JP2014173106A - Deposition preventive plate for vacuum film deposition apparatus, vacuum film deposition apparatus, and vacuum film deposition method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deposition preventive plate for a vacuum film deposition apparatus which has an excellent separation preventive effect for film deposition material even when evaporation is repeated, a manufacturing method of the deposition preventive plate, a vacuum film deposition apparatus using the deposition preventive plate, and a vacuum film deposition method.SOLUTION: In a vacuum film deposition apparatus, a deposition preventive plate for the vacuum film deposition apparatus is provided for preventing film deposition material from attaching to an unnecessary place, which is made of aluminum, has a surface with an uneven structure formed including a concavity part with an average opening diameter of 0.01 - 9 μm, and has multiple projections arranged on the surface, which have an average height of 30 - 1000 μm, and an average density of 10 pieces/10 mm square or more, and in which a bottom area ratio of the projections is more than 90% in a 10 mm square area.

Description

  The present invention relates to an adhesion-preventing plate used in a vacuum film-forming apparatus such as a vacuum vapor deposition apparatus or a sputtering apparatus, and more particularly to an adhesion-preventing plate for a vacuum film-forming apparatus that can prevent peeling of attached film-forming material.

Vacuum deposition equipment such as sputtering equipment is equipped with a deposition plate (a deposition sheet) around the substrate to be deposited in order to prevent contamination due to deposition of deposition materials on the inner wall of the vacuum chamber and various components. ing.
It is known to form irregularities on the surface of such a deposition preventing plate from the viewpoint of preventing the peeling of the deposited film forming material and suppressing the generation of particles due to the peeling of the film forming material.

  For example, Patent Document 1 states that “a metal sheet base material that has a first surface and can be bent into an arbitrary shape, and is formed on the first surface and has an island shape in the first surface. A film forming apparatus sheet comprising a plurality of protrusions distributed on the surface, and uneven portions formed on the first surface and the surface of the protrusions ([Claim 1]). Further, it is described that the protruding portion is formed by embossing and the uneven portion is formed by blasting ([Claim 2] [Claim 3]).

JP 2012-153842 A

  However, it has been clarified that the film forming apparatus sheet (protection plate) described in Patent Document 1 may not have a sufficient effect of preventing the film forming material from being peeled off when repeated deposition is performed.

  Accordingly, the present invention provides an adhesion preventing plate for a vacuum film forming apparatus that is excellent in the effect of preventing the peeling of the film forming material even when deposition is repeated, a manufacturing method thereof, a vacuum film forming apparatus using the adhesion preventing plate, and a vacuum forming apparatus. An object is to provide a membrane method.

As a result of earnest research to achieve the above object, the inventor has a surface on which an uneven structure including a recess having a specific average opening diameter is formed, and a plurality of protrusions having a specific average height are formed on the surface. By arranging at a predetermined ratio, it was found that the effect of preventing the film-forming material from peeling off was increased even when deposition was repeated, and the present invention was completed.
That is, it has been found that the above object can be achieved by the following configuration.

(1) In a vacuum film forming apparatus, a deposition plate for a vacuum film forming apparatus for preventing adhesion of a film forming material to an unnecessary position,
Made of aluminum,
It has a surface on which a concavo-convex structure including recesses having an average opening diameter of 0.01 to 9 μm is formed,
A plurality of protrusions having an average height of 30 to 1000 μm are arranged on the surface,
The average density of the protrusions is 10 pieces / 10 mm square or more,
A deposition preventing plate for a vacuum film-forming apparatus, wherein the ratio of the bottom area of the protruding portion is more than 90% in a 10 mm square region.
(2) The deposition plate for a vacuum film forming apparatus according to (1), wherein the outer shape of the protruding portion when viewed from above in the vertical direction is a rhombus, a rectangle, or a circle.
(3) The concavo-convex structure is a concavo-convex structure including a concave portion having an average opening diameter of 0.5 to 9 μm, or a concavo-convex structure including a concave portion having an average opening diameter of 0.01 to 0.3 μm (1) or (2) 2. An adhesion-preventing plate for a vacuum film-forming apparatus as described in 1.
(4) The concavo-convex structure is a concavo-convex structure in which a concavo-convex structure including concave portions having an average opening diameter of 0.01 to 0.3 μm is superimposed on a concavo-convex structure including concave portions having an average opening diameter of 0.5 to 9 μm. The deposition preventing plate for a vacuum film-forming apparatus according to any one of (1) to (3).
(5) The deposition preventing plate for a vacuum film forming apparatus according to any one of (1) to (4), wherein the surface is composed of an anodized film of aluminum.
(6) The deposition preventing plate for a vacuum film forming apparatus according to any one of (1) to (5), wherein the surface has a crack.
(7) The deposition preventing plate for a vacuum film forming apparatus according to any one of (1) to (6), wherein the protrusion is formed by embossing.
(8) The deposition structure for a vacuum film forming apparatus according to any one of (1) to (7), wherein a concavo-convex structure including a concave portion having an average opening diameter of 0.01 to 9 μm is formed by an electrochemical roughening treatment. Board.

(9) In a vacuum film forming apparatus, a manufacturing method for manufacturing a deposition plate for a vacuum film forming apparatus for preventing adhesion of a film forming material to an unnecessary position,
An uneven surface forming step of performing an electrochemical surface roughening treatment on the surface of the aluminum plate and forming an uneven structure including recesses having an average opening diameter of 0.01 to 9 μm on the surface;
The manufacturing method which has a protrusion part formation process which gives the embossing to the surface of an aluminum plate, and forms several protrusion part with an average height of 30-1000 micrometers in a part of surface.
(10) The method for producing a deposition-preventing plate for a vacuum film-forming apparatus according to (9), further comprising an anodizing treatment step of forming an aluminum anodized film on the surface after an unevenness forming step.
(11) The manufacturing method of the deposition prevention board for vacuum film-forming apparatuses as described in (9) or (10) which has an annealing treatment process which performs an annealing process after a protrusion part formation process.

