inside the vacuum chamber. It was made. Subsequently, the magnetron sputtering deposition source equipped with the silicon target in step S50 is supplied with pulsed DC power of -550 V, 0.064 A, pulse width 30 μs, and pulse frequency 600 Hz, and the magnetron sputtering deposition equipped with an aluminum metal target. A circle was applied with a pulse power of −311 V, 1.40 A, and a 40% occupancy rate and deposited for 90 minutes to form a 2800 kW aluminum-silicon-nitride film.

In addition, by applying the power to only the aluminum sputtering target by the above method, the aluminum nitride film was applied to the silicon sputtering target and the silicon nitride film was deposited on the silicon wafer with the same thickness, respectively.

As can be seen from the Knoop microhardness measurement results of the 10g load of FIG. .

Example 2

In step S10, a polycarbonate substrate material on which a SiO ₂ film having a thickness of ˜5 μm is deposited is mounted on a sample mounting table in the vacuum chamber, and after evacuating the inside of the vacuum chamber to 10 ⁻⁶ Torr in step S20, In step S30, 24 sccm of argon (Ar) gas and 3 sccm of nitrogen (N ₂ ) gas are simultaneously introduced to adjust the process pressure to 10 mTorr, and in step S40, 50 W RF power is applied to the RF antenna. Was supplied to form a plasma inside the vacuum chamber. Subsequently, the pulsed direct current power of -450 V, 0.26 A, and 80% occupancy of the magnetron sputtering deposition source equipped with the silicon target in the 'S50' step is -452 V, 1.50 A of the magnetron sputtering deposition source equipped with the aluminum metal target. A pulsed direct current power of 20% occupancy was applied to deposit an aluminum-silicon nitride film for 45 minutes.

In order to evaluate the wear resistance characteristics of the deposited aluminum-silicon-nitride film, a pin-on-disk wear test was performed using a ruby ball having a diameter of 3 mm at a load of 15 gf. The rotational speed of the sample was 100 rpm. After 1000 revolutions, the worn surface was observed using an alpha-step profilometer and an optical microscope.

As shown in (a) of FIG. 3, in the case of the sample on which the aluminum-silicon nitride film was deposited, no wear or cracking occurred in the depth direction, while the poly-silicon film on which the aluminum-silicon nitride film of FIG. In the case of the carbonate sample, the upper SiO 2 film was broken and fragments existed, and it was measured that the wear was ˜1450 mm 3 in the depth direction and ˜180 μm in the width direction.

Example 3

According to the method of the present invention, in step 'S10', five 0.5 mm thick glass substrates (Eagle 2000) having a transparent shape in a vacuum chamber are placed in a line between the silicon target mounted on the left side and the aluminum target mounted on the right side, respectively. After evacuating the inside of the vacuum chamber to 10 ^-6 Torr in the step S20, 24 sccm of argon gas and 5 sccm of nitrogen (N ₂ ) gas are introduced to 10 mTorr in the step S30. After adjusting the process pressure, the RF power of 200 W was supplied to the RF antenna in step S40 to form a plasma inside the vacuum chamber. Subsequently, in the 'S50' step, the magnetron sputtering deposition source equipped with the silicon target is pulsed power of -780 V, 0.315 A, pulse width 100 μs, frequency 400 Hz, and the magnetron sputtering deposition source equipped with the aluminum metal target. An aluminum-silicon-nitride film was deposited for 60 minutes by applying pulsed direct current power of -410 V, 1.10 A, 40% occupancy.

Using this method, aluminum-silicon nitride films having different thicknesses and compositions can be simultaneously produced. The thickness of the fabricated aluminum-silicon-nitride film was measured as (a) 4850 Å, (b) 5450 Å, (c) 5650 Å, (d) 6100 Å and (e) 6700 Å. Were measured as (a) 55:45, (b) 58:42, (c) 67:33, (d) 74:26 and (e) 83:17.

The deposited aluminum-silicon-nitride film samples were measured for light transmittance using a UV-VIS measuring apparatus, and as shown in FIG. 4, all samples showed excellent visible light transmittance of 88 to 90%.

As described above, although the present invention has been described by means of a limited embodiment and drawings, the present invention is not limited thereto and by those skilled in the art to which the present invention pertains, Of course, various modifications and variations are possible within the scope of equivalents of the claims to be described.

