U.S. patent application number 16/392965 was filed with the patent office on 2019-08-15 for method for depositing film.
This patent application is currently assigned to SHINCRON CO., LTD.. The applicant listed for this patent is SHINCRON CO., LTD.. Invention is credited to Yousong JIANG, Ekishu NAGAE, Ichiro SHIONO, Takuya SUGAWARA.
Application Number | 20190249307 16/392965 |
Document ID | / |
Family ID | 41797057 |
Filed Date | 2019-08-15 |
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United States Patent
Application |
20190249307 |
Kind Code |
A1 |
SHIONO; Ichiro ; et
al. |
August 15, 2019 |
METHOD FOR DEPOSITING FILM
Abstract
The method for depositing a film of the present invention
includes the first film deposition step of depositing a first film
103 having hardness higher than hardness of a substrate 101 on a
surface of the substrate 101, the first irradiation step of
irradiating particles having energy on the first film 103, and the
second film deposition step of depositing an oil-repellent film 105
on a surface of the first film 103 subjected to the first
irradiation step. A method for depositing a film enabling
production of an oil-repellent substrate includes an oil-repellent
film having abrasion resistance of a practically sufficient level
can be provided.
Inventors: |
SHIONO; Ichiro; (Kanagawa,
JP) ; NAGAE; Ekishu; (Kanagawa, JP) ; JIANG;
Yousong; (Kanagawa, JP) ; SUGAWARA; Takuya;
(Kanagawa, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHINCRON CO., LTD. |
Kanagawa |
|
JP |
|
|
Assignee: |
SHINCRON CO., LTD.
Kanagawa
JP
|
Family ID: |
41797057 |
Appl. No.: |
16/392965 |
Filed: |
April 24, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15055660 |
Feb 29, 2016 |
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16392965 |
|
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13059145 |
Feb 15, 2011 |
9315415 |
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PCT/JP2009/064730 |
Aug 24, 2009 |
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15055660 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
Y10T 428/265 20150115;
C23C 14/5833 20130101; C23C 14/0652 20130101; C23C 14/08 20130101;
C23C 14/22 20130101; C23C 14/221 20130101; C09D 5/00 20130101; C23C
16/56 20130101; C09D 1/00 20130101; C23C 14/24 20130101; C03C
2218/32 20130101; C23C 14/541 20130101; C03C 2217/76 20130101; C03C
17/42 20130101; C23C 14/12 20130101; C03C 2217/77 20130101 |
International
Class: |
C23C 16/56 20060101
C23C016/56; C23C 14/22 20060101 C23C014/22; C23C 14/24 20060101
C23C014/24; C03C 17/42 20060101 C03C017/42; C23C 14/06 20060101
C23C014/06; C23C 14/08 20060101 C23C014/08; C09D 5/00 20060101
C09D005/00; C09D 1/00 20060101 C09D001/00; C23C 14/58 20060101
C23C014/58; C23C 14/54 20060101 C23C014/54; C23C 14/12 20060101
C23C014/12 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 5, 2008 |
JP |
20080228587 |
Claims
1. A method for preparing an abrasion resistant oil-repellent film
on a substrate comprising: a first film deposition process for
depositing a first film on a surface of a substrate by a film
deposition method of repeating a sputtering treatment and a plasma
exposure treatment alternately, a first irradiation process for
irradiating first particles having energy to the first film, and a
second film deposition process for depositing a second film having
oil repellency on a surface of the first film after the first
irradiation process.
2. The method for depositing a film according to claim 1, wherein
the film deposition method is used to deposit a first film on a
substrate surface to form a film having a predetermined thickness
and the film deposition stops at the point; as a first irradiation
step, irradiation of the first particles starts from reaction gas
active species in a first ion beam or first plasma so as to perform
a treatment on the deposited first film surface; and a vacuum
deposition method is used to deposit a second film having oil
repellency on the surface subjected to the treatment so as to form
an abrasion resistant oil-repellent film on the substrate.
3. The method for depositing a film according to claim 2, wherein
the first film is configured in a way so that the first film and
the second film form the abrasion resistant oil-repellent film on
the substrate; and the abrasion resistance is provided by
depositing components constituting the second film in a way such
that the components coat a surface of the first film, which the
surface is subjected to the treatment as the first irradiation
step.
4. The method for depositing a film according to claim 2, wherein a
first film deposited on a substrate surface by the film deposition
method is formed of an inorganic material selected from SiO.sub.2,
ZrO.sub.2, Si.sub.3N.sub.4 and Al.sub.2O.sub.3 and configured to be
a single layer or multilayer.
5. The method for depositing a film according to claim 2, wherein a
thickness of the first film is 3 to 1000 nm and a thickness of the
second film is 1 to 20 nm.
6. The method for depositing a film according to claim 2, wherein,
prior to deposition of a first film on a substrate surface, second
particles having energy, which are different from first particles
to be irradiated after deposition of the first film, are irradiated
to the substrate surface so as to perform a treatment on the
substrate surface.
7. The method for depositing a film according to claim 6, wherein
second particles are irradiated from reaction gas active species in
a second ion beam, which is different from a first ion beam, or
second plasma, which is different from first plasma.
8. The method for depositing a film according to claim 1, wherein
the film deposition method is used for depositing a first film on a
substrate surface so as to form a film having a predetermined
thickness and stopping only sputtering processing at the point;
irradiation of plasma is continued as a first irradiation step to
perform a treatment on a surface of the deposited first film; and a
vacuum deposition method is used to deposit a second film having
oil repellency on a surface subjected to the treatment so as to
form an abrasion resistant oil-repellent film on the substrate.
9. The method of depositing a film according to claim 8, wherein
the first film is configured in a way so that the first film and
the second film form the abrasion resistant oil-repellent film on
the substrate; and the abrasion resistance is provided by
depositing components constituting the second film in a way such
that the components coat a surface of the first film, which the
surface is subjected to the treatment as the first irradiation
step.
10. The method for depositing a film according to claim 8, wherein
the first film deposited on the substrate surface by the film
deposition method is formed of an inorganic material selected from
SiO.sub.2, ZrO.sub.2, Si.sub.3N.sub.4 and Al.sub.2O.sub.3 and
configured to be a single layer or multilayer.
11. The method for depositing a film according to claim 8, wherein
a thickness of the first film is 3 to 1000 nm and a thickness of
the second film is 1 to 20 nm.
12. The method for depositing a film according to claim 8, wherein,
prior to deposition of the first film on the substrate surface,
second plasma irradiation, which is different from plasma
irradiation subsequent to deposition of the first film, is
performed on the substrate surface so as to perform a treatment on
the substrate surface.
13. The method for depositing a film according to claim 1, wherein
the substrate is a glass substrate with a pencil hardness of 6H and
the second film is formed from a fluorine-containing organosilicon
compound.
14. The method for depositing a film according to claim 1, wherein
the substrate is a display for a plasma display panel, cathode ray
tube, liquid crystal display, electroluminescence display, cover
glass for watches or gauges, or touch surfaces of touch-sensitive
electronic equipment.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of pending U.S.
patent application Ser. No. 15/055,660, filed Feb. 29, 2016, which
is a divisional of U.S. patent application Ser. No. 13/059,145,
filed Feb. 15, 2011, now U.S. Pat. No. 9,315,415, issued Apr. 19,
2016, which is a 371 of International Application No.
PCT/JP2009/064730, filed Aug. 24, 2009 (of which the entire
disclosure of the pending, prior application is hereby incorporated
by reference).
TECHNICAL FIELD
[0002] The present invention relates to a method for depositing a
film and an oil-repellent substrate.
BACKGROUND ART
[0003] There is known an oil-repellent article prepared by coating
scratches having a depth of 10 to 400 nm on a surface of a
substrate consisting of glass, plastics, or the like so that the
surface has fine streaky convexes and concaves in a predetermined
direction, and then coating an oil-repellent film having a
predetermined composition on the surface having the fine convexes
and concaves (Patent document 1).
PRIOR ART REFERENCE
Patent Document
[0004] Patent document 1: Japanese Patent Unexamined Publication
(KOKAI) No. 9-309745
SUMMARY OF THE INVENTION
Object to be Achieved by the Invention
[0005] When oil components, such as fingerprint components, adhere
to an oil-repellent film surface of an oil-repellent article of
this type, the oil components are wiped off with wiping cloth or
the like.
[0006] In an oil-repellent article formed by the method of Patent
document 1, streaky scratches are coated in a predetermined
direction with a predetermined depth on the surface of the
substrate. Therefore, it has a problem that when wiping cloth or
the like is slid on the surface in a direction crossing the
scratches to wipe off the oil components, the oil-repellent film
coated as the outermost surface layer is easily shaved off, and oil
repellency of the oil-repellent film is eliminated by such
wear.
[0007] In particular, the traverse friction test of the
oil-repellent article formed by the method of Patent document 1 was
performed with canvas cloth under a condition that a small load of
0.1 kg/cm.sup.2 was applied (refer to the paragraph [0038] of
Patent document 1), and it cannot be said that the oil-repellent
film has practically sufficient abrasion resistance only with such
a test.
[0008] An object of the present invention is to provide an
oil-repellent substrate having an oil-repellent film showing
practically sufficient abrasion resistance, and a method for
depositing a film, which enables production of such an
oil-repellent substrate.
Means for Achieving the Object
[0009] The present invention achieves the aforementioned object
with the means for achieving the object described below. The means
for achieving the object described below is explained with
numerical notations corresponding to those used in the drawings
showing embodiments of the present invention. However, these
notations are used only for making it easier to understand the
present invention, and are not intended to limit the scope of the
present invention.
[0010] The method for depositing a film of the present invention
comprises the first film deposition step of depositing a first film
(103) on a surface of a substrate (101) by using a dry process, the
first irradiation step (postoperative irradiation) of irradiating
particles having energy on the first film (103), and the second
film deposition step of depositing a second film (105) having oil
repellency on a surface of the first film (103) subjected to the
first irradiation step.
[0011] As the particles having energy used for the first
irradiation step, for example, particles having energy of
accelerating voltage at 100 to 2000 V, particles having energy of
current density at 1 to 120 .mu.A/cm.sup.2, or particles having
energy of accelerating voltage at 100 to 2000 V and current density
at 1 to 120 .mu.A/cm.sup.2 can be used. In the first irradiation
step, the irradiation time of the particles having energy may be,
for example, 1 to 800 seconds, and the number of particles having
energy to be irradiated may be, for example, 1.times.10.sup.13 to
5.times.10.sup.17 particles/cm.sup.2. The particles having energy
used for the first irradiation step may consist of an ion beam
containing at least argon (for example, ion beam of argon, or ion
beam of a mixed gas of oxygen and argon).
[0012] In the first film deposition step, the first film (103) can
be deposited with a thickness of 3 to 1000 nm. Further, in the
first film deposition step, the first film (103) can be deposited
by the ion-assisted deposition method using an ion beam, or can be
deposited by repeating a sputtering treatment and a plasma
treatment. When the first film deposition step is performed by the
ion-assisted deposition method, as the ion beam used for this film
deposition, for example, an ion beam of accelerating voltage at 100
to 2000 V, an ion beam of current density at 1 to 120
.mu.A/cm.sup.2, or an ion beam of accelerating voltage at 100 to
2000 V and current density at 1 to 120 .mu.A/cm.sup.2 can be used.
In the first film deposition step, the irradiation time of the ion
beam may be, for example, 1 to 800 seconds, and the number of
particles of the ion beam to be irradiated may be, for example,
1.times.10.sup.13 to 5.times.10.sup.17 particles/cm.sup.2. The ion
beam used for the first film deposition step may be an ion beam of
oxygen, an ion beam of argon, or an ion beam of a mixed gas of
oxygen and argon.
