JPH01316455A - Formation of film excellent in uniformity and adhesive strength at high speed - Google Patents

Abstract

PURPOSE:To accelerate the ionization of a reactant gas and to improve the adhesive strength and uniformity of a film by using the inside of a focusing coil provided to the part ranging from a crucible to the close vicinity of a substrate as a moving path for an evaporation material and also disposing an RF(ratio frequency) coil in the above moving path. CONSTITUTION:At the time of applying ion plating treatment to a substrate 6 by using an HCD gun 1, a focusing coil 4 is provided to the position ranging from a crucible 2 to the close vicinity of the substrate 6, and the inside of the above focusing coil 4 is used as a moving path for an evaporation material. An RF coil 8 is provided to the rear of the substrate 6 in this moving path. By heating a fine wire consisting of one kind among Ta, W and LaB6 and provided to a reactant gas-introducing pipe, the ionization of the reactant gas is accelerated. By this method, respective ionization rates of the evaporation material and the reactant gas are increased and high-speed film formation can be attained. Further, the quality of a formed film can be improved.

Description

[Detailed Description of the Invention] (Industrial Application Field) This invention is directed to the so-called HCD (Hollow Cat
The present invention relates to a method for rapidly forming a film with excellent uniformity and adhesion on, for example, a steel plate, glass, or a zone-shaped substrate thereof, using an ion plating process using a hode discharge method.

(Conventional technology) Ion plating method using plasma is TiN,
It is applied to ceramic coatings such as TiC and Ti(CN). As the ion plating method, H
CD method, EB (Electron Bean+)+R
F (Radi.

Techniques such as the Frequen, Cy) method, the multi-arc method, and the arc discharge method have been implemented.

Among these methods, the IIcD method has an ionization rate of 20 to 4
It is as high as 0%, and the film formation rate is 0.05 to 0.5 u-a.
/lll1n, which is relatively fast, so TINI TiC+
It is widely used for ceramic coatings with Ti(CN) or CrN. In particular, the HCD method has the advantage that ceramic coating can be easily and smoothly performed even if the requirements such as N2 gas flow rate, degree of vacuum, bias voltage, substrate temperature, and substrate pretreatment change slightly.

In other words, regarding ion plating using the HCD method, see Metal Surface Technology 35 (1) p16-24 (1
984), Powder and Powder Metallurgy 32 (1985) p.
55-60.

(Problems to be Solved by the Invention) Recently, the hollow cathode method has been used to improve the corrosion resistance, decorativeness, and abrasion resistance of wide plate-shaped bodies with large surface areas used for construction materials, such as steel plates and copper strips. Attempts have been made to use it, but it has not yet been put to practical use. This is because, as mentioned above, the HCD method has a high film formation rate of about 0.05 to 0.5μIl/llin, which is sufficient for batch-type coatings, but it is not suitable for targeting large surface areas. Because there is. Therefore, in order to apply the HCD method to coatings with large surface areas,
It is necessary to increase the ionization rate of the evaporated substance and perform high-speed film formation.

Now, the film formation rate in a conventional ion plating device with a conventional HCD gun capacity of 300A or 5008 is, for example, 0.05 to 065μ for TiN coating.
m /min, and the ionization rate at this time was about 30 to 40% at most, but in recent years, in order to increase the film formation rate to about several μnl/lll1n, 100OA
Alternatively, the development of HCD guns for evaporation with a large capacity of about 150 OA has progressed, and when the capacity of the HCD gun is increased in this way, the ionization rate increases to over 50%, which has the advantage of significantly improving the film quality by ion plating. be.

However, when forming a film using such a large-capacity HCD gun, the ionization rate of dissolved and evaporated substances is greatly improved. It was difficult to obtain a film, and it was necessary to simultaneously ensure sufficient ionization of the reaction gas.

Therefore, this invention eliminates the various problems mentioned above,
The purpose of this paper is to propose an ion plating process that can promote not only the ionization of evaporated substances but also the ionization of reactive gases.

(Means for Solving the Problems) This invention provides a method for forming a film with excellent uniformity and adhesion at high speed. In performing ion plating treatment on the substrate by melting and vaporizing it with a hollow cathode gun and ionizing it at the same time, (1) The inside of the focusing coil placed from the crucible to the immediate vicinity of the substrate is used as a movement path for the evaporated substance, A method characterized in that the ionization of the reaction gas is promoted by an RF coil placed on this movement path (first invention) (2) The movement path of the evaporated substance is inside the focusing coil placed from the crucible to the immediate vicinity of the substrate. and (2) a method characterized in that the ionization of the reaction gas is promoted by an RF coil placed behind the substrate (3) evaporating the inside of a focusing coil placed from the crucible to the immediate vicinity of the substrate. It has excellent uniformity and adhesion, and is characterized by being used as a material transfer path and promoting ionization of the reaction gas by heating a thin wire made of one of Ta, W, and LaB6 attached to the reaction gas introduction tube. This is a method (third invention) for forming a coated film at high speed.

