JP5869507B2 - Depositing plate for vacuum film forming apparatus, vacuum film forming apparatus, and vacuum film forming method - Google Patents

Description

  The present invention relates to a deposition preventing plate used in a vacuum film forming apparatus such as a vacuum vapor deposition apparatus or a sputtering apparatus. Specifically, the present invention relates to a deposition preventing plate for a vacuum film forming apparatus that can prevent peeling of the deposited film forming material.

Vacuum film formation methods such as vacuum deposition, sputtering, and plasma CVD are used for manufacturing semiconductor devices, electronic component materials, and various functional films.
For example, in the manufacture of semiconductor devices and electronic component materials, a thin film of conductive metal such as gold, silver, copper, aluminum, titanium, and molybdenum is formed on a semiconductor substrate or glass substrate by a vacuum film formation method. Electrodes and wiring are produced.

In such a vacuum film-forming method, it is known that a film-forming material adheres and deposits at a place other than a substrate to be film-formed in a vacuum chamber of a vacuum film-forming apparatus.
For this reason, the vacuum film-forming apparatus used for the vacuum film-forming method has an anti-adhesion covering the inner wall surface of the apparatus in order to prevent the deposition and deposition of film-forming materials on unnecessary places other than the substrate in the apparatus. A plate is provided.

  Further, in the vacuum film forming method, it is known that the film forming material attached to the inner wall surface of the vacuum film forming apparatus not provided with the deposition plate or the deposition plate is peeled off to generate particles. It is known that when these particles adhere to a substrate to be deposited, the quality of the product is deteriorated or defective.

For example, in the manufacture of semiconductor devices and electronic material components, if particles adhere to or mix in wiring, wiring failure occurs, and yield in production deteriorates.
In particular, in order to produce a highly integrated semiconductor device, it is necessary to narrow the wiring width (for example, about 0.3 μm or less). In such wiring, a fineness of about 0.3 μm is required. Even if particles are mixed in the wiring, a wiring defect occurs.
Therefore, in manufacturing a semiconductor device that requires such high-density wiring, it is necessary to reduce the generation of particles in the vacuum film forming apparatus in order to improve the yield.

In response to such a problem, it is known that the surface of the deposition preventive plate is roughened in order to prevent the deposition material deposited on the deposition preventing plate from peeling off and forming particles. ing.
For example, in Patent Document 1, for example, a sprayed film having a surface roughness Ra of about 10 to 20 μm is formed on the surface of the deposition preventing plate, and the height of the sprayed film is larger than the surface roughness of the sprayed film itself. Describes that the film-forming material deposited on the surface of the adhesion-preventing plate is prevented from being peeled off by forming irregularities of about 50 to 2000 μm ([0016] [0041]).

  In Patent Document 2, large unevenness having a surface roughness Ra of about 200 to 2000 μm is formed on the surface of the deposition preventing plate, and small unevenness having a surface roughness Ra of about 10 to 100 μm is superimposed on the large unevenness. It is described that the film forming material deposited on the surface of the deposition preventing plate is prevented from being peeled off ([Claim 1] [Claim 2] [Claim 8] [0023]).

  Further, Patent Document 3 describes a roughening treatment method that can be used for roughening treatment of a jig such as a deposition plate of a thin film manufacturing apparatus. Specifically, the surface roughness Ra is set to 2 to 2. An aluminum surface roughening method for roughening to 20 μm is described ([claim 3] [0030]).

JP 2001-49419 A JP 2001-226776 A JP 2006-274437 A

  The inventors of the present invention have studied the adhesion preventing plates described in Patent Documents 1 to 3, and it is clear that even if the surface is roughened, the effect of preventing the peeling of the film forming material is not sufficient. It was.

  Therefore, the present invention provides an adhesion preventing plate for a vacuum film forming apparatus that is excellent in the effect of preventing the film forming material from peeling off, a method for manufacturing the same, and a vacuum film forming apparatus and a vacuum film forming method using the adhesion preventing plate. Objective.

As a result of earnest research to achieve the above object, the present inventor has a concavo-convex structure including a recess having a specific average opening diameter, and providing a surface having an arithmetic average roughness Ra within a predetermined range. The inventors have found that the effect of preventing the film-forming material from peeling off is high, and completed the present invention.
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,
Is made of aluminum, has a surface relief structure including a recessed portion having an average opening diameter 0.01～9Myuemu, arithmetic average roughness Ra of the surface Ri der than 0.20 [mu] m,
A deposition preventing plate for a vacuum film forming apparatus having a surface area ratio ΔS of 5% or more and a steepness a45 of 3% or more .
Here, the surface area ratio ΔS is an actual area S _x obtained by an approximate three-point method from three-dimensional data obtained by measuring 256 × 256 points on the surface of 25 μm × 25 μm using an atomic force microscope, It is a value obtained from the geometric measurement area S ₀ by the following formula (i), and the steepness a45 has an inclination with an angle of 45 ° or more with respect to the actual area S _x (an inclination of 45 ° or more). The area ratio of the part.
ΔS = (S _x −S ₀ ) / S ₀ × 100 (%) (i)

(2) The vacuum according to (1), 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.
(3) The concavo-convex structure is a concavo-convex structure in which a concavo-convex structure including a recess having an average opening diameter of 0.01 to 0.3 μm is superimposed on a concavo-convex structure including a recess having an average opening diameter of 0.5 to 9 μm. ) Or the deposition preventing plate for a vacuum film forming apparatus according to (2).
(4) The deposition preventing plate for a vacuum film forming apparatus according to any one of (1) to (3), wherein the surface is composed of an anodized film of aluminum.
(5) The deposition preventing plate for a vacuum film forming apparatus according to (4), wherein the anodized film has micropores.
(6) The deposition method for a vacuum film forming apparatus according to any one of (1) to (5), wherein a concavo-convex structure including a concave portion having an average opening diameter of 0.01 to 9 μm is superimposed on a larger concavo-convex structure. Board.
(7) The deposition preventing plate for a vacuum film forming apparatus according to any one of (1) to (6), wherein the aluminum has a thickness of 30 to 300 μm.
(8) The deposition preventing plate for a vacuum film forming apparatus according to any one of (1) to (7), wherein the tensile elastic modulus is 65 GPa or less.