  (12) A vacuum film forming apparatus having the deposition preventive plate for a vacuum film forming apparatus according to any one of (1) to (8).

  (13) Using the vacuum film-forming apparatus having the vacuum film-forming apparatus deposition plate according to any one of (1) to (8), Ti, Zr, Nb, Ta, One element selected from Cr, Mo, W, Pt, Au, Ag, Fe, Ni, Mn, Sn, Zn, Co, Al, Cu and Si, or an alloy, nitride or oxide thereof is formed. Vacuum film forming method for film formation.

  According to the present invention, the deposition preventing plate for a vacuum film forming apparatus that is excellent in the effect of preventing the peeling of the film forming material even when deposition is repeated, the manufacturing method thereof, the vacuum film forming apparatus using this deposition preventing plate, and the vacuum deposition A membrane method can be provided.

It is a figure which shows notionally an example of the vacuum film-forming apparatus of this invention. It is a perspective view which shows an example of the deposition preventing plate for vacuum film-forming apparatuses of this invention. It is a schematic diagram which shows the external shape when the protrusion part arranged on the surface of the vacuum-adhesion board for vacuum film-forming apparatuses shown in FIG. 2 is seen from the perpendicular direction upper direction. It is typical sectional drawing which shows an example of the uneven structure and protrusion part in the surface of the adhesion-preventing board for vacuum film-forming apparatuses of this invention. It is typical sectional drawing which shows an example of the uneven structure in the surface of the adhesion prevention board for vacuum film-forming apparatuses of this invention. It is typical sectional drawing which shows another example of the uneven structure in the surface of the adhesion prevention board for vacuum film-forming apparatuses of this invention. It is a typical perspective view explaining the crack formed in the protrusion part. It is the electron micrograph which image | photographed the surface of the adhesion prevention board produced in Example 1 with the high resolution scanning electron microscope (SEM) (50-times multiplication factor). It is the electron micrograph which image | photographed the surface (uneven | corrugated structure) of the adhesion prevention board produced in Example 1 with the high resolution scanning electron microscope (SEM) (magnification 350 times). FIGS. 10A and 10B are electron micrographs obtained by photographing the apex and the slope at the protruding portion of the deposition preventive plate produced in Example 1 with a high-resolution scanning electron microscope (SEM) (magnification 2000 times), respectively. is there.

In the following, preferred embodiments of the vacuum deposition apparatus for vacuum film-forming apparatus and the method for producing the same, and the vacuum film-forming apparatus and vacuum film-forming method using this deposition board will be described in detail.
First, the feature point compared with the prior art of this invention is explained in full detail.
As described above, one of the features of the present invention has a surface on which a concavo-convex structure including a concave portion having a specific average opening diameter is formed, and a plurality of protrusions having a specific average height are predetermined on the surface. It is the point which is arranged in the ratio of. The inventor presumes the reason why the effect of the present invention is obtained as follows. Note that the scope of the present invention is not limitedly interpreted by this estimation.
That is, since the concave portion having an average opening diameter of 0.01 to 9 μm included in the concavo-convex structure holds the film forming material adhering to the adhesion preventing plate very strongly, even if the adhering material is thin, it is peeled off. It is considered that the generation of particles due to the can be suppressed.
Further, protrusions having an average height of 30 to 1000 μm are generated in the base material and the film forming material of the deposition plate due to the residual stress of the film deposition material adhering to the deposition plate, particularly the temperature change (thermal cycle) due to repeated vapor deposition. Since stress due to thermal expansion can be relieved, it is considered that generation of particles due to peeling can be suppressed even when deposition is repeated. Specifically, by allowing this protrusion to exist over most of the surface, it is possible to expand and contract in an isotropic direction (isotropic property), and as a result, the component adhered to the base material and the anti-adhesion plate of the anti-adhesion plate. It is considered that deformation and peeling due to the warp of the film forming material due to the residual stress (internal stress) of the film material can be prevented.
According to the present invention having such characteristics, it is possible to stably produce a high-quality product that is free from product defects and quality degradation caused by particles peeled off from the deposition preventing plate adhering to the substrate.
Therefore, according to the present invention, in the manufacture of semiconductor devices and electronic component materials using the vacuum film formation method, the product yield is prevented by preventing the occurrence of product defects due to the particles peeled off from the deposition preventive plate. Improvement of productivity, improvement of productivity, reduction of production cost, etc. can be aimed at.

  In the following, first, the vacuum film forming method and the vacuum film forming apparatus of the present invention will be described, and thereafter, the deposition preventing plate for the vacuum deposition apparatus of the present invention (hereinafter abbreviated as “an adhesion preventing plate” of the present invention) and. The manufacturing method will be described in detail.

[Vacuum film forming method and vacuum film forming apparatus]
FIG. 1 conceptually shows an example of a vacuum film forming apparatus of the present invention, which implements an example of the vacuum film forming method of the present invention.