[0013] In advance of the first film deposition step, a second
irradiation step (preoperative irradiation) for irradiating a
surface of the substrate (101) with particles having energy may be
performed. As the particles having energy used for the second
irradiation step, for example, particles having energy of
accelerating voltage at 100 to 2000 V, particles having energy of
current density at 1 to 120 .mu.A/cm.sup.2, or particles having
energy of accelerating voltage at 100 to 2000 V and current density
at 1 to 120 .mu.A/cm.sup.2 can be used. In the second irradiation
step, the irradiation time of the particles having energy may be,
for example, 60 to 1200 seconds, and the number of particles having
energy to be irradiated may be, for example, 5.times.10.sup.14 to
5.times.10.sup.17 particles/cm.sup.2. The particles having energy
used for the second irradiation step may consist of an ion beam
containing at least argon or oxygen (for example, ion beam of
argon, ion beam of oxygen, or ion beam of a mixed gas of oxygen and
argon).
[0014] In the oil-repellent substrate (100) of the present
invention, the first film (103) is coated on the surface of the
substrate (101), the second film (105) having oil repellency is
coated on the surface of the first film (103), and the first film
(103) has the following surface characteristics as measured by the
methods defined in JIS-B0601: center line average height (Ra): 0.1
to 1000 nm, 10-point average height (Rz): 5 to 2000 nm, and maximum
valley depth (Pv): 15 to 2000 nm.
[0015] The convexes observed on the surface of the first film (103)
may exist with periodic intervals of 0.1 to 5000 nm. Even after the
second film (105) is reciprocally rubbed with steel wool #0000 with
a load of 1 kg/cm.sup.2 over 500 times, oily pen ink on the film
can be wiped off. The first film (103) may be composed of a
material having hardness higher than that of the substrate (101).
The hardness is represented by a value of pencil hardness measured
by the method defined in JIS-K5600-5-4. Difference of the hardness
values of the first film (103) and the substrate (101) is
preferably two or more in terms of score of the pencil hardness
measured by the method defined in JIS-K5600-5-4 (for example, when
the latter is 7H, the former is 9H or higher).
Effect of the Invention
[0016] According to the present invention, since particles having
predetermined energy are irradiated on the predetermined first film
that is deposited on the surface of the substrate (the first
irradiation step), appropriate concaves are formed on the surface
of the first film subjected to the irradiation. Therefore, the
components constituting the second film having oil repellency
(oil-repellent molecules), which are deposited thereafter, can also
adhere to the concaves of the first film. Abrasion resistance of
the second film deposited on the surface of the first film can be
thereby improved to a practically sufficient level.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a sectional view of an oil-repellent substrate
according to the first embodiment.
[0018] FIG. 2 is a sectional view of a film deposition system
according to the second embodiment seen from the front, which
enables production of the oil-repellent substrate of FIG. 1.
[0019] FIG. 3 is a sectional view of a film deposition system
according to the third embodiment seen from the front, which
enables production of the oil-repellent substrate of FIG. 1.
[0020] FIG. 4 is a sectional view of an important part of the film
deposition system of FIG. 3 seen from the side.
[0021] FIG. 5 is an enlarged explanatory view of a part of the film
deposition system of FIG. 3 around the sputtering region.
[0022] FIG. 6 is an enlarged explanatory view of a part of the film
deposition system of FIG. 3 around the plasma treatment region.
DESCRIPTION OF NUMERICAL NOTATIONS
[0023] 100 . . . Oil-repellent substrate, 101 . . . substrate, 103
. . . first film, 105 . . . oil-repellent film (second film), 1, 1a
. . . film deposition system, 2 . . . vacuum vessel, 30A . . .
vapor deposition region, 34, 36 . . . vapor deposition source, 34a,
36a, 38a . . . shutter, 34b, 36b . . . crucible, 34c . . . electron
gun, 34d . . . electron gun power supply, 38 . . . ion gun, 38b . .
. adjustment wall, 5 . . . neutralizer, 5a . . . adjustment wall, 4
. . . rotary drum, 4a, 4a' . . . substrate holder, 40 . . . motor,
50 . . . crystal monitor, 51 . . . film thickness detector, 52 . .
. controller, 53 . . . electric heater, 54 . . . temperature
sensor, 60A . . . plasma treatment region, 60 . . . plasma
generation means, 70 . . . reactive gas supply means, 71 . . .
oxygen gas cylinder, 72 . . . massflow controller, 80A . . .
sputtering region, 80 . . . sputtering means, 81a, 81b . . .
sputtering electrode, 82a, 82b . . . target, 83 . . . transformer,
84 . . . AC power supply, 90 . . . sputtering gas feeding means, 92
. . . sputtering gas cylinder.
MODES FOR CARRYING OUT THE INVENTION
[0024] Hereafter, embodiments of the aforementioned invention will
be explained with reference to the drawings.
First Embodiment
[0025] In this embodiment, an example of the oil-repellent
substrate is explained.
[0026] As shown in FIG. 1, the oil-repellent substrate 100 of this
embodiment comprises the substrate 101, and the first film 103 is
coated on at least one surface of the substrate 101. On the first
film 103, the second film 105 having oil repellency (henceforth
referred to as "oil-repellent film") is coated.
[0027] As the substrate 101, a plastic substrate (organic glass
substrate) or an inorganic substrate (inorganic glass substrate) as
well as a substrate of metal such as stainless steel can be used,
and the thickness thereof is, for example, 0.1 to 5 mm. Examples of
the inorganic glass substrate, which is an example of the substrate
101, include, for example, those of soda lime glass (6H to 7H),
borosilicate glass (6H to 7H), and so forth.
[0028] First, the first film 103 is deposited by using a dry
deposition process. For example, when the first film 103 is
constituted with SiO.sub.2, if it is coated by a wet deposition
process such as the sol-gel method, sufficient scratch resistance
may not be imparted, and as a result, the oil-repellent film 105
having practically sufficient abrasion resistance, which is
described later, may not be deposited. The first film 103 is
preferably constituted with a material showing pencil hardness
higher than 9H measured by, for example, the method defined in
JIS-K5600-5-4, including, for example, SiO.sub.2, ZrO.sub.2,
Si.sub.3N.sub.4, Al.sub.2O.sub.3, and so forth. By coating the
first film 103 consisting of a material having hardness higher than
the hardness of the substrate 101 on the surface of the substrate
101, it is made easier to improve the abrasion resistance of the
oil-repellent film 105 described later to a practically sufficient
level.
[0029] Second, the surface characteristics (surface roughness) of
the first film 103 are appropriately controlled so that appropriate
concaves are formed on the surface. Specifically, center line
average height (Ra), 10-point average height (Rz), and maximum
valley depth (Pv) are appropriately adjusted. All of Ra, Rz, and Pv
are indices indicating unevenness of the surface of the first film
103. In this embodiment, although the definition of the surface
roughness (Ra, Rz, Pv) of the first film 103 is based on JIS-B0601,
it is also surface roughness in a minute region or in a minute
scale measured by using, for example, a non-contact surface
roughness profiler, an atomic force microscope (AFM), or the
like.
[0030] In order to improve abrasion resistance of the oil-repellent
film 105 described later to a practically sufficient level, the
inventors of the present invention conducted researches for forming
appropriate concaves on the surface of the first film 103 with
paying attention to the specific indices concerning the surface
characteristics. As a result, they found that, by appropriately
controlling values of Ra, Rz and Pv concerning surface roughness
among many parameters representing surface characteristics,
appropriate concaves were formed on the surface of the first film
103, and abrasion resistance of the oil-repellent film 105 formed
thereafter could be improved to a practically sufficient level.
That is, since the surface characteristics of the first film 103
according to this embodiment are appropriately controlled, abrasion
resistance of the oil-repellent film 105 described later can be
improved to a practically sufficient level.
[0031] All of the center line average height (Ra), 10-point average
height (Rz), and maximum valley depth (Pv) are indices representing
unevenness of the surface of the first film 103.
[0032] According to this embodiment, Ra of the first film 103 is
preferably adjusted to be 0.1 nm or larger, more preferably 1 nm or
larger, still more preferably 3 nm or larger. If Ra of the first
film 103 is adjusted to be the predetermined value or larger, even
after the surface of the oil-repellent film 105 described later is
scratched by rubbing with steel wool, components constituting the
oil-repellent film 105 (oil-repellent molecules) adhering to the
concaves of the first film 103 can be remained. As a result,
expression of the oil repellency can be secured. On the other hand,
when Ra of the first film 103 is too large, the oil repellency of
the oil-repellent film 105 tends to be degraded. Therefore, in this
embodiment, it is desirable that Ra of the first film 103 is
preferably adjusted to be 1000 nm or smaller, more preferably 100
nm or smaller, still more preferably 20 nm or smaller.
[0033] According to this embodiment, Rz of the first film 103 is
preferably adjusted to be 5 nm or larger, more preferably 7 nm or
larger, still more preferably 10 nm or larger. If Rz of the first
film 103 is adjusted to be the predetermined value or larger, even
after the surface of the oil-repellent film 105 described later is
scratched by rubbing with steel wool, components constituting the
oil-repellent film 105 (oil-repellent molecules) adhering to the
concaves of the first film 103 can be remained. As a result,
expression of the oil repellency can be secured. On the other hand,
when Rz of the first film 103 is too large, the oil repellency of
the oil-repellent film 105 tends to be degraded. Therefore, in this
embodiment, it is desirable that Rz of the first film 103 is
preferably adjusted to be 2000 nm or smaller, more preferably 200
nm or smaller, still more preferably 50 nm or smaller.
[0034] According to this embodiment, Pv of the first film 103 is
preferably adjusted to be 15 nm or larger, more preferably 20 nm or
larger, still more preferably 30 nm or larger. If Pv of the first
film 103 is adjusted to be the predetermined value or larger, even
after the surface of the oil-repellent film 105 described later is
scratched by rubbing with steel wool, components constituting the
oil-repellent film 105 (oil-repellent molecules) adhering to the
concaves of the first film 103 can be remained. As a result,
expression of the oil repellency can be secured. On the other hand,
when Pv of the first film 103 is too large, the oil repellency of
the oil-repellent film 105 tends to be degraded. Therefore, in this
embodiment, it is desirable that Pv of the first film 103 is
preferably adjusted to be 2000 nm or smaller, more preferably 300
nm or smaller, still more preferably 150 nm or smaller.
[0035] The values of Ra, Rz and Pv are values measured according to
JIS-B0601.
[0036] In this embodiment, the first film 103 is preferably
prepared so that appropriate concaves are formed on the surface
thereof, and the convexes observed on the surface thereof exist
with predetermined periodic intervals. Specifically, it is
desirable that convexes observed when the surface roughness of the
first film 103 is measured by linear scanning preferably exist with
periodic intervals of 0.1 to 5000 nm, more preferably 1 to 1000 nm,
still more preferably 1 to 50 nm.
[0037] The periodic interval of the convexes existing on the
surface of the first film 103 referred to here means an interval A
between a certain convex to the next convex beyond a concave
between them in the surface profile of the first film 103, and it
can be calculated by dividing the linearly scanned (measured)
length with the number of peaks counted. If the intervals of the
convexes are adjusted to be within the aforementioned range, even
after the surface of the oil-repellent film 105 described later is
scratched by rubbing with steel wool, components constituting the
oil-repellent film 105 (oil-repellent molecules) adhering to the
concaves of the first film 103 can be remained. As a result,
expression of the oil repellency can be secured.
[0038] Such measurement of the periodic intervals of the convexes
existing on the surface of the first film 103 can be performed by
using a non-contact surface profiler, an atomic force microscope
(AFM), or the like, as in the case of Ra, Rz, etc. mentioned
above.
[0039] For the reasons described above, the first film 103
according to this embodiment can be coated by a dry deposition
process, for example, a dry plating method (PVD method) such as
vacuum vapor deposition method (including ion-assisted deposition
method), sputtering method, ion-plating method, and arcing
deposition, not wet deposition process, with appropriately
controlling the deposition conditions.