( 9 ) A manufacturing method for manufacturing the deposition preventing plate for a vacuum film forming apparatus according to (1),
The surface of the aluminum plate is subjected to an electrochemical roughening treatment to form a concavo-convex structure including concave portions having an average opening diameter of 0.01 to 9 μm, an arithmetic average roughness Ra is set to 0.20 μm or more, and a surface area ratio ΔS is 5 %, And a method for manufacturing a deposition preventing plate for a vacuum film forming apparatus, which includes a step of setting the steepness a45 to 3% or more.
Here, the surface area ratio ΔS is an actual area S _x obtained by an approximate three-point method from three-dimensional data obtained by measuring 256 × 256 points on the surface of 25 μm × 25 μm using an atomic force microscope, It is a value obtained from the geometric measurement area S ₀ by the following formula (i), and the steepness a45 is an inclination having an angle of 45 ° or more with respect to the actual area S _x (an inclination of 45 ° or more). It is the area ratio of the part which has.
ΔS = (S _x −S ₀ ) / S ₀ × 100 (%) (i)
( 10 ) The deposition plate for a vacuum film-forming apparatus according to ( 9 ), which has a step of performing anodizing treatment and forming an anodized film of aluminum on the surface after the step of applying the electrochemical surface roughening treatment. Production method.
( 11 ) The method for producing an adhesion-preventing plate for a vacuum film-forming apparatus according to ( 10 ), including a step of performing an annealing treatment after the anodizing treatment.

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

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

  ADVANTAGE OF THE INVENTION According to this invention, the vacuum deposition apparatus for vacuum film-forming apparatuses excellent in the peeling prevention effect of film-forming material, its manufacturing method, and the vacuum film-forming apparatus and vacuum film-forming method using this deposition board are provided. it can.

It is a figure which shows notionally an example of the vacuum film-forming apparatus 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 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 the electron micrograph which image | photographed (2000-times multiplication factor) the surface of the adhesion prevention board produced in Example 7 with the high-resolution scanning electron microscope (SEM).

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 characteristic points of the present invention is that a surface having a concavo-convex structure including a recess having a specific average opening diameter is provided. 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.
In other words, 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 due to the anchor effect or the like. However, it is considered that the generation of particles due to peeling can be suppressed.

  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 according to the present invention shown in FIG. 1 forms a film on the surface of a substrate Z as a film forming member by vacuum vapor deposition, and has a deposition plate 12 according to 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, One element selected from W, Pt, Au, Ag, Fe, Ni, Mn, Sn, Zn, Co, Al, Cu and Si, or an alloy thereof is formed.

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. The same applies 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 with a concavo-convex structure including recesses of 0.01 to 9 μm and an arithmetic average roughness Ra of the surface of 0.20 μm or more.
Next, regarding the deposition preventing plate of the present invention, the base material made of aluminum will be described, and then the surface of the base material will be described with reference to FIGS.

<Base material>
The deposition 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 is preferably a plate shape or a sheet shape.
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.
Moreover, it is preferable that the deposition preventing plate 12 of the present invention has a certain degree of flexibility from the viewpoint of covering the entire inner surface of the vacuum chamber 14 without difficulty according to the configuration of the vacuum film forming apparatus 10.
In addition, since the deposition preventing plate of the present invention is made of aluminum, in the case of a disposable use, after the film formation was finished, the aluminum and the film formation material were separated and the film was not formed on the substrate Z. The film forming material can be collected.
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.

<Surface>
2 to 4 are schematic sectional views showing examples of the concavo-convex structure on the surface of the adhesion-preventing plate of the present invention.
As shown in FIG. 2, the deposition preventing plate 12 of the present invention has the surface of the concavo-convex structure 30 including the concave portions 30a having an average opening diameter of 0.01 to 9 μm.
Here, as shown in FIG. 2, the opening diameter of the recessed part 30a is the diameter of the recessed part 30a (circumferentially connected to the periphery forming the recessed part 30a), and the average opening diameter is the average thereof.
Specifically, using an electron microscope, the surface of the adhesion preventing plate 12 was photographed from right above at a magnification of 2000 to 30000 times, and in the obtained electron micrograph, the recess 30a (which will be described later) is connected in an annular shape. Extract at least 50 recesses due to micropores formed on the anodized film), read the diameter (or the diameter of the circle inscribed in the recess 30a) as the opening diameter, and calculate the average opening diameter To do.
Further, the concavo-convex structure including the concave portion may be a wave-shaped structure as shown in FIG. 2, and is a repeating structure of the concave portion in which the convex portion is a flat portion of the surface as shown in FIG. There may be.

