JPS5867016A - Manufacture of thin film - Google Patents

Abstract

PURPOSE:To provide a thin film with high orientation, by a method wherein the film is formed by eliminating atoms that do not incident in the vertical direction agaist a substrate. The method is related to the dry process such as the sputtering, the vacuum deposition and the ion plating processes. CONSTITUTION:RF diode sputtering device is used to form film, and it is fully baked. Before starting of sputtering, the vacuum degree in a belljar must be made less than 5.0X10<-7> Torr. A mask made of stainless steel is attached on the front surface of a substrate. Film is formed for each mask Fig (d), (e) and (f) show-the masks eliminating the atoms that incidents in the inclined direction. H-cut mask is used to form film on the atoms that incident in the vertical direction against the subtrate. The length of a pipe 4 is in order of (d), (e), (f). The angle between the center P of the substrate 3 and the upper edge of the pipe 4, that is potential angle alpha from the substrate center becomes 30 deg. for (d),40 deg. for (e), and 60 deg. for (f). The film made by using the masks is I0002/d larger than the one made without using the masks, and its crystallizability as well as the orientation in the C axis direction is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a thin film having oriented crystal orientation.

Today, there is a strong hope that a technology for producing thin films with oriented crystal orientation will be established. An example of applying an oriented thin film is C.
o-Ru, Co-Cr hcp#g C in film formation
In addition, perpendicular recording media for Wi:8* density using the axis alignment film 7, surface acoustic wave elements using C-axis orientation m such as ZnU, CdS, ALN, etc. can be used.

To achieve a perpendicular magnetization state in a magnetic thin film, the total maximum demagnetizing field (4πM
s). Therefore, in order to realize the perpendicular magnetization state by using the CO basin in yis, (1) the ex-Msf decrease δ and the reciprocal reciprocation must be reduced. (2) The hcp phase C@ is sharply distributed in the direction perpendicular to the substrate, and the HK phase is made as large as possible.The Co-based alloy thin film exhibiting the conventional IH magnetization state is fabricated by RF sputtering and vacuum evaporation. Co-Go-'Ru film and Co-Cr
membrane has been reported. (S. Hiron.

et at: Jpn, J, Appl, Ph
ya, 201981 L571, Y, Maeda
et at: Jpn, J, Appl, Pb)'
s, 20 (1981), L467) previously considered
It is known that C@ cannot be sharply aligned with respect to the substrate in the initial stage of film formation when using the manufacturing method that has been developed. Go-C
In the r film, the half-width of the rocking curve of the ['0002] plane is large at the initial stage of film formation, and as the film formation progresses, the half-width decreases. νI'' In the initial stage of film formation, the C-axis dispersion is large and the C-axis orientation is not good. -Man, co-R
In the U film, the initial stage of film formation is [1000:] orientation 9
It has been reported that as the film thickness increases, the direction of the orientation force changes, and a film with a floating slant and [0001] orientation can be obtained. In addition, for a Co-Ru film exhibiting perpendicular magnetization shape M, it is necessary to
It is also known that the + -H curve is saturated even when the external a field is 14.5 K (g), and that this is true for magnetically hard films.
are doing. (S. Hiron.

etaj: Same as above) This lack of C1111 orientation causes a decrease in the salt content of the alloy film, which has a suppressive effect on realizing the perpendicular magnetization state, but also causes a decrease in coercive force (Ha), resulting in shallow trade magnetization. This method has the disadvantage that it causes a decrease in (Mr), that is, a decrease in reproduction output t.

Furthermore, with the conventional magnetically noded Co-Ru film, a minor M-H curve is followed during recording.
This phenomenon also has the disadvantage of causing a decrease in 1fcMr, that is, a decrease in the reproduction output.As mentioned above, the C-axis orientation is insufficient in the conventional manufacturing method, and technology has been established to further improve the orientation. is required.

The present invention is characterized by forming a thin film while removing atoms incident from a direction deviated from the perpendicular direction to the substrate when the entire thin film is manufactured by a dry method such as a sputtering method, a vacuum evaporation method, or an ion grating method. The purpose of this method is to fabricate a thin film with a higher degree of orientation than conventional fabrication methods.