[0040] The first film 103 to be coated on the substrate 101 by the
vacuum vapor deposition method, the sputtering method, or the like
may be coated with a single layer or multiple layers. Thickness of
the first film 103 at this stage is, for example, about 3 to 1000
nm. If the thickness of the first film 103 at this stage is too
small, there arises a problem that the first film 103 is totally
shaved off thereafter by the irradiation of energy particles
described later, and no longer remained. On the other hand, if the
thickness of the first film 103 is too large, uneven surface
roughness may not be appropriately imparted to the surface of the
first film 103, even after irradiation of the energy particles
described later.
[0041] According to this embodiment, after the first film 103 is
deposited on the substrate 101, this first film 103 is subjected to
a treatment of irradiating particles having energy (first
irradiation treatment, postoperative irradiation). The particles
having energy are irradiated on the first film 103 in advance of
the coating of the oil-repellent film 105 described later, in order
to adjust the surface characteristics of the first film 103 to be
within the ranges described above.
[0042] Examples of the particles having energy include, for
example, ion beam emitted by an ion gun, active species of reactive
gas in plasma, and so forth. Therefore, when the first film 103 is
coated by the ion-assisted deposition method with an ion beam, for
example, after completion of the deposition, the irradiation
conditions can be changed to predetermined conditions, and then
irradiation of the ion beam can be continued. On the other hand,
when the first film 103 is deposited by repetition of a sputtering
step and a reaction step, after completion of this treatment, an
ion beam can be irradiated with predetermined irradiation
conditions. Alternatively, after the first film 103 is coated by
repetition of a sputtering step and a reaction step, active species
in plasma for which operation conditions are changed to
predetermined operation conditions may be irradiated on the first
film 103.
[0043] Thickness of the first film 103 subjected to the
postoperative irradiation is, for example, 0.1 to 500 nm,
preferably 5 to 50 nm. Unduly small or large thickness of the first
film 103 at this stage may result in insufficient abrasion
resistance of the surface, after the coating of the oil-repellent
film 105 described later.
[0044] The oil-repellent film 105 has a function of preventing
adhesion of oil stains. The expression "preventing adhesion of oil
stains" used here means to attain not only a condition that oil
stains do not adhere, but also a condition that oil stains can be
easily wiped off, even if they adhere.
[0045] That is, the oil-repellent film 105 maintains oil
repellency. Specifically, abrasion resistance of the oil-repellent
film 105 of this embodiment is improved to such a practically
sufficient level that even after it is reciprocally rubbed with
steel wool #0000 at a load of 1 kg/cm.sup.2 over 500 times
(preferably 1000 times), ink of oily pen adhering to it can be
wiped off. The abrasion resistance is improved as described above,
because appropriate concaves are formed on the surface of the base
for coating the oil-repellent film 105 (first film 103) by the
treatment of irradiating energy particles mentioned above, so that
the surface characteristics are controlled.
[0046] The oil-repellent film 105 can be constituted with an
organic compound having at least one hydrophobic group and at least
one reactive group that can bind with hydroxyl group in the
molecule (also referred to simply as "hydrophobic reactive organic
compound"), or the like.
[0047] Examples of the hydrophobic reactive organic compound
include, for example, fluorine-containing organic compounds
containing a polyfluoroether group or a polyfluoroalkyl group, and
so forth.
[0048] Thickness of the oil-repellent film 105 is preferably 0.5 to
100 nm, more preferably 1 to 20 nm.
[0049] The oil-repellent film 105 can be deposited by, for example,
using the vacuum vapor deposition method, chemical vapor deposition
(CVD) method, or the like, with appropriately controlling the
deposition conditions thereof.
[0050] Although coating of the oil-repellent film 105 may be
performed separately from coating of the first film 103 with
different apparatuses, they are preferably performed successively
in the same apparatus. Such film deposition scheme can be attained
by changing the deposition source from the material for coating the
first film 103 to the material for coating the oil-repellent film
105. The coating of the films can also be performed with a single
deposition apparatus by providing a plurality of deposition
sources.
[0051] In the oil-repellent substrate 100 according to this
embodiment, the surface characteristics of the first film 103
coated on at least one surface of the substrate 101 are
appropriately controlled as described above. Therefore, abrasion
resistance of the oil-repellent film 105 coated on the surface of
the first film 103 is improved to a practically sufficient
level.
[0052] Therefore, the oil-repellent substrate 100 of this
embodiment is preferably applied to uses requiring oil repellency,
for example, various displays (for example, plasma display panel
(PDP), cathode ray tube (CRT), liquid crystal display (LCD),
electroluminescence display (ELD) etc.); showcases; cover glass
such as that of watches and gauges; touch surfaces of
touch-sensitive electronic equipments such as bank ATMs and ticket
machines; various electronic equipments having such various
displays as mentioned above such as cellular phones and personal
computers; and so forth.
Second Embodiment
[0053] In this embodiment, an example of a film deposition system
that enables production of the oil-repellent substrate 100 of FIG.
1 is explained.
[0054] As shown in FIG. 2, the film deposition system 1 of this
embodiment comprises a vertically disposed cylindrical vacuum
vessel 2. The vacuum vessel 2 is constituted so that it is
evacuated by an evacuating means (not shown in the drawing) to a
predetermined pressure. A load lock chamber may be connected to the
vacuum vessel 2 via a door. If a load lock chamber is provided, it
becomes possible to carry in and out the substrate 101 with
maintaining the vacuum in the vacuum vessel 2.
[0055] At an upper position in the vacuum vessel 2, a substrate
holder 4a' made of stainless steel having a spherical shape is
rotatably held around a vertical axis. An aperture is provided at
the center of the substrate holder 4a', and a crystal monitor 50 is
disposed there. The crystal monitor 50 detects physical film
thickness by a thickness detector 51 on the basis of change of the
resonance frequency due to deposition of a thin film on the surface
thereof. The result of film thickness detection is sent to a
controller 52.
[0056] In the inside of the vacuum vessel 2, an electric heater 53
is disposed so as to wrap the substrate holder 4a'. Temperature of
the substrate holder 4a' is detected with a temperature sensor 54
such as a thermocouple, and the result is sent to the controller
52. The controller 52 controls the electric heater 53 using output
from the temperature sensor 54 to appropriately control the
temperature of the substrate 101.
[0057] At lower positions in the inside of the vacuum vessel 2,
evaporation sources 34 and 36 for adhering materials for film
deposition to the substrates 101 held by the substrate holder 4a',
and an ion gun 38 for irradiating positive ions on the substrates
101 are disposed.
[0058] The evaporation source 34 is provided with a crucible (boat)
34b having a pitting for carrying a film deposition material on the
upper part, an electron gun 34c for irradiating an electron beam
(e.sup.-) on the film deposition material to evaporate it, and a
shutter 34a openably and closably disposed at a position for
intercepting the film deposition material going to the substrates
101 from the crucible 34b. When the film deposition material is put
on the crucible 34b, and electric power is supplied to the electron
gun 34c by the electron gun power supply 34d to generate an
electron beam from the electron gun 34c and irradiate this electron
beam on the film deposition material, the film deposition material
is heated and evaporated. If the shutter 34a is opened in such a
state, the film deposition material evaporating from the crucible
34b moves towards the substrates 101 in the inside of the vacuum
vessel 2, and adheres to the surfaces of the substrates 101.
[0059] The evaporation source 36 is an evaporation source of
resistance heating type such as those of direct heating type and
indirect heating type in this embodiment, and is provided with a
crucible (boat) 36b having a pitting for carrying a film deposition
material on the upper part, and a shutter 36a openably and closably
disposed at a position for intercepting the film deposition
material going to the substrates 101 from the crucible 36b.
According to the direct heating method, electrodes are attached to
the metal boat to flow electric current so as to directly heat the
metal boat using the boat itself as an electrical resistance
heater, and heat the film deposition material put into it. The
indirect heating method is a method in which the boat is not a
direct heat source, and it is heated by applying an electric
current to a heating means separately disposed apart from the boat,
for example, a deposition filament consisting of a rare metal such
as a transition metal. If the film deposition material put on the
crucible 36b is heated by the boat itself or a heater provided
apart from the boat, and the shutter 36a is opened in this state,
the film deposition material evaporating from the crucible 36b
moves towards the substrates 101 in the inside of the vacuum vessel
2, and adhere to the surfaces of the substrates 101.
[0060] The ion gun 38 is an ion source for ion assistance, and it
withdraws charged ions (O.sup.2+, Ar.sup.+) from plasma of reactive
gas (O.sub.2 etc.) or rare gas (Ar etc.) and radiates them towards
the substrates 101 with acceleration at a predetermined
accelerating voltage. Above the ion gun 38, a shutter 38a is
openably and closably disposed. Adjustment walls 38b and 38b for
adjusting directivity of the ions withdrawn by the ion gun 38 are
provided above the shutter 38a.
[0061] With the collision energy of the cations irradiated from the
ion gun 38, the film deposition material moved towards the
substrates 101 from the evaporation sources 34 and 36 highly
densely and firmly adheres to the surfaces of the substrates 101.
At this time, the substrate 101 is positively charged with the
cations contained in the ion beam.
[0062] In addition, there occurs a phenomenon that the whole
substrate 101 is positively charged (charge up) due to accumulation
of cations radiated from the ion gun 38 (for example, O.sup.2+ in
the substrate 101. If charge up occurs, abnormal discharge may
occur between the positively charged substrate 101 and another
member, and the thin film (insulating layer) coated on the surface
of the substrate 101 may be destroyed by impact of the discharge.
Further, since the collision energy of the cations radiated from
the ion gun 38 is reduced by the positive charging of the substrate
101, denseness, adhesion strength, etc. of the thin film may be
decreased.
[0063] Therefore, according to this embodiment, in order to
electrically neutralize the positive charge accumulated in the
substrate 101, a neutralizer 5 is disposed in the middle of the
sidewall of the vacuum vessel 2. During the irradiation of the ion
beam by the ion gun 38, the neutralizer 5 discharges electrons
(e.sup.-) towards the substrate 101, that is, it withdraws
electrons from plasma of a rare gas such as Ar, and radiates them
with acceleration by accelerating voltage. The electrons radiated
from it neutralize electrification due to the ions adhering to the
surface of the substrate 101. In addition, adjustment walls 5a and
5a for adjusting directivity of the electrons discharged from the
neutralizer 5 are disposed above the neutralizer 5.
[0064] Hereafter, an example of the method for depositing a film
using the film deposition system 1 will be explained.
[0065] In this embodiment, a case where metallic silicon (Si) or
silicon oxide (SiO.sub.2) is used as the first film deposition
material charged in the boat of the evaporation source 34 is
exemplified. The second film deposition material as a material for
coating the oil-repellent film charged in the boat of the
evaporation source 36 is not particularly limited.
[0066] Further, in this embodiment, there is exemplified a case
where the first film 103 is deposited by the ion-beam assisted
deposition method (IAD) using an ion gun, the first irradiation
treatment (postoperative irradiation) is carried out with an ion
beam generated by the ion gun for the first film 103, and the
oil-repellent film 105 is deposited by the vacuum vapor deposition
method of resistance heating type.
[0067] Form of the first film deposition material is not
particularly limited, and for example, the material in the form of
a pellet can be used. The heating method for the first film
deposition material is not limited to the electron beam heating
method, and a heat source enabling sufficient heating for
evaporating the deposition material, such as halogen lamp, sheathed
heater, resistance heating, and induction heating can be used.
[0068] Form of the second film deposition material is not
particularly limited, and for example, (a) a hydrophobic reactive
organic compound impregnated in porous ceramics, or (b) a
hydrophobic reactive organic compound impregnated in a mass of
metal fibers or filaments can be used. These can quickly absorb a
lot of the hydrophobic reactive organic compound, and evaporate it.