Since the deposition preventing plate 12 of the present invention has a concavo-convex structure including the recesses 30a having an average opening diameter of 0.01 to 9 μm, as described above, the film deposition material attached to the deposition preventing plate 12 has a very strong adhesion strength. It can be held on the adhesion preventing plate 12. That is, in the deposition preventing plate 12 of the present invention, the opening diameter is small by having a concavo-convex structure including a recess having a much smaller opening diameter than the conventional deposition preventing plate subjected to the roughening treatment. By obtaining a high anchoring effect by the recesses and increasing the adhesion strength, it is possible to prevent peeling of the deposited film forming material. In addition, when the average opening diameter of the recessed part 30 exceeds 9 micrometers, sufficient contact | adhesion intensity | strength cannot be obtained and it becomes easy to peel film-forming material.
Therefore, according to the present invention, it is possible to prevent the generation of particles due to the film forming material peeled off from the deposition preventing plate 12, and to prevent product defects and quality deterioration due to the adhesion of the particles to the substrate Z. Improvement, improvement of productivity, reduction of production cost, etc. can be aimed at.

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 the medium wave structure and the small wave structure are superposed is preferable because the effect of preventing peeling of the film forming material is further improved. Specifically, as shown in FIG. 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 further superimposed on the medium wave structure 32 including a concave portion 32a having a thickness of 0.5 to 9 μm is preferably exemplified.
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.

In the deposition preventing plate 12 of the present invention, basically, the concave portions 30a constituting the concavo-convex structure are formed almost uniformly over the entire surface.
Here, in the adhesion prevention board 12 of this invention, it is preferable to have 10 or more of the recessed parts 30a whose opening diameter is 0.5 micrometer or more among 0.003 mm < ² > among recessed parts 30a.
By having such a configuration, the adhesion of the film forming material adhered to the deposition preventing plate 12 can be sufficiently secured, and peeling of the film forming material can be more suitably prevented.
Furthermore, the adhesion preventing plate 12 of the present invention has 20 or more per 0.003 mm ^{2 in} the case of the concave portion 30a having an opening diameter of 5 μm or more in that a more excellent film-forming material peeling prevention effect is obtained. It is preferable to have 120 or less. Similarly, in the case of the recess 30a having an opening diameter of 2 μm or more, it is preferably 20 or more per 0.003 mm ² , more preferably 50 or more, and preferably 1500 or less. Further, similarly, in the case of the recesses 30a having an opening diameter of 0.5 μm or more, it is preferable to have 30 or more per 0.003 mm ² , and more preferably 150 or more.

(Large wave structure)
In the present invention, the concavo-convex structure including the concave portions having an average opening diameter of 0.01 to 9 μm may be superimposed on a concavo-convex structure larger than the concavo-convex structure (hereinafter also referred to as “large wave structure”). Preferably, the concavo-convex structure including the concave portions having the average opening diameter of 0.5 to 9 μm described above may be superimposed on a large concavo-convex structure having concavo-convex portions having an average wavelength of 5 to 100 μm.
Specifically, the large uneven structure having unevenness with an average wavelength of 5 to 100 μm is obtained by measuring the two-dimensional roughness with a stylus type roughness meter and measuring the average peak interval Sm defined in ISO 4287 five times. , An uneven structure having an average value of 5 to 100 μm.
By superimposing a concavo-convex structure including a concave portion having an average opening diameter of 0.01 to 9 μm on such a large wave structure, it is possible to hold the film forming material attached to the deposition preventing plate more stably, Generation | occurrence | production of a particle | grain can be prevented more suitably because film-forming material peels from a deposition board.

(Arithmetic mean roughness Ra)
The arithmetic average roughness Ra of the surface of the deposition preventing plate 12 of the present invention is not particularly limited as long as it is 0.20 μm or more, preferably 0.25 μm or more, and more preferably 0.30 μm or more. Moreover, it is preferable that it is 8 micrometers or less, it is preferable that it is 2 micrometers or less, and it is more preferable that it is 1 micrometer or less. Specifically, it is preferably about 0.25 to 0.9 μm, and more preferably 0.30 to 0.60 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.

(Surface area ratio ΔS and steepness a45)
The deposition preventing plate 12 of the present invention preferably has a surface area ratio ΔS of 5% or more and a steepness a45 of 3% or more, a surface area ratio ΔS of 30% or more and a steepness a45. More preferably, it is 25% or more, the surface area ratio ΔS is 40% or more, the steepness a45 is more preferably 30% or more, the surface area ratio ΔS is 45% or more, and the steepness is It is particularly preferable that a45 is 40% or more. In view of cost and the like, the surface area ratio ΔS is preferably 90% or less, and the steepness a45 is preferably 85% or less.
Here, the surface area ratio ΔS is an actual area S _x obtained by an approximate three-point method from three-dimensional data obtained by measuring 256 × 256 points on the surface of 25 μm × 25 μm using an atomic force microscope, It is a value obtained from the geometric measurement area S ₀ by the following formula (i), and the steepness a45 is a slope having an angle of 45 ° or more (gradient of 45 ° or more) with respect to the actual area S _x . It is the area ratio of the part which has.
ΔS = (S _x −S ₀ ) / S ₀ × 100 (%) (i)

The surface area difference ΔS is one of the factors indicating the frequency of the uneven structure on the surface of the deposition preventing plate 12 of the present invention. The steepness a45 is a factor representing the sharpness of the concavo-convex structure on the surface of the deposition preventing plate 12 of the present invention.
When the surface area difference ΔS is 5% or more and the steepness a45 is 3% or more, it is possible to produce an adhesion-preventing plate that further improves the effect of preventing the film-forming material from peeling off.