A vacuum film forming apparatus 10 of the present invention shown in FIG. 1 is an apparatus for forming a film on the surface of a substrate Z as a film forming member by vacuum vapor deposition, and has a deposition plate 12 of the present invention to be described later. .
Moreover, the vacuum film-forming method of the present invention uses the vacuum film-forming apparatus 10 of the present invention having the adhesion-preventing plate 12 of the present invention to form Ti, Zr, Nb, Ta, Cr, Mo, Film formation for forming one element selected from W, Pt, Au, Ag, Fe, Ni, Mn, Sn, Zn, Co, Al, Cu and Si, or an alloy, nitride or oxide thereof. Is the method.

Here, the vacuum film forming method and the vacuum film forming apparatus of the present invention are not limited to those which form a film on the surface of the substrate Z by vacuum vapor deposition as shown in the illustrated example.
That is, the vacuum film forming method and the vacuum film forming apparatus of the present invention include various known CVD (chemical vapor deposition) and PVD (physical vapor) methods such as sputtering, CVD, plasma CVD, and ion plating. Deposition can be applied to vacuum deposition by physical vapor deposition.
Similarly, in the vacuum film forming method and the vacuum film forming apparatus of the present invention, the film forming conditions are not particularly limited, depending on the film forming method, the film to be formed, the film forming rate, the film thickness of the film to be formed, and the like. And may be set as appropriate.

As shown in FIG. 1, a vacuum film forming apparatus 10 according to the present invention includes a vacuum chamber 14, a vapor deposition source 16 and a substrate holder 18 disposed in the vacuum chamber 14, and a vacuum pump, as in a known vacuum vapor deposition apparatus. And 20.
And the vacuum film-forming apparatus 10 of this invention covers the inner wall face of the vacuum chamber 14, and the adhesion prevention board 12 of this invention is provided.

Here, the vacuum film forming apparatus 10 of the present invention is basically the same as a known vacuum deposition apparatus except that the deposition preventing plate 12 of the present invention is used. This is the same even when applied to other vacuum film forming apparatuses (methods) such as a sputtering apparatus and a plasma CVD apparatus.
Therefore, in the vacuum film forming apparatus 10 of the present invention, the vapor deposition source 16 is a known vapor deposition source (evaporation source) that is filled with a film forming material and melts and evaporates. The substrate holder 18 is also a known substrate holder that holds the substrate Z by a known means. Further, the vacuum pump 20 is also a known vacuum pump for evacuating the vacuum chamber 14 and maintaining a predetermined film forming pressure.
Moreover, the vacuum film-forming apparatus 10 of this invention may have a rotation means which rotates the substrate holder 18 (substrate | substrate Z) as needed (rotation, revolution, self-revolution).

As described above, the vacuum film forming apparatus 10 of the present invention covers the inner wall surface of the vacuum chamber 14 and is provided with the deposition preventing plate 12 of the present invention.
In the illustrated example, as the adhesion preventing plate 12, an upper surface adhesion preventing plate 12a covering the upper surface (ceiling surface) in the vacuum chamber 14, a side adhesion preventing plate 12b covering the same side surface, and a lower surface covering the same lower surface (floor surface). A protection plate 12c is provided.

In a preferred embodiment, the vacuum film forming apparatus 10 in the illustrated example covers almost the entire inner wall surface of the vacuum chamber 14 with the deposition preventing plate 12 of the present invention, except for the region corresponding to the substrate holder 18 and the vapor deposition source 16. .
The present invention is not limited to this. For example, only the side surface protection plate 12b may be provided, or only the top surface protection plate 12a may be provided.
However, in order to more suitably prevent the deposition and deposition of the film forming material, at least the surface facing the vapor deposition source 16 (the space where the film forming material exists) in the vacuum chamber 14, that is, the upper surface protection plate 12a. It is preferable to cover the inner wall surface of the vacuum chamber 14 with the deposition preventing plate 12 of the present invention as much as possible.
Further, since the deposition preventive plate 12 of the present invention is made of aluminum, when a metal film such as Au or Pt or an alloy film is formed on the substrate Z, the deposition material attached to the deposition preventive plate 12 is separated. And can be recovered. For this reason, it is advantageous to cover the inner wall surface of the vacuum chamber 14 with an anti-adhesion plate as much as possible in terms of the recovery rate of the film forming material that has not been formed on the substrate Z.

  Moreover, in the vacuum film-forming method and the vacuum film-forming apparatus of the present invention, there is a possibility that film-forming materials other than the inner wall surface of the vacuum chamber 14 such as the back surface of the substrate holder 18 adhere and deposit as necessary. The part may be covered with the deposition preventing plate 12 of the present invention.

In the vacuum film forming apparatus 10 of the present invention, there is no particular limitation on the method of attaching the deposition plate 12, and a known plate-like object or sheet shape that is used as a method of attaching the deposition plate in the vacuum deposition apparatus. Various attachment methods can be used.
As an example, a method of adhering the deposition preventing plate 12 in the vacuum chamber 14 using an adhesive tape having sufficient heat resistance such as Kapton tape is exemplified. In addition, a known mechanical plate-like or sheet-like attachment method such as a method using a screw or an attachment jig or a method using a hook or the like can be used. Further, when the deposition preventing plate 12 is a cylindrical object having sufficient rigidity, the deposition preventing plate 12 is attached in the vacuum chamber 14 by surrounding the evaporation source and placing it on the lower surface of the vacuum chamber 14. Also good.

[Protection plate]
The adhesion-preventing plate of the present invention is an adhesion-preventing plate for a vacuum film forming apparatus for preventing adhesion of a film forming material to an unnecessary position in the vacuum film forming apparatus, and is made of aluminum and has an average opening diameter of 0. This is an adhesion-preventing plate having a surface on which a concavo-convex structure including recesses of 0.01 to 9 μm is formed, and a plurality of protrusions having an average height of 30 to 1000 μm arranged on the surface.
Next, the adhesion prevention board of this invention is demonstrated using FIGS.

