SILVER LAYER FORMED BY ELECTROSILVERING SUBSTRATE MATERIAL

Abstract

The inventors have conducted vigorous studies, and discovered as a result that it is possible to form a silver layer having a high reflectance of about 90 to 99% in a visible light are a by setting a grain size of an outermost surface of a silver plated layer within a range of 0.5 μm or more to 30 μm or less.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

Exemplary embodiments of the invention will become more fully apparent from the following description and appended claims, taken in conjunction with the accompanying drawings. Understanding that these drawings depict only exemplary embodiments and are, therefore, not to be considered limiting of the invention's scope, the exemplary embodiments of the invention will be described with additional specificity and detail through use of the accompanying drawings in which:

FIGS. 1A to 1H are sectional flow diagrams showing a manufacturing process of a LED mounted substrate according to an embodiment of the present invention;

FIG. 2 is a diagram showing a SEM photograph of a silver plated layer surface according to Example 1;

FIG. 3 is a diagram showing a SEM photograph of a silver plated layer surface according to Example 2;

FIG. 4 is a diagram showing a SEM photograph of a silver plated layer surface according to Example 3;

FIG. 5 is a diagram showing a SEM photograph of a silver plated layer surface according to Comparative Example 1;

FIG. 6 is a diagram showing a SEM photograph of a silver plated layer surface according to Comparative Example 2;

FIG. 7 is a diagram showing a change in reflectance of a silver plated layer which accompanies a change in film thickness of the silver plated layer;

FIG. 8 is a diagram showing a change in reflectance of a silver plated layer which accompanies heating of the silver plated layer; and

FIG. 9 is a diagram showing a change in reflectance which accompanies a difference in a type of bath used for silver plating.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention can be applied to, for example, a manufacturing process of a LED mounted substrate which includes a silver plated layer as a reflective surface. Referring to FIGS. 1A to 1H, the manufacturing process of the LED mounted substrate according to an embodiment of the invention will be described.

[Manufacturing Process of LED Mounted Substrate]

In the manufacturing process of the LED mounted substrate according to the embodiment of the invention, first, as shown in FIG. 1A, an insulating substrate (abbreviated to substrate herein after) 1 made of a ceramic base material such as alumina (purity of 92 to 99%), aluminum nitride or silicon carbide, or a heat-resistive polymer base material such as a crystal polymer (LCP) or PEED® is formed. Then, as shown in FIG. 1B, metal films 2 are formed in both surfaces of the substrate 1. For the metal films 2, preferably, metal materials such as copper, chromium, titanium, nickel, or platinum having high adhesiveness to the substrate 1 are used The metal films 2 are preferably formed by a physical deposition method such as vacuum deposition or ion plating. However, the invention is not limited to such a method. For example, the metal films 2 may be formed by electroless plating.

Then, as shown in FIG. 1C, laser beams are applied to the metal films 2 along a boundary between a circuit forming section and an on-circuit forming section by using One-shot Laser Structuring (Laser structuring process is utilized in ablating copper, and creating the outline of the required circuit) to remove the metal film 2 from the boundary portion, thereby separating the metal film 2 of the circuit forming section as a circuit pattern from other portions of the metal films 2. As shown in FIG. 1D, a thick copper plated layer 3 is formed by turn electricity on the metal film 2 of the circuit forming section and using a copper plating bath of one selected from copper sulfate, copper cyanide, copper pyrophosphate, and copper fluoroborate to execute electric copper plating. As shown in FIG. 1E, the metal film 2 left in the non-circuit forming section is removed by soft etching using one selected from ammonium persulfate, a nitric acid, a sulfuric acid, and a hydrochloric acid. A desired circuit pattern is formed by leaving the electric copper plated circuit forming section. As shown in FIG. 1F, both surfaces of the substrate 1 are electrically plated with nickel by using one selected from Watts bath, a sulfamate bath, a citrate bath, a fluoroborate bath, a full chloride bath, and a full sulfate bath, thereby forming a nickel plated layer 4. The bath used for electric nickel plating is not limited to the aforementioned example. Commercial special baths may be used. It is not always necessary to form a nickel plated layer 4.

Then, as shown in FIG. 1G, to secure an adhesive force of a silver plated layer 6 (described below) to the substrate material, a strike plated layer 5 is formed by subjecting the substrate 1 to electric strike plating. For the electric strike plating, one selected from silver strike, copper strike, gold strike, palladium strike, and nickel strike may be used. From the standpoint of costs and long-term reliability, however, the copper strike or the silver strike is used. Lastly, as shown in FIG. 1H, a silver plated layer 6 is formed by electrosilvering both surfaces of the substrate 1 (described below in detail), and then a series of manufacturing steps is finished. The manufactured LED mounted substrate may be cut as occasion demands.