In the present invention, in order to obtain the surface area difference ΔS and the steepness a45, the surface shape is measured by an atomic force microscope (AFM) to obtain three-dimensional data. The measurement can be performed, for example, under the following conditions.
That is, cut the aluminum substrate into 1cm square size, set it on the horizontal sample stage on the piezo scanner, approach the sample surface with the cantilever, and when it reaches the region where the atomic force works, it scans in XY direction At that time, the surface shape (wave structure) of the sample is captured by the displacement of the piezoelectric element in the Z direction. A piezo scanner that can scan 150 μm in the XY direction and 10 μm in the Z direction is used. A cantilever having a resonance frequency of 130 to 170 kHz and a spring constant of 6 to 14 N / m (OMCL-AC200TS, manufactured by OLYMPUS) is used for measurement in a DFM mode (Dynamic Force Mode). Further, the reference plane is obtained by correcting the slight inclination of the sample by approximating the obtained three-dimensional data by least squares. The measurement is performed by measuring 256 × 256 points in a 25 μm × 25 μm range of the surface. The resolution in the XY direction is 0.1 μm, the resolution in the Z direction is 1 nm, and the scan speed is 15 μm / sec.

Using the three-dimensional data (f (x, y)) obtained above, three adjacent points are extracted, and the sum of the areas of the minute triangles formed by the three points is obtained to obtain the actual area S _x . The surface area difference ΔS is obtained by the above formula (i) from the obtained real area S _x and the geometric measurement area S ₀ .
In addition, using the three-dimensional data (f (x, y)) obtained above, a small triangle formed by three points of each reference point and two adjacent points in a predetermined direction (for example, right and bottom) And the angle formed by the reference plane is calculated for each reference point. The number of reference points where the inclination of the micro triangle is 45 degrees or more is obtained by subtracting the number of all reference points (the number of all data points from 256 × 256 points that do not have two adjacent points in a predetermined direction). In other words, the area ratio a45 of the portion having the inclination of 45 degrees or more is calculated by dividing by 255).

Such a surface area ratio ΔS and steepness a45 can be measured using an atomic force microscope (atomic force microscope SPA400 manufactured by SII Nanotechnology (now Hitachi High-Tech Science)), as described in Examples described later. it can.
Here, when an uneven structure is formed by performing an electrochemical surface roughening process, which will be described later, the formed uneven structure is small, and evaluation in the nano-order such as an atomic force microscope (AFM) is possible. I need it. On the other hand, when forming a concavo-convex structure by performing a surface roughening process by thermal spraying, the concavo-convex structure to be formed is large, the piezo operating range in the AFM is over-range, or the concavo-convex becomes three-dimensional The terminal (harness) cannot follow and measurement is impossible. In addition, when performing mechanical surface roughening processes, such as a brush grain method, the large wave structure mentioned later can be formed, but the uneven structure containing a recessed part with an average opening diameter of 0.01-9 micrometers cannot be formed.

(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 prevented from being peeled off.
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 setting the thickness of the anodized film within the above range, the effect of having the anodized 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. Thereby, generation | occurrence | production of a particle can be prevented more suitably.

In addition, from the viewpoint of adhesion strength (prevention of peeling) and scratch resistance, the average diameter (average pore diameter) of the micropores in the anodized film is preferably 5 to 80 nm, and the average density (average pore density) is The number is preferably 50 to 750 / μm ² .
Here, in the present invention, the average pore diameter is obtained by photographing the surface of the anodized film at a magnification of about 150,000 times using a field emission scanning electron microscope (FE-SEM), and observing three fields of view with the obtained SEM photograph. And an average diameter is measured about arbitrary 100 micropores, The average value is made into the average pore diameter. Further, the average pore density is taken as an average pore density by extracting three fields of view of a 300 nm square from the above SEM photograph and counting the number of micropores therein to obtain an average value of the density.

[Manufacturing method of deposition prevention plate]
The method for producing an adhesion-preventing plate of the present invention is a production method for producing the above-described adhesion-preventing plate according to the present invention, wherein the surface of the aluminum plate is subjected to an electrochemical roughening treatment, and an average opening diameter of 0.01 to It is a manufacturing method having a step of forming a concavo-convex structure including a 9 μm concave portion (hereinafter also referred to as “concave-convex forming step”).
Moreover, the manufacturing method of the deposition preventive plate of the present invention provides an anodizing treatment after the unevenness forming step from the viewpoint of forming an anodic oxide film on the surface of the above-described deposition preventive plate of the present invention, and an aluminum anode on the surface. It is preferable to have a step of forming an oxide film (hereinafter also referred to as “anodizing treatment step”).
Furthermore, the manufacturing method of the adhesion prevention board of this invention has the process (henceforth an "annealing treatment process") which performs an annealing process after an anodizing process process from a viewpoint of the workability of an adhesion prevention board. Is preferred.
Next, each process mentioned above is demonstrated about the manufacturing method of the deposition preventing board of this invention.

<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.

  The above-described large wave structure is processed by brush grain method, shot blasting, ball grain method, electric discharge machining, plasma etching, transfer roll on the surface of the aluminum substrate before forming the above-described medium wave structure or small wave structure. It can form by performing roughening processes, such as.

<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.
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 annealing treatment (annealing treatment) in a vacuum atmosphere or in the air after the above-described anodizing treatment step (after the sealing treatment or hydrophilic treatment described later, after these treatments). Is an optional step.
Here, 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.

By performing such an annealing treatment, the workability of the adhesion-preventing plate is improved, and deformation and drilling along the inner wall surface of the vacuum chamber are facilitated. It is also possible to expect the effect that the abnormal discharge generated from the above is suppressed and the evacuation time is shortened.
Here, the adhesion preventing plate after the annealing treatment preferably has a tensile elastic modulus defined by JIS K7127: 1999 of 65 GPa or less, more preferably 60 GPa or less, and more preferably 55 GPa or less.