(Function) First, the experimental results that formed the basis of the first and second inventions will be explained.

C: 0.043 wt% (hereinafter simply expressed as %), Si
: 3.39%, Mn: 0.066%, Mo:
0.013%, Se: 0.021% and Sb
: Silicon steel hot-rolled plate containing 0.026% (thickness 2.0
mm, width 500 mm) was cold-rolled twice with intermediate annealing at 950°C to form a final cold-rolled sheet with a thickness of 0.20 mm, and then decarburized and primary recrystallized in wet hydrogen at 820°C. After annealing, MgO (35%), 8β203 (6
0%), Zn0 (3%) and Ti0z (2%) as main components, and then heated at 850°C for 5
After performing secondary recrystallization annealing for 0 hr, purification annealing was performed in dry hydrogen at 1200'C, oxides on the steel plate surface were removed, and the center line average roughness was finished to 0.05 μm by electrolytic polishing. . Thereafter, using the ion plating equipment shown in cylinders 1 and 2, Ti was plated under the conditions shown in Table 1, respectively.
A N coating (approximately 1.0 pm thick) was applied.

In the figure, 1 is a IIcD gun, 2 is a crucible, 3 is an evaporation substance (Ti), 4 is a focusing coil arranged in the movement path of the evaporation substance, 5 is a shutter, 6 is a substrate, 7 is a heater, and 8 is a reaction gas. 9 is a matching device, IO is a high frequency power supply, 11 is a reactant gas (N2) inlet,
12 is an exhaust port and 13 is a vacuum chamber. Note that the RF coil 8 is placed on the movement path of the evaporated substance in the case of FIG. 1, and is placed behind the substrate 6, that is, facing the back side of the vapor deposition surface of the substrate 6 in the case of FIG.

Similar experiments were also carried out using the conventional IICD method ion plating apparatus shown in Fig. 3 (Metal Surface Technology, 34 (1984).
) P, 16) and EB + RF shown in FIG.
Method ion plating equipment (metal surface technology, 35 (1)
985) P, 330) under the conditions shown in Table 1.

Table 1 shows the results of investigating the film formation rate, magnetic properties of the obtained products, and color tone of the films in each experiment.

As is clear from Table 1, Experiment Seed 1 according to the first invention and Experiment Nα2 according to the second invention were superior to the conventional experiments Nα3 and 4 in all items such as film formation speed, film color tone, and magnetic properties. The results were shown.

In other words, the film formation rate in experiments Nα1 and 2 was 1.5
and a high speed of 1.7 μm/min, whereas experiments No. 3 and 4 had a high speed of 0.2–0.5 μm
/win, the color tone is blackish gold compared to the golden yellow peculiar to TiN, and the magnetic properties are 1.
/,. : 0.65 and 0.64 W/kg and 0.70-0.75 W/kg for noni.

As described above, the methods according to the first and second inventions were able to achieve high-speed film formation, and when observed under an electron microscope, the golden coating had a smooth surface with no irregularities, and improved magnetic properties were also achieved. Here, the improvement in magnetic properties is thought to be due to the improved adhesion between the TiN film and the silicon steel sheet, and the uniform quality of the film, which caused strong tension to be applied to the steel sheet near the surface of the steel sheet. That is, it has been found that promoting ionization using the focusing coil and the RF coil according to the first and second inventions is effective in realizing an extremely good plasma state.

Next, the experimental results that formed the basis of the third invention will be explained.

C: 0.042%, Si: 3.36%, Mn:
0.063%, M.

: 0.012%, Ss: 0.020% and Sb
: Silicon steel hot-rolled plate containing 0.023% (thickness 2.
0 mm, width 500 mm) was cold-rolled twice with intermediate annealing at 950°C to form a final cold-rolled sheet with a thickness of 0.2, 2011101, and then decarburized in wet hydrogen at 820°C.
After the next recrystallization annealing, MgO (30%), Al
203 (65%), TiO□ (3%) and ZrO
After applying an annealing separator mainly composed of
Purification annealing was performed in soft hydrogen at 200°C, oxides on the surface of the steel plate were removed, and the steel plate was finished to an average center line roughness of 0.06 μm by electrolytic polishing. Thereafter, using the ion plating apparatus shown in Fig. 5, the voltage of 700 A and 60 V) was applied.
When forming a TiN film (approximately 1.5 ata thick) under IcD conditions, N2 gas was introduced according to the following steps 1 to 2.

Note that 14 in the figure is a reaction gas introduction pipe.

That is, (1) the reaction gas introduction tube shown in FIG. 6(a) was connected to the introduction port 11 to promote ionization of the introduced N2 gas.