<Overall configuration>
As shown in FIGS. 2 and 4, the deposition preventing plate 12 of the present invention has a surface on which an uneven structure 30 including recesses having an average opening diameter of 0.01 to 9 μm is formed, and an average height on this surface. A plurality of protrusions 40 of 30 to 1000 μm are arranged at a predetermined ratio.

<Base material>
The adhesion-preventing plate 12 of the present invention is not particularly limited as long as it is made of aluminum made of pure aluminum or an aluminum alloy, and the shape thereof is preferably plate-shaped or sheet-shaped as shown in FIG.
Here, as an aluminum base material, various aluminum plate-like materials and sheet-like materials such as an aluminum foil commercially available as a deposition preventing plate for a vacuum film forming apparatus can be used.
In addition, the aluminum constituting the base material has a purity of 97% or more in order to prevent impurities in the aluminum from being mixed into the recovered material and reducing the purity of the recovered material when recovering the deposit. Is preferable, 98% or more is more preferable, 99% or more is further preferable, and 99.5% or more is particularly preferable.

The thickness of the deposition preventing plate 12 of the present invention is not particularly limited, and the configuration of the vacuum film forming apparatus to be mounted, the method of using the deposition preventing plate (disposable type or the type to be reused after washing), the deposition preventing plate. According to the size, film forming method, film forming conditions, etc., sufficient mechanical strength and thermal strength can be secured, and a thickness that is easy to handle when mounting in the vacuum chamber 14 is appropriately set. You only have to set it.
Considering the ease of handling and workability, the ease of collecting the film forming material, etc., the thickness of the deposition preventing plate 12 of the present invention is preferably about 30 to 300 μm.

<Uneven structure>
The concavo-convex structure 30 including a recess having an average opening diameter of 0.01 to 9 μm (excluding a recess due to a micropore formed in an anodic oxide film described later) constitutes the surface of the deposition preventing plate 12 of the present invention. It is.
Here, as shown in FIG. 5, the opening diameter of the recessed part 30a is the diameter of the recessed part 30a (circumferential continuous circumference forming the recessed part 30a), and the average opening diameter is an average thereof.
Specifically, using an electron microscope, the surface of the deposition preventing plate 12 was photographed from directly above at a magnification of 2000 to 30000 times, and in the obtained electron micrograph, at least 50 concave portions 30a that are connected in a ring shape are provided. The diameter is extracted, the diameter (or the diameter of a circle inscribed in the concave portion 30a) is read and set as the opening diameter, and the average opening diameter is calculated.
Further, the concavo-convex structure including the concave portion may be a corrugated structure as shown in FIG. 5 (A), and the convex portion is constituted by a flat portion on the surface as shown in FIG. 5 (B). The concave structure may be a repeated structure.

  The deposition preventive plate 12 of the present invention has a film-forming material attached to the deposition preventive plate as described above by having the concave / convex structure 30 including the concave portions 30a having an average opening diameter of 0.01 to 9 μm on the surface. Therefore, the generation of particles due to peeling can be suppressed.

In the present invention, the uneven structure 30 including the recesses 30a having the average opening diameter of 0.01 to 9 μm is the unevenness including the recesses having the average opening diameter of 0.5 to 9 μm because the effect of preventing the peeling of the film forming material is further improved. A structure (hereinafter also referred to as “medium wave structure”), a concavo-convex structure including recesses having an average opening diameter of 0.01 to 0.3 μm (hereinafter also referred to as “small wave structure”), or a combination thereof. It is preferable that it is a structure.
Of these, a structure in which a medium wave structure and a small wave structure are overlapped is preferable. Specifically, as shown in FIG. 6, the medium wave structure 32 including the recesses 32 a having an average opening diameter of 0.5 to 9 μm. Furthermore, a mode in which a small wave structure 34 including a concave portion 34a having an average opening diameter of 0.01 to 0.3 μm is preferably mentioned.
Here, the average opening diameter of the recesses 32a in the medium wave structure 32 is obtained by photographing the surface of the deposition preventing plate from directly above at a magnification of 2000 using an electron microscope. In the obtained electron micrograph, the periphery is circular. At least 50 consecutive recesses 32a (excluding the recesses 34a in the overlapping small wave structure 34) are extracted, and the diameter (or the diameter of a circle inscribed in the recess 32a) is read as an opening diameter to calculate an average opening diameter. To do.
Similarly, the average opening diameter of the concave portion 34a in the small wave structure 34 is obtained by photographing the surface of the deposition preventing plate from directly above at a magnification of 10,000 to 30,000 times using an electron microscope. At least 50 recesses 34a (excluding the recesses 32a in the overlapping medium wave structure 32) are extracted, and the diameter (or the diameter of a circle inscribed in the recess 34a) is read as the opening diameter, and the average opening diameter Is calculated.

(Medium wave structure)
In the present invention, the average opening diameter of the recesses 32a constituting the medium wave structure 32 is preferably 0.5 to 5 μm, more preferably 1 to 5 μm, because the effect of preventing the film-forming material from peeling off is further improved. More preferably, it is 5-3 micrometers.
Further, the depth of the concave portion 32a constituting the medium wave structure 32 is not particularly limited. In addition, since the deposition preventing plate of the present invention forms an uneven structure by subjecting the aluminum plate to an electrochemical roughening treatment, as shown in a manufacturing method of the deposition preventing plate described later, the depth of the recess 32a is reduced. This is considered to be substantially equal to the opening diameter of the recess 32a.