<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 described above, the deposition plate for vacuum film formation apparatus, the vacuum film formation apparatus, and the vacuum film formation method of the present invention have been described in detail. However, the present invention is not limited to the above-described examples, and does not depart from the gist of the present invention. Of course, various improvements and changes may be made.

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

[Example 1]
An aluminum plate (JIS 1050 material) having a thickness of 150 μm is placed in an electrolytic cell having a nitric acid concentration of 10 g / L kept at 40 ° C., and subjected to electrolytic treatment under the condition that the total amount of electricity is 300 C / dm ^2. Was made.
The electrolytic treatment was performed with a trapezoidal AC power supply wave at a frequency of 60 Hz. Current density was set to 100A / dm ^2.

[Example 2]
An aluminum plate (JIS 1050 material) with a thickness of 150 μm is placed in an electrolytic cell having a nitric acid concentration of 2 g / L kept at 35 ° C. and subjected to electrolytic treatment under the condition that the total amount of electricity is 300 C / dm ² , thereby preventing adhesion. A plate was made.
As the AC power source wave, a trapezoidal wave of 60 Hz was used as in the first embodiment. Current density was 20A / dm ^2.

[Example 3]
An aluminum plate (JIS 1050 material) having a thickness of 150 μm is placed in an electrolytic cell having a hydrochloric acid concentration of 20 g / L and a nitric acid concentration of 4 g / L kept at 50 ° C., and subjected to electrolytic treatment under the condition that the total amount of electricity is 500 C / dm ^2. Then, a deposition preventing plate was produced.
A 60 Hz sine wave was used as the AC power supply wave. Current density was set to 125A / dm ^2.

[Example 4]
An aluminum plate (JIS 1050 material) having a thickness of 150 μm was placed in an electrolytic cell having a nitric acid concentration of 10 g / L kept at 40 ° C., and electrolysis was performed under a condition where the total amount of electricity was 300 C / dm ² .
As the AC power source wave, a trapezoidal wave of 60 Hz was used as in the first embodiment. Current density was set to 100A / dm ^2.
Next, this aluminum plate was put 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 producing a deposition preventing plate.
As the AC power source wave, a trapezoidal wave of 60 Hz was used as in the first embodiment. Current density was 50A / dm ^2.

[Example 5]
An aluminum plate (JIS 1050 material) having a thickness of 150 μm was placed in an electrolytic cell having a nitric acid concentration of 10 g / L kept at 40 ° C., and electrolysis was performed under a condition where the total amount of electricity was 300 C / dm ² .
As the AC power source wave, a trapezoidal wave of 60 Hz was used as in the first embodiment. Current density was set to 100A / dm ^2.
Next, this aluminum plate was put 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 producing a deposition preventing plate.
As the AC power source wave, a trapezoidal wave of 60 Hz was used as in the first embodiment. Current density was 50A / dm ^2.
Furthermore, a solution having a sulfuric acid concentration of 250 g / L and an aluminum concentration of 5% or less was used for this deposition preventing plate, and an aluminum plate was used as an anode, a DC voltage was applied for 45 minutes, and a 1.0 μm thick anodic oxide film was formed on the surface. Formed. Current density was 50A / dm ^2.

[Example 6]
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 surface was roughened by moving on the aluminum plate.
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.
Thereafter, the electrolytic treatment and the anodic oxidation treatment were performed twice in the same manner as in Example 5 to prepare an adhesion preventing plate.

[Example 7]
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 surface was roughened by moving on the aluminum plate.
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.
Thereafter, the electrolytic treatment was performed in the same manner as in Example 1, and then the same anodizing treatment as in Example 5 was performed. Then, the adhesion prevention board was produced by performing a hydrophilic treatment for 10 second at 70 degreeC using 2.5 mass% 3 sodium silicate aqueous solution. The adhesion amount of Si was 10 mg / m ² .
In FIG. 5, the electron micrograph which image | photographed the surface of the adhesion prevention board produced in Example 7 with the high resolution scanning electron microscope (SEM) (2000-times multiplication factor) is shown.

[Example 8]
An adhesion-preventing plate was produced in the same manner as in Example 7 except that the silicate treatment was not performed.

[Examples 9 to 12]
About Examples 9-12, the adhesion prevention board was produced by the method similar to Examples 1-4, respectively except having performed the anodic oxidation process similar to Example 5. FIG.

[ Reference Example 13]
An adhesion-preventing plate was produced in the same manner as in Example 2 except that the current density was 10 A / dm ² . In the following description, Reference Example 13 is referred to as Example 13.

[Example 14]
An adhesion-preventing plate was produced in the same manner as in Example 2, except that blasting was performed by blowing glass beads having a particle size of 100 mesh with 0.5 MPa air before the electrolytic treatment.

[Example 15]
An aluminum plate (JIS 1050 material) with a thickness of 150 μm is placed in an electrolytic cell with 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 is 70 C / dm ² to prevent adhesion. A plate was made.
The electrolytic treatment was performed with a trapezoidal AC power supply wave at a frequency of 60 Hz. Current density was 50A / dm ^2.

[Example 16]
An aluminum plate (JIS 1050 material) with a thickness of 150 μm is placed in an electrolytic cell with 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 is 70 C / dm ² to prevent adhesion. A plate was made.
As in the case of Example 15, a 60 Hz trapezoidal wave was used as the AC power source wave. Current density was 50A / dm ^2.
Furthermore, a solution having a sulfuric acid concentration of 250 g / L and an aluminum concentration of 5% or less was used for this deposition preventing plate, and an aluminum plate was used as an anode, a DC voltage was applied for 45 minutes, and a 1.0 μm thick anodic oxide film was formed on the surface. Formed. Current density was 50A / dm ^2.