The inventors of the present invention have conducted a detailed study on two manufacturing factors regarding a perpendicular magnetization medium that requires a pan-isolated film. As a result, residual gas and h
Precipitation of phases other than the cp phase (fee, tetragonal phase),
In addition to fabrication factors such as deposition rate, it has been found that the angle of incidence of the incident atoms with respect to the substrate has a significant effect on the orientation of the film. When the angle of incidence of incident atoms on the substrate has many components parallel to the substrate, the C-axis orientation is limited and % [0001
) plane, but also [1010] plane and (xoig plane) are deposited parallel to the substrate, and the C-axis orientation of the film is significantly reduced.
It was observed that the magnetocrystalline anisotropy in the direction perpendicular to the film surface decreased. On the other hand, when forming II by removing all of the incident atoms whose incident angle has many components parallel to the substrate and using incident atoms whose main component is perpendicular to the substrate, the C-axis It was found that the orientation was improved and the crystalline magnetic anisotropy was improved. In this way, the C-axis orientation of the film can be clearly improved by providing a shield in front of the substrate to remove atoms incident on the substrate in a direction deviating from the perpendicular direction.

Hereinafter, the present invention will be explained in detail based on Examples.

[Example 1] RF diode spanner device 1 for film formation
111. I spent money. As a target, a ruthenium pellet with an L diameter of 4 days was placed on a pure cobalt disk with a diameter of 83 mm to produce a Co-Ru film. The allocation of the ruthenium pellets in the target surrounding area was determined to be 27x. A sputtering device using a glass sheet metal manufactured by Corning Co., Ltd. with a scale of 0.5 is thoroughly baked, and the degree of vacuum in the Pelger before starting sputtering is 5. OX 1O-7Tor
Make it less than or equal to r. Sputtering conditions are argon pressure 1.0X
10"-2 Torr, 4 sub distances between target and board,
The substrate temperature was 200° C., and the sputtering power density was 4 W/−. Further, stainless steel masks shown in FIG. 1 were attached to the front surface of the substrate, and a film was formed for each mask. 1st
In the figure, the masks shown in (a) = Q)) and (c) are masks for removing incident atoms in the vertical direction of the substrate and forming a film mainly on obliquely incident atoms. The structure has two legs, and the lengths of the legs are (a) and (b).
), the center P of the 0 substrate becomes longer sequentially to (c)
The angle of view α formed between the line viewed from the periphery of the disk and the substrate is 30° in (a), 45' in (a), and 60' in (c). This (a),
(b).

The mask in (e) is called t-■ cut mask. On the other hand, the first
In the figure, the masks (d), (e), and (f) are used to remove all obliquely incident atoms and form a film mainly on the incident atoms in the vertical direction of the substrate. It has a structure in which a cylindrical pipe 4 is attached on top of the pipe 3.
The length of the pipe 4 increases in the order of (d), (e), and (f). The board is placed in this pipe from the center P of the board, and the angle between the board and the line looking at the upper edge of the pipe from the center P of the board, that is, the viewing angle a from the center of the board is (d). 30°, (e) is 45', (
f) is manufactured to be ■°. This (ct)
Mask f of p (e), (f): It is called an H-cut mask.

First, the characteristics of the film produced using ① Ka)-r will be described. FIG. 2(a) shows the complete X-ray diffraction patterns (using CuKa rays) of the film produced using the mask of (a) and the film produced without using the mask. In the film produced without using a mask (see Low), only the (0002) diffraction line exists, and the film has a complete C-axis alignment. However, in the film prepared using (a) mask, [xo
io), cxoix: It can be seen that the + diffraction edges are introduced and the C-axis orientation is significantly reduced. In order to evaluate the degree of C-axis orientation, I 10 with respect to the viewing angle of the mask
00/I 0002 k shown in Figure 3. From this figure, it can be seen that when the cut mask is used, the 11010 diffraction line is present and the C-axis orientation is lower than when no mask is used. The above is the result of removing the vertically incident component and forming a film mainly on the obliquely incident component.Next, in contrast to this method, when using an H-cut mask, the film is formed mainly on the vertically incident component. Let's talk about the case.