The porous ceramics is preferably used in the form of pellet in
view of handling property.
[0069] Examples of the metal fibers or filaments include, for
example, those of iron, platinum, silver, copper, and so forth. As
the metal fibers or filaments, it is preferable to use those of
such an entangled state that they can hold a sufficient amount of
the hydrophobic reactive organic compound, for example, those in
the form of woven fabric or nonwoven fabric. Void ratio of the mass
of metal fibers or filaments can be determined according to amount
of the hydrophobic reactive organic compound to be held.
[0070] When a mass of metal fibers or filaments is used for the
second film deposition material, it is preferably held in a
container of which one end is opened. The mass of metal fibers or
filaments held in a container can also be regarded as a pellet.
Although shape of the container is not particularly limited,
examples include those of Knudsen type, divergent nozzle type,
straight cylinder type, divergent cylinder type, boat type,
filament type, and so forth, and type of the container can be
suitably chosen according to the specification of the vapor
deposition apparatus. At least one end of the container is opened,
so that the hydrophobic reactive organic compound evaporates from
the open end. As the material of the container, metals such as
copper, tungsten, tantalum, molybdenum and nickel, ceramics such as
alumina, carbon, and so forth can be used, and it is appropriately
chosen according to types of the vapor deposition apparatus, the
hydrophobic reactive organic compound, and so forth.
[0071] Sizes of both the porous ceramic pellet and the pellet
consisting of a mass of metal fibers or filaments held in a
container are not limited.
[0072] When porous ceramics or a mass of metal fibers or filaments
is impregnated with the hydrophobic reactive organic compound, a
solution of the hydrophobic reactive organic compound in an organic
solvent is prepared first, porous ceramics or a mass of metal
fibers or filaments is impregnated with the solution by the dipping
method, dropping method, spraying method, or the like, and then the
organic solvent is evaporated. Since the hydrophobic reactive
organic compound has a reactive group (hydrolysable group), it is
preferable to use an inert organic solvent.
[0073] Examples of the inert organic solvent include
fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane,
perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon
solvents (m-xylene hexafluoride, benzotrifluoride etc.),
fluorine-modified ether solvents (methyl perfluorobutyl ether,
perfluoro(2-butyltetrahydrofuran) etc.), fluorine-modified
alkylamine solvents (perfluorotributylamine,
perfluorotripentylamine etc.), hydrocarbon solvents (toluene,
xylene etc.), ketone solvents (acetone, methyl ethyl ketone, methyl
isobutyl ketone etc.), and so forth. These organic solvents can be
used independently or as any combination of two or more kinds of
them. Concentration of the hydrophobic reactive organic compound
solution is not limited, and it can be appropriately determined
according to shape of the carrier to be impregnated with the
hydrophobic reactive organic compound.
[0074] The method for heating the second film deposition material
is not limited to the resistance heating method, and a halogen
lamp, sheathed heater, electron beam, plasma electron beam,
induction heating, and so forth can be used.
[0075] (1) First, a plurality of the substrates 101 are fixed on
the substrate holder 4a'. The substrates 101 fixed on the substrate
holder 4a' can be constituted from glass, plastics or metal
processed into a tabular shape, lenticular shape, or the like. In
addition, the substrates 101 are preferably subjected to wet
cleaning before or after the fixation.
[0076] (2) Then, after the substrate holder 4a' is set in the
inside of the vacuum vessel 2, the inside of the vacuum vessel 2 is
evacuated to about 10.sup.-4 to 10.sup.-2 Pa. If the pressure is
lower than 10.sup.-4 Pa, too much time may be required for the
evacuation to degrade the productivity. On the other hand, if the
pressure is higher than 10.sup.-2 Pa, film deposition may become
insufficient, and thus film characteristics may be degraded.
[0077] (3) Then, the electric heater 53 is electrified and thereby
made to generate heat, and the substrate holder 4a' is rotated at a
low speed. This rotation provides uniform temperature and uniform
film deposition conditions of a plurality of the substrates
101.
[0078] When the controller 52 determines that the temperature of
the substrates 101 has reached a temperature of from ordinary
temperature to 120.degree. C., preferably 50 to 90.degree. C.,
according to the output of the temperature sensor 54, it starts the
film deposition step. If the substrate temperature is lower than
ordinary temperature, there is observed a tendency that density of
the first film 103 to be deposited becomes low, and sufficient
durability of the film cannot be obtained. If the substrate
temperature exceeds 120.degree. C., plastic substrates used as the
substrates 101 may be degraded or deformed. In addition, when a
material suitable for unheated film deposition is used, the film
deposition may be carried out at ordinary temperature.
[0079] In this embodiment, before starting the film deposition
step, the ion gun 38 is made to be in an idling operation state.
Further, the evaporation sources 34 and 36 are also prepared so
that the first film deposition material and the second film
deposition material can be immediately diffused (discharged) by
opening operation of the shutters 34a and 36a.
[0080] (4) Then, the controller 52 increases the irradiation
electric power for the ion gun 38 from that of the idling state to
a predetermined irradiation power, and opens the shutter 38a and
the shutter 34a to perform ion beam-assisted deposition (IAD) of
the first film deposition material. The operation of the
neutralizer 5 is also started at this time. That is, the step of
dispersing the first film deposition material from the evaporation
source 34, the step of irradiating an ion beam of introduced gas
(oxygen in this case) withdrawn from the ion gun 38, and the step
of irradiating electrons, to the film deposition surface of the
substrate 101, are performed in parallel (first film deposition
process).
[0081] The assisting conditions of the ion beam are as follows. As
for type of the gas introduced into the ion gun 38, for example,
oxygen, argon, or a mixed gas of oxygen and argon is preferred.
Volume of the gas of the aforementioned type introduced into the
ion gun 38 is, for example, 1 to 100 sccm, preferably 5 to 50 sccm.
The unit "sccm" is an abbreviation for "standard cc/m", and
indicates a value at 0.degree. C. and 101.3 kPa (1 atmosphere).
[0082] The accelerating voltage (V1) of the ions is, for example,
100 to 2000 V, preferably 200 to 1500 V. The current density (I1)
of the ions is, for example, 1 to 120 .mu.A/cm.sup.2, preferably 5
to 50 .mu.A/cm.sup.2.
[0083] The irradiation time (T1) of the ions is, for example, 1 to
800 seconds, preferably 10 to 100 seconds. The value obtained by
dividing the product of I1 and T1 with the elementary electric
charge of electron e (=1.602.times.10.sup.-19 C) (=(I1.times.T1)/e)
represents number of ions to be irradiated, and in this embodiment,
the ion beam can be irradiated at an irradiated ion number in the
range of, for example, 1.times.10.sup.13 to 5.times.10.sup.17
ions/cm.sup.2, preferably 5.times.10.sup.13 to 5.times.10.sup.14
ions/cm.sup.2.
[0084] In addition, the irradiation energy density
(=V1.times.I1.times.T1) can also be controlled by, for example,
shortening the irradiation time (T1) for increasing the irradiation
electric power density, or lengthening the irradiation time (T1)
for decreasing the irradiation electric power density.
[0085] The operation conditions of the neutralizer 5 are as
follows. As for type of the gas introduced into the neutralizer 5,
it is, for example, argon. Introduction volume of the gas of the
aforementioned type is, for example, 10 to 100 sccm, preferably 30
to 50 sccm. The accelerating voltage of electrons is, for example,
20 to 80 V, preferably 30 to 70 V. The electronic current may be
such a current that an electric current higher than the ionic
current is supplied.
[0086] As the first film 103, three-dimensional nuclei are
deposited on the substrate 101 first at an early stage of the film
deposition, and then they grow with increase of the film deposition
amount (vapor deposition amount), combine together, and eventually
grow into a continuous film (island growth).
[0087] As described above, the first film 103 consisting of
SiO.sub.2 is deposited on the surface of the substrate 101 with a
predetermined thickness. The controller 52 continues monitoring of
the thickness of the thin film coated on the substrate 101 with the
crystal monitor 50, and when it reaches a predetermined thickness,
the controller 52 terminates the film deposition.
[0088] (5) Then, when the controller 52 terminates the film
deposition, it closes only the shutter 34a, while the shutter 38a
is maintained to be opened. In this state, the controller 52
changes the irradiation electric power of the ion gun 38 to a
predetermined irradiation electric power, and continues the
irradiation of ion beam. This step is an example of the first
irradiation treatment (postoperative irradiation). This embodiment
is characterized in that a postoperative irradiation is performed
for the first film 103 coated on the surface of the substrate
101.
[0089] By performing the postoperative irradiation, a surface
portion of the first film 103 is shaved off, and as a result,
appropriate concaves are provided on the surface of the first film
103.
[0090] Conditions of the postoperative irradiation are as follows.
As for type of the gas introduced into the ion gun 38, it is
sufficient that it contains at least argon or oxygen, and it may be
a mixed gas of argon and oxygen, but it preferably contains at
least argon. Volume to be introduced of the gas of the
aforementioned type (total volume in the case of a mixed gas) is,
for example, 10 to 100 sccm, preferably 20 to 70 sccm.
[0091] The accelerating voltage (V2) of the ions is, for example,
100 to 2000 V, preferably 200 to 1500 V. The current density (I2)
of the ions is, for example, 1 to 120 .mu.A/cm.sup.2, preferably 5
to 50 .mu.A/cm.sup.2.
[0092] The irradiation time (T2) of the ions is, for example, 1 to
800 seconds, preferably 10 to 100 seconds. The value obtained by
dividing the product of I2 and T2 with the elementary electric
charge of electron e (=1.602.times.10.sup.-19 C) (=(I2.times.T2)/e)
represents number of ions to be irradiated, and the ion beam can be
irradiated at an irradiated ion number in the range of, for
example, 1.times.10.sup.13 to 5.times.10.sup.17 ions/cm.sup.2,
preferably 1.times.10.sup.13 to 1.times.10.sup.17 ions/cm.sup.2,
more preferably 1.times.10.sup.14 to 1.times.10.sup.16
ions/cm.sup.2.
[0093] In addition, the irradiation energy density
(=V2.times.I2.times.T2) can also be controlled by, for example,
shortening the irradiation time (T2) for increasing the irradiation
electric power density, or lengthening the irradiation time (T2)
for decreasing the irradiation electric power density.
[0094] (6) Then, the controller 52 returns the irradiation electric
power of the ion gun 38 to the level of the idling state, closes
the shutter 38a, and opens the shutter 36a to perform vacuum vapor
deposition of the second film deposition material as a raw material
for coating an oil-repellent film by the resistance heating method.
That is, to the surface of the first film 103 subjected to the
postoperative irradiation, the second film deposition material is
dispersed, for example, for 3 to 20 minutes, from the evaporation
source 36 to perform the film deposition process (second film
deposition process).
[0095] As a result, the oil-repellent film 105 is coated on the
first film 103 subjected to the postoperative irradiation in a
predetermined thickness (for example, 1 to 50 nm). The controller
52 continues monitoring of the thickness of the thin film deposited
on the first film 103 with the crystal monitor 50, and when it
reaches a predetermined thickness, the controller 52 terminates the
vapor deposition. By the aforementioned steps, the oil-repellent
substrate 100 shown in FIG. 1 is produced.
[0096] According to the method for depositing a film using the film
deposition system 1 of this embodiment, an ion beam of the gas to
be introduced as an example of the energy particles is irradiated
on the first film 103 coated on the surface of the substrate 101 in
advance of the film deposition of the oil-repellent film 105
(postoperative irradiation). Appropriate concaves are thereby
provided on the surface of the first film 103 subjected to the ion
beam irradiation. Accordingly, the oil-repellent molecules as
constituent components of the oil-repellent film 105 to be
deposited thereafter can be adhered also to the concaves of the
first film 103. By adhering the constituent components of the
oil-repellent film 105 to the concaves of the first film 103, even
if oil components such as fingerprint components adhering to the
surface of the oil-repellent film 105 are wiped off with a heavy
load (for example, load of about 1 kg/cm.sup.2), the constituent
components of the oil-repellent film 105 can be effectively
remained on the outermost surface. That is, according to this
embodiment, it becomes possible to coat the oil-repellent film 105
having abrasion resistance of a practically sufficient level.