[Example 17]
An aluminum plate (JIS 1050 material) having a thickness of 150 μm was placed in an electrolytic cell having a nitric acid concentration of 10 g / L kept at 40 ° C., and electrolysis was performed under a condition where the total amount of electricity was 300 C / dm ² .
As in the case of Example 15, a 60 Hz trapezoidal wave was used as the AC power source wave. Current density was set to 100A / dm ^2.
Next, this aluminum plate was put 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 producing a deposition preventing plate.
As in the case of Example 15, a 60 Hz trapezoidal wave was used as the AC power source wave. Current density was 50A / dm ^2.

[Example 18]
An aluminum plate (JIS 1050 material) having a thickness of 150 μm was placed in an electrolytic cell having a nitric acid concentration of 10 g / L kept at 40 ° C., and electrolysis was performed under a condition where the total amount of electricity was 300 C / dm ² .
As in the case of Example 15, a 60 Hz trapezoidal wave was used as the AC power source wave. Current density was set to 100A / dm ^2.
Next, this aluminum plate was put 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 producing a deposition preventing plate.
As in the case of Example 15, a 60 Hz trapezoidal wave was used as the AC power source wave. Current density was 50A / dm ^2.
Furthermore, a solution having a sulfuric acid concentration of 250 g / L and an aluminum concentration of 5% or less was used for this deposition preventing plate, and an aluminum plate was used as an anode, a DC voltage was applied for 45 minutes, and a 1.0 μm thick anodic oxide film was formed on the surface. Formed. Current density was 50A / dm ^2.

[Example 19]
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 surface was roughened by moving on the aluminum plate.
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.
Thereafter, the electrolytic treatment and the anodic oxidation treatment were performed twice in the same manner as in Example 18 to produce an adhesion preventing plate.

[Comparative Example 1]
Using an aluminum plate (JIS 1050 material) having a thickness of 150 μm as an adhesion-preventing plate, Au was vacuum-deposited on the substrate Z in the same manner as in Example 1. Therefore, the surface of this deposition preventing plate is smooth and does not have an uneven structure. The surface roughness Ra was 0.15 μm.

[Comparative Example 2]
Using an aluminum foil (made by Showa Vacuum Co., Ltd.) plate having a thickness of 50 μm as an adhesion-preventing plate, Au was vacuum deposited on the substrate Z in the same manner as in Example 1. Therefore, the surface of this deposition preventing plate is smooth and does not have an uneven structure. The surface roughness Ra was 0.15 μm.

[Comparative Example 3]
A slurry liquid having a specific gravity of 1.12 using pumiston with an average particle diameter of 70 μm as an abrasive is supplied to the surface of an aluminum plate (JIS 1050 material) having a thickness of 150 μm, and five rotating nylon brushes are rotated. The surface was roughened by moving on the aluminum plate to produce a deposition preventing plate.
The diameter of the nylon brush used was 0.9 mm, the bristle density was 450 / cm ² , and the brush rotation speed was 400 rpm.

[Comparative Example 4]
A slurry liquid having a specific gravity of 1.12 using Pamiston with an average particle size 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 five rotating nylon brushes are rotated. The surface of the aluminum plate was moved and the surface was roughened to produce a deposition preventing plate.
The diameter of the nylon brush used was 0.9 mm, the bristle density was 450 / cm ² , and the brush rotation speed was 350 rpm.

[Comparative Example 5]
An electrolytic surface-roughening treatment was performed in a solution tank (liquid temperature: 20 ° C.) containing hydrochloric acid (hydrogen chloride concentration: 5% by weight) to prepare an adhesion preventing plate.
Specifically, 40 mm x 50 mm x 1 mm of SUS304 is placed at an interval of 1 mm on the opposite side of the aluminum alloy (A6061, surface Ra = 0.1 μm, size 40 mm x 50 mm x 1 mm flat plate) used as a test piece. Installed as a counter electrode.
Next, lead wires from the power supply equipment were placed on the aluminum alloy and SUS304, and an oxidation current of 0.5 A / cm ² was applied to the aluminum alloy.

[Comparative Example 6]
A deposition preventing plate was produced in the same manner as in Comparative Example 4 except that the same anodizing treatment as in Example 18 was performed.

<Surface properties>
(1) Concavity and convexity structure and number of concavities The surface of each of the prepared protective plates was observed with an electron microscope at a magnification of 2000 times (observation magnification of large waves and medium waves) and a magnification of 30000 times (observation magnification of small waves). The average opening diameter of the recesses in the structure, medium wave structure and small wave structure) was measured. These results are shown in Table 1 below. In Table 1 below, an item represented by “-” indicates that the item does not exist.
As a result of observation, it was confirmed that the adhesion preventing plates produced in Examples 1 to 19 and Comparative Examples 3 to 6 were substantially uniformly formed with recesses. The number of recesses shown in the following Table 1 shown in Table 1 below is the result of counting the number of recesses having an opening diameter equal to or larger than the value (μm) shown in parentheses in the following Table 1 per 0.003 mm ^2. It is.
(2) Arithmetic mean roughness Ra
The surface roughness Ra of each of the prepared adhesion-preventing plates was measured by a surface roughness measuring machine (SJ-401 / Mitutoyo Corporation radius 2 μm). The results are shown in Table 1 below.
(3) Micropores An anti-adhesion plate produced by anodizing was obtained by photographing the surface anodized film at a magnification of 150,000 using a field emission scanning electron microscope (FE-SEM). Three fields of view were observed with SEM photographs, and the average aperture diameter (average pore diameter) was measured for any 100 micropores. Similarly, three fields of 300 nm square were extracted from the SEM photograph, and the average value of the density (average pore density) was calculated by counting the number of micropores therein. These results are shown in Table 1 below. In Table 1 below, the item represented by “−” indicates that no anodized film is present.