In the X-ray diffraction patterns of the films produced using R-cut masks (d), (e), and (f), only the (0002) diffraction line was observed, indicating that the films were C-axis oriented. In order to evaluate the crystallinity in the direction perpendicular to the substrate surface, the degree of (0002) diffraction iut per unit film thickness is shown in FIG. From this figure, the film produced using the H-cut mask has a lower weight of 1000 g/m compared to the nine films produced without using a mask.
d is large, especially a mask with a viewing angle of 60° (mask f
) is found to have a value about 10 times larger. In this way, the film produced using the H-cut mask has the same crystallinity in the C-axis direction.

The C-axis orientation is the same as above. In order to evaluate the C-axis orientation as a magnetic property, the residual magnetization (Mr (±
))/Residual magnetization measured in the direction parallel to the film surface (Mr(//)
) is shown in Figure 5.

For the film using H-cut mask, Mr(±)/Mr
(//) is larger than the film prepared without using a mask, especially when all phases are present at 60°-rx, Mr(±)/
Mr (, //) was introduced as above about 2.2 times.

When an H-cut mask is used, the magnetic anisotropy in the direction perpendicular to the film surface is improved, and this also shows that the C-axis orientation is improved.

Figure 6 (a) shows when no mask is used, and (b) shows 6
It was prepared using a 0° mask and measured in the direction perpendicular to the film surface of fcMlk, showing nine M-H loops. In the film without a mask, the M-H loop is not saturated even with an external tIa field of 10 KOe, whereas in the film with a 60′ mask, it is saturated at about 5 K(t).

As explained above, if the atoms incident perpendicularly to the substrate are removed and the film is formed mainly by obliquely incident atoms, the C-axis orientation deteriorates significantly, whereas if all obliquely incident atoms are removed and the film is formed mainly by obliquely incident atoms, When the film is formed mainly by atoms, the C-axis orientation is significantly improved. Example 2 Co--Cr film f: Produced by RF diode sputtering method. The sputtering conditions and substrate were the same as in Example 1. The ratio of the area of the Cr pellet to the area of the entire target is %. All film formation was performed using the H-cut mask shown in FIG. In Fig. 7, Mr(±)/Mr
The dependence of (〃) on the mask viewing angle is shown.

%H cut mask for Co-Cr film as well as Co-Ru film? Since the C-axis orientation improves when using a mask, Mr(±) / Mr(
Improvement in 〃) was observed.

[Example 3] A mask shown in FIG. 8 was prepared in order to form a film on a disk substrate having a diameter of 8 cfR. This mask is provided inside a cylinder 11 with a diameter of 10 m, parallel to the axial direction of the shingle plate 1211. When viewed from the entire surface of this mask, a partition plate ν is provided so that the inside of the mask forms a square with one side of 5 m. The thickness of this mask is 4.5cm
and 2.5 tea masks were used. An RF diode sputtering device was used for film formation. As a target, a ruthenium pellet with a diameter of 4 cm was set on a 0 disc with a diameter of 17 cIn, and Co-RuW! 1. was created. The proportion of ruthenium pellets in the target area was set at 71'X.

The substrate has a diameter of 8 mm and a thickness of 0.2 cm. An At substrate gold whose surface was anodized (an alumite layer of 2 μm thick) was used.

Thoroughly bake the sputtering equipment and check the degree of vacuum in the Pelger before starting sputtering. 5. OX 1O-7Torr
Do the following. Sputtering conditions are argon pressure 1.0 x 10"
-2 Torr.

Pressure between target and substrate 1w15 cm, substrate temperature 15
0℃.

The sputtering power density was 2 W/cII.

The substrate, mask, and target are parallel to each other.

The mask and target were placed so that their centers were aligned in a straight line. Furthermore, the distance between the mask and the board was set to one circle. FIG. 9 shows the mask thickness dependence of Mr(±)/Mr(yy). As can be seen from this factor, compared to the case where no mask is used, the film prepared using the masked kumquat has a lower Mr(
1) An improvement was observed in / Mr (//), indicating that the C-axis orientation of the film was also improved in this case. In the above-mentioned shield, it is preferable that the square of the length of the pipe is 11,500 to 200 times the average value of the divided areas of the parts divided by the υ plates.

