TWI303665B - Silver alloy for use as reflective or semi-reflective layer - Google Patents

Description

.1303665 * r IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a silver alloy and its use as a reflective or semi-reflective layer. 5 [Prior Art] With the rapid advancement of technology in the electronics industry, the optoelectronics industry, such as the optical disc industry and the flat panel display industry, have developed a large number of consumer products, among which metal reflective films play an indispensable role. Different optical components can be designed using features such as metal reflection, semi-reflection, spectroscopic, and 10 filter. For example, during reading of the data of the optical data recording medium, the laser beam passes through the polycarbonate substrate and the recording layer to read the information on the reflective layer by the reflected beam. Reflectivity, thermal shock resistance and chemical stability are factors that are required for the selection of reflective layer materials. Materials known for the reflective layer 15 are silver, silver alloys (e.g., alloys), and aluminum alloys (e.g., Al-Ti alloys). The laser wavelengths commonly used in optical data recording media are around 780, 650, and 405, and such metals or alloys exhibit a south reflectance in the wide range of wavelengths from 400 to 80 〇 nm. In the case of a display device, an alloy of a good name (such as Al_Nd alloy) is often used as a material for the reflective layer. 2〇 Recently, the DVD era with high capacity, high sound quality and high quality has come. Among them, single-sided double-layer DVD discs have a + reflective layer in addition to a highly reflective layer. In the application of the semi-reflective layer, in order to obtain a combination of reflectance and penetration _ material, it is usually achieved by using a multilayer film. For example, Taiwan Patent Application No. 90118577 discloses a combination of a silver alloy layer and a titanium oxide layer 1303665 to obtain an effect of approximately equal reflectance and transmittance. In view of this, it is more desirable to meet the needs of the industry by simply plating a single layer of film to achieve the same effect. SUMMARY OF THE INVENTION The present invention provides a silver alloy which has both optical properties of reflection and translucency, thereby achieving stable reflectance and transmittance combination over a wide wavelength range by forming a single layer film. . Further, by adjusting the thickness of the alloy film, a desired combination of reflection and transmittance can be obtained, and it can be applied to the I reflective layer or the semi-reflective layer of the optical element. In order to meet the above needs, one of the objects of the present invention is to provide a silver alloy mainly composed of Ag, a metal selected from the group consisting of Zn, Sn, and Cd, and a metal selected from the group consisting of A, Ga, In, Si, Ge, and Sb. It is represented by the formula AgxXzYr, where X is Zn, Sn or Cd, Y is A, Ga, In, Si, Ge or Sb; and based on the total weight of the silver alloy, z is 0·01~5 wt%, r is 0.01 to 3 15% by weight and X is the balance. The invention further provides a silver alloy mainly composed of Ag, Cu and a metal selected from Zn, Sn and Cd, which is represented by the formula AgxCuyXz, wherein X is Zn, Sn or Cd; and the total weight of the silver alloy is For the reference, y is 0.01 to 8 wt%, z is 0.01 to 5 wt%, and X is the balance. 2) The silver alloy of the present invention may further comprise a metal selected from the group consisting of Al, Ga, In, Si, Ge and Sb, which is represented by the formula AgxCuyXzYr, wherein X is Zn, Sn or Cd, and Y is A, Ga, In, Si, Ge or Sb; and based on the total weight of the silver alloy, y is 0.01 to 8% by weight, z is 0. 01 to 5% by weight, r is 0.01 to 3% by weight, and X is the balance. -6- H:\Wendyc(WW)\ Domestic Application \94693-spec(final).doc .1303665 The silver alloy of the present invention not only has unique optical properties, but also has a simpler method than the conventional method. Specifically, the silver alloy of the present invention can be heated to melt by first using a cycle induction melting process. Then, an appropriate amount of alloying elements (adjusted according to the ratio of the alloy) is added and cast into an ingot. Compared to other alloys 5, a vacuum electric fox melting system (Vacuum Arc Remelting) is required.