(4) Surface area ratio ΔS and steepness a45
In order to obtain the surface area difference ΔS and the steepness a45 for the surface of the produced deposition preventive plate, the surface shape was measured by an atomic force microscope SII nanotechnology (currently Hitachi High-Tech Science) to obtain three-dimensional data. A specific procedure will be described below.
Cut the adhesion plate to 1cm square size, set it on the horizontal sample stage on the piezo scanner, approach the cantilever to the sample surface, and when it reaches the area where the atomic force works, scan in XY direction, At that time, the surface shape (wave structure) of the sample was captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan 150 μm in the XY direction and 10 μm in the Z direction was used. A cantilever having a resonance frequency of 130 to 170 kHz and a spring constant of 6 to 14 N / m (OMCL-AC200TS, manufactured by OLYMPUS) was used and measured in a DFM mode (Dynamic Force Mode). Further, the reference plane was obtained by correcting the slight inclination of the sample by least-square approximation of the obtained three-dimensional data.
At the time of measurement, 256 × 256 points were measured in a 25 μm × 25 μm range of the surface. The resolution in the XY direction was 0.1 μm, the resolution in the Z direction was 1 nm, and the scan speed was 15 μm / sec.
Using the three-dimensional data (f (x, y)) obtained above, three adjacent points were extracted, and the sum of the areas of the minute triangles formed by the three points was obtained to obtain the actual area _Sx . The surface area difference ΔS was determined by the above formula (i) from the obtained real area S _x and the geometric measurement area S ₀ .
In addition, using the three-dimensional data (f (x, y)) obtained above, a small triangle formed by three points of each reference point and two adjacent points in a predetermined direction (for example, right and bottom) And the angle formed by the reference plane is calculated for each reference point. The number of reference points where the inclination of the micro triangle is 45 degrees or more is obtained by subtracting the number of all reference points (the number of all data points from 256 × 256 points that do not have two adjacent points in a predetermined direction). In other words, the area ratio a45 of the portion having the inclination of 45 degrees or more is calculated by dividing by 255).
The results are shown in Table 1 below.

Each produced protection board was affixed on the inner wall surface of a vacuum evaporation system (Showa Vacuum SGC-22SA) as shown in FIG. 1 using the Kapton tape.
Using a vacuum film forming apparatus to which each protective plate was attached, a gold film of 0.5 μm was formed on the surface of the substrate Z by vacuum deposition. The film forming pressure was 1 × 10 ⁻³ Pa.

<Peel test and adhesion strength>
After the film formation was completed, a part of each deposition preventing plate was sampled, and a peel test was performed using a tape defined in JIS Z 1522: 2009.
Good, when there is no adhesion of Au peeled from the protective plate on the tape;
Acceptable when Au is peeled off from the protective plate on part of the tape;
When the adhesion of Au peeled off from the protective plate is recognized on the entire surface of the tape, it is evaluated as “No”.
Furthermore, the adhesion strength of Au adhering to the adhesion-preventing plate was measured using a thin film adhesion strength measuring machine (Romulus).
These results are shown in Table 1 below.

<Scratch resistance>
A scratch test was performed on the surface of each of the produced adhesion prevention plates to evaluate scratch resistance.
The scratch test was performed using a continuous load-type scratch strength tester (SB-53, manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a sapphire needle of 0.4 mmφ and a needle moving speed of 10 cm / second under a load of 100 g.
As a result, the case where scratches could not be visually confirmed was evaluated as “A” as being excellent in scratch resistance, and the case where scratches could be visually confirmed was evaluated as “B” as being poor in scratch resistance.
These results are shown in Table 1 below.

As shown in Table 1 above, the adhesion-preventing plate of the present invention having a concavo-convex structure including a concave portion having an average opening diameter of 0.01 to 9 μm has a strong adhesion force of adhered Au. Therefore, it can be seen that by using this deposition preventing plate, it is possible to prevent the deposited film forming material from peeling off and generating particles (Examples 1 to 19).
Particularly, an embodiment in which a concavo-convex structure (small wave structure) including a concave portion having an average opening diameter of 0.01 to 0.3 μm is superimposed on a concavo-convex structure (medium wave structure) including a concave portion having an average opening diameter of 0.5 to 9 μm. Examples 3 to 6, Examples 11 and 12, and Examples 17 to 19 have high Au adhesion.
In addition, Examples 5 to 12 and Examples 16, 18 and 19 in which an anodizing treatment was performed and an aluminum anodized film was provided on the surface of the deposition preventing plate had an anchor effect due to micropores existing in the anodized film. It was found that the adhesion strength was improved and the scratch resistance was also improved.
Moreover, it turned out that the contact | adhesion intensity | strength improves from the comparison with Example 1 and Example 7 which has a concavo-convex structure containing a recessed part larger than a recessed part with an average opening diameter of 0.5-9 micrometers.
Further, from comparison between Example 2 and Example 13, it was found that the adhesion strength was improved when the surface area ratio ΔS was 5% or more and the steepness a45 was 3% or more.
On the other hand, the adhesion preventing plates of Comparative Examples 1 and 2 having no uneven structure on the surface have a very low adhesion force of the adhered Au. Further, Comparative Examples 3, 4 and 6 having only a concavo-convex structure (large wave structure) including a large concave portion having an average opening diameter exceeding 10 μm have a certain degree of improvement in Au adhesion compared to a deposition preventing plate having a smooth surface. Although the effect is obtained, it cannot be said that it is sufficient, and it is still impossible to prevent the deposited film forming material from peeling off and generating particles. Similarly, even if it has the surface of the uneven structure (small wave structure) containing a recessed part with an average opening diameter of 0.01-0.3 micrometer, the surface roughness Ra of the adhesion prevention board of the comparative example 5 smaller than 0.2 micrometer Compared to the adhesion prevention plate with a smooth surface, the effect of improving the adhesion strength of Au is obtained to some extent, but it cannot be said that it is sufficient. I can't prevent you from doing it.
From the above results, the effects of the present invention are clear.

