| (19) |
 |
|
(11) |
EP 1 518 235 B9 |
| (12) |
CORRECTED EUROPEAN PATENT SPECIFICATION |
|
Note: Bibliography reflects the latest situation |
| (15) |
Correction information: |
|
Corrected version no 1 (W1 B1) |
|
Corrections, see Description |
| (48) |
Corrigendum issued on: |
|
30.08.2006 Bulletin 2006/35 |
| (45) |
Mention of the grant of the patent: |
|
24.05.2006 Bulletin 2006/21 |
| (22) |
Date of filing: 24.06.2003 |
|
| (51) |
International Patent Classification (IPC):
|
| (86) |
International application number: |
|
PCT/US2003/019866 |
| (87) |
International publication number: |
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WO 2004/003903 (08.01.2004 Gazette 2004/02) |
|
| (54) |
CORROSION RESISTIVE SILVER METAL ALLOYS FOR OPTICAL DATA STORAGE AND RECORDABLE OPTICAL
STORAGE MEDIA CONTAINING SAME
KORROSIONSBESTÄNDIGE SILBERMETALLLEGIERUNGEN FÜR OPTISCHES AUFZEICHNEN UND BESCHREIBBARE
OPTISCHE AUFZEICHNUNGSMEDIEN WELCHE DIESE LEGIERUNG ENTHALTEN
ALLIAGES METALLIQUES D'ARGENT RESISTANT A LA CORROSION POUR LE STOCKAGE DE DONNEES
OPTIQUES ET SUPPORTS DE STOCKAGE ENREGISTRABLES CONTENANT CES DERNIERS
|
| (84) |
Designated Contracting States: |
|
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
| (30) |
Priority: |
28.06.2002 US 392729 P
|
| (43) |
Date of publication of application: |
|
30.03.2005 Bulletin 2005/13 |
| (73) |
Proprietor: WILLIAMS ADVANCED MATERIALS INC. |
|
Buffalo, NY 14214 (US) |
|
| (72) |
Inventors: |
|
- LICHTENBERGER, Heiner
Williamsville, NY 14221 (US)
- BROWN, Derrick, L.
Buffalo NY 14214 (US)
- HALUSKA, Scott
Amherst, NY 14051 (US)
|
| (74) |
Representative: Emde, Eric |
|
Wagner & Geyer,
Gewürzmühlstrasse 5 80538 München 80538 München (DE) |
| (56) |
References cited: :
US-A- 4 743 526
|
US-A- 5 716 761
|
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| |
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| |
|
| Note: Within nine months from the publication of the mention of the grant of the European
patent, any person may give notice to the European Patent Office of opposition to
the European patent
granted. Notice of opposition shall be filed in a written reasoned statement. It shall
not be deemed to
have been filed until the opposition fee has been paid. (Art. 99(1) European Patent
Convention).
|
Cross-Reference to Related Application
[0001] This application claims priority from Provisional Application Serial No. 60/392,729,
filed June 28, 2002.
Field of the Invention
[0002] The present invention relates to optical data storage and, more particularly to storage
media containing reflective layers formed from silver-reactive metal alloys, specifically
alloys of silver with the rare earth metal samarium.
Background of the Invention
[0003] Reflective metal thin films are used in creating optical storage media. These thin
metal layers are sputtered onto patterned transparent disks to reflect a laser light
source. The reflected laser light is read as light and dark spots of certain length,
converted into electrical signals, and transformed into images and sounds associated
with music, movies, and data. All optical media formats, including compact disk (CD),
laser disk (LD), and digital video disk (DVD), employ at least a single reflective
metal layer, L1, for which aluminum is the metal of choice. More advanced optical
media technology utilizes multiple reflective layers to increase the storage capacity
of the media. For instance, many DVD's such as DVD 9, DVD 14, and DVD 18 contain two
reflective layers, which enables two layers of information to be read from one side
of the disk. The second layer, known as the L0 semi-reflective layer, must be thin
enough, typically less than 10 nm, to allow the underlying L1 layer to be read, but
it must still be sufficiently reflective, about 18% to about 30% reflectivity, to
be read. The disk can further include one or more additional semi-reflective layers
read from the same side as the L1 and L0 layers. The construction and reading methodology
of a DVD containing two reflective layers is shown in FIG. 1.
[0004] When digital data is read from an optical storage medium, the lengths of the pits,
typically of 9 different lengths, are read using an internal clock timing and converted
into a high frequency electrical signal, which is truncated to generate square waves
and transformed into a binary electrical data stream.
[0005] Variances in the length of the pits caused by molding the polycarbonate or the incomplete
metallization of the entire pit can cause errors in interpreting the data reflected
by the laser. For optical media applications, the electronic circuits that interpret
the data are specially designed to allow for a certain number of errors. There are
four primary error indicators for optical media data. These critical parameters are
categorized as:
- 1) PI - the total number of unreadable pits within a specified area; while industry
standards allow for 280 defects, many companies hold this parameter to a maximum of
100
- 2) Jitter - the timing variation in pit or land length compared to the internal clock
pulses; the industry maximum is 8%
- 3) Reflectivity - the percentage of laser light reflected from the pits; the industry
standard is 18 to 30%
- 4) I-14 - the variance in the longest pit length; the industry standard is less than
0.15% within one revolution and less than 0.33% within the disk.
[0006] The initial quality of the master used for making the polycarbonate disks, the polycarbonate,
and the reflective materials are critical to the production of accurate data. Not
only must the metallizing material be capable of uniform deposition and reflectivity,
it must also be capable of fully filling the data storage pits that store the data.
In addition, the industry uses an environmental test that subjects the disk to a specific
temperature and humidity for a specified period of time. The industry standard for
this test is temperature of 70°C at 50% relative humidity for 96 hours (70/50/96).