(Small wave structure)
In the present invention, the average opening diameter of the recesses 34a constituting the small wave structure 34 is preferably 0.1 to 0.2 μm because the effect of preventing the film-forming material from peeling off is further improved.
For the same reason, the average of the ratio of the depth to the opening diameter of the recesses 34a constituting the small wave structure 34 is preferably 0.2 to 0.5.
Here, the average of the ratio of the depth to the opening diameter in the recess 34a is obtained by photographing the fractured surface of the adhesion-preventing plate at a magnification of 50000 times using a high-resolution scanning electron microscope (SEM). At least 20 recesses are extracted, the aperture diameter and depth are read, the ratio is obtained, and the average value is calculated.

The arithmetic average roughness Ra of the surface (uneven structure 30) of the deposition preventing plate 12 of the present invention is not particularly limited, and is preferably 0.25 to 0.60 μm, and preferably 0.30 to 0.60 μm. More preferably, it is 0.30 to 0.55 μm.
Here, the surface roughness Ra is an arithmetic average roughness based on JIS B0601: 2001, measured using a stylus type surface roughness meter (for example, a surface roughness measuring machine SJ-401 manufactured by Mitutoyo Corporation). That's it.

<Projection>
The plurality of protrusions 40 having an average height of 30 to 1000 μm are arranged at a predetermined ratio on the surface of the deposition preventing plate 12 of the present invention.
Here, as shown in FIG. 4, the height of the protrusion 40 is a distance from the bottom surface 40a of the protrusion 40 to the top side (vertex 40b), and the average height is an average thereof. As shown in FIGS. 2A, 4, 7, and 8, the protrusion 40 has an inclined structure, that is, a mountain-like structure having a ridge line (reference numeral 40 c in FIGS. 4 and 7). The height in that case refers to the distance from the bottom to the apex.
Specifically, using a high-resolution scanning electron microscope (SEM), the cross section of the deposition preventing plate 12 was photographed at a magnification of 50 to 100 times, and at least 20 protrusions 40 were extracted from the obtained electron micrograph. And the average value of the height is calculated.
In the present invention, the average height of the protrusions 40 is preferably 100 to 500 μm because the effect of preventing the film-forming material from peeling off is further improved.

The outer shape of the protrusion 40 as viewed from above in the vertical direction is not an indeterminate shape but a rhombus (see FIGS. 3 and 8), a rectangle, or a circle because the effect of preventing the peeling of the film forming material is further improved. Among them, a rhombus is more preferable.
Here, if the outer shape of the protruding portion is a fixed shape, the effect of reducing the residual stress of the film forming material adhering to the deposition preventing plate becomes uniform, and the effect of preventing the film forming material from peeling off tends to be improved.

Moreover, the average density of the protrusions 40 is 10 pieces / 10 mm square or more, and it is preferably 10-100 pieces / 10 mm square, for the reason that the peeling prevention effect of the film forming material is further improved, and 30-100 pieces. / 10 mm square is more preferable, and 50 to 90 pieces / 10 mm square is more preferable.
Here, the average density of the protrusions 40 may be calculated as an average value obtained by measuring the number of protrusions in a 10 mm square (10 mm × 10 mm) region at any five locations and dividing the total value by five. it can.

Further, the ratio of the bottom area of the protrusion 40 is more than 90% in a 10 mm square region, and is 95 to 100% because the effect of preventing the peeling of the film forming material is further improved even when the deposition is repeated. Is preferred.
Here, the bottom area of the protrusion 40 refers to the area of the bottom of the protrusion 40 shown in FIG. 2, for example, the portion indicated by the wavy line in FIG. 4, and the ratio is a 10 mm square region, that is, 100 mm ² . It refers to the proportion of the bottom area of the protrusion 40 in the area, and in the present invention, it refers to the average value at any five locations.

  As described above, the deposition preventing plate 12 of the present invention adheres to the deposition preventing plate as described above by uniformly arranging the plurality of protrusions 40 having an average height of 30 to 1000 μm at the ratio of the predetermined average density and the bottom area described above. Since it is possible to relieve the residual stress of the deposited material, it is considered that the generation of particles due to peeling can be suppressed even when the deposition is repeated.

<Anodized film>
The surface of the deposition preventing plate 12 of the present invention is preferably composed of an anodized aluminum film.
By being composed of an anodized film, a large number of micropores called micropores can be retained on the surface. As a result, a higher anchor effect is obtained, and the adhesion strength is increased, so that the film-forming material attached to the deposition preventing plate 12 can be more suitably prevented from peeling.
Although there is no limitation in the thickness of an anodized film, 0.05-30 micrometers is preferable and especially 0.25-5 micrometers is preferable. By making the thickness of the anodic oxide film within the above range, the effect of having the anodic oxide film on the surface of the deposition preventive plate can be obtained more suitably, and the film forming material is peeled off from the deposition preventive plate. Thus, the generation of particles can be more suitably prevented.

<Crack>
The deposition preventing plate 12 of the present invention preferably has a crack on the surface thereof.
By having a crack on the surface, the film forming material attached to the deposition preventing plate 12 enters the crack, and the adhesion strength is increased, so that peeling of the film forming material adhered to the deposition preventing plate 12 can be more suitably prevented.
In the present invention, for the reason that peeling of the film forming material can be more preferably prevented, as shown in FIG. It is more preferable to have in the vicinity of the apex 40b and the inclined surface 40d.
Here, the crack is preferably a linear crack having a width of 0.05 to 20 μm, and the length thereof is 0.5 μm or more and not more than the peripheral diameter (for example, about 4 mm) of the protruding portion. Is preferred.
Moreover, it is preferable to have one or more such cracks, and more preferably ten or more.