Process ’ VAR) or vacuum Induction Melting Process (VIM) is a more complex and expensive process that is more competitive. After using the circumferential induction melting, the oxide of the surface of the obtained silver alloy is removed and processed to a size of 9 X 9 cm by a rolling machine, and then heat-treated to homogenize the material and level the surface of the material for subsequent processing, and then use a wire cutting machine. Cut 2 round targets (about 3 mm thick). Since the standard target thickness is about 6.35 mm, the alloy target is soft welded to the copper back plate with indium to bring the target to a standard thickness. The silver alloy of the present invention can be formed into a metal layer by a conventional sputtering method. 15: Generally speaking, the surface roughness of the alloy coating is mainly affected by the working pressure and the substrate. If the working pressure is increased, the plasma dissociation rate can be increased, but the film density is reduced due to the easy inclusion of gas in the film layer, resulting in loose film structure and high surface roughness. Heating the substrate causes the film grain to follow the substrate temperature. When the growth is increased, the growth becomes large, and a distinct grain boundary groove appears, so that the surface roughness and the roughness are relatively increased. The main process parameters (e.g., 2 glaze pressure, working pressure, sputtering power, and substrate temperature) used in the present invention are all controlled to be the same. Therefore, the average roughness of the film formed by the silver alloy of the present invention is not significantly different. Further, the silver alloy of the present invention also has a marked improvement in heat resistance, since the alloy film of the alloy has a small average roughness under heat treatment. -7- H:\Wendyc(WW)\Domestic application\94693_spec(fmal) d〇c .1303665

Another object of the present invention is to provide a reflective ruthenium formed by soybeans. The silver alloy film of the present invention has an effect of a thickness of about 8 Å, which is a silver-rich total reflection layer. On the other hand, when the cup is on the surface, it can be applied to the semi-reflective layer, and the opening is preferably about 20% to 40% and the transmittance is about 20%. Medium reflectance is about the application range of the silver alloy of the present invention.

10 15

In addition to DVD), it can also be used for various industries such as % 曰 I, 1 α first disc manufacturing (such as assistant (PDA). Slope or personal digital [Embodiment] The following examples are merely illustrative of the present invention. The application is not intended to be used in the present invention. (4) Various modifications and alterations that are not inconsistent with the spirit of the present invention are within the scope of the present invention. X 4 Preparation of Silver Alloy 眚 Your Alloy The smelting silver is placed in the cycle induction melting furnace as shown in Figure 1 (Reference: Μ· Ρ·

Groover, "Fundamentals of Modem Manufacturing 2/e", 2002 John

In Wiley & S〇nS, InC. P235.), the silver is heated to melt. Subsequent addition of other alloying elements, the composition ratio of which is shown, for example. Casting into ingots. H:\Wendyc(WW)\Domestic Application \94693-spec(final).doc 20 1303665 Ingredients •------ Estimated Actual Ratio (ICP)

98.062% by weight Dry material processing 眚t Using a centrifugal induction smelting silver character and using a roller press to 9 Q i, remove the gas flat material table on the surface of the silver alloy; =: rationale * 2 pairs of 3 mm thick round冉 裁 裁 冉 冉 冉 冉 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁 裁r point, „coupled electric quality 1 ICP (ICP_MS) is made into an analysis of the sounds made, and the actual alloy composition is recorded in the table. The alloy is made into eight results using the optical microscope. As shown in Fig. 2 and Fig. 3(a), the knife 15 performs an energy dispersive optical reader (10) phantom analysis on the obtained silver alloy dry material. The result is shown in Fig. 3 (b). The preparation of the silver alloy of the invention The targets were prepared by conventional sputtering methods with thicknesses of 3 〇 nm and 100 nm, respectively, and the sputtering parameters used are shown in Table 2. -9- H:\Wendyc(WW)\Domestic Application\94693- Spec(final).doc 1303665 Table 2 Upset parameter substrate Si wafer, BK7 glass background pressure 7.0 X l〇-4Torr Ar flow rate about 100 seem Working pressure 5.0 X ΙΟ'3 Torr DC power supply 100W Impact time 15 seconds Coating time 5 seconds to 45 seconds coating analysis 5 field emission electron microscope observation using a field emission electron microscope to observe the surface morphology of the silver alloy film of the invention with a thickness of 30 nm and 100 nm, as shown in Figures 4(a) and 4(b) Atomic force microscopy (AFM) observation using an atomic force microscope to observe thicknesses of 30 nm and 100 nm The surface profile of the invented silver® alloy film is shown in Figures 5(a) and 5(b). The surface roughness (Ra) of the film is less than 0.8 nm by surface roughness measurement. Comparing the surface roughness of the silver alloy film of the present invention with other conventional alloy films by surface roughness measurement, as shown in Table 3. -10- H:\Wendyc(WW)\Domestic Application\94693-spec( Final).doc 15 1303665 Table 3 Comparison of Surface Roughness of Primary Membrane Film Roughness; Degree\nm) Thickness (nm)\AC0.5 (Comparative Example) AC1.5 (Comparative Example) ACT1 (Comparative Example) ACT3 ( Comparative Example) ACZ1 (Invention) 100 0.746 0.752 0.416 0.589 0.169 30 0.262 0.299 0.334 0.677 0.155 The surface roughness of each alloy film after heat treatment at different temperatures is as follows