[0097] For this embodiment, an example where only the SiO.sub.2
thin film is coated as the first film 103 on the substrate 101 is
described. However, together with this SiO.sub.2 thin film, another
thin film such as a Si.sub.3N.sub.4 thin film and a ZrO.sub.2 thin
film can also be deposited. Further, as the first film 103 coated
on the substrate 101, another thin film such as a Si.sub.3N.sub.4
thin film and a ZrO.sub.2 thin film may be coated instead of the
SiO.sub.2 thin film. For this purpose, the material or shape of the
first film deposition material charged in the deposition source 34
may be changed in any of these cases.
[0098] Further, in this embodiment, a surface treatment of the
substrate 101 can also be performed in advance of the first film
deposition process. Specific examples of such a surface treatment
include 1) plasma treatment under an oxygen or argon atmosphere, 2)
chemical treatment with an acid or an alkali, 3) irradiation
treatment with particles having energy by the ion gun 38 (second
irradiation treatment, preoperative irradiation), and so forth.
Among these, the second irradiation treatment (preoperative
irradiation) is preferred. If the second irradiation treatment
(preoperative irradiation) is performed for the substrate 101 in
advance of the first film deposition process, the controller 52 can
increase the irradiation electric power for the ion gun 38 from the
level of the idling state to a predetermined level of irradiation
electric power, open the shutter 38a and irradiate an ion beam on
the surface of the substrate 101 in the middle of the rotation
before the first film deposition process. By performing the
preoperative irradiation for the substrate 101 before performing
the postoperative irradiation for the first film 103 deposited on
the substrate 101, more appropriate concaves can be provided on the
surface of the first film 103.
[0099] The conditions of the preoperative irradiation may be the
same as or different from those of the postoperative irradiation
mentioned above.
[0100] For example, the conditions of the preoperative irradiation
are as follows. As for type of the gas introduced into the ion gun
38, it is sufficient that it contains at least argon or oxygen, and
it may be a mixed gas of argon and oxygen. However, it is
preferably a mixed gas of argon and oxygen. Volume to be introduced
of the gas of the aforementioned type (total volume in the case of
a mixed gas) is, for example, 10 to 100 sccm, preferably 20 to 70
sccm.
[0101] The accelerating voltage (V3) of the ions is, for example,
100 to 2000 V, preferably 200 to 1500 V. The current density (I3)
of the ions is, for example, 1 to 120 .mu.A/cm.sup.2, preferably 5
to 50 .mu.A/cm.sup.2.
[0102] The irradiation time (T3) of the ions is, for example, 60 to
1200 seconds, preferably 120 to 900 seconds, more preferably 180 to
720 seconds. The value obtained by dividing the product of I3 and
T3 with the elementary electric charge of electron e
(=1.602.times.10.sup.-19 C) (=(I3.times.T3)/e) represents number of
ions to be irradiated, and in this embodiment, the ion beam is
preferably irradiated at an irradiated ion number in the range of,
for example, 5.times.10.sup.14 to 5.times.10.sup.17 ions/cm.sup.2,
preferably 1.times.10.sup.15 to 1.times.10.sup.17 ions/cm.sup.2,
more preferably 1.times.10.sup.16 to 1.times.10.sup.17
ions/cm.sup.2.
[0103] In addition, the irradiation energy density
(=V3.times.I3.times.T3) can also be controlled by, for example,
shortening the irradiation time (T3) for increasing the irradiation
electric power density, or lengthening the irradiation time (T3)
for decreasing the irradiation electric power density.
[0104] Further, depending on the conditions of the ion-assisted
deposition with the ion beam in the step (4) mentioned above, the
surface of the first film 103 may have unevenness before the
postoperative irradiation of the step (5) mentioned above is
performed. In such a case, the concaves already exist on the first
film 103 may be shaved off first by the postoperative irradiation
of the step (5) mentioned above, and the substrate 101 may be
exposed. This embodiment also includes an embodiment in which a
part of the substrate 101 is exposed by the postoperative
irradiation.
Third Embodiment
[0105] In this embodiment, another example of the film deposition
system enabling production of the oil-repellent substrate 100 of
FIG. 1 is explained. The same numerical notations as those of the
second embodiment are given to the same members, and explanations
thereof are omitted.
[0106] As shown in FIG. 3, the film deposition system 1a of this
embodiment comprises a vacuum vessel 2. At an upper position in the
inside of the vacuum vessel 2, a rotary drum 4 is rotatably held
around an axis perpendicular to the vertical axis. The rotary drum
4 as a substrate holding mechanism is a cylindrical member for
holding the substrate 101 on which film deposition is performed in
the inside of the vacuum vessel 2.
[0107] As shown in FIG. 4, the rotary drum 4 comprises a plurality
of substrate holders 4a, frames 4b, and connection means 4c for
connecting the substrate holders 4a and the frames 4b.
[0108] The substrate holder 4a has a plurality of substrate holding
holes for holding the substrates 101 on a center part of the plate
surface in a row along the longer direction of the substrate holder
4a. The substrate 101 is held in the substrate holding hole of the
substrate holder 4a, and fixed to the substrate holder 4a with a
screw member or the like so that it should not drop out of the
holder. Further, at the both ends of the substrate holder 4a along
the longer direction (z-direction), screw holes into which the
connection means 4c can be inserted are provided on the plate
surface.
[0109] The frame 4b consists of two ring members disposed on the
upper and lower sides (x-direction). In each of the ring members,
screw holes are provided at positions corresponding to the screw
holes of the substrate holder 4a. The substrate holder 4a and the
frame 4b are fixed by using the connection means 4c consisting of,
for example, a bolt and a nut.
[0110] The rotary drum 4 is constituted so that it can move between
the inside of the vacuum vessel 2 and a load lock chamber connected
to the vacuum vessel 2 through a door. The rotary drum 4 is
disposed in the inside of the vacuum vessel 2 so that the central
axis line Z1 along the cylindrical direction of the cylinder
(z-direction) corresponds to the anterior-posterior direction of
the vacuum vessel 2 (z-direction).
[0111] When the substrate holder 4a is attached to the frame 4b or
detached from the frame 4b, the rotary drum 4 is conveyed to the
load lock chamber, and the substrate holder 4a is detached from and
attached to the frame 4b in this load lock chamber. On the other
hand, at the time of film deposition, the rotary drum 4 is conveyed
to the inside of the vacuum vessel 2, and rotatably disposed in the
vacuum vessel 2.
[0112] The posterior surface center part of the rotary drum 4 has a
shape that can engage with the front of a motor rotating shaft 40a.
The rotary drum 4 and the motor rotating shaft 40a are positioned
so that the central axis line of the motor rotating shaft 40a and
the central axis line Z1 of the rotary drum 4 should coincide with
each other, and are connected by engagement of them. The surface of
the rotary drum 4 in the posterior surface thereof that engages
with the motor rotating shaft 40a consists of an insulating member.
Abnormal discharge of the substrate 101 can be thereby prevented.
Further, airtightness between the vacuum vessel 2 and the motor
rotating shaft 40a is maintained with an O-ring.
[0113] The motor rotating shaft 40a is rotated by driving a motor
40 provided behind the vacuum vessel 2 in a state that vacuum in
the inside of the vacuum vessel 2 is maintained. With this
rotation, the rotary drum 4 connected with the motor rotating shaft
40a rotates around the axis line Z1. Since each substrate 101 is
held on the rotary drum 4, it revolves around the axis line Z1 as a
revolution axis with rotation of the rotary drum 4.
[0114] The drum-rotating shaft 42 is provided on the front of the
rotary drum 4, and the drum-rotating shaft 42 also rotates with the
rotation of the rotary drum 4. A hole is formed in the front wall
(z-direction) of the vacuum vessel 2, and the drum-rotating shaft
42 penetrates this hole and leads to the outside of the vacuum
vessel 2. Bearing is provided on the internal surface of the hole
and allows smooth rotation of the rotary drum 4. Between the vacuum
vessel 2 and the drum-rotating shaft 42, airtightness is maintained
with an O-ring.
<<Sputtering Region and Sputtering Means>>
[0115] Returning back to FIG. 3, a partition wall 12 is provided on
the side of the vacuum vessel 2 in the vertical direction
(x-direction) at a position facing the rotary drum 4. The partition
wall 12 is a member made from the same stainless steel as that of
the vacuum vessel 2. The partition wall 12 is constituted by planar
members each disposed up and down, and left and right, and disposed
from the internal wall of the vacuum vessel 2 towards the rotary
drum 4 so as to form a closed square. A sputtering region 80A is
thereby partitioned in the inside of the vacuum vessel 2.
[0116] The sidewall of the vacuum vessel 2 has a section having a
convex projecting outward, and a sputtering means 80 is provided on
the projecting wall surface.
[0117] The sputtering region 80A is formed in a region surrounded
by the internal wall of the vacuum vessel 2, the partition wall 12,
the external surface of the rotary drum 4, and the sputtering means
80. In the sputtering region 80A, a sputtering treatment for
depositing a film material on the surface of the substrate 101 is
performed.
[0118] As shown in FIG. 5, the sputtering means 80 is constituted
by a pair of targets 82a and 82b, a pair of sputtering electrodes
81a and 81b holding the targets 82a and 82b, an AC power supply 84
for supplying electric power to the sputtering electrodes 81a and
81b, and a transformer 83 as an electric power control means for
controlling electric power from the AC power supply 84.
[0119] The wall surface of the vacuum vessel 2 is projected
outward, and the sputtering electrodes 81a and 81b are disposed on
the internal wall of the vacuum vessel 2 at the projected portion
so as to penetrate the sidewall. These sputtering electrodes 81a
and 81b are fixed to the vacuum vessel 2 at the earth potential via
insulating members.
[0120] The targets 82a and 82b consist of the first film deposition
material formed in the form of a plate, and they are held by the
sputtering electrodes 81a and 81b, respectively, so as to face the
side of the rotary drum 4 as described later. In this embodiment,
as the targets 82a and 82b, a material to which hardness higher
than the hardness of the substrate 101 can be imparted by
oxidation, nitridation or oxynitridation, such as metallic silicon
(Si), aluminum (Al) and zirconium (Zr), is used. In this
embodiment, use of a Si target is exemplified.
[0121] The sputtering electrodes 81a and 81b have a structure that
a plurality of magnets are disposed in a predetermined direction.
The sputtering electrodes 81a and 81b are connected to the AC power
supply 84 via the transformer 83, and constituted so that an
alternating electric field of 1 to 100 kHz can be applied to the
both electrodes. The targets 82a and 82b are held by the sputtering
electrodes 81a and 81b, respectively. The targets 82a and 82b have
a plate shape, and as shown in FIG. 2, the targets 82a and 82b are
disposed so that the longer direction thereof is parallel to the
rotating-shaft line Z1 of the rotary drum 4.
[0122] A sputtering gas feeding means 90 for supplying a sputtering
gas such as argon is provided around the sputtering region 80A. The
sputtering gas feeding means 90 comprises a sputtering gas cylinder
92 as a sputtering gas storage means, piping 95a and piping 95c as
a sputtering gas supply route, and a massflow controller 91 as a
sputtering gas flow rate control means for controlling flow rate of
the sputtering gas.
[0123] Examples of the sputtering gas include, for example, an
inert gas such as argon and helium.