[Examples 20 to 22]
After the final anodic oxidation treatment, an adhesion-preventing plate was produced in the same manner as in Example 6 except that the annealing treatment was performed under the conditions shown in Table 2 below. Note that the annealing rate was 15 ° C./min.

[Examples 23 to 25]
After the hydrophilization treatment, an adhesion preventing plate was produced in the same manner as in Example 7 except that the annealing treatment was performed under the conditions shown in Table 2 below. Note that the annealing rate was 15 ° C./min.

The processability of the adhesion-preventing plates produced in Example 6 and Examples 20 to 22, and Example 7 and Examples 23 to 25 was evaluated by the following methods.
<Processability>
As in Example 1, when using a Kapton tape to attach the adhesion-preventing plate to the inner wall surface of the vacuum deposition apparatus (SGC-22SA, manufactured by Showa Vacuum Co., Ltd.), it does not lift up from the inner wall surface of the vacuum chamber and is easily pasted. What was able to be attached was evaluated as “A” as being extremely excellent in workability, and although it slightly lifted from the inner wall surface of the vacuum chamber, it was easy to attach it. “B” was evaluated as an excellent material, and “C” was evaluated as a product that was lifted from the inner wall surface of the vacuum chamber and took a long time for sticking, and was inferior in workability.
Moreover, the tensile elasticity modulus of each produced protection board was measured by the method prescribed | regulated by JISK7127: 1999.
These results are shown in Table 2 below.

  From the results shown in Table 2, it was found that by performing the annealing treatment, the tensile elastic modulus was lowered and the workability of the deposition preventing plate was improved.

  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 30, 32, 34 Uneven structure 30a, 32a, 34a, Concave part

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,
It is made of aluminum, has a surface with a concavo-convex structure including a recess having an average opening diameter of 0.01 to 9 μm, and the arithmetic average roughness Ra of the surface is 0.20 μm or more,
A deposition preventing plate for a vacuum film forming apparatus having a surface area ratio ΔS of 5% or more and a steepness a45 of 3% or more.
Here, the surface area ratio ΔS is an actual area S _x obtained by an approximate three-point method from three-dimensional data obtained by measuring 256 × 256 points on the surface of 25 μm × 25 μm using an atomic force microscope, It is a value obtained from the geometric measurement area S ₀ by the following formula (i), and the steepness a45 is an inclination having an angle of 45 ° or more with respect to the actual area S _x (an inclination of 45 ° or more). It is the area ratio of the part which has.
ΔS = (S _x −S ₀ ) / S ₀ × 100 (%) (i)   The vacuum film formation according to claim 1, 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. Equipment protection plate.   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. 2. A deposition preventing plate for a vacuum film forming apparatus according to 2.   The deposition surface for a vacuum film forming apparatus according to any one of claims 1 to 3, wherein the surface is made of an anodized aluminum film.   The deposition plate for a vacuum film-forming apparatus according to claim 4, wherein the anodized film has micropores.   The deposition preventing plate for a vacuum film forming apparatus according to any one of claims 1 to 5, wherein the concavo-convex structure including the concave portions having an average opening diameter of 0.01 to 9 µm is superimposed on a larger concavo-convex structure.   The deposition preventing plate for a vacuum film forming apparatus according to claim 1, wherein the aluminum has a thickness of 30 to 300 μm.   The deposition preventing plate for a vacuum film forming apparatus according to any one of claims 1 to 7, wherein the tensile elastic modulus is 65 GPa or less. A manufacturing method for manufacturing the deposition preventing plate for a vacuum film forming apparatus according to claim 1,
The surface of the aluminum plate is subjected to an electrochemical roughening treatment to form a concavo-convex structure including concave portions having an average opening diameter of 0.01 to 9 μm, an arithmetic average roughness Ra is set to 0.20 μm or more, and a surface area ratio ΔS is 5 %, And a method for manufacturing a deposition preventing plate for a vacuum film forming apparatus, which includes a step of setting the steepness a45 to 3% or more.
Here, the surface area ratio ΔS is an actual area S _x obtained by an approximate three-point method from three-dimensional data obtained by measuring 256 × 256 points on the surface of 25 μm × 25 μm using an atomic force microscope, It is a value obtained from the geometric measurement area S ₀ by the following formula (i), and the steepness a45 is an inclination having an angle of 45 ° or more with respect to the actual area S _x (an inclination of 45 ° or more). It is the area ratio of the part which has.
ΔS = (S _x −S ₀ ) / S ₀ × 100 (%) (i) The method for producing a deposition preventing plate for a vacuum film forming apparatus according to claim 9 , further comprising a step of performing an anodizing treatment and forming an anodized film of aluminum on the surface after the step of performing the electrochemical surface roughening treatment. . The manufacturing method of the deposition prevention board for vacuum film-forming apparatuses of Claim 10 which has the process of performing an annealing process after giving the said anodizing process. The vacuum film-forming apparatus which has a deposition preventing plate 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 any one of claims 1 to 8 , 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.