4 and Table 5. Table 4 Surface roughness of each alloy film (thickness = 100 nm) after heat treatment at different temperatures \nm) AC0.5 (Comparative Example) AC1.5 (Comparative Example) ACT1 (Comparative Example) ACT3 (Comparative Example) ACZ1 (Invention) Initial coating 0.746 0.752 0.416 0.589 0.169 100°C 0.628 0.892 0.381 0.628 0.311 200°C 1.389 0.323 0.628 0.548 0.266 -11 - H:\Wendyc(WW)\Domestic application\94693-spec(fmal). Doc 1303665 Table 5 Surface roughness of each alloy film (thickness = 30 nm) after heat treatment at different temperatures \Qirn) AC0.5 (Comparative Example) AC1.5 (Comparative Example) ACT1 (Comparative Example) ACT3 (Comparative Example) ACZ1 (Invention) Initial coating 0.262 0.299 0.334 0.677 0.155 100°C 0.405 0.292 0.347 0.177 0.499 200°C 0.471 0.556 0.268 0.834 0.234 5 Figure 6(a), (b) and Figure 7(a) and (b) are The surface topography measurement results of the ACZ1 alloy coating film of the invention after heat treatment at 100 ° C and 200 ° C. The results show that ACZ1 has a significant improvement in heat resistance, regardless of the heat treatment of 1 〇〇艽 or 2 〇〇 °c. The average crude sugar content is around 2.2 nm. 10 Gold and gold film to learn characteristics