[0124] The sputtering gas cylinder 92 and the massflow controller
91 are both provided outside the vacuum vessel 2. The massflow
controller 91 is connected to the single sputtering gas cylinder 92
storing the sputtering gas via the piping 95c. The massflow
controller 91 is connected to the piping 95a, and one end of the
piping 95a penetrates the sidewall of the vacuum vessel 2 and leads
to neighborhood of the targets 82a and 82b in the sputtering region
80A.
[0125] The end of the piping 95a is disposed below the targets 82a
and 82b near the center of them, and a feed port 95b is opened at
the tip thereof towards the center of the front surfaces of the
targets 82a and 82b.
[0126] The massflow controller 91 is an apparatus for controlling
flow rate of the gas, and comprises an inlet through which the gas
from the sputtering gas cylinder 92 flows in, an outlet for flowing
the sputtering gas into the piping 95a, a sensor for detecting
massflow rate of the gas, a control valve for controlling flow rate
of the gas, a sensor for detecting massflow rate of the gas flown
in via the inlet, and an electronic circuit for controlling the
control valve on the basis of the flow rate detected by the sensor.
The electronic circuit is designed so that a desired flow rate can
be set from the outside.
[0127] The sputtering gas fed from the sputtering gas cylinder 92
is introduced into the piping 95a at a flow rate controlled by the
massflow controller 91. The sputtering gas flown into the piping
95a is introduced from the feed port 95b into the region in front
of the targets 82a and 82b disposed in the sputtering region
80A.
[0128] In a state that the sputtering gas is supplied to the
sputtering region 80A by the sputtering gas feeding means 90, and
the targets 82a and 82b are surrounded by an inert gas atmosphere,
if an alternate current is applied to the sputtering electrodes 81a
and 81b from the AC power supply 84, a part of the sputtering gas
around the targets 82a and 82b emits electrons, and it is thereby
ionized. Since a leakage magnetic field is formed on the surfaces
of the targets 82a and 82b by the magnets disposed in the
sputtering electrodes 81a and 81b, those electrons go around in the
magnetic field generated near the surfaces of the targets 82a and
82b with describing a toroidal curve. Intense plasma is generated
along the orbits of the electrons, and ions of the sputtering gas
are accelerated towards the plasma, and collide with the targets
82a and 82b to drive out atoms and particles of the surfaces of the
targets 82a and 82b (Si atoms and Si particles when the targets 82a
and 82b consist of Si). The Si atoms and Si particles driven out
adhere to the surface of the substrate 101 to coat a microfilm.
<<Plasma Treatment Region and Plasma Generation
Means>>
[0129] Returning back to FIG. 3, a partition wall 14 is disposed on
the upper internal wall of the vacuum vessel 2 in the vertical
direction (x-direction) at a position facing the rotary drum 4. The
partition wall 14 is a member made from, for example, the same
stainless steel as that of the vacuum vessel 2. The partition wall
14 is constituted by planar members each disposed up and down, and
left and right, and disposed from the internal wall of the vacuum
vessel 2 towards the rotary drum 4 so as to form a closed square. A
plasma treatment region 60A is thereby partitioned in the inside of
the vacuum vessel 2. Thus, in this embodiment, the plasma treatment
region 60A is provided at a position opposite to the vapor
deposition region 30A with respect to the rotary drum 4 (upper part
of the vacuum vessel 2 in the vertical direction, in a direction of
substantially 180.degree. from the vapor deposition region 30A),
remote from the sputtering region 80A by an angle of substantially
90.degree., and spatially separated from both the vapor deposition
region 30A and the sputtering region 80A.
[0130] The upper internal wall of the vacuum vessel 2 has a section
having a convex projecting outward (upward), and a plasma
generation means 60 is provided on the projected wall surface so as
to face the plasma treatment region 60A.
[0131] The plasma treatment region 60A is formed in a region
surrounded by the internal wall surface of the vacuum vessel 2, the
partition wall 14, the external surface of the rotary drum 4, and
the plasma generation means 60, and coats a thin film consisting of
a compound or incompletely-reacted compound of Si by a reactive
treatment of the microfilm adhered to the surface of the substrate
101 in the sputtering region 80A.
[0132] As shown in FIG. 6, at a position on the upper wall surface
of the vacuum vessel 2 corresponding to the plasma treatment region
60A, a hole 2a for installing the plasma generation means 60 is
formed. Further, the piping 75a is connected to the plasma
treatment region 60A. The massflow controller 72 is connected to
one end of the piping 75a, and this massflow controller 72 is
further connected to the reactive gas cylinder 71. Therefore, the
reactive gas can be supplied from the reactive gas cylinder 71 into
the plasma treatment region 60A.
[0133] The plasma generation means 60 comprises a case 61, a
dielectric plate 62, an antenna 63, a matching box 64, and a radio
frequency power supply 65.
[0134] The case 61 has a shape closing the hole 2a formed on the
wall surface of the vacuum vessel 2, and is fixed with bolts so as
to close the hole 2a of the vacuum vessel 2. By fixing the case 61
on the wall surface of the vacuum vessel 2, the plasma generation
means 60 is attached to the wall surface of the vacuum vessel 2.
The case 61 is formed with stainless steel.
[0135] The dielectric plate 62 is formed with a tabular dielectric
substance. Although the dielectric plate 62 is formed with quartz
in this embodiment, the material of the dielectric plate 62 is not
limited to quartz, and it may be one formed with a ceramic material
such as Al.sub.2O.sub.3. The dielectric plate 62 is fixed to the
case 61 with a fixing frame. By fixing the dielectric plate 62 to
the case 61, an antenna housing 61A is formed in a region
surrounded by the case 61 and the dielectric plate 62.
[0136] The dielectric plate 62 fixed to the case 61 is disposed so
as to face the inside of the vacuum vessel 2 (plasma treatment
region 60A) through the hole 2a. In this configuration, the antenna
housing 61A is separated from the inside of the vacuum vessel 2.
That is, the antenna housing 61A and the inside of the vacuum
vessel 2 are partitioned by the dielectric plate 62 to form
independent spaces. Further, the antenna housing 61A and the
outside of the vacuum vessel 2 are partitioned by the case 61 to
form independent spaces. In this embodiment, the antenna 63 is
disposed in the antenna housing 61A formed as an independent space
as described above. In addition, airtightness between the antenna
housing 61A and the inside of the vacuum vessel 2, and between the
antenna housing 61A and the outside of the vacuum vessel 2 is
maintained with an O-ring, respectively.
[0137] In this embodiment, a piping 16a-2 is branched from a piping
16a-1. This piping 16a-2 is connected to the antenna housing 61A,
and has a role of functioning as an exhausting pipe at the time of
evacuating the inside of the antenna housing 61A to obtain
vacuum.
[0138] Valves V1 and V2 are provided in the piping 16a-1 at
positions on the way of from a vacuum pump 15a to the inside of the
vacuum vessel 2. Further, a valve V3 is provided in the piping
16a-2 at a position on the way of from the vacuum pump 15a to the
antenna housing 61A. By closing either one of the valves V2 and V3,
movement of gas between the insides of the antenna housing 61A and
the vacuum vessel 2 is prevented. Internal pressure of the vacuum
vessel 2 and internal pressure of the antenna housing 61A are
measured with a vacuum gage.
[0139] The film deposition system 1a of this embodiment (refer to
FIG. 3) is provided with a control unit. Output of the vacuum gage
is inputted into this control unit. The control unit has a function
of controlling evacuation by the vacuum pump 15a on the basis of
the inputted value measured by the vacuum gage to adjust degree of
vacuum in the inside of the vacuum vessel 2 and the inside of the
antenna housing 61A. According to this embodiment, the control unit
controls opening and closing of the valves V1, V2, and V3, and
thereby the insides of the vacuum vessel 2 and the antenna housing
61A can be independently or simultaneously evacuated.
[0140] According to this embodiment, by appropriately controlling
the vacuum pump 15a, film deposition atmosphere in the sputtering
region 80A can be stabilized.
[0141] The antenna 63 is a means for being supplied electric power
from the radio frequency power supply 65 to generate an induction
field inside the vacuum vessel 2 (plasma treatment region 60A) and
generate plasma in the plasma treatment region 60A. The antenna 63
comprises a tubular body formed with copper, and a covering layer
covering the body surface and formed with silver. That is, the body
of the antenna 63 is formed with inexpensive and easily processible
copper, which also shows low electric resistance, in the form of
tube, and the surface of the antenna 63 is covered with silver of
which electric resistance is lower than that of copper. The
impedance of the antenna 63 for radio frequency is thereby reduced
to efficiently flow an electric current through the antenna 63 and
improve the efficiency of generation of plasma.
[0142] The film deposition system 1a of this embodiment (refer to
FIG. 3) is configured so that an alternating voltage having a
frequency of 1 to 27 MHz is applied to the antenna 63 from the
radio frequency power supply 65 to generate plasma of a reactive
gas in the plasma treatment region 60A.
[0143] The antenna 63 is connected to the radio frequency power
supply 65 via the matching box 64 holding a matching circuit. In
the matching box 64, a variable capacitor not shown in the drawing
is provided.
[0144] The antenna 63 is connected to the matching box 64 via a
lead wire. The lead wire consists of a material similar to that of
the antenna 63. On the case 61, an insertion hole for inserting the
lead wire is formed, and the antenna 63 in the antenna housing 61A
and the matching box 64 outside the antenna housing 61A are
connected via the lead wire inserted into the insertion hole. A
sealing member is provided between the lead wire and the insertion
hole to maintain airtightness between the inside and outside of the
antenna housing 61A.
[0145] Between the antenna 63 and the rotary drum 4, a grid 66 may
be provided as an ion-annihilating means. The grid 66 is for
annihilating a part of ions and a part of electrons generated by
the antenna 63. The grid 66 is a hollow member consisting of an
electric conductor, and is grounded. In order to flow a cooling
medium (for example, cooling water) inside the grid 66 consisting
of a hollow member, a hose for supplying a cooling medium is
connected to the end of the grid 66.
[0146] Further, the reactive gas supply means 70 is disposed in the
plasma treatment region 60A and around it. The reactive gas supply
means 70 of this embodiment comprises the reactive gas cylinder 71
for storing a reactive gas (for example, oxygen gas, nitrogen gas,
fluorine gas, ozone gas, etc.), the massflow controller 72 for
controlling flow rate of the reactive gas supplied from the
reactive gas cylinder 71, and the piping 75a for introducing the
reactive gas into the plasma treatment region 60A.
[0147] When the rotary drum 4 is rotated by the motor 40 (refer to
FIG. 4), the substrate 101 held on the outer surface of the rotary
drum 4 revolves and repeatedly moves from a position facing the
sputtering region 80A to a position facing the plasma treatment
region 60A, or vice versa. As a result of such revolution of the
substrate 101 as described above, the substrate 101 is successively
and repeatedly subjected to a sputtering treatment in the
sputtering region 80A and a plasma treatment in the plasma
treatment region 60A, and a thin film (first film 103) is thereby
coated on the surface of the substrate 101. In particular, when
electric power is supplied to the antenna 63 from the radio
frequency power supply 65 in a state that the reactive gas is
introduced into the plasma treatment region 60A from the reactive
gas cylinder 71 via the piping 75a, plasma is generated in a region
facing the antenna 63 in the plasma treatment region 60A, and the
first film deposition material deposited on the surface of the
substrate 101 is densified to coat a thin film (first film 103)
having sufficient characteristics.
<<Vapor Deposition Region, Vapor Deposition Source and Ion
Gun>>
[0148] Returning back to FIG. 3, the vapor deposition region 30A is
provided at a lower part of the vacuum vessel 2 in the vertical
direction (x-direction). The vapor deposition region 30A is a
region for coating the oil-repellent film 105 by vapor deposition
on the surface of the first film 103 coated on the surface of the
substrate 101.