[Manufacturing method of deposition prevention plate]
The manufacturing method of the deposition preventing plate of the present invention is a manufacturing method for manufacturing the deposition preventing plate of the present invention described above, and includes a concavo-convex forming step for forming the concavo-convex structure and a protruding portion forming step for forming the protruding portion. It is a manufacturing method.
In addition, in this invention, although the unevenness | corrugation formation process and a protrusion part formation process do not ask | require the order, it is preferable that it is an aspect which performs a protrusion part formation process after an unevenness | corrugation formation process.

<Roughness formation process>
The concavo-convex forming step is a step in which the surface of the aluminum plate is subjected to an electrochemical roughening treatment to form the concavo-convex structure including the concave portions having the average opening diameter of 0.01 to 9 μm on the surface.
Examples of the electrochemical surface roughening treatment include a method of performing an electrolytic treatment with an alternating current using an electrolytic solution containing hydrochloric acid or nitric acid.

Specifically, in order to obtain the above-described uneven structure having a medium wave structure, the total amount of electricity involved in the anode reaction of the aluminum substrate at the time when the electrolytic reaction is completed is 1 to 1000 C / dm ² . Is preferable, and it is more preferable that it is 50-300 C / dm < ² >. The current density is preferably ²⁰ to 100 A / dm2.
More specifically, for example, the treatment is preferably performed in an electrolyte solution containing 0.1 to 50% by mass of hydrochloric acid or nitric acid at a temperature of 20 to 80 ° C. and a time of 1 second to 10 minutes.

Further, in order to obtain the above-described concave / convex structure of the small wave structure, it is preferable to perform treatment using an electrolytic solution containing hydrochloric acid, and specifically, to participate in the anodic reaction of the aluminum substrate when the electrolytic reaction is completed. total amount of electricity is, is preferably from 1~100C / dm ^2, and more preferably 20~70C / dm ^2. The current density at this time is preferably ²⁰ to 50 A / dm ² .
More specifically, for example, the treatment is preferably performed in an electrolytic solution containing 0.1 to 10% by mass of hydrochloric acid at a temperature of 20 to 80 ° C. and a time of 1 second to 10 minutes. Note that it is also possible to form a small wave structure superimposed on a medium wave structure in the same process with an electrolyte containing hydrochloric acid.

  In addition, an uneven surface structure in which a small wave structure is superimposed on the above-described medium wave structure is obtained by performing an electrochemical surface roughening process in which an aluminum base material is electrolytically treated using a mixed solution of hydrochloric acid and sulfuric acid. Can be formed.

<Projection formation process>
The protruding portion forming step is a step of embossing the surface of the aluminum plate to form the plurality of protruding portions having the average height of 30 to 1000 μm described above on part or all of the surface.
Here, the embossing may be, for example, press working, but in the present invention, the embossing roll described in paragraphs [0012] to [0033] of JP-A-2005-205444 is used. Roll forming is preferred.

<Anodizing process>
The anodizing process is an arbitrary process in which an anodizing process is performed after the above-described unevenness forming process to form an anodized aluminum film over the entire surface. The anodizing process may be a pre-process or a post-process of the protrusion forming process described above, but is a pre-process of the protrusion forming process for the reason of forming the crack described above on the surface. Is preferred.
By this step, an anodic oxide film that is an arbitrary configuration of the deposition-preventing plate of the present invention can be formed.

What is necessary is just to perform the anodic oxidation of the surface of a deposition preventing plate by a well-known method.
Specifically, a method of energizing an aluminum plate as an anode in a solution having a sulfuric acid concentration of 50 to 300 g / L and an aluminum concentration of 5% by mass or less is suitably exemplified.
As the solution used for the anodizing treatment, not only sulfuric acid but also phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid, etc. may be used alone or in combination of two or more. it can.
The preferred conditions for the anodizing treatment vary depending on the electrolyte used, but in general, the electrolyte concentration is 1 to 80% by mass, the solution temperature is 5 to 70 ° C., the current density is 0.5 to 60 A / dm ² , and the voltage is 1 What is necessary is just to adjust suitably so that it may be 100V and electrolysis time is 15 second-about 50 minutes, and the desired amount of anodic oxide films can be formed.

<Annealing process>
An annealing treatment process is an arbitrary process which performs an annealing treatment (annealing treatment) in a vacuum atmosphere or air after the above-mentioned projection formation process.
This process improves the workability of the deposition plate and facilitates deformation and drilling along the inner wall surface of the vacuum chamber. As a result, abnormal vacuum generated from the deposition source is suppressed in the vacuum film forming apparatus that is produced. In addition, the effect of shortening the evacuation time can be expected.

The heating conditions for the annealing treatment are not particularly limited, and are preferably 200 to 500 ° C, more preferably 300 to 400 ° C. In addition, as a heating furnace used for an annealing process, general furnaces, such as a heater type and radiation heating, can be used.
Moreover, the processing time of an annealing process is not specifically limited, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.

<Other optional processing steps>
(Mechanical roughening treatment)
In the present invention, a mechanical surface roughening treatment such as brush grain may be performed on the surface of the aluminum plate before the electrolytic surface roughening treatment described above.

(Sealing treatment etc.)
In this invention, you may perform the sealing process which seals the micropore which exists in an anodized film after an anodizing process. The sealing treatment can be performed according to a known method such as boiling water treatment, hot water treatment, steam treatment, sodium silicate treatment, nitrite treatment, ammonium acetate treatment and the like.
Hydrophilization that attaches an acid such as silicate or polyvinylphosphonic acid, organic carboxylic acid compound, organic sulfonic acid compound to the surface that has been anodized or the surface that has been sealed. Processing may be performed.