Many companies have adapted stricter internal specifications to raise the temperature
to 80°C and humidity to 85% for 96 hours (80/85/96).
[0007] After manufacturing, the data storage disks are scanned for errors, exposed to the
environmental testing chamber, and subsequently re-analyzed for errors. Any failures
at any testing stage, based on industry standards for error rates, or marked deterioration,
even if not actually failing, after environmental testing will lead to rejections.
The environmental testing demands a corrosion resistant material for the reflective
metallizations. While a thickness of 20 nm of Al generally is adequate for the fully
reflective layer as produced, a thickness of 40 nm may be required to provide adequate
reflectivity after environmental exposure. Typically, about half of the original aluminum
layer is transformed into transparent aluminum oxide during this environmental test.
The semi-reflective layer is dramatically more critical since its apparent thickness
and reflecting qualities cannot change by more than about 10% of its original relative
value during environmental exposure.
[0008] In addition to the testing noted above, there is also a non-industry specification
regarding UV or sunlight exposure. It has been found that disks made with silver alloys
can discolor when subjected to sunlight. While the chemistry of the reaction is not
fully understood, it is caused by a combination of the silver alloy used for the semi-reflective
layer and the adhesive used to attach it to the fully reflective layer. A disk is
deemed to have failed once its reflectance falls below 18% for either the semi-reflective
layer or the fully reflective layer, the latter being viewed through the adhesive
and the semi-reflective layer.
[0009] Aluminum, gold, silicon and silver alloys have been successfully used to create reflective
layers for optical storage media. Because of its low cost, excellent reflectivity
and sputtering characteristics on polymeric materials, aluminum is an especially preferred
metal for a reflective coating that is used almost exclusively whenever there is only
one reflective data layer and is also used to form the fully reflective L1 layer on
a two-layer DVD. However, aluminum oxidizes readily, and its reflectivity can be compromised
upon environmental exposure. This oxidation prohibits the use of aluminum for all
but the fully reflective layer, where it is deposited more heavily than the semi-reflective
layer would allow. Gold and silicon were the first materials to be used for the semi-reflective
layer in DVD construction, but both materials have significant drawbacks. Gold provides
excellent reflectivity of red laser light, excellent sputtering characteristics, and
superior corrosion resistance but is very costly. Silicon is also reflective and free
from corrosion but does not sputter as efficiently as the other metals. Furthermore,
silicon is brittle, and cracks may form during thermal cycling and mechanical flexing,
which prevents delicate data from being read. U.S. Patent No. 5,640,382 describes
the construction of a DVD data storage disk, and U.S. Patent No. 5,171,392 describes
the use of gold and silicon for the semi-reflective data storage layer.
[0010] Silver, like gold, has excellent sputtering characteristics and reflectivity, but
the corrosion resistance of pure silver is inadequate for it to be used as the semi-reflective
layer. Considerable effort has been expended to make silver sufficiently corrosion
resistant so that it can be used for the semi-reflective layer, as described, for
example, in U.S. Patent Nos. 6,280,811,6,292,457, and 6,351,446. These patents describe
silver based alloys for optical media whose corrosion resistance is improved by the
addition of other precious metals such as palladium, platinum, and gold. While markedly
less expensive than gold alone, the addition of these precious metals to silver in
contents up to 30 wt.% dramatically increases their cost over that of pure silver.
U.S. Patent No. 4,743,526 discloses an Ag alloy containing ZnSm.
[0011] For the manufacture of optical data recording and storage media, there is an ongoing
need for silver alloys with uniform sputtering characteristics and improved corrosion
resistance that do not require the inclusion of more expensive precious metals. This
need is met by the alloys of the present invention, whose properties make them especially
suitable for use in optical data recording and storage media, in particular, for use
in the semi-reflective layer of a DVD.
Summary of the Invention
[0012] The present invention is directed to an optical data recording and storage medium
that includes a reflective layer formed from a silver-based alloy that contains at
least about 97.0 wt.% silver and comprises, in addition to silver, about 0.1 to about
3.0 wt.%, based on the total weight of the alloy, of samarium (Sm).
Brief Description of the Drawings
[0013]
FIG. 1 is a schematic representation of an optical data storage disk that depicts
two reflective layers, one of which is a thin semi-reflective layer, and their positions
in the disk.
FIG 2 is a shematic representation of pits and lands corresponding to digital data
recorded on an optical data storage disk, together with a reflective signal produced
by this layer.
FIG 3 is a graph showing the reflectivity of metallic silver, aluminium, and gold
over the visible spectrum of light.
FIG 4 is a schematic illustration of an electrical signal as it is read from an optical
media storage disk.
FIG 5 is an illustration of the data tracks in various optical media formats.
Detailed Description of the Invention
[0014] Pure silver has excellent reflectivity but insufficient corrosion resistance to be
used as the semi-reflective layer in a multilayered optical data storage disk. Addition
of small amounts of certain readily oxidizable metals, in particular, the rare earth
metal samarium (Sm), to silver can improve its corrosion resistance while maintaining
its desirable reflectivity, thereby providing a desirable material for use in reflective
layers of optical recording and storage media. Although the alloys of the invention
are especially suited for use in thin-film semi-reflective layers, they may also be
beneficially employed in fully reflective layers of single or multiple layered media,
whether in disk or in other media formats.
[0015] FIG. 1 schematically depicts an optical data storage disk D containing reflective
layers L1 and L0. Reflective layer L1 is the fully reflective layer and is typically
formed from aluminum. The thin semireflective layer L0 is formed from a silver alloy
of the present invention. Light from a laser source that is reflected from layer L1
is designated RL1; similarly, light reflected from layer L0 is designated RL0. The
reflected light RL1 and RL0 is sensed by detectors. It should be noted that the light
from a laser source must penetrate the semi-reflective layer L0 twice in order to
read layer L1.