[Example 4] All film formation was performed while rotating the substrate by 3°, 6°, and 12° per second. The film forming conditions other than substrate rotation are exactly the same as in Example 3. In this case as well, Mr(±)/Mr(//) was the same as that without the mask, and even when the substrate was rotated, the improvement in C-axis orientation due to the mask was observed. Figure 10 shows the rotation angle of the board 6°/aec
Mr(1)/Mr(//) of the film prepared in is shown.

[Example 5] Inner diameter 6 m, length 2 as shown in Figure 11 (a)
．． A mask 22 having a hateno-like structure in which cylinders 21 of 5 m and 4.5 wi were arranged in parallel as shown in FIG. Using this mask, film formation was performed under the same conditions as in Example 3. In figure ν, Mr (J-) /
The mask thickness dependence of Mr (tυ is shown. Even when this mask is used, the C-axis orientation is improved as in Example 3. Furthermore, as in Example 4, using this mask, the base surface,
In the above-mentioned shield, it is preferable that the square of the length of the tube is 200 times the average cross-sectional area of each tube vsoo.

[Example 6] A mask 23 shown in FIG. 13 was manufactured in which the small cylinder 21 used in Example 5 was tilted at 6 degrees with respect to the thickness direction of the mask. The diameter of the disc is 10 on.

The thickness is 2.5 mm or 4.5 m. Using this mask, a film was formed under the same sputtering conditions as in Example 4.

The substrate rotation angle is 6°/sec. As shown in FIG. 13, the small cylinder is set to be inclined in the direction of rotation of the substrate. Figure 14 shows a film produced without using a mask, and a film produced using a 7c mask used in Example 5 (in the figure,
Mr (±) / of the film produced using the mask shown in FIG.
Mr (//) (-v thickness 4.5 sam)k is shown.

The film produced using a mask has larger Mr (±) and /Mr (//) and improved C-axis orientation compared to a film that does not use a mask. Furthermore, even with a membrane using a mask,
For films using a tilted mask, use of a right-angled mask is more effective in terms of C-axis orientation. In addition, it is preferable that the inclination angle of the partition plate or hollow tube in the shield is 115 to 5 times the rotation angle per second of the substrate. [Example 7] Co-Cr l [ ' was created. Before deposition, thoroughly bake the chamber and
Xl0-7 Torr or less. An ion pump and a Ti sublimation pump were used as vacuum pumps. The substrate and evaporation source mass market a were heated using 155I, and an electron beam heating method was used as the heating method. Using a Co-Cr (Cr 20 at%) ingot produced by arc melting, the substrate temperature was 150°C and the deposition rate was 500°C.
; Corning 2 was used for the 0 board that was v4gM in 7 minutes.
The fcH cut mask (e
), (f) Mr (±) in 0 Figure 15 using k
/ Mr(//) shows mask viewing angle dependence. Compared to the film produced without using a mask, 7'CM produced using an H-cut mask does not suffer from collapse as much as the sputtering process, but
It can be seen that the H-cut mask has a large Mr(±)/Mr(tt) and improves the C-axis orientation even in the vacuum evaporation method.

As shown in Examples 1 and 2.7, when forming a thin film by a dry method, a shield is used to remove atoms incident on the substrate from directions deviating from the perpendicular direction, and a target or an evaporation source is used. When placed between the two, the orientation of the thin film is significantly improved. On the other hand, if the perpendicularly incident component is removed and a film is formed mainly of obliquely incident atoms, the orientation of the film will be significantly degraded. Therefore, in the present invention, it is an essential requirement to remove all obliquely incident atoms during film formation, and when this method is used, the orientation of the film is significantly improved. -Ru, Co-Cr film, by using the present invention, 5. As a result of improved C-axis orientation and improved crystalline magnetic anisotropy in the direction perpendicular to the film surface, there is a further advantage in producing media that can increase recording density. The manufacturing method had the disadvantage that it could only produce a film in which the M-H loop was not saturated even with an external magnetic field of 10 KOe, but by using the present invention, the external magnetic field could be reduced to 5 KOe.
A film that is saturated even with K Oe could be produced, making it possible to remove high-density inhibiting factors.