In the figure, 14-1 is a graphite tube, 14-2 is a tungsten heating wire arranged in a coil inside the tube 14-1, and I4-3 is an N2 gas injection hole.

(2) The reaction gas introduction tube shown in FIG. 2(b) was connected to the introduction port 11 to promote ionization of the introduced N and gas.

In addition, 14-4 in the figure is a tungsten heating wire installed on the outlet side of the jet hole 14-3 of the tube 14-1.

(2) N2 gas was introduced without using a reaction gas introduction tube.

Processing by the conventional HCD method was also carried out using the apparatus shown in FIG. 3 described above.

Table 2 shows the results of investigating the film formation rate of each experiment, the film quality and magnetic properties of the obtained products.

As is clear from experiments Na 1 to 3 shown in Table 2, the film formation rate can be increased (2.7 to 2.9 μm/m1n) by surrounding the movement path of the vapor deposited substance with a focusing coil, and the experimental The film forming speed is about 4 to 5 times that of the conventional HCD method of No. 4. However, Experiment Nα3 was inferior to Experiments Nα1 and 2 in terms of film quality and magnetic properties, which is thought to be due to insufficient ionization of the reaction gas.

That is, it has been found that promoting ionization using a reaction gas introduction tube equipped with a focusing coil and a thin heating wire according to the third invention is extremely effective in realizing a good plasma state.

Note that ceramics such as alumina or graphite are advantageously suitable for the reaction gas introduction tube, and the attached thin wire for heating is made of a high melting point metal, that is, Ta, which has good discharge characteristics.
, W and LaB are preferred.

In addition, the HCD gun applied to this invention has a voltage of 40V or more.
It is effective to use a large capacity type with a current of 500 A or more because the amount of evaporation increases. Incidentally, when such a large-capacity IICD gun is used, the amount of input current is large (and the ionization of the evaporated substance is also promoted, so it is essential to promote the ionization of the reaction gas at the same time.

(Example) Tsubasa Kaido ■C: 0.058%, Si: 3.39%, Mn
: 0.076%, S: 0.026%, 8N:
0.028%, Cu: 0.1% and Sn: 0.0
6%, or ■C: 0.044%, Si: 3.2
6%, Mn: 0.071%, Mo: 0.013
%, Se: 0.020% and Sb: 0.02
10 silicon steel hot-rolled plates (2,2 now thick) containing 5%
0.20m by cold rolling twice with intermediate annealing at 50°C (■ sample) or 950'C (■ sample)
A final cold-rolled sheet with a thickness of m was obtained. Next, after performing primary recrystallization annealing that also serves as decarburization in wet hydrogen at 840°C (sample ■) or 820°C (sample ■), a
zo: + (60%), Mg0 (35%), Ti02
(3%) and ZrO□ (2%) as main components, and then the specimen of
The temperature was raised to 1100"C/hr to develop Goss-oriented secondary recrystallized grains, and the sample (■) was subjected to secondary recrystallization annealing at 850°C for 50 hours, and then both samples were annealed at 1200"C. The steel plate was subjected to purification annealing in soft hydrogen for 10 hours, and then oxides on the surface of the steel plate were removed by pickling, and electrolytically polished to a mirror surface with a center line average roughness of 0.04 μm.

And the device shown in Figure 1 (1 (CD condition: 55■, 600
A.

CrN was formed to a thickness of 1.5 μm using RF: 1200 W).

The film formation rate at that time was 2.0μi/min, and the magnetic properties of the product were as follows: B+o=1.93T, 1ll
B/s・=0.63 W/kg and ■ sample is B+o
=1.927. I'l+, /s.

=0.62i/kg.

Example 5 IC: 0.042%, Mn: 0.32%, P:
0.008% and S: 0.007. After degreasing the surface of a low carbon cold-rolled steel plate (0.5 nu thick) containing 0.5%, it was electrolytically polished to a mirror surface with a center line average roughness of 0.06 μm, and then processed using the apparatus shown in Figure 2 (HCD conditions = 70
(2) A TiN film (0.9 μm thick) was formed on the surface of the steel plate using a 100 OA, RF: 950 W). The film formation rate at this time was as high as 3.0 μm/mtn, and the obtained product did not peel off even after repeated 90° bending twice, and no unevenness was observed on the surface when observed with a scanning electron microscope. In other words, both adhesion and uniformity were good.