[0149] Below the vapor deposition region 30A (on the internal
bottom wall of the vacuum vessel 2), a vapor deposition source 36
of resistance heating type is provided. Since the configuration of
the vapor deposition source 36 is the same as that of the second
embodiment, explanation thereof is omitted.
[0150] A piping 23 for evacuation is connected to the internal
bottom wall of the vacuum vessel 2, and a vacuum pump 24 for
evacuating a space around the deposition source 36 is connected to
the piping 23. The degree of vacuum in the vacuum vessel 2 can be
controlled by the vacuum pump 24 and a controller (not shown in the
drawing).
[0151] A door 3 is provided on the side of the vacuum vessel 2
(z-direction), and the door 3 is opened and closed by sliding or
rotating it. A load lock chamber may be separately connected
outside the door 3.
[0152] According to this embodiment, the ion gun 38 is further
disposed at a lower part of the vacuum vessel 2 in the vertical
direction (x-direction). Since the configuration of the ion gun 38
is the same as that of the second embodiment, explanation thereof
is omitted.
[0153] Hereafter, an example of the method for depositing a film
using the film deposition system 1a will be explained.
[0154] In this embodiment, a case where metallic silicon (Si) as
the first film deposition material is used as the targets 82a and
82b, and the second film deposition material as a material for
coating the oil-repellent film is charged in the boat of the
evaporation source 36 is exemplified. Further, a case where
nitrogen gas is used as the reactive gas is exemplified.
[0155] In this embodiment, there is exemplified a case where the
first film 103 is deposited by the sputtering method, then the
first irradiation treatment (postoperative irradiation) is carried
out with an ion beam generated by the ion gun for the first film
103, and then the oil-repellent film 105 is further deposited by
the vacuum vapor deposition method of resistance heating type.
[0156] In the film deposition of the first film 103 by the
sputtering method, for example, an intermediate thin film is coated
by a sputtering step for adhering a thin film having a thickness
considerably smaller than the objective thickness to the surface of
the substrate 101 and a reaction step for performing a nitridation
treatment of the thin film to convert the composition of the thin
film, and these sputtering step and reaction step are repeated a
plurality of times to laminate a plurality of the intermediate thin
layers to coat the first film 103 as a final thin film having the
objective thickness on the surface of the substrate 101.
Specifically, by repeating a step of coating an intermediate thin
film having an average thickness of about 0.01 to 1.5 nm determined
after conversion of the composition on the surface of the substrate
101 through the sputtering step and the reaction step, the first
film 103 as the final thin film having an objective thickness of
about several to several hundreds of nanometers is coated.
[0157] (1) First, the substrate 101 is set on the rotary drum 4
outside the vacuum vessel 2, and accommodated in the load lock
chamber of the vacuum vessel 2. The substrate 101 is preferably
subjected to wet cleaning before or after the setting.
[0158] Then, the rotary drum 4 is moved to the inside of the vacuum
vessel 2 along a rail. At the same time, the targets 82a and 82b in
the sputtering region 80A are held by the sputtering electrodes 81a
and 81b, respectively. Then, the inside of the vacuum vessel 2 is
sealed, and the inside of the vacuum vessel 2 is decompressed to a
predetermined pressure by using the vacuum pump 15a.
[0159] (2) Then, by driving the motor 40 provided behind the vacuum
vessel 2, rotation of the rotary drum 4 is started. The revolving
speed (RS) of the rotary drum 4 is selected to be, for example, 25
rpm or higher, preferably 30 rpm or higher, more preferably 50 rpm
or higher. If the value of RS is made unduly small, there arises a
tendency that the sputtering time for one sheet of the substrate
101 becomes longer, as a result, the thickness of the thin film
coated on the substrate 101 becomes thicker, and thus the plasma
treatment in the plasma treatment region 60A cannot be sufficiently
performed. On the other hand, if the value of RS is made unduly
large, the sputtering time for one sheet of the substrate 101
becomes shorter, the number of particles deposited on each
substrate 101 decreases to make the thickness of the thin film
unduly thin, and thus production efficiency may be affected. For
this reason, the value of RS is preferably 250 rpm, more preferably
200 rpm, still more preferably 100 rpm, at most.
[0160] (3) Then, electric power is supplied to the sputtering
electrodes 81a and 81b from the AC power supply 84 in a state that
argon gas is introduced into the sputtering region 80A from the
sputtering gas feeding means 90 to carry out the sputtering of the
targets 82a and 82b. Flow rate of the argon gas is appropriately
set to be in the range of about 250 to 1000 sccm. In this state,
the rotary drum 4 is rotated to transfer the substrate 101 to the
sputtering region 80A, and coat deposit (microfilm) of metallic
silicon (Si) on the surface of the substrate 101. For this
deposition, heating of the substrate 101 is not required (room
temperature). However, the substrate 101 may be heated to a
temperature as low as, for example, 220.degree. C. or lower,
preferably 150.degree. C. or lower, more preferably 100.degree. C.
or lower, still more preferably 80.degree. C. or lower, and
preferably about 50.degree. C. or higher.
[0161] (4) Then, an alternating voltage is applied to the antenna
63 from the radio frequency power supply 65 in a state that
nitrogen gas is introduced into the inside of the plasma treatment
region 60A from the reactive gas supply means 70 to generate plasma
of nitrogen gas in the plasma treatment region 60A. In this state,
the rotary drum 4 is rotated to transfer the substrate 101 to the
plasma treatment region 60A. Inside the plasma treatment region
60A, plasma of nitrogen gas is generated, and therefore 3 moles of
metallic silicon Si adhering to the surface of the substrate 101
reacts with 2 moles of nitrogen gas to coat 1 mole of silicon
nitride (Si.sub.3N.sub.4), which constitute the intermediate thin
film. In addition, heating of the substrate 101 is not particularly
required also in this step (room temperature).
[0162] Time of this step is appropriately chosen to be within the
range of, for example, about 1 to 60 minutes. Flow rate of the
nitrogen gas is also appropriately chosen to be about 70 to 500
sccm, and the electric power supplied from the radio frequency
power supply 65 is also appropriately determined to be within the
range of about 1.0 to 5.0 kW. Pressure of the nitrogen gas
introduced into the plasma treatment region 60A (film deposition
pressure) is preferably about 0.3 to 0.6 Pa. The flow rate of the
nitrogen gas can be controlled with the massflow controller 72, and
the electric power supplied from the radio frequency power supply
65 can be controlled with the matching box 64.
[0163] In this embodiment, the rotary drum 4 is continuously
rotated to successively repeat the sputtering treatment and the
plasma treatment to laminate a plurality of intermediate thin films
and thereby coat the first film 103 that consists of an
Si.sub.3N.sub.4 thin film having a desired thickness (first film
deposition process).
[0164] In addition, in this embodiment, it is also preferable to
subject the substrate 101 to a pretreatment by the plasma treatment
described in (4) mentioned above in advance of the first film
deposition process. This pretreatment may be performed for a short
time of, for example, about 1 to 10 minutes.
[0165] (5) Then, after the operations in the sputtering region 80A
and the plasma treatment region 60A are terminated, the irradiation
electric power for the ion gun 38 is increased from that of the
idling state to a predetermined irradiation electric power, and the
shutter 38a is opened to start irradiation of an ion beam on the
first film 103. This step is an example of the first irradiation
treatment (postoperative irradiation). This embodiment is also
characterized in that the postoperative irradiation is performed
for the first film 103 coated on the surface of the substrate 101.
The postoperative irradiation can be performed with the same
conditions as those explained for the second embodiment.
[0166] (6) Then, the irradiation electric power for the ion gun 38
is returned to the level of the idling state, the shutter 38a is
closed, and the shutter 36a is opened to start the operation in the
vapor deposition region 30A. Specifically, the second film
deposition material as a material for coating the oil-repellent
film charged in the crucible (boat) 36b is heated. And the inside
of the vacuum vessel 2 is sealed, and the inside of the vacuum
vessel 2 is decompressed to a predetermined pressure using the
vacuum pump 15a.
[0167] (7) Then, as in the case of (2) mentioned above, by driving
the motor 40 provided behind the vacuum vessel 2, rotation of the
rotary drum 4 is started. The rotary drum 4 is rotated at a
revolving speed (RS) similar to that used in (2) mentioned
above.
[0168] If the shutter 36a is opened, the heated second film
deposition material diffuses into the vapor deposition region 30A,
and a part of it adheres to the surface of the first film 103 of
the substrate 101 subjected to the postoperative irradiation and
held by the rotary drum 4 under rotation, so that deposition of a
film having a predetermined thickness is attained (second film
deposition process). In this embodiment, film deposition rate of
the second film deposition material is, for example, 0.1 nm/second
or higher, preferably 0.2 to 0.4 nm/second.
[0169] As a result, the oil-repellent film 105 is deposited with a
predetermined thickness on the first film 103 subjected to the
postoperative irradiation. By performing the steps described above,
the oil-repellent substrate 100 shown in FIG. 1 is produced.
[0170] The method for depositing a film using the film deposition
system 1a according to this embodiment also exhibits the same
effects as those obtained by the second embodiment.
[0171] In this embodiment, an example of coating only the
Si.sub.3N.sub.4 thin film as the first film 103 on the substrate
101 is explained. However, together with this Si.sub.3N.sub.4 thin
film, another thin film such as SiO.sub.2 thin film and
Al.sub.2O.sub.3 thin film can also be laminated. In such a case,
what is necessary is to appropriately change materials of the
targets 82a and 82b of the sputtering means 80 disposed in the
sputtering region 80A. Further, as the first film 103 coated on the
substrate 101, a thin film other than Si.sub.3N.sub.4 thin film,
for example, an SiO.sub.2 thin film or Al.sub.2O.sub.3 thin film
may be coated instead of the Si.sub.3N.sub.4 thin film. In such a
case, what is necessary is to appropriately change the materials of
the targets 82a and 82b to any of various metals such as Al, Zr and
Cr, or a plurality of kinds of metals, or to change type of the
reactive gas to, for example, oxygen gas, fluorine gas, ozone gas,
or the like.
[0172] Further, in this embodiment, a second irradiation treatment
(preoperative irradiation) similar to that of the second embodiment
can also be performed for the substrate 101 in advance of the first
film deposition process. The preoperative irradiation also includes
the plasma treatment described in (4) mentioned above.
[0173] In addition, in the explained example of this embodiment,
the ion gun 38 is disposed at a lower part of the vacuum vessel 2
in the vertical direction. However, disposition of the ion gun 38
is not essential. If the ion gun 38 is not disposed, it is
preferable to dispose a mechanism for positively applying a bias
voltage to the rotary drum 4 as a substrate holding mechanism. If a
bias voltage is applied to the rotary drum 4, directivity is
imparted to the ions in the thermal plasma generated by the plasma
generation means 60 by the bias voltage. If such ions imparted with
directivity collide with the surface of the first film 103 coated
in (3) and (4) mentioned above under appropriate conditions,
appropriate unevenness is imparted to the first film 103.
EXAMPLES
[0174] Hereafter, the present invention will be explained in detail
with reference to examples, which more specifically embodies the
aforementioned embodiments of the present invention.
Example 1
[0175] In this example, a film deposition system having the
configuration of the film deposition system 1 shown in FIG. 2 for
performing ion beam-assisted vapor deposition was prepared, and
oil-repellent substrate samples were obtained by film deposition
performed under the conditions shown in Table 1A, 1B, 1C and
1D.
[0176] As the substrate 101, a glass substrate having a pencil
hardness of 6H was used. The "hardness" used here is a value of the
pencil hardness measured by the method defined in
JIS-K5600-5-4.
[0177] The substrate 101 was subjected to wet cleaning before film
deposition.