Examples 3 to 7 were attempted in order to make it possible to manufacture an all-magnetic disk according to the present invention. As I will state again here, the requirement of the present invention is to remove obliquely incident atoms, and the methods described in Examples 3 to 7 are just one example of this. It is clear that the method of installing the shield between the evaporation sources is applicable to the present invention regardless of the shape of the shield.

In addition, for shielding objects, those whose cross-sectional shape when cut at right angles to the axial direction has an arbitrary shape such as a circle, square, or ellipse, and are divided into two or more parts by a cutting board are used. It is clear that all of these are included in the present invention.

[Brief explanation of drawings]

Figure 1 shows a mask that controls the direction of incidence of atoms incident on the substrate, and (a), (b), and (c) are masks that remove vertically incident components; s (d), (e) t
(f) is a mask that removes obliquely incident components;
X-ray diffraction of Co-Ru
(b) is the diffraction pattern of the Co-Ru vine film produced without using a mask.
Mask viewing angle dependence of sputtered film Ixoio/I 0002, Figure 4 shows mask viewing angle dependence of diffraction line intensity 10002/d per unit film thickness when using H-cut mask, Figure 5 shows H-cut mask. Figure 6 shows the mask viewing angle dependence of the ratio of residual magnetization in the in-plane direction to the perpendicular direction in a Co-Ru snow film when using a C6-Ru film. In the diagrams, (a) is the M-H loop of nine films made without using a mask, (b) is the M-H loop of (f) the film made with a mask, and Figure 7 is the H cut. Mask viewing angle dependence of the ratio of residual magnetization in the in-plane direction to the vertical direction in a Co-Cr snow ivy film when using a mask, 8th
Figure 1'' shows a mask with a No-Tinos-like structure provided with multiple partition plates in the hollow direction of the tube, and Figure 9 shows the vertical direction of the Co-Ru sputtered film when using the mask shown in Figure 8. Figure 10: Mask thickness dependence of the ratio of residual magnetization in the in-plane direction to Mask thickness dependence of the ratio of the residual magnetization in the in-plane direction to the direction, Figure 1L G) is the lower tube constituting the mask, (B) is a mask in which w of (A) is arranged in parallel, 12th
The figure shows the Co-
The mask thickness dependence of the ratio of residual magnetization in the in-plane direction to the perpendicular direction in a dynamic spatter film, FIG. 13 shows another example of a mask using a hollow tube, and FIG. 14 shows FIGS.
Co-Ru sputtered film using the mask shown in Figure 3,
Figure 15 shows the ratio of residual magnetization in the in-plane direction to the perpendicular direction of the Co-Ru sputtered film produced without using a mask.
The ratio of residual magnetization in the in-plane direction to the perpendicular direction in the Co--Cr vaporized film when using the masks (e) and (f) shown in FIG. 1 is shown. 1... Disc, 2... Legs, 11...
...Cylinder, L...Shikiri plate, 21...
・Cylinder, 22...Mask, 23...Mask Figure 1 (a) (b) (c) (d)
(e) (f) Fig. 2 2e (,ri 2e (71) Fig. 3 Mask angle (cliff) Fig. 6 Fig. 7 Fig. 813IO Fig. 9 Mask 4 (mm) Fig. 10 Mask 4 (mm ) Figure 11 (a) (b) Figure 12 Mask 4 (mm) Figure 13yA Figure 145A Figure 15 E included and angle (degrees) Ministry of Procedure and Correction (self-motivated) 1930 Corridor 12 21 Commissioner of the Patent Office Shima 1) Spring 411 Lord 1, Indication of the case 1982 Special WLF Application No. 165684 2, Name of the invention Method for producing thin film 3, Relationship with the person making the amendment Patent applicant name (422) Nippon Electric @ Tokina Public Corporation 4 , Agent 〒160 Specification rIl #Claims” and “Detailed Description of the Invention” - 6. Contents of amendments as shown in Attachment 1, Special Ilr!l-Silver ice yoke as follows: Corrected to 1.
A method for manufacturing a thin film, which is characterized in that a shield for removing all atoms incident from a direction perpendicular to the substrate is installed between the substrate and the terkelat or evaporation source. (2) A method for producing a thin film according to claim 1, characterized in that the film shape is I! Department,
Is it possible to use a hatenose-like shield with a plurality of baffles installed in the length direction of the tube, or a hatenose-like shield with a plurality of hollow tubes with arbitrary external shapes arranged in parallel? !
The method for producing a thin film according to claim 1, wherein the thin film has a f-character. (4) In a structure in which the circular part of the pipe is divided by a sill plate, the square of the length of the pipe is divided by ρ by the sill plates, and the average area divided by nfCvh is 11
Claim 1, characterized in that: installing a shield having a value of 11500 to 200 times 11;
IR manufacturing method of thin film described in Section 3 0 (5) A hollow W having an arbitrary external shape? It is characterized by installing a shielding object having a housing in which the square of the tube length is 11,500 to 200 times the average cross-sectional area of the six tubes, based on a plurality of hateno-shaped shields arranged in parallel. A method for producing a thin film according to claims 1 and 3. (6) In a Hateno-like shielding structure in which the inner S of the tube is divided by a partition plate, or in a Hateno-shaped shielding structure in which a plurality of hollow tubes are arranged in parallel, the partition plate or the hollow The first and third terms of the range of % depression, characterized in that the tube has a structure that is tilted in the direction of substrate rotation from the vertical direction of the substrate by 115 to 5 times the rotation angle per second of the substrate. Method for producing a thin film according to Items 4 and 5 (7) A thin film according to a patent claim, characterized in that a perpendicular magnetic anisotropic thin film of a cobalt alloy whose main components are cobalt-ruthenium and cobalt-chromium is produced. A method for producing a thin film according to items 1 to 6. ”2. It is corrected as r ZnL] jt= l ZnOJ on page 3, line 12 of the specification. 3. From the center P of the 1st board, page 8, line 7, delete all 0