  As mentioned above, although the deposition board for vacuum film-forming apparatuses of this invention, its manufacturing method, and the vacuum film-forming apparatus and vacuum film-forming method using the same were demonstrated in detail, this invention is limited to the above-mentioned example. Needless to say, various improvements and modifications may be made without departing from the scope of the present invention.

  Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.

[Examples 1 to 10 and Comparative Examples 1 to 5]
<Roughness forming step (roughening treatment)>
A slurry liquid having a specific gravity of 1.12 using pumiston with an average particle diameter of 30 μm as an abrasive is supplied to the surface of an aluminum plate (JIS 1050 material) having a thickness of 150 μm, and two rotating roller nylon brushes are used. The aluminum plate was moved to perform surface treatment. The diameter of the nylon brush used was 0.5 mm, the hair density was 450 / cm ² , and the brush rotation speed was 150 rpm.
Subsequently, it was put into an electrolytic cell having a nitric acid concentration of 10 g / L kept at 40 ° C., and electrolytic treatment was performed under the condition that the total amount of electricity was 300 C / dm ² . Note that a trapezoidal wave having a frequency of 60 Hz was used as the AC power source wave. Current density was set to 100A / dm ^2.
Next, this aluminum plate was placed in an electrolytic cell having a hydrochloric acid concentration of 10 g / L kept at 45 ° C., and subjected to electrolytic treatment under the condition that the total amount of electricity was 70 C / dm ² , thereby preventing adhesion as shown in FIG. A plate was made. Note that a trapezoidal wave having a frequency of 60 Hz was used as the AC power source wave. Current density was 50A / dm ^2.
Here, the surface of the adhesion-preventing plate after the roughening treatment, that is, the arithmetic average roughness Ra of the concavo-convex structure was 0.53 μm.
In Comparative Example 5, the unevenness forming step was not performed.

<Anodizing treatment>
A solution having a sulfuric acid concentration of 250 g / L and an aluminum concentration of 5% or less was used for the produced deposition preventing plate, and an aluminum plate was used as an anode and a DC voltage was applied for 45 minutes to form a 1.0 μm thick anodic oxide film on the surface. Formed. Current density was 50A / dm ^2.
Here, the surface of the adhesion-preventing plate after the anodic oxidation treatment, that is, the arithmetic average roughness Ra of the concavo-convex structure was the same as the value after the concavo-convex formation step (roughening treatment) described above.
In addition, about Example 7, the anodic oxidation process was performed after the protrusion part formation process (embossing) mentioned later.

<Projection formation process (embossing)>
Various embossing rolls are prepared by the method described in paragraphs [0012] to [0033] of Japanese Patent Application Laid-Open No. 2005-205444, and the following are used for the aluminum plate after the above irregularity forming step using the roll. By forming protrusions having the outer shape, height and density shown in Table 1, a deposition preventing plate was produced.
Here, the nip was performed by correcting the clearance so that the molds had a plate thickness to a plate thickness +0.02 mm.
In addition, about the comparative example 1, the protrusion part formation process was not performed.

<Annealing process>
About the adhesion prevention board produced in Example 10, the annealing process was given on the conditions shown in the following Table 1 after the protrusion part formation process. In addition, the temperature increase rate of annealing treatment was performed at 15 degrees C / min.

The surface and cross-section of the prepared protective plate were observed with an electron microscope at a magnification of 2000 times and a magnification of 30000 times, the average opening diameter of the recesses in the concavo-convex structure (medium wave structure and small wave structure), the outer shape of the protrusions, and the average height The average density and the bottom area ratio were measured. These results are shown in Table 1 below together with the presence or absence of an anodized film and the presence or absence of cracks. In Table 1 below, an item represented by “-” indicates that the item does not exist.
Moreover, it was found by observation with an electron microscope that the surface of the deposition preventive plate produced in the example had a concavo-convex structure and a plurality of protrusions arranged. 8 and 9 show photographs of the surface of the adhesion-preventing plate produced in Example 1 at a magnification of 50 times and 350 times, respectively, and the apex at the protrusion of the adhesion-prevention plate produced in Example 1 and FIGS. 10A and 10B show photographs of the slope magnification of 2000 times, respectively.

<Peeling prevention property>
The produced adhesion prevention board was affixed on the inner wall surface of the vacuum evaporation system (Showa Vacuum SGC-22SA) as shown in FIG. 1 using the Kapton tape.
A gold film was formed on the surface of the substrate Z by vacuum vapor deposition using a film forming apparatus to which an adhesion preventing plate was attached. Specifically, the deposition amount per deposition was 1 μm, the deposition pressure was 1 × 10 ⁻³ Pa, the sample temperature was 250 ° C., and the thermal cycle (room temperature to 250 ° C.) was repeated for each deposition. At that time, the anti-peeling property was evaluated according to the following criteria.
A1: Deposition by visual observation is not observed after repeated 200 depositions.
A2: Visual peeling is observed by vapor deposition of 180 times or more and less than 200 times.
B: Peeling by visual observation is observed by vapor deposition of 100 times or more and less than 180 times.
C: Visual peeling is observed by vapor deposition of 50 times or more and less than 100 times.
D: Visual peeling is observed by vapor deposition 30 times or more and less than 50 times.