Hereinafter, a plasma reactive magnetron sputtering thin film deposition apparatus for depositing an aluminum-silicon-nitride film and a hydrogenated silicon nitride film of the present invention will be described with reference to FIGS. 6 to 9B.

1. 증착 장치1. Deposition apparatus

6 illustrates a plasma reactive magnetron sputtering thin film deposition apparatus 61 for deposition of the aluminum-silicon-nitride film and the hydrogenated silicon nitride film of the present invention. The plasma reactive magnetron sputtering thin film deposition apparatus 61 has a vacuum inside and a power source for applying direct current, pulse direct current, or RF power to the silicon sputtering target 64 and the silicon sputtering target 64 mounted therein. Device 62, an aluminum sputtering target 65 mounted inside the vacuum, a power supply 63 for applying direct current, RF or pulsed direct current power to the aluminum sputtering target 65, and a gas drawn into the vacuum chamber. RF (Radio Frequency) antenna 67 for plasma, RF power supply 611 for supplying RF power to the antenna 67, matching system for impedance matching of the RF power supply 611 ), A sample mount 69 configured to mount the polycarbonate sample 68, a plasma use gas storage 612, and a gas flow rate from the plasma use gas storage 612. A low flow rate pump 616, which operates a flow rate adjusting device 613, a vacuum gauge 614 for measuring an internal vacuum degree, a high vacuum pump 615 for maintaining an internal high vacuum, and a pump of the high vacuum pump 615. It includes.

Gas is supplied from the plasma use gas storage unit 612 into the thin film deposition apparatus 61, and the plasma use gas is converted into plasma by an electromagnetic field induced by the antenna 67. The plasmalized gas is sputtered by the silicon sputtering target 64 and the aluminum sputtering target 65 and deposited on the surface of the polycarbonate sample 68. In FIG. 6, reference numeral 66 denotes a plasma generated by the sputtering targets 64 and 65.

2. 수소화된 실리콘 질화막 증착2. Hydrogenated Silicon Nitride Deposition

The principle of hydrogenated silicon nitride film deposition according to the present invention is as follows.

After the sample 68 is mounted on the sample mount 69 located in the thin film deposition apparatus 61, the vacuum degree inside the deposition apparatus 61 is exhausted to a high vacuum region using the vacuum pump 615.

Thereafter, argon gas is introduced from the plasma use gas storage unit 612 containing argon (Ar) gas, which is an inert gas, to generate a plasma, through the gas flow control device 613, so that the pressure inside the deposition apparatus 61 is reduced. Is adjusted to a pressure of 0.5 mTorr to 20 mTorr. For this reason, plasma generation is difficult at low pressures below 0.5 mTorr, while at higher pressures above 20 mTorr, the plasma density increases during deposition, increasing the sputtering rate, but also increasing the degree of sputtered atoms being scattered by high pressure. This is because the deposition rate is reduced.

As described above, when the pressure inside the deposition apparatus 61 is stabilized after the use gas is introduced, RF power is applied to the RF antenna 67 inside the vacuum chamber to form a plasma of the introduced gas. The RF power used is from 0 to 300W, which is mainly 50W. If the RF power is not applied, the nitride film may not be formed well, the film may be opaquely raised, and if the RF power is too high, the temperature of the sample may be increased to cause cracks in the deposited thin film.

After plasma formation, when direct current, pulse direct current, or RF power is applied from the power supply device 62 to the silicon sputtering target 64 attached to the deposition device 61, plasma for thin film deposition is generated. In the case of pulsed DC power, a voltage ratio of -300 to -600 V is applied to allow the deposition to be performed at a duty ratio of 20, 40, 60, or 80%.

When the power is stabilized, nitrogen (N ₂ ) gas and hydrogen (H ₂ ) gas are introduced to deposit hydrogenated silicon nitride film. Hydrogen gas is suitable to draw 6 ~ 9 sccm. In the case of 6 sccm or less, it is difficult to obtain the UV blocking property of the deposited film, and in the case of 9 sccm or more, an arc may occur in the silicon sputtering target 64.

Hydrogenated silicon nitride film is deposited on the surface of the polycarbonate sample 68 located on the sample holder 69 inside the vacuum chamber by the material sputtered from the deposition source and nitrogen and hydrogen gas introduced into the vacuum chamber.

3. 알루미늄-실리콘-질화막 증착3. Aluminum-silicon-nitride deposition

On the other hand, the principle of aluminum-silicon-nitride film deposition is as follows.