[0016] In disk D, layers 1 and 3, which typically are formed from a plastic such as polycarbonate
or poly(methyl methacrylate) (PMMA), are imprinted with digital information comprising
pits and lands. Layer 2 is an adhesive layer, typically comprising a UV-curable epoxy
material, that is used to join layers 1 and 3.
[0017] FIG. 2 schematically illustrates the digital interpretation of the information stored
on optical data disk D. The lands are at a distance from the laser and the detector
such that reflected signals return to the detector in phase (bright), while the pits
are at a second distance such that the signal returns to the detector out of phase
(dark).
[0018] FIG. 3 shows the reflectivity of several important metals -- -silver, aluminum, and
gold--- over the visible spectrum of light. Most optical data disks are read with
light waves approximately 650 nm, in the red portion of the visible spectrum. More
recently, however, blue light-emitting laser diodes have become commercially available,
which enables the storage and reading of much denser data. As shown in FIG. 3, metallic
silver exhibits high reflectivity across the entire visible light spectrum.
[0019] FIG 4 illustrates the sinusoidal electrical signal read from an optical media storage
disk that depicts how it is truncated and compared to an internal clock to decipher
the pulse length and data contained on the disk.
[0020] FIG 5 is an illustration of the data tracks and pits used for data storage on CD,
DVD and Blu-ray optical media formats. The new blue laser format, which employs a
higher frequency (higher clock rate) laser to discern smaller data pits with less
distance between tracks, allows for five times as much data as on a disk using a red
laser, making it especially useful for high definition television (HDTV) formats.
Optical data recording and storage disks having reflective layers formed from silver
alloys of the present invention can be used with blue lasers.
[0021] Corrosion resistant silver based alloys are formed, in accordance with the present
invention, by the inclusion of about 0.1 to about 4.0 wt.%, preferably about 0.2 to
about 1.0 wt.%, more preferably, about 0.25 to about 0.35 wt.%, based on the total
weight of alloy, of the rare earth metal samarium (Sm). The high solubility of samarium
(Sm) compared to other reactive rare earth metals enables it to be added in relatively
large amounts of the metal without the formation of secondary phases, which can become
particulates during sputtering and cause defects in the reflective coating. A multiphase
alloy may sputter as a single-phase layer, but if the coated layer is not stable as
a single-phase material, then thermal exposure can cause the precipitation of the
second phase, and this too will result in defects, particularly under harsh test conditions.
For example, separation of a rare earth metal phase in a silver alloy comprising a
semi-reflective layer may create dark spots and cause errors in the optical data.
[0022] In addition to exhibiting good silver solubility, it is also desirable that the added
rare earth metal exhibit high reactivity to air. The inclusion in silver alloys of
samarium (Sm), which is highly reactive, has been found to produce a highly protective
effect compared with pure silver in DVDs that are subjected to stringent environmental
testing. The solubility limits and relative reactivity of the rare earth metals are
presented in TABLE 1 below:
TABLE 1
| Element |
Solubility |
Reactivity |
Element |
Solubility |
Reactivity |
| La |
0.06 |
High |
Gd |
1.4 |
Medium |
| Ce |
0.06 |
High |
Tb |
1.6 |
Medium |
| Pr |
0.05 |
High |
Dy |
1.9 |
Medium |
| Nd |
0.25 |
High |
Ho |
2.4 |
Medium |
| Sm |
0.35* |
High |
Er |
5.5 |
Medium |
| Eu |
0.0 |
High |
Tm |
7.0 |
Medium |
| |
|
|
Lu |
9.0 |
Medium |
| * During our investigation we determined by metallographic examination that the correct
solubility of samarium in silver is about 0.35 wt%, much less than the 1.4 wt.% commonly
cited in reference sources. |
[0023] As shown by the entries in TABLE 1, among the rare earth metals having high reactivity,
samarium (Sm) has the highest solubility in silver. Also, as a consequence of its
high reactivity, addition of small amounts of samarium (Sm) provides desirably high
corrosion resistance. The rare earth metal neodymium (Nd) is included in silver-based
alloys described in U.S. Patent Application Publication No. 2002/0150772, the disclosure
of which is incorporated by reference. However, as shown in TABLE 1, the solubility
in silver of neodymium (Nd) is substantially less than that of Samarium (Sm).
[0024] Copper (Cu) can also be optionally included in the silver alloys of the present invention
to facilitate their manufacturability as well as to improve their shelf life and their
corrosion resistance when exposed to the harshest environmental testing conditions.
The amount of copper (Cu) included in the alloys is preferably about 0.2 to about
2.0 wt.%, more preferably, about 0.25 to about 1.0 wt.%, based on the total weight
of alloy.
[0025] Titanium (Ti), while it does not add substantially to corrosion resistance, has good
solubility, 2 wt.%, in silver, and can also be optionally included in the silver alloys
of the present invention because of its scavenging effect during melting and alloying.
It also acts as a grain refiner during rolling and annealing of the cast alloy ingots
used to make the sputtering targets. The amount of titanium (Ti) included in the alloys
is preferably about 0.05 to about 0.5 wt%, more preferably, about 0.1 to about 0.3
wt%, based on the total weight of the alloy.
[0026] Manganese (Mn), although it may add only marginally to corrosion resistance, has
high solubility, 33 wt%, in silver and can also be optionally included in the silver
alloys of the present invention, providing improvement in sputtering characteristics
and control of reflectivity. The amount of manganese (Mn) included in the alloys is
preferably about 0.1 to about 1.5 wt%, more preferably, about 0.2 to about 0.8 wt%,
based on the total weight of the alloy.