Implementation 1- ■C: 0.062%, Si: 3.36%, Mn
: 0.072%, S: 0.025%, Af:
0.026%, Cu; 0.1% and Sn:
0.08%, or ■C: 0.042%, Si:
3.32%, Mn: 0.063%, Mo: 0.
015%, Se: 0.019% and Sb: 0
．． A silicon steel hot-rolled plate (2.2 mm thick) containing 0.026% was cold rolled twice with intermediate annealing at 1100°C (■ sample) and 950°C (■ sample). .2
A final cold-rolled sheet with a thickness of 0 mm was obtained. Next, after performing primary recrystallization annealing that also serves as decarburization in wet hydrogen at 840°C (sample ■) or 820°C (sample ■), A
f203 (60%), Mg0 (35%), Ti
An annealing separator containing O□ (3%) and Zr0z (2%) as main components was applied, and then the specimen of
The temperature was raised to 1100'C at 0'C/hr to develop Goss-oriented secondary recrystallized grains, and the sample in
After secondary recrystallization annealing for 12 hours, the samples of ■ and
Purification annealing was performed for 10 hours in soft hydrogen at 00°C, and then oxides on the surface of the steel plate were removed by pickling, and the steel plate was electrolytically polished to a mirror surface with a center line average roughness of 0.06 μm.

And the installation W in Figure 5 (HCD condition = 70■, 100OA
) was used to form a VN film with a thickness of 1.2 μm using an apparatus to which the reaction gas inlet tube shown in FIG. 6(a) was applied. The film formation rate at that time was 2.5 μn+/min, and the magnetic properties of the product were B for the sample (■). =1.94T, 77. =
0.66 W/kg and ■ sample is 81° = 1.92
T, IL7/s.

= 0.63 匈/kg.

Chise plate clay C: 0.036%, Mn: 0.35%, P:
After degreasing the surface of a low carbon cold rolled steel plate (0.6 mm thick) containing 0.009% and S: 0.009%, it was electrolytically polished to a mirror-like state with a center line average roughness of 0.07 μm. The same apparatus as in Example 3 (HCD conditions:
A CrN film with a thickness of 1.5 μm was formed on the surface of the steel plate using a 65 V, 800 A). At this time, the film formation rate was 2
．． At a high speed of 3 μm/min, the obtained product did not peel off even after repeated 90° bending twice, and no unevenness was observed on the surface when observed with a scanning electron microscope.
That is, both adhesion and uniformity were good.

(Effects of the Invention) According to the present invention, high-speed film formation can be achieved by increasing both the ionization rate of the evaporated substance and the reaction gas, and the quality of the formed film can also be improved.

[Brief explanation of the drawing]

Fig. 1 is an explanatory diagram showing an ion plating apparatus applied to the first invention, Fig. 2 is an explanatory diagram showing an ion plating apparatus applied to the second invention, and Fig. 3 is an explanatory diagram showing an ion plating apparatus applied to the second invention. Apparatus diagram, Fig. 4 is a conventional EB + RF method ion plating apparatus, Fig. 5 is an explanatory diagram of an ion plating apparatus applied to the second invention, and Fig. 6 (a) and (b) are illustrations of a reaction gas introduction tube. It is a sectional view. 1...HCD gun 2...crucible 3...
Evaporation material 4... Focusing coil 5... Shutter 6... Substrate 7... Heater
8... RF coil 9... Matching device 10.
・High frequency power supply 11 ・Reactant gas inlet 12 ・・
- Exhaust port 13... Vacuum chamber 14... Reaction gas introduction tube 14-1... Tube 14-2. 14-4... Heating wire 14-3...
Nozzle hole patent applicant Kawasaki Steel Corporation Patent applicant Japan Vacuum Technology Co., Ltd. Figure 1 Figure 2 Figure 3 Jz Figure 4 Figure 6 (a) (b)

Claims (1)

[Claims] 1. In a vacuum chamber into which a reaction gas is introduced, an evaporation substance contained in a crucible is melted and evaporated using a large-capacity hollow cathode gun, and simultaneously ionized to perform ion plating treatment on a substrate. At the same time, the ionization of the reactant gas is promoted by an RF coil arranged on this movement path, and the inside of a focusing coil arranged from the crucible to the immediate vicinity of the substrate is used as a movement path for the evaporated substance. A method for forming a film with excellent adhesion at high speed. 2. In a vacuum chamber into which a reaction gas is introduced, the evaporation material contained in the crucible is melted and evaporated using a large-capacity hollow cathode gun, and at the same time ionized. A coating with excellent uniformity and adhesion is used, in which the inside of the focusing coil placed in close proximity is used as a path for the movement of evaporated substances, and the RF coil placed behind the substrate promotes ionization of the reactive gas. How to form at high speed. 3. In a vacuum chamber into which a reaction gas has been introduced, the evaporation material contained in the crucible is melted and ionized at the same time as it is evaporated and ionized using a large-capacity hollow cathode gun. The inside of the focusing coil disposed in the immediate vicinity is used as a movement path for the evaporated substance, and one of Ta, W and LaB_6 attached to the reaction gas introduction pipe is used.
A method for rapidly forming a film with excellent uniformity and adhesion, which is characterized by promoting ionization of a reactive gas by heating a thin wire made of seeds.