After mounting the polycarbonate sample 68 on which the hydrogenated silicon nitride film is deposited on the sample holder 69 positioned inside the deposition apparatus 61, the vacuum degree inside the deposition apparatus 61 is measured using the vacuum pump 615. Exhaust to high vacuum area.

Thereafter, an argon (Ar) gas 612, which is an inert gas, is introduced through the gas flow controller 613 to generate a plasma to adjust the pressure inside the vacuum chamber to a pressure of 0.5 mTorr to 20 mTorr.

When the pressure inside the deposition apparatus is stabilized after the use gas is introduced, RF power is applied to the RF antenna 67 inside the deposition apparatus to form a plasma of the introduced gas. The RF power used is from 0 to 300W, which is mainly 50W.

After plasma formation, when direct current, pulsed direct current, or RF power is applied to the silicon sputtering target 64 mounted on the magnetron deposition source attached to the deposition apparatus and the aluminum sputtering target 65 mounted on the magnetron deposition source, thin film deposition is performed. Plasma is generated for. In the case of pulsed direct current power, a voltage ratio of 300 to -600 V is applied, and the duty ratio can be deposited at 20, 40, 60, 80%.

When the incoming power is stabilized, nitrogen (N ₂ ) gas is introduced for aluminum-silicon-nitride deposition. Nitrogen gas is suitable to draw 3 to 6 sccm. Because less than 3 sccm, the nitride film may be deposited untransparent, and if more than 6 sccm, the nitriding speed is faster than the sputtering speed of the silicon and aluminum sputtering targets 64 and 65, so that the deposition rate may be significantly lower. to be.

Nitrogen gas introduced into the deposition apparatus and the material sputtered from the deposition source causes the aluminum-silicon-nitride film to be deposited on the uppermost layer of the polycarbonate sample 68 positioned on the sample mount 69 in the deposition apparatus.

Through the following examples, it was confirmed that the nitride film is deposited according to the above method and has an excellent effect.

Example 4

The Eagle 2000 glass substrate and the silicon wafer were placed in the deposition apparatus according to the method specified in the present invention, and after exhausting the inside of the deposition apparatus to 10 ^-6 Torr, 8 sccm of argon (Ar) gas was introduced, and the opening ratio of the vacuum pump was adjusted. After adjusting the process pressure to 5 mTorr, 50 W power was supplied to the RF antenna to form a plasma inside the deposition apparatus. After applying the silicon evaporation source equipped with a jeonryeokreul 80% to the DC power supply 490 V, 0.41 A, share of the pulse to the magnetron sputtering apparatus, and nitrogen (N ₂₎ gas 2 sccm, hydrogen (H ₂₎ the incoming gas 8 sccm Then, a hydrogenated silicon nitride film was deposited for 21 minutes to form a film of 1350 kPa, and a sample for Knoop hardness measurement was deposited with a thin film of 3700 kPa for 58 minutes.

As a result of six measurements of the Knoop hardness test of 10 g load on a 3700 kPa thick hydrogenated silicon nitride film, 17 GPa was shown as shown in FIG. In addition, as shown in Figure 8, the light transmittance in the visible light region 400 nm ~ 700 nm range of the sample on which a film of 1350 증착 was deposited was measured at 79%, the light transmittance at an ultraviolet wavelength of 300 nm is 3%, The sunscreen effect could be confirmed.

Example 5

The Eagle 2000 glass substrate and silicon wafer were placed in the deposition apparatus, the inside of the deposition apparatus was evacuated to 10 ^-6 Torr, and 8 sccm of argon (Ar) gas was introduced, and the process pressure was adjusted to 3 mTorr by adjusting the vacuum pump opening ratio. Then, 50 W of power was supplied to the RF antenna to form a plasma inside the deposition apparatus. Subsequently, 406 V, 0.26 A, 80% pulsed DC power was applied to the magnetron sputtering device equipped with silicon deposition source, and 331 V, 1.43 A, 60% pulse rate was applied to the magnetron sputtering device equipped with aluminum metal deposition source. A DC film was applied, 5 sccm of nitrogen (N ₂ ) gas was introduced to form a nitride film, and an aluminum-silicon nitride film was deposited for 60 minutes to form a film of 4000 kV.

As shown in FIG. 7 and FIG. 8, 31 GPa was shown as an average value of 6 Knoop hardness tests of 10 g load, and the light transmittance of 86% was confirmed in the visible light range of 400 nm to 700 nm.