[0027] Aluminum (Al), which also has good silver solubility, 6 wt.%, can also be optionally
included in the silver alloys of the present invention for controlled reduction in
reflectivity. The amount of aluminum (Al) included in the alloys is preferably about
0.1 to about 0.8 wt%, more preferably, about 0.2 to about 0.4 wt%, based on the total
weight of the alloy.
[0028] Samarium (Sm) is included in the silver-based alloy of the present invention in an
amount not exceeding more than about 4.0 wt.%, based on the total weight of the alloy.
Addition of samarium (Sm) in an amount greater than about 4.0 wt.% may negatively
affect silver reflectivity and thereby compromise the semi-reflective layer.
[0029] Optionally, the silver alloys of the present invention can also include, for the
purpose of further enhancing corrosion resistance, a small amount of a precious metal
such as gold, palladium, platinum, or mixtures thereof, preferably in a combined amount
of up to about 2.5 wt.% based on the total weight of alloy.
[0030] Thin semi-reflective layers can be formed from the alloys of the present invention
by sputtering techniques well known in the art. The following examples of useful silver
alloys are presented to illustrate the scope of the invention:
Example 1: A silver based alloy containing about 3.0 wt.% Sm
Example 2: A silver based alloy containing about 1.0 wt.% Sm
Example 3 : A silver based alloy containing about 0.5 wt.% Sm and about 0.5 wt.% Ti
Example 4 : A silver based alloy containing about 0.3 wt% Sm and about 1.0 wt.% Cu
Example 5 : A silver based alloy containing about 1.5 wt.% Sm and about 0.5 wt.% Mn
Example 6 : A silver based alloy containing about 0.7 wt.% Sm and about 0.4 wt.% Al
Example 7 : A silver based alloy containing about 0.1 wt.% Sm, about 1.0 wt.% Cu, and about 0.5
wt.% Ti
Example 8 : A silver based alloy containing about 0.9 wt.% Sm, about 0.1 wt.% Ti, and about 1.0
wt.% Mn
Example 9 : A silver based alloy containing about 0.3 wt.% Sm, about 0.7 wt.% Cu, and about 0.7
wt.% Pt
Example 10 : A silver based alloy containing about 0.3 wt.% Sm, about 0.7 wt.% Cu, and about 0.7
wt.% Pd
Example 11 : A silver based alloy containing about 0.3 wt.% Sm, about 0.5 wt.% Ti , and about
0.5 wt.% Au
Example 12 : A silver based alloy containing about 1.0 wt.% Sm, about 0.3 wt.% Mn, and about 0.3
wt.% Pd
Example 13 : A silver based alloy containing about 0.5 wt.% Sm, about 1.0 wt.% Cu, about 0.5 wt.%
Ti, and about 1.0 wt.% Mn
Example 14 : A silver based alloy containing about 0.3 wt.% Sm, about 0.7 wt.% Cu, about 0.2 wt.%
Ti, and about 0.5 wt.% Mn
[0031] TABLE 2 below contains test data showing the testing data from DVD's containing semi-reflective
layers made from samarium (Sm)-containing silver alloys, along with various comparison
DVD's. Three test conditions are shown for each alloy: 1) an initial test run shortly
after preparation of the DVD; 2) 70/50/96 - a test following exposure of the DVD to
a chamber at 70°C, 50% relative humidity (RH) for 96 hours; 3) 80/85/96 - a test following
chamber exposure at 80°C, 85%RH for 96 hours. As previously noted, PI is the industry
standard terminology for defective pits within a certain area, jitter is caused by
a combination of factors and is limited to 8%, and I-14 is a measure of the longest
pit based on the length of the internal clock. The test data are presented in pass
(P) and fail (F) notation for each of the conditions and criteria. Current requirements
for DVD environmental testing are based on the less harsh test of 70/50/96. However,
most of the major DVD replicators use the more severe 80/85/96 test for internal quality
assurance.
[0032] As shown by the first entry for comparison DVD C-1 in TABLE 2, a pure silver semi-reflective
layer almost passes the industry specifications, failing only in jitter after the
70/50/96 test. However, after the 80/85/96 exposure conditions, control C-1 can no
longer be read.
[0033] Inclusion of 0.7 wt.% copper (Cu) in the silver semi-reflective layer in comparison
DVD C-2 improves jitter to a passing result under the standard industry test, but
the more severe 80/85/96 exposure results in failure in all tests.
[0034] The semi-reflective layers in comparison DVD's C-3 and C-4 are formed from silver-copper
alloys that further include, respectively, 0.25 wt.% aluminum (Al) and 0.75 wt.% manganese
(Mn). Inclusion of these metals results in passing results in both the PI and jitter
tests under 80/85/96 exposure conditions. However DVD's C-3 and C-4 fail the I-14
test initially and under the two environmental exposure conditions.
[0035] The semi-reflective layer in comparison DVD's C-5 and C-6 are formed from silver-copper
alloys that further include, respectively, 0.75 wt% of the medium air-reactive rare
earth metal dysprosium (Dy) and 1.0 wt.% of the more air-reactive rare earth metal
neodymium (Nd). As with DVD's C-3 and C-4, comparison DVD's C-5 and C-6 fail the I-14
test initially and under the two environmental exposure conditions. In addition, DVD
C-5 also fails the 80/85/96 PI test.
[0036] DVD's C-7, C-8, and C-9 are formed from silver alloys each containing 0.7 wt.% copper
(Cu) and 0.5 wt.% manganese (Mn) and, in addition, 0.25 wt.% of, respectively, the
rare earth metals dysprosium (Dy), neodymium (Nd), and.cerium (Ce). Similar results
are obtained from DVD's C-7, C-8, and C-9; each passes all tests except PI and Jitter
under the 80/85/96 exposure conditions. As shown by comparison with DVD's C-5 and
C-6, inclusion of manganese (Mn) in DVD's C-7, C-8, and C-9 results in improved I-14
results under all test conditions.