'Using a spectrophotometer (SP 1024 USB spectrophotometer, IZOVAC

Ltd.) Measure the reflectance of the alloy of the present invention having a thickness of 20 nm and 30 rim and a conventional alloy initial plating film in the wavelength range of 400 to 800 nm, as shown in FIG. Further, the reflectance of the alloy of the present invention having a thickness of 30 nm and the conventional I5 gold ore film was measured using a spectrophotometer. A reflectance vs. transmittance spectrum of each alloy film in the wavelength range of 4 〇〇 to 8 〇〇 nm is obtained, as shown in Figs. 9(a) to (e). It can be seen from the spectrogram that the ACZ1 alloy film of the present invention has a stable ratio of reflectance to transmittance in the wavelength range of 400 to 800 nm compared to other conventional alloy films. -12 - H:\Wendyc(WW)\ Domestic Application\94693-spec(fmal).doc J303665 Comparing the reflectance changes of the ACZ1 alloy film of the present invention and the conventional ACT1 alloy film after various tests, as shown in Fig. 10 (a ) and 10(b). As can be seen from the figure, the reflectance of ACT1 decreased greatly after one week of standing, but ACZ1 showed a linear moderate decrease in the reflectance after each test. The ACZ1 alloy thin film of the present invention was measured for its reflectance in the wavelength range of 400 to 800 nm after each test, and a spectrum was obtained, as shown in Figs. a (a) and 11 (b). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cycle induction melting furnace for preparing a silver alloy of the present invention. Fig. 2 is a view showing the microstructure of an ACZ1 alloy target according to one embodiment of the present invention. Fig. 3(a) shows a precipitate in an ACZ1 alloy target which is one of the specific examples of the present invention. Figure 3 (b) is an EDX analysis of an ACZ1 alloy target in one of the specific examples of the present invention. Fig. 4(a) is a field emission electron microscope observation of the original surface morphology of the ACZ1 alloy thin film of the present invention having a film thickness of 30 nm. Fig. 4(b) is a field emission electron microscope observation of the original surface morphology of the ACZ1 alloy thin film of the present invention having a film thickness of 100 nm. Fig. 5 (a) is an atomic force microscope observation of the original surface morphology of the ACZ1 alloy film of the present invention having an initial plating thickness of 1 〇〇 nm. Fig. 5(b) is an atomic force microscope observation of the original surface morphology of the ACZ1 alloy thin film of the present invention having a thickness of 30 nm. Fig. 6(a) is an atomic force microscope observation of the original surface morphology of the aczi alloy film of the present invention having a thickness of 1 〇〇 nm after heat treatment at 1003⁄4. -13- H:\Wendyc(WW)\Domestic Application\94693-spec(final).doc Figure 6 (b) is the atomic force of the original surface topography of the ACZ1 alloy film of the invention with a thickness of 100 nm after heat treatment at 200 °C. Microscopic observation. Fig. 7(a) is an atomic force microscope observation of the original surface morphology of the inventive ACZ1 alloy film having a thickness of 30 nm after heat treatment at 100 °C. Fig. 7(b) is an atomic force microscope observation of the original surface morphology of the inventive ACZ1 alloy film having a thickness of 30 nm after heat treatment at 200 °C. Figure 8 shows the reflectance spectra of the primary bond films of silver-copper series alloys with thicknesses of 20 nm and 30 nm. Figure 9 (a) to (e) are the reflectance vs. transmittance spectra of the initial coating film of each alloy. Fig. 10 (a) shows the change in reflectance of ACT1 and the ACZ1 alloy film of the present invention after different tests at a wavelength of 405 nm. Figure 10 (b) shows the change in reflectance of ACT1 and the ACZ1 alloy film of the present invention after different tests at a wavelength of 650 nm. Figure 11 is a spectrum diagram of the reflectance of the film of ACZ1 in the initial coating, one week, 100 °C heat treatment, 20 (TC treatment and weathering test). [Main component symbol description] R Reflectance T transmittance AC0.5 It is indicated that 0.5% by weight of <3\1 is added to the silver alloy. AC1.5 means 1.5% by weight of the silver alloy is added: <:11. ACT1 means that 1% by weight of 〇1 and 1% by weight of Ti are added to the silver alloy. H:\Wendyc(WW)\ Domestic application\94693-spec(final).doc 1303665 ACT3 means adding 1% by weight of <3\1 and 3% by weight of 11 in the silver alloy. ACZ1 means adding 1% by weight to the silver alloy. Cu and 1% by weight of Zn. ACZ3 means 1% by weight (: 11 and 3% by weight of Zn) added to the silver alloy.

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Claims (1)

:1303665 Patent Application No. 95102970 ROC Patent Appb. No95102970 Amendment of the scope of application of the revised text - Annex (II) Amended Claims in Chinese - Enel. (ID (January 24, 1997) (Submitted on January) 24, 2008) X. Patent application scope: 1. A silver alloy consisting mainly of Ag, Cu and a metal selected from the group consisting of Zn, Sn and Cd, represented by the formula AgxCuyXz, wherein X is Zn, Sn or Cd; And based on the total weight of the silver alloy, y is 0.01 to 8 weights 0/〇, z is 0.01 to 5 weight%, and X is the balance. 2. The silver alloy of claim 1 is further included a metal selected from the group consisting of A1, Ga, In, Ge, and Sb, represented by the formula AgxCuyXzYr, wherein X is Zn, Sn, or Cd, and Y is A, Ga, In, Ge, or Sb; and based on the total weight of the silver alloy, y It is 0.01 to 8% by weight, z is 0.01 to 5% by weight, r is 0.01 to 3% by weight, and X is the balance. 3. A silver alloy film, as claimed in claim 1 or 2 Silver alloy formation 4. A silver alloy film as in claim 3 of the patent application, which is used as a reflective layer or a 15 semi-reflective layer. 5. The silver alloy film according to item 4 of the patent application is applied to an optical recording medium. * 6. The silver alloy film according to item 4 of the patent application is used for a display device. 2〇7· A method of preparing a silver alloy according to claim 1 of the patent application, characterized in that it is smelted using a cycle induction melting furnace. -16- 94693 - Invention Specification - 1 / range