Example 6

The Eagle 2000 glass substrate and silicon wafer were placed in the deposition apparatus, the inside of the deposition apparatus was evacuated to 10 ^-6 Torr, and 8 sccm of argon (Ar) gas was introduced, and the process pressure was adjusted to 5 mTorr by adjusting the vacuum pump opening ratio. Then, 50 W of power was supplied to the RF antenna to form a plasma inside the deposition apparatus. After applying the silicon evaporation source equipped with a jeonryeokreul 80% to the DC power supply 490 V, 0.41 A, share of the pulse to the magnetron sputtering apparatus, and nitrogen (N ₂₎ gas 2 sccm, hydrogen (H ₂₎ the incoming gas 8 sccm Then, a nitride film was formed, and a hydrogenated silicon nitride film was deposited for 21 minutes to form a film of 1350 Pa.

In order to deposit aluminum-silicon-nitride on hydrogenated silicon nitride, the process pressure was adjusted to 3 mTorr by adjusting the vacuum pump aperture ratio, and then a magnetron sputtering device equipped with a silicon deposition source had a 406 V, 0.26 A, 80% occupancy ratio. Pulsed DC power was applied, and a magnetron sputtering device equipped with an aluminum metal deposition source was applied with pulsed DC power of 331 V, 1.43 A, and 60% of the occupancy rate. Nitrogen (N ₂ ) gas was introduced into 5 sccm to form a nitride film. , An aluminum-silicon-nitride film was deposited for 60 minutes to form a film of 4000 kPa.

As shown in FIG. 7 and FIG. 8, 29 GPa was shown as an average value of Knob hardness test 6 times at 10 g load, and a light transmittance of 78% was observed in the visible light range of 400 nm to 700 nm, and 300 nm. At the ultraviolet wavelength, the light transmittance was measured at 3%. In this way, it was confirmed that a high hardness two-layer thin film having high visible light transmittance and UV blocking effect could be formed.

Example 7

After mounting a polycarbonate sample in the deposition apparatus, evacuating the inside of the deposition apparatus to 10 ^-6 Torr, introducing 8 sccm of argon (Ar) gas, and adjusting the process pressure to 5 mTorr by adjusting the vacuum pump opening ratio, 50 W power was supplied to the RF antenna to form a plasma inside the deposition apparatus. After applying the silicon evaporation source of the attached magnetron sputtering apparatus 490 V, 0.41 A, share 80% of the pulse direct current jeonryeokreul, and the nitride film formed by pulling a nitrogen (N ₂₎ gas 2 sccm, hydrogen (H ₂₎ gas 8 sccm To this end, a hydrogenated silicon nitride film was deposited for 21 minutes to form a film of 1350 kcal.

Subsequently, the process pressure was adjusted to 3 mTorr by adjusting the vacuum pump opening ratio, and a magnetron sputtering device equipped with a silicon deposition source had a pulsed direct current power of 406 V, 0.26 A, and 80% occupancy, and a magnetron equipped with an aluminum metal deposition source. A pulsed direct current power of 331 V, 1.43 A, and 60% occupancy was applied to the sputtering apparatus, and 5 sccm of nitrogen (N ₂ ) gas was introduced to form a nitride film. Then, an aluminum-silicon-nitride film was deposited for 60 minutes to form a film of 4000 Å. It was.

Using a pin-on-disk abrasion tester adapted to perform taber abrasion tests, the sample was loaded with 43 g of hydrogen nitride on top of polycarbonate and a two-layer film of aluminum-silicon-nitride. Was rotated at a speed of 100 RPM around the lower axis of rotation to perform a Taber wear experiment to rotate 2000 times. The light transmittance was measured after the Taber wear test.

As can be seen through FIG. 9A, in the case of the polycarbonate sample not deposited with the deposited film, the light transmittance was 87% in the wavelength range of 400 nm to 700 nm before performing the Taber wear test, but after the Taber wear test was performed Scratch generation due to low hardness reduced the light transmittance to 42%.

On the other hand, as can be seen in Figure 9b, in the case of a sample in which a hydrogenated silicon nitride film and a two-layer film of aluminum-silicon-nitride film is deposited on the top of the polycarbonate, before the Taber wear test is performed in the wavelength range of 400 nm to 700 nm The light transmittance was measured at 75% and the light transmittance was maintained at 72% even after the Taber wear test.