[0037] DVD's I-1 and 1-2 of the present invention, which include, respectively, 1.0 and
0.25 wt.% samarium (Sm) in the silver semi-reflective layer, produce passing results
in all three of the standard industry tests under 70/50/96 exposure conditions but
failure in the same tests under 80/85/96 conditions.
[0038] DVD I-3 of the invention, in which the semi-reflective layer is formed from a silver
alloy containing 0.25 wt.% samarium (Sm) and 0.7 wt.% copper (Cu), gives passing results
in the three tests both under the standard 70/50/96 exposure conditions as well as
under the more stringent 80/85/96 conditions.
[0039] Similar excellent test results under both the 70/50/96 and 80/85/96 test conditions
are shown by DVD's I-4 and I-5 of the present invention, in which the silver alloys
contain, in addition to samarium (Sm) and copper (Cu), 0.5 wt.% manganese (Mn) and
0.2 wt.% titanium (Ti), respectively.
[0040] A comparison of the results of DVD's I-3, I-4, and I-5 of the present invention,
whose semi-reflective layers are formed from samarium (Sm)-containing silver alloys,
with DVD's C-5 through C-9, in which the semi-reflective layers are formed from alloys
containing other rare earth metals, specifically, dysprosium (Dy), neodymium (Nd),
and cerium (Ce), shows the advantage of samarium (Sm) over other rare earths for protecting
DVD's against damage, even under severe exposure conditions.
[0041] DVD I-6 of the invention is similar to DVD I-3 except for its silver alloy containing
a higher concentration of samarium (Sm), 0.75 wt.% vs 0.25 wt.%; the concentration
of copper in both alloys is the same, 0.7 wt.%. DVD I-6 also produces very good test
results, failing only the PI test under the stringent 80/85/96 conditions.
[0042] Similarly, DVD I-7 of the invention, which contains the same concentration of samarium
(Sm), 1.0 wt.%, as DVD I-1 but also includes 0.5 wt.% copper (Cu), gives very good
results, failing only the I-14 test under the 80/85/96 exposure conditions.
[0043] DVD I-8 of the invention is similar to DVD I-3 except for its silver alloy containing
a considerably higher concentration of samarium (Sm), 4.0 wt.% vs 0.25 wt.%; the concentration
of copper in both alloys is the same, 0.7 wt.%. DVD I-8 passes all three tests under
the industry standard conditions but fails the PI and I-14 tests under the stringent
80/85/96 conditions.
[0044] As demonstrated by the results presented in TABLE 2, inclusion of samarium (Sm) at
levels of preferably up to about 1.0 wt.%, more preferably, about 0.25 to about 0.35
wt%, in silver alloys comprising DVD semi-reflective layers, provides beneficial results
under severe environmental test conditions. Further inclusion of copper (Cu) in amounts
preferably up to about 1.0 wt.%, in the samarium (Sm)-containing silver alloys enhances
the benefit.
[0045] The invention has been described in detail with particular reference to certain preferred
embodiments thereof, but it is understood that variations and modifications can be
effected within the scope of the invention, which is defined by the claims that follow.
TABLE 2
| Ag Alloy |
Condition |
PI |
Jitter |
I-14 |
| |
| |
|
Initial |
P |
P |
P |
| C-1 |
|
70/50/96 |
P |
F |
P |
| comparison |
pure Ag |
80/85/96 |
F |
F |
F |
| |
|
Initial |
P |
P |
F |
| C-2 |
Ag |
70/50/96 |
P |
P |
F |
| comparison |
0.7% Cu |
80/85/96 |
F |
F |
F |
| |
Ag |
Initial |
P |
P |
F |
| C-3 |
0.7% Cu |
70/50/96 |
P |
P |
F |
| comparison |
0.25% Al |
80/85/96 |
P |
P |
F |
| |
Ag |
Initial |
P |
P |
F |
| C-4 |
0.5% Cu |
70/50/96 |
P |
P |
F |
| comparison |
0.75% Mn |
80/85/96 |
P |
P |
F |
| |
Ag |
Initial |
P |
P |
F |
| C-5 |
0.75% Dy |
70/50/96 |
P |
P |
F |
| comparison |
0.7% Cu |
80/85/96 |
F |
P |
F |
| |
Ag |
Initial |
P |
P |
F |
| C-6 |
1.0% Nd |
70/50/96 |
P |
P |
F |
| comparison |
0.5% Cu |
80/85/96 |
P |
P |
F |
| |
Ag |
Initial |
P |
P |
P |
| C-7 |
0.25% Dy 0.7% Cu |
70/50/96 70/50/96 |
P |
P |
P |
| comparison |
0.5% Mn |
80/85/96 |
F |
F |
P |
| |
Ag |
Initial |
P |
P |
P |
| C-8 |
0.25% Nd 0.7% Cu |
70/50/96 70/50/96 |
P |
P |
P |
| comparison |
0.5% Mn |
80/85/96 |
F |
F |
P |
| |
Ag |
Initial |
P |
P |
P |
| C-9 |
0.25% Ce 0.7 % Cu |
70/50/96 70/50/96 |
P |
P |
P |
| comparison |
0.5% Mn |
80/85/96 |
F |
F |
P |
| |
|
Initial |
P |
P |
P |
| I-1 |
Ag |
70/50/96 |
P |
P |
P |
| invention |
1.0% Sm |
80/85/96 |
F |
F |
F |
| |
|
Initial |
P |
P |
P |
| I-2 |
Ag |
70/50/96 |
P |
P |
P |
| invention |
0.25% Sm |
80/85/96 |
F |
F |
F |
| |
Ag |
Initial |
P |
P |
P |
| I-3 |
0.25% Sm |
70/50/96 |
P |
P |
P |
| invention |
0.7% Cu |
80/85/96 |
P |
P |
P |
| |
Ag |
Initial |
P |
P |
P |
| I-4 |
0.35%Sm 0.7% Cu 0.5% Mn |
70/50/96 |
P |
P |
P |
| invention |
80/85/96 |
P |
P |
P |
| |
Ag |
Initial |
P |
P |
P |
| I-5 |
0.35% Sm 1.0% Cu 0.2% Ti |
70/50/96 |
P |
P |
P |
| invention |
80/85/96 |
P |
P |
P |
| |
Ag |
Initial |
P |
P |
P |
| I-6 |
0.75% Sm |
70/50/96 |
P |
P |
P |
| invention |
0.7% Cu |
80/85/96 |
F |
P |
P |
| |
Ag |
Initial |
P |
P |
P |
| I-7 |
1.0% Sm |
70/50/96 |
P |
P |
P |
| invention |
0.5% Cu |
80/85/96 |
P |
P |
F |
| |
Ag |
Initial |
P |
P |
P |
| I-8 |
4.0% Sm |
70/50/96 |
P |
P |
P |
| invention |
0.7% Cu |
80/85/96 |
F |
P |
F |
1. An optical data recording and storage medium that includes a first reflective layer
formed from a silver-based alloy comprising from about 0.1 to about 3.0 wt.%, based
on the total weight of said alloy, of samarium (Sm), characterized in that said silver-based alloy contains at least about 97.0 wt% silver.