<Processability>
About each produced adhesion prevention board, workability was evaluated by the method shown below.
That is, when using a Kapton tape to attach an adhesion-preventing plate to the inner wall surface of a vacuum vapor deposition apparatus (SGC-22SA manufactured by Showa Vacuum Co., Ltd.), it can be easily attached without lifting from the inner wall surface of the vacuum chamber. The product was evaluated as “A” as having excellent workability, and although it was slightly lifted from the inner wall surface of the vacuum chamber, it could be easily pasted and had excellent workability. Rated “B”. The results are shown in Table 1 below.

As shown in Table 1, the surface has a concavo-convex structure including a recess having a specific average opening diameter, and a plurality of protrusions having a specific average height are arranged on the surface at a predetermined ratio. It was found that the adhesion preventing plate was excellent in the effect of preventing peeling even when the deposition was repeated (Examples 1 to 10). In particular, as can be seen from the comparison between Example 1 and Example 2, it was found that the higher the bottom area ratio of the protrusions, the more improved the anti-peeling effect upon repeated deposition. Moreover, it turned out from the comparison with Example 2 and Example 7 that the peeling prevention effect at the time of repeating vapor deposition improves the adhesion prevention board which has a crack in the surface. Furthermore, it was found from the comparison between Example 2 and Example 10 that the workability of the adhesion-preventing plate is improved by performing the annealing treatment.
On the other hand, the adhesion preventing plate that does not have protrusions or uneven structures on the surface and the adhesion preventing plate that does not satisfy the ratio of the protrusions arranged on the surface are effective in preventing peeling when repeated deposition is performed. Was found to be inferior (Comparative Examples 1 to 5).

  The present invention can be suitably used for manufacturing various products using vacuum film forming methods such as vacuum deposition, sputtering, and plasma CVD, such as manufacturing semiconductor devices and electronic component materials.

DESCRIPTION OF SYMBOLS 10 Vacuum film-forming apparatus 12 Adhesion board 12a Upper surface adhesion board 12b Side surface adhesion board 12c Lower surface adhesion board 14 Vacuum chamber 16 Deposition source 18 Substrate holder 20 Vacuum pump 30, 32, 34 Uneven structure 30a, 32a, 34a, Concave part 30b, 32b, 34b Projection 40 Projection 40a Bottom 40b Vertex 40c Ridge 40d Slope 42 Crack

Claims (13)

In a vacuum film forming apparatus, a deposition plate for a vacuum film forming apparatus for preventing adhesion of a film forming material to an unnecessary position,
Made of aluminum,
It has a surface on which a concavo-convex structure including recesses having an average opening diameter of 0.01 to 9 μm is formed,
A plurality of protrusions having an average height of 30 to 1000 μm are arranged on the surface,
The average density of the protrusions is 10 pieces / 10 mm square or more,
An adhesion-preventing plate for a vacuum film-forming apparatus, wherein the ratio of the bottom area of the protrusion is more than 90% in a 10 mm square region.   2. The deposition preventing plate for a vacuum film forming apparatus according to claim 1, wherein an outer shape of the projecting portion when viewed from above in a vertical direction is a rhombus, a rectangle, or a circle.   The vacuum according to claim 1 or 2, wherein the concavo-convex structure is a concavo-convex structure including a concave portion having an average opening diameter of 0.5 to 9 µm or a concavo-convex structure including a concave portion having an average opening diameter of 0.01 to 0.3 µm. Depositing plate for film forming equipment.   The concavo-convex structure is a concavo-convex structure in which a concavo-convex structure including a concave portion having an average opening diameter of 0.01 to 0.3 μm is superimposed on a concavo-convex structure including a concave portion having an average opening diameter of 0.5 to 9 μm. 4. The deposition preventing plate for a vacuum film forming apparatus according to any one of 3 above.   The deposition surface for a vacuum film-forming apparatus according to any one of claims 1 to 4, wherein the surface is made of an anodized aluminum film.   The deposition preventing plate for a vacuum film forming apparatus according to any one of claims 1 to 5, wherein the surface has a crack.   The deposition plate for a vacuum film forming apparatus according to claim 1, wherein the protrusion is formed by embossing.   The deposition preventing plate for a vacuum film forming apparatus according to any one of claims 1 to 7, wherein the concavo-convex structure including a concave portion having an average opening diameter of 0.01 to 9 µm is formed by an electrochemical roughening treatment. In a vacuum film forming apparatus, a manufacturing method for manufacturing a deposition plate for a vacuum film forming apparatus for preventing adhesion of a film forming material to an unnecessary position,
An uneven surface forming step of performing an electrochemical surface roughening treatment on the surface of the aluminum plate and forming an uneven structure including recesses having an average opening diameter of 0.01 to 9 μm on the surface;
The manufacturing method which has a protrusion part formation process which gives the embossing to the surface of an aluminum plate, and forms several protrusion part with an average height of 30-1000 micrometers in a part of surface.   The method for producing an adhesion-preventing plate for a vacuum film forming apparatus according to claim 9, further comprising an anodizing treatment step of forming an anodized film of aluminum on the surface by performing anodizing treatment after the unevenness forming step.   The manufacturing method of the deposition prevention board for vacuum film-forming apparatuses of Claim 9 or 10 which has an annealing treatment process which performs an annealing process after the said protrusion part formation process.   The vacuum film-forming apparatus which has an adhesion prevention board for vacuum film-forming apparatuses of any one of Claims 1-8.   Using the vacuum film-forming apparatus having the deposition plate for a vacuum film-forming apparatus according to claim 1, Ti, Zr, Nb, Ta, Cr, Mo are formed on the surface of the deposition target substrate. , W, Pt, Au, Ag, Fe, Ni, Mn, Sn, Zn, Co, Al, Cu and Si, or a vacuum for forming a film of an alloy, nitride or oxide thereof Film forming method.