Claims

(a) Located inside vacuum chamber (1) for thin film deposition using magnetron sputtering

Mounting a polycarbonate substrate with sample 6 on one conductive sample mount 7;

(b) evacuating the vacuum degree inside the vacuum chamber (1) to a high vacuum region with a high vacuum turbo pump (13) and a low vacuum pump (14) which assists the operation of the turbo high vacuum pump (13);

(c) In order to operate the aluminum and silicon sputtering targets 3 mounted on the magnetron deposition source, argon (Ar), which is inert gas, and nitrogen (N 2 ), which are reactive gases, are operated by a gas flow adjusting device. Adjusting the pressure inside the vacuum chamber (1) by introducing into the inside;

(d) applying RF power to the RF antenna (5) inside the vacuum chamber (1) to form a plasma of the gas introduced in step (c); And

(e) Pulsed DC by a direct current or pulsed DC power supply device 2 to the magnetron sputtering deposition source on which the aluminum metal target 3 and the silicon target 3 are mounted after plasma formation in the step (d). Generating a plasma for thin film deposition by applying power; Aluminum-silicon-nitride film deposition method for improving the surface hardness and wear resistance of the polycarbonate material comprising a.
The method of claim 1,

In the step (c),

Pressure inside the vacuum chamber (1) is 0.5 mTorr ~ 30 mTorr aluminum-silicon-nitride film deposition method for improving the surface hardness and wear resistance of the polycarbonate material.
The method of claim 1,

In the step (c),

A flow rate ratio of the argon (Ar) and nitrogen (N 2 ) gas to be introduced is 10: 1 to 1: 1, the aluminum-silicon-nitride film deposition method for improving the surface hardness and wear resistance of the polycarbonate material.
The method of claim 1,

In the step (d),

RF power applied to the RF antenna (5) is aluminum-silicon-nitride film deposition method for improving the surface hardness and wear resistance of the polycarbonate material, characterized in that 0 ~ 300W.
The method of claim 1,

In the step (e),

The average power density of the direct current or pulsed DC is 1 W / cm 2 ~ 20 W / cm 2 The aluminum-silicon-nitride film deposition method for improving the surface hardness and wear resistance of the polycarbonate material.
A vacuum chamber 1 for thin film deposition using magnetron sputtering;

A pulse direct current power supply (2) for applying direct current or pulse direct current power to the aluminum and silicon sputtering targets (3) mounted on the deposition source of the magnetron sputtering;

A plasma (4) generated by the sputtering target (3) mounted to the deposition source;

An RF antenna (5) introduced into the vacuum chamber (1) to convert gas into plasma;

A conductive sample holder (7) for mounting a sample deposited in the vacuum chamber (1);

An RF power supply unit 9 for supplying power to the RF antenna 5;

A high vacuum turbopump 13 for maintaining a high vacuum inside the vacuum chamber 1;

A vacuum gauge (12) for measuring the degree of vacuum inside the vacuum chamber (1); And

Aluminum flow rate for improving the surface hardness and wear resistance of the polycarbonate material, characterized in that it comprises ;; gas flow rate control unit 11 for adjusting the flow rate of argon (Ar) and nitrogen (N 2 ) gas used for plasma generation Silicon-nitride film deposition apparatus.
The method of claim 6,

The pressure inside the vacuum chamber (1) is 0.5 mTorr ~ 30 mTorr aluminum-silicon-nitride film deposition apparatus for improving the surface hardness and wear resistance of the polycarbonate material.
The method of claim 6,

For improving the surface hardness and wear resistance of the polycarbonate material, characterized in that for adjusting the flow rate ratio of the argon (Ar) and nitrogen (N2) gas to which the gas flow rate adjusting unit 11 is introduced in a range of 10: 1 to 1: 1. Aluminum-silicon nitride film deposition apparatus.
The method of claim 6,

The RF power applied to the RF antenna (5) from the RF power supply (9) is an aluminum-silicon-nitride film deposition apparatus for improving the surface hardness and wear resistance of the polycarbonate material, characterized in that 0 ~ 300W.
The method of claim 6,

The surface of the polycarbonate material, characterized in that the average power density of the direct current or pulse direct current applied to the aluminum and silicon sputtering target 3 by the pulse direct current power supply 2 is 1 W / cm 2 to 20 W / cm 2 . Aluminum-silicon nitride film deposition apparatus for improving the hardness and wear resistance.
Hydrogenated Silicon Nitride deposited on one or both sides; And