2. The optical data recording and storage medium of claim 1 wherein said silver-based
alloy comprises from about 0.2 to about 1.0 wt.%, based on the total weight of said
alloy, of samarium (Sm).
3. The optical data recording and storage medium of claim 1 wherein said silver-based
alloy comprises from about 0.25 to about 0.35 wt.%, based on the total weight of said
alloy, of samarium (Sm).
4. The optical data recording and storage medium of claim 1 wherein said silver-based
alloy further comprises copper (Cu).
5. The optical data recording and storage medium of claim 4 wherein said silver-based
alloy comprises from about 0.2 to about 2.0 wt.% copper (Cu).
6. The optical data recording and storage medium of claim 5 wherein said silver-based
alloy comprises from about 0.25 to about 1.0 wt.% copper (Cu).
7. The optical data recording and storage medium of claim 1 wherein said silver-based
alloy further comprises titanium (Ti).
8. The optical data recording and storage medium of claim 7 wherein said silver-based
alloy comprises from about 0.05 to about 0.5 wt.% titanium (Ti).
9. The optical data recording and storage medium of claim 8 wherein said silver-based
alloy comprises from about 0.1 to about 0.3 wt.% titanium (Ti).
10. The optical data recording and storage medium of claim 1 wherein said silver-based
alloy further comprises manganese (Mn).
11. The optical data recording and storage medium of claim 10 wherein said silver-based
alloy comprises from about 0.1 to about 1.5 wt.% manganese (Mn).
12. The optical data recording and storage medium of claim 11 wherein said silver-based
alloy comprises from about 0.2 to about 0.8 wt.% manganese (Mn).
13. The optical data recording and storage medium of claim 1 wherein said silver-based
alloy further comprises aluminum (Al).
14. The optical data recording and storage medium of claim 13 wherein said silver-based
alloy comprises from about 0.1 to about 0.8 wt.% aluminum (Al).
15. The optical data recording and storage medium of claim 1 wherein said silver-based
alloy comprises from about 0.2 to about 0.4 wt.% aluminum (Al).
16. The optical data recording and storage medium of claim 1 wherein said si lver-based
alloy further comprises a precious metal selected from the group consisting of gold
(Au), palladium (Pd), platinum (Pt), and mixtures thereof, in a total amount of up
to about 2.5 wt.% of said alloy.
17. The optical data recording and storage medium of claim 1 wherein said silver-based
alloy further comprises copper (Cu), titanium (Ti), and manganese (Mn).
18. The optical data recording and storage medium of claim 17 wherein said silver-based
alloy consists essentially of from about 0.25 to about 0.35 wt.% samarium (Sm), from
about 0.25 to about 1.0 wt.% copper (Cu), from about 0.1 to about 0.3 wt.% titanium
(Ti), and from about 0.2 to about 0.8 wt.% manganese (Mn), the balance being silver
(Ag).
19. The optical data recording and storage medium of claim 18 wherein said silver-based
alloy consists essentially of about 0.3 wt.% samarium (Sm), about 0.7 wt.% copper
(Cu), about 0.2 wt% titanium (Ti), and about 0.5 wt.% manganese (Mn), the balance
being silver (Ag).
20. The optical data recording and storage medium of claim 1 wherein said first reflective
layer is a thin semi-reflective film.
21. The optical data recording and storage medium of claim 1 further comprising a second
reflective layer.
22. The optical data recording and storage medium of claim 1 included in a DVD.
23. The optical data recording and storage medium of claim 1 included in a high-density
disk readable by a high frequency blue light laser.
24. A silver-based alloy comprising silver and from about 0.1 to about 3.0 wt.%, based
on the total weight of said alloy, of samarium (Sm).
25. The silver-based alloy of claim 24 comprising from about 0.25 to about 0.35 wt.%,
based on the total weight of said alloy, of samarium (Sm).
26. The silver-based alloy of claim 24 further comprising a metal selected from the group
consisting of copper (Cu), titanium (Ti), manganese (Mn), aluminum (Al), gold (Au),
palladium (Pd), platinum (Pt), and mixtures thereof.
27. The silver-based alloy of claim 26 further comprising from about 0.2 to about 2.0
wt.% copper (Cu).