[0178] SiO.sub.2 was used as the first film deposition material,
and only for Experimental Examples 1-1 and 1-2, in advance of the
ion beam-assisted vapor deposition (first film deposition process)
with this first film deposition material, the surface of the
substrate 101 was subjected to ion cleaning using the ion gun 38
for a predetermined time (10 minutes and 5 minutes) (preoperative
irradiation, number of irradiated ions: 1.1.times.10.sup.17
ions/cm.sup.2 in the case of 10 minutes, 5.6.times.10.sup.16
ions/cm.sup.2 in the case of 5 minutes).
[0179] Conditions of the ion cleaning were as follows: accelerating
voltage: 1000 V, electric current: 30 .mu.A/cm.sup.2, type and
introduced volume of introduced gas: O.sub.2 at 30 sccm+Ar at 20
sccm).
[0180] Substrate temperature at the time of the first film
deposition process was 150.degree. C. Operation conditions of the
neutralizer except for Experimental Example 2 were as follows:
accelerating voltage: 30 to 70 V, electronic current: 1 A, type of
introduced gas: (O.sub.2+Ar), and introduced volume of gas: 50
sccm. The values of hardness of the SiO.sub.2 thin films observed
before and after the first irradiation treatment (postoperative
irradiation) are values of pencil hardness measured by the method
described above. The values of the "center line average height
(Ra)", "10-point average height (Rz)", and "maximum valley depth
(Pv)" of the SiO.sub.2 thin films observed after the postoperative
irradiation are values measured according to JIS-B0601. The values
of "convex cycle" of the SiO.sub.2 thin films observed after the
postoperative irradiation are values measured with an atomic force
microscope (AFM, trade name: SPI-3700, Seiko Instruments Inc.). As
the second film deposition material, an oil repellent agent
produced by Canon Optron, Inc. (trade name: OF-SR, component:
fluorine-containing organosilicon compound) was used.
TABLE-US-00001 TABLE 1A (Example 1) Preoperative irradiation (ion
cleaning) Introduced Number gas of Accelerating Current Introduced
irradiated Experimental voltage density volume Time ions Example
(V) (.mu.A/cm.sup.2) Type (sccm) (second) (ions/cm.sup.2) 1 -- --
-- -- -- -- 1-1 1000 30 Ar + O.sub.2 20 + 30 600 1.1E+17 1-2 1000
30 Ar + O.sub.2 20 + 30 300 5.6E+16 2 -- -- -- -- -- -- 3 -- -- --
-- -- -- 4 -- -- -- -- -- -- 5 -- -- -- -- -- -- 6 -- -- -- -- --
-- 7 -- -- -- -- -- -- 8 -- -- -- -- -- -- 9 -- -- -- -- -- --
TABLE-US-00002 TABLE 1B (Example 1) First film deposition process
(electron beam-assisted deposition) Ion assistance conditions
Introduced Accelerating Current gas voltage density Introduced
Deposition SiO.sub.2 thin film Experimental V1 I1 volume rate
Thickness Example (V) (.mu.A/cm.sup.2) Type (sccm) (nm/second) (nm)
Hardness 1 1000 30 O.sub.2 40 0.125 15 9H 1-1 1000 30 O.sub.2 40
0.125 15 9H 1-2 1000 30 O.sub.2 40 0.125 15 9H 2 -- -- -- -- 0.25
15 6H 3 1000 30 O.sub.2 40 0.125 15 9H 4 800 30 O.sub.2 40 0.125 5
9H 5 800 30 O.sub.2 40 0.125 15 9H 6 1000 30 O.sub.2 40 0.125 10 9H
7 1000 30 O.sub.2 40 0.125 15 9H 8 1000 60 O.sub.2 40 0.25 10 9H 9
1000 120 O.sub.2 40 1 30 9H
TABLE-US-00003 TABLE 1C (Example 1) First irradiation treatment
(irradiation of energy particles) Number of Accelerating Current
Introduced gas irradiated SiO.sub.2 thin film voltage density
Introduced Time particles Convex Experimental V2 I2 volume T2
(particles/ Ra Rz Pv cycle Thickness Example (V) (.mu.A/cm.sup.2)
Type (sccm) (second) cm.sup.2) (nm) (nm) (nm) (nm) (nm) 1 1000 30
Ar 40 20 3.7E+15 5 17 31 22 10 1-1 1000 30 Ar 40 20 3.7E+15 5 17 31
22 10 1-2 1000 30 Ar 40 20 3.7E+15 5 17 31 22 10 2 -- -- -- -- --
-- 3 5 30 3 15 3 -- -- -- -- -- -- 1 3 30 5 15 4 300 30 Ar 40 20
3.7E+15 4 9 19 45 3 5 1200 30 Ar 40 20 3.7E+15 7 21 43 31 8 6 1000
10 Ar 40 20 1.2E+15 3 9 13 21 8 7 1000 60 Ar 40 20 7.5E+15 9 38 74
57 5 8 1000 30 Ar 40 4 7.5E+14 2 7 12 39 8 9 1000 30 Ar 40 100
1.9E+16 13 38 134 61 5
TABLE-US-00004 TABLE 1D (Example 1) Maximum Second film deposition
process number (vapor deposition by resistance of times of
Deposition reciprocating Experimental rate Thickness cycles in
Example Material (nm/minute) (nm) scratching test 1 OF-SR 0.5 4
2400 1-1 OF-SR 0.5 4 2600 1-2 OF-SR 0.5 4 1700 2 OF-SR 0.5 4 400 3
OF-SR 0.5 4 200 4 OF-SR 0.5 4 1200 5 OF-SR 0.5 4 2500 6 OF-SR 0.5 4
2200 7 OF-SR 0.5 4 1700 8 OF-SR 0.5 4 2200 9 OF-SR 0.5 4 1500
Example 2
[0181] In this example, a film deposition system having the
configuration of the film deposition system 1a shown in FIGS. 3 to
6 for performing magnetron sputtering was prepared, and
oil-repellent substrate samples were obtained by film deposition
performed under the conditions shown in Table 2A, 2B, and 2C.
[0182] As the substrate 101, a glass substrate having a pencil
hardness of 6H was used. The "hardness" used here is a value of the
pencil hardness measured by the method defined in
JIS-K5600-5-4.
[0183] The substrate 101 was subjected to wet cleaning before film
deposition.
[0184] As the targets 82a and 82b, tabular metallic silicon (Si)
targets were used, and in advance of the first film deposition
process, the surface of the substrate 101 was subjected to a
pretreatment by a plasma treatment for 1 minute.
[0185] Revolving speed (RS) of the rotary drum 4 was 100 rpm.
Substrate temperature at the time of the first film deposition
process was 100.degree. C.
[0186] The values of hardness of Si.sub.3N.sub.4 observed before
and after the first irradiation treatment (postoperative
irradiation) are values of pencil hardness measured by the
aforementioned method in terms of hardness for a thickness of 100
nm. The values of Ra, Rz and Pv of the Si.sub.3N.sub.4 thin films
observed after the postoperative irradiation are values measured
according to JIS-B0601. The values of "convex cycle" of the
Si.sub.3N.sub.4 thin films observed after the postoperative
irradiation are values measured with an atomic force microscope
(AFM, trade name: SPI-3700, Seiko Instruments Inc.). As the second
film deposition material, an oil repellent agent produced by Canon
Optron, Inc. (trade name: OF-SR, component: fluorine-containing
organosilicon compound) was used.
TABLE-US-00005 TABLE 2A (Example 2) First film deposition process
(sputtering treatment and reaction treatment) Sputtering region
Introduced Plasma treatment region Applied gas Applied AC
Introduced gas Si.sub.3N.sub.4 thin electric Introduced Deposition
electric voltage Introduced film Experimental power volume rate
power Frequency volume Thickness Example (kW) Type (sccm)
(nm/second) (kW) (MHz) Type (sccm) (nm) Hardness 10 5 Ar 100 0.25 1
13.56 N.sub.2 100 10 9H 11
TABLE-US-00006 TABLE 2B (Example 2) First irradiation treatment
(irradiation of energy particles) Number of Accelerating Current
Introduced gas irradiated Si.sub.3N.sub.4 thin film voltage density
Introduced Time particles Convex Experimental V2 I2 volume T2
(particles/ Ra Rz Pv cycle Thickness Example (V) (.mu.A/cm.sup.2)
Type (sccm) (second) cm.sup.2) (nm) (nm) (nm) (nm) (nm) 10 1000 30
Ar 50 20 3.7E+15 5 14 41 25 7 11 -- -- -- -- -- -- 2 4 19 4 10
TABLE-US-00007 TABLE 2C (Example 2) Maximum Second film deposition
process number (vapor deposition by resistance of times of
Deposition reciprocating Experimental rate Thickness cycles in
Example Material (nm/minute) (nm) scratching test 10 OF-SR 0.5 4
2800 11 OF-SR 0.5 4 500
<<Evaluation>>
[0187] A scratching test was performed by placing steel wool #0000
of 1 cm.sup.2 on the surface of the oil-repellent film 105 of each
of the obtained oil-repellent substrate samples, and reciprocally
moving the steel wool along a straight line of 50 mm at a speed of
1 second for one reciprocating cycle with a load of 1 kg/cm.sup.2.
After every 500 times of the reciprocating cycles of the scratching
test, lines were drawn on the test surface (surface of the
oil-repellent film 105) with an oily marker (organic solvent type
marker, trade name: Mckee Extra Fine, Zebra Co., Ltd.), and it was
evaluated whether the organic solvent type ink of the organic
solvent type marker could be wiped off with dry cloth. As a result,
the maximum numbers of times of the reciprocating cycles allowing
wiping off of the organic solvent type ink were as shown in Tables
1A, 1B, 1C and 1D and Table 2A, 2B, and 2C mentioned above.
<<Discussion>>
[0188] From the results shown in Table 1A, 1B, 1C and 1D, superior
usefulness of the samples of Experimental Examples 1, 1-1 and 1-2
could be confirmed compared with the samples of Experimental
Examples 2 and 3. In particular, it could be confirmed that the
maximum number of times of the reciprocating cycles in the
scratching test could be increased by performing ion cleaning
(preoperative irradiation) for the surface of the substrate 101 for
a predetermined time in advance of the first film deposition
process (ion beam-assisted) (Experimental Example 1-1) compared
with the case where ion cleaning was not performed (Experimental
Example 1). In addition, it could be confirmed that, when the time
of the preoperative irradiation was shortened from 10 minutes to 5
minutes, the maximum number of times of the reciprocating cycles in
the scratching test was decreased, but sufficient maximum number of
times of the reciprocating cycles in the scratching test could be
still obtained compared with the results of Experimental Examples 2
and 3.
[0189] Further, it could also be confirmed that even if the
conditions of the irradiation of energy particles were changed,
evaluation results substantially the same as those of Experimental
Example 1 could be obtained (Experimental Examples 2 to 7).
[0190] From the results shown in Table 2A, 2B, and 2C, superior
usefulness of the sample of Experimental Example 10 could be
confirmed compared with the sample of Experimental Example 11.
[0191] The reason why the organic solvent type ink of the oily
marker could be wiped off with dry cloth even after the number of
times of the reciprocating cycles in the scratching test exceeded
500 for the samples of Experimental Examples 1, 1-1, 1-2 and 4 to
10 as shown in Table 1A, 1B, 1C, and 1D is not necessarily clear.
However, it is estimated as follows. That is, appropriate convexes
and concaves are imparted to the surface of the first film 103
(SiO.sub.2 thin film or Si.sub.3N.sub.4 thin film) having hardness
higher than that of the substrate 101 by the irradiation of energy
particles (postoperative irradiation). Thus, it is considered that,
among the convexes and concaves imparted to the first film 103, the
convexes secured abrasion resistance, the concaves held the
components of the oil-repellent film 105 therein to secure oil
repellency of the sample surfaces, and thereby abrasion resistance
of practically sufficient level was imparted.
* * * * *