And a silicon-silicon nitride film deposited on the hydrogenated silicon nitride film.
The method of claim 11,

The hydrogenated silicon nitride film to improve the UV blocking properties,

The aluminum-silicon nitride film improves hardness and wear resistance,

Polycarbonate.
The method of claim 11,

The hydrogenated silicon nitride film is formed by a reactive sputtering method by introducing an inert gas, nitrogen and hydrogen in a plasma reactive magnetron sputtering thin film deposition apparatus comprising a silicon sputtering target,

Polycarbonate.
The method of claim 13,

The reactive sputtering method,

Forming a plasma of an inert gas, hydrogen, and nitrogen gas in a plasma reactive magnetron sputtering thin film deposition apparatus;

A sputtering step in which the plasma of the gas collides with a silicon sputtering target; And;

Characterized by depositing a hydrogenated silicon nitride film on the surface of the polycarbonate due to spotting,

Polycarbonate.
The method of claim 11,

The aluminum silicon nitride film is formed by a reactive sputtering method by introducing an inert gas and nitrogen in a plasma reactive magnetron sputtering thin film deposition apparatus including a silicon sputtering target and an aluminum sputtering target.

Polycarbonate.
The method of claim 15,

The reactive sputtering method,

Forming a plasma of inert gas and nitrogen gas in the plasma reactive magnetron sputtering thin film deposition apparatus;

A sputtering step in which the plasma of the gas collides with a silicon sputtering target and an aluminum sputtering target; And

And depositing an aluminum silicon nitride film on the surface of the polycarbonate on which the hydrogenated silicon nitride film is deposited due to sputtering.

Polycarbonate.
The method according to claim 13 or 15,

The pressure inside the deposition apparatus is characterized in that 0.5 mTorr to 20 mTorr,

Polycarbonate.
The method according to claim 13 or 15,

The inert gas, characterized in that the argon,

Polycarbonate.
Mounting a polycarbonate substrate having a polycarbonate substrate or a silicon oxide film on a plasma reactive magnetron sputtering thin film deposition apparatus;

Depositing a silicon hydride nitride film on the polycarbonate substrate by sputtering from a silicon sputtering target; And

Depositing an aluminum silicon nitride film on the hydrogenated silicon nitride film from a silicon sputtering target and an aluminum sputtering target,

Method to improve the sun protection and wear resistance of polycarbonate.
The method of claim 19,

The hydrogenated silicon nitride film to improve the UV blocking properties,

The aluminum-silicon nitride film improves hardness and wear resistance,

Method to improve the sun protection and wear resistance of polycarbonate.
The method of claim 19,

The hydrogenated silicon nitride film deposition is characterized in that by the reactive sputtering method by introducing an inert gas, nitrogen and hydrogen into the deposition apparatus,

Method to improve the sun protection and wear resistance of polycarbonate.
The method of claim 21,

The reactive sputtering method,

Forming a plasma of inert gas, hydrogen and nitrogen in a plasma reactive magnetron sputtering thin film deposition apparatus;

A sputtering step in which the plasma of the gas collides with a silicon sputtering target; And

Characterized in that it comprises depositing a hydrogenated silicon nitride film on the surface of the polycarbonate due to sputtering,

Method to improve the sun protection and wear resistance of polycarbonate.
The method of claim 19,

The aluminum silicon nitride film deposition is by a reactive sputtering method by introducing an inert gas and nitrogen in the plasma reactive magnetron sputtering thin film deposition apparatus comprising a silicon sputtering target and an aluminum sputtering target,

Method to improve the sun protection and wear resistance of polycarbonate.
The method of claim 23, wherein

The reactive sputtering method,

Forming a plasma of inert gas and nitrogen gas in the plasma reactive magnetron sputtering thin film deposition apparatus;

A sputtering step in which the plasma of the gas collides with a silicon sputtering target and an aluminum sputtering target; And

And depositing an aluminum silicon nitride film on the surface of the polycarbonate on which the hydrogenated silicon nitride film is deposited due to sputtering.

Method to improve the sun protection and wear resistance of polycarbonate.
The method of claim 22 or 24,

The pressure inside the deposition apparatus is characterized in that 0.5 mTorr to 20 mTorr,

Method to improve the sun protection and wear resistance of polycarbonate.
The method of claim 22 or 24,

The inert gas, characterized in that the argon,

Method to improve the sun protection and wear resistance of polycarbonate.