28. The silver-based alloy of claim 26 consists essentially of from about 0.25 to about
0.35 wt.% samarium (Sm), from about 0.25 to about 1.0 wt.% copper (Cu), from about
0.1 to about 0.3 wt.% titanium (Ti), and from about 0.2 to about 0.8 wt.% manganese
(Mn), the balance being silver (Ag).
1. Ein optisches Datenaufzeichnungs- und Speichermedium, das eine erste reflektierende
Schicht aufweist, die aus einer auf Silber basierenden Legierung ausgebildet ist,
die von ungefähr 0,1 bis ungefähr 3,0 Gewichtsprozent basierend auf dem Gesamtgewicht
der Legierung Samarium (Sm) enthält, dadurch gekennzeichnet, dass die auf Silber basierende Legierung wenigstens ungefähr 97,0 Gewichtsprozent Silber
enthält.
2. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, wobei die auf Silber
basierende Legierung von ungefähr 0,2 bis ungefähr 1,0 Gewichtsprozent basierend auf
dem Gesamtgewicht der Legierung aus Samarium (Sm) aufweist.
3. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, wobei die auf Silber
basierende Legierung von ungefähr 0,25 bis ungefähr 0,35 Gewichtsprozent basierend
auf dem Gesamtgewicht der Legierung aus Samarium (Sm) aufweist.
4. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, wobei die auf Silber
basierende Legierung ferner Kupfer (Cu) aufweist.
5. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 4, wobei die auf Silber
basierende Legierung von ungefähr 0,2 bis 2,0 ungefähr Gewichtsprozent Kupfer (Cu)
aufweist.
6. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 5, wobei die auf Silber
basierende Legierung von ungefähr 0,25 bis ungefähr 1,0 Gewichtsprozent Kupfer (Cu)
aufweist.
7. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, wobei die auf Silber
basierende Legierung ferner Titan (Ti) aufweist.
8. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 7, wobei die auf Silber
basierende Legierung von ungefähr 0,05 bis ungefähr 0,5 Gewichtsprozent Titan (Ti)
aufweist.
9. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 8, wobei die auf Silber
basierende Legierung von ungefähr 0,1 bis ungefähr 0,3 Gewichtsprozent Titan (Ti)
aufweist.
10. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, wobei die auf Silber
basierende Legierung ferner Mangan (Mn) aufweist.
11. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 10, wobei die auf Silber
basierende Legierung von ungefähr 0,1 bis ungefähr 1,5 Gewichtsprozent Mangan (Mn)
aufweist.
12. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 11, wobei die auf Silber
basierende Legierung von ungefähr 0,2 bis ungefähr 0,8 Gewichtsprozent Mangan (Mn)
aufweist.
13. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, wobei die auf Silber
basierende Legierung ferner Aluminium (Al) aufweist.
14. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 13, wobei die auf Silber
basierende Legierung von ungefähr 0,1 bis ungefähr 0,8 Gewichtsprozent Aluminium (Al)
aufweist.
15. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, wobei die auf Silber
basierende Legierung von ungefähr 0,2 bis ungefähr 0,4 Gewichtsprozent Aluminium (Al)
aufweist.
16. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, wobei die auf Silber
basierende Legierung ferner ein Edelmetall aufweist, ausgewählt aus der Gruppe bestehend
aus Gold (Au), Palladium (Pd), Platin (Pt), und Mischungen davon, in einer Gesamtmenge
von ungefähr 2,5 Gewichtsprozent der Legierung.
17. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, wobei die auf Silber
basierende Legierung ferner Kupfer (Cu), Titan (Ti) und Mangan (Mn) aufweist.
18. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 17, wobei die auf Silber
basierende Legierung im Wesentlichen besteht aus ungefähr 0,25 bis ungefähr 0,35 Gewichtsprozent
Samarium (Sm), von ungefähr 0,25 bis ungefähr 1,0 Gewichtsprozent Kupfer (Cu), ungefähr
0,1 bis ungefähr 0,3 Gewichtsprozent Titan (Ti) und ungefähr 0,2 bis ungefähr 0,8
Gewichtsprozent Mangan (Mn), wobei der Rest Silber (Ag) ist.
19. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 18, wobei die auf Silber
basierende Legierung im Wesentlichen besteht aus ungefähr 0,3 Gewichtsprozent Samarium
(Sm), ungefähr 0,7 Gewichtsprozent Kupfer (Cu), ungefähr 0,2 Gewichtsprozent Titan
(Ti) und ungefähr 0,5 Gewichtsprozent Mangan (Mn), wobei der Rest Silber (Ag) ist.
20. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, wobei die erste
reflektierende Schicht eine dünne halbreflektierende Schicht ist.
21. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, das ferner eine
zweite reflektierende Schicht aufweist.
22. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, das in einer DVD
enthalten ist.
23. Optisches Datenaufzeichnungs- und Speichermedium nach Anspruch 1, das in einer hochdichten
Disk, die durch einen hochfrequenten Blaulichtlaser lesbar ist, enthalten ist.
24. Eine auf Silber basierende Legierung, die Silber und von ungefähr 0,1 bis ungefähr
0,3 Gewichtsprozent, basierend auf dem Gesamtgewicht der Legierung, Samarium (Sm)
enthält.
25. Die auf Silber basierende Legierung nach Anspruch 24, die von ungefähr 0,25 bis ungefähr
0,35 Gewichtsprozent basierende auf dem Gesamtgewicht der Legierung Samarium (Sm)
enthält.
26. Die auf Silber basierende Legierung nach Anspruch 24, die ferner ein Metall aufweist,
ausgewählt aus der Gruppe bestehend aus Kupfer (Cu), Titan (Ti), Mangan (Mn), Aluminium
(Al), Gold (Au), Palladium (Pd), Platin (Pt) und Mischungen davon.