Claims (7)

[Claims] (1) Sputtering method, Ji4 air vaporization 7/jif:
, a thin film is entirely fabricated using a dry formation method such as the ion routing method, and a shield is installed between the private plate and the target or evaporation source to remove atoms incident from the direction perpendicular to the substrate. A method for producing a thin film, characterized by: (2) The method for manufacturing a thin film according to claim 1, wherein the substrate is rotated during film formation. (3) A 71 tenos-shaped shield, which has a hollow tube with an arbitrary external shape and is provided with a board in the length direction of the shrine;
Alternatively, manufacturing a thin film according to the first item of the claims, which has an arbitrary external shape and uses a shielding member in the shape of a cylindrical shape in which 1 of 1 is arranged in parallel with multiple gold ribs. Method. (4) In a Hananos-like shield having rLfc Sakaki slack divided by an internal sill plate, the height of the mount is measured. Claim 1, characterized in that a shield is installed whose square value is 11,500 to 200 times the average value of the divided area of the portion divided by the partition plate,
The method for producing a thin film according to item 3. (5) In a Hateno-like shield VC in which mantissas of hollow tubes with arbitrary external shapes are arranged in parallel, the square of Miya's Naga-O is 1. A method for selecting a thin film as described in paragraphs 1 and 3 above, characterized in that it completely defeats all shielding objects. (6) A cylindrical shield with a structure in which the inside of the tube is divided by a partition plate, or a cylindrical shield with a structure in which multiple hollow tubes are arranged in parallel. The plate plate or hollow tube rotates in the direction of substrate rotation, with a rotation angle of 115 ml for 1 second per 7c9 from the substrate vertically.
The method for manufacturing a thin film according to claims 1, 3, 4, and 5, characterized in that the structure has a structure tilted by a factor of ~5. (7) Is it possible to produce a perpendicular magnetic/anisotropic cobalt alloy thin film with cobalt-ruthenium or cobalt-chromium as the main components? Features Claims 1 to 6
Method for manufacturing the thin film listed in Section BG.