27. Die auf Silber basierende Legierung nach Anspruch 26, die ferner von ungefähr 0,2
bis ungefähr 2,0 Gewichtsprozent Kupfer (Cu) aufweist.
28. Die auf Silber basierende Legierung nach Anspruch 26, die im Wesentlichen aus ungefähr
0,25 bis ungefähr 0,35 Gewichtsprozent Samarium (Sm), von ungefähr 0,25 bis ungefähr
1,0 Gewichtsprozent Kupfer (Cu), von ungefähr 0,1 bis ungefähr 0,3 Gewichtsprozent
Titan (Ti) und von ungefähr 0,2 bis ungefähr 0,8 Gewichtsprozent Mangan (Mn) aufweist,
wobei der Rest Silber (Ag) ist.
1. Milieu d'enregistrement et de mémorisation optique de données comprenant une première
couche réflectrice en alliage à base d'argent comprenant d'environ 0,1 à environ 3,0
% du poids total de l'alliage en samarium (Sm), caractérisé en ce que l'alliage à base d'argent contient au moins environ 97 % en poids d'argent.
2. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, dans lequel l'alliage à base d'argent comprend d'environ 0,2 à environ 1,0 % du
poids total de l'alliage en samarium (Sm).
3. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, dans lequel l'alliage à base d'argent comprend d'environ 0,25 à environ 0,35 %
du poids total de l'alliage en samarium (Sm).
4. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, dans lequel l'alliage à base d'argent comprend en outre du cuivre (Cu).
5. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
4, dans lequel l'alliage à base d'argent comprend d'environ 0,2 à environ 2,0 % en
poids de cuivre (Cu).
6. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
5, dans lequel l'alliage à base d'argent comprend d'environ 0,25 à environ 1,0 % en
poids de cuivre (Cu).
7. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, dans lequel l'alliage à base d'argent comprend en outre du titane (Ti).
8. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
7, dans lequel l'alliage à base d'argent comprend d'environ 0,05 à environ 0,5 % en
poids de titane (Ti).
9. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
8, dans lequel l'alliage à base d'argent comprend d'environ 0,1 à environ 0,3 % en
poids de titane (Ti).
10. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, dans lequel l'alliage à base d'argent comprend en outre du manganèse (Mn).
11. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
10, dans lequel l'alliage à base d'argent comprend d'environ 0,1 à environ 1,5 % en
poids de manganèse (Mn).
12. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
11, dans lequel l'alliage à base d'argent comprend d'environ 0,2 à environ 0,8 % en
poids de manganèse (Mn).
13. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, dans lequel l'alliage à base d'argent comprend en outre de l'aluminium (Al).
14. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
13, dans lequel l'alliage à base d'argent comprend d'environ 0,1 à environ 0,8 % en
poids d'aluminium (Al).
15. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, dans lequel l'alliage à base d'argent comprend d'environ 0,2 à environ 0,4 % en
poids d'aluminium (Al).
16. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, dans lequel l'alliage à base d'argent comprend en outre un métal précieux choisi
dans le groupe comprenant l'or (Au), le palladium (Pd), le platine (Pt) et leurs mélanges
selon une quantité totale allant jusqu'à environ 2,5 % en poids de l'alliage.
17. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, dans lequel l'alliage à base d'argent comprend en outre du cuivre (Cu), du titane
(Ti) et du manganèse (Mn).
18. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
17, dans lequel l'alliage à base d'argent comprend essentiellement d'environ 0,25
à environ 0,35 % en poids de samarium (Sm), d'environ 0,25 à environ 1,0 % en poids
de cuivre (Cu), d'environ 0,1 à environ 0,3 % en poids de titane (Ti), et d'environ
0,2 à environ 0,8 % en poids de manganèse (Mn), le reste étant de l'argent (Ag).
19. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
18, dans lequel l'alliage à base d'argent comprend essentiellement environ 0,3 % en
poids de samarium (Sm), environ 0,7 % en poids de cuivre (Cu), environ 0,2 % en poids
de titane (Ti), et environ 0,5 % en poids de manganèse (Mn), le reste étant de l'argent
(Ag).
20. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, dans lequel la couche réflectrice est une couche semi-réfléchissante.
21. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, comprenant en outre une seconde couche réflectrice.
22. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, inclus dans un DVD.
23. Milieu d'enregistrement et de mémorisation optique de données selon la revendication
1, inclus dans un disque à haute densité lisible par un laser en lumière bleue à haute
fréquence.
24. Alliage à base d'argent comprenant de l'argent et d'environ 0,1 à environ 3,0 % du
poids total de l'alliage en samarium (Sm).
25. Alliage à base d'argent selon la revendication 24, comprenant de l'argent et d'environ
0,25 à environ 0,35 % du poids total de l'alliage en samarium (Sm).
26. Alliage à base d'argent selon la revendication 24, comprenant en outre un métal choisi
dans le groupe comprenant le cuivre (Cu), le titane (Ti), le manganèse (Mn), l'aluminium
(Al), l'or (Au), le palladium (Pd), le platine (Pt) et leurs mélanges.
27. Alliage à base d'argent selon la revendication 26, comprenant d'environ 0,2 à environ
2,0 % en poids de cuivre (Cu) .
28. Alliage à base d'argent selon la revendication 26, comprenant essentiellement d'environ
0,25 à environ 0,35 % en poids de samarium (Sm), d'environ 0,25 à environ 1 % en poids
de cuivre (Cu), d'environ 0,1 à environ 0,3 % en poids de titane (Ti), et d'environ
0,2 à environ 0,8 % en poids de manganèse (Mn), le reste étant de l'argent (Ag).