[Electrosilvering]

Next, the preferred modes of the electrosilvering process will be described through Examples and Comparative Examples.

[Grain Size and Surface Roughness of Substrate Material]

The inventors formed silver plated layers of Examples 1 to 3 and Comparative Examples 1 and 2 by methods described below, and examined relations between outermost surface grain sizes and surface roughness of substrate materials of the silver plated layers of the Examples 1 to 3 and the Comparative Examples 1 and 2 and reflectances.

EXAMPLE 1

According to the Example 1, first, an alumina substrate of a flat plate shape (30×40×1.5 mm) was prepared. The substrate was dipped in a copper sulfate bath of a copper sulfate/pentahydrate concentration of 110 g/l, a sulfuric acid concentration 180 g/l and a chlorine ion concentration of 50 mg/l. The substrate was subjected to electric copper plating at a temperature of 22° C. for 136 seconds by setting current density to 2 A/dm² to form a copper plated layer with a film thickness of 10 μm on a substrate surface. Then, the substrate was dipped in a low (concentration) cyan bath of a silver concentration of 65 g/l, a free cyanide concentration of 2 g/l, and a brightening agent concentration of 10 ml/l. The substrate was subjected to electrosilvering at a temperature 30° C. for 95 seconds by setting a current density to 2 A/dm² to obtain a silver plated layer of the Example 1 with a film thickness of 2 μm on the copper plated layer.

EXAMPLE 2

According to the Example 2, a substrate was dipped in a low cyan bath of a silver concentration of 65 g/l, a free cyanide concentration 2 g/l and a brightening agent concentration of 0 ml/l. The substrate was subjected to electrosilvering at a temperature 30° C. for 750 seconds by setting a current density to 2 A/dm² to obtain a silver plated layer of the Example 2 with a film thickness of 16 μm on the copper plated layer.

EXAMPLE 3

According to the Example 3, a substrate was dipped in a low cyan bath of a silver concentration of 65 g/l, a free cyanide concentration of 2 g/l, and a brightening agent concentration of 0 ml/l. The substrate was subjected to electrosilvering at a temperature 60° C. for 190 seconds by setting a current density to 2 A/dm² to obtain a silver plated layer of the Example 3 with a film thickness of 4 μm on the copper plated layer.

COMPARATIVE EXAMPLE 1

According to the Comparative Example 1, a substrate was dipped in a high (concentration) cyan bath of a silver concentration of 40 g/l, a free cyanide concentration of 120 g/l, a potassium carbonate concentration of 30 g/l, and a brightening agent concentration of 30 ml/l. The substrate was subjected to electrosilvering at a temperature 25° C. for 190 seconds by setting a current density to 2 A/dm² to obtain a silver plated layer of the Comparative Example 1 with a film thickness of 4 μm on the copper plated layer.

COMPARATIVE EXAMPLE 2

According to the comparative Example 2, a substrate including a copper plated layer was dipped in Watts bath of a nickel sulfate concentration of 300 g/l, a nickel chloride concentration 45 g/l and a boric acid concentration of: 30 g/l. The substrate was subjected to electric nickel plating at a temperature of 50° C. for 730 seconds by setting current density to 2 A/dm² to form a nickel plated layer with a film thickness of 6 μm on the copper plated layer. Then, the substrate was dipped in a low cyan bath of a silver concentration of 65 g/l, a free cyanide concentration of 2 g/l, and a brightening agent concentration of 10 ml/l The substrate was subjected to electrosilvering at a temperature 30° C. for 50 seconds by setting a current density to 2 A/dm² to obtain a silver plated layer of the Comparative Example 2 with a film thickness of 1 μm on the nickel plated layer.

[Evaluation]

FIGS. 2 to 4 and FIGS. 5 and 6 respectively show SEM photographs of outermost surfaces of the silver plated layers of the Examples 1 to 3 and the Comparative Examples 1 and 2 (magnification rate is 1000 in the case of the Example 3, while magnification rates are 10000 in the other examples). Table 1 shows grain sizes of the silver plated layer outermost surfaces measured from the SEM photographs. As shown in Table 1, the grain sizes of the outermost surfaces of the silver plated layers of the Comparative Examples 1 and 2 are 1 μm, while the grain sizes of the outermost layers of the silver plated layers of the Examples 1 to 3 are within a range of 1 to 20 μm. Surface roughness Ry of a substrate material of each silver plated layer was measured. As shown in Table 2, surface roughness. By of each of the Comparative Examples is 0.5 or less, while surface roughness Ry of each of the Examples 1 to 3 is 0.5 or more.

	TABLE 1
	SPECTRAL
	REFLECTANCE
	GRAIN SIZE	@400 nm	@700 nm
	COMPARATIVE	<1 μm	83.4%	97.4%
	EXAMPLE 1
	COMPARATIVE	<1 μm	79.0%	95.7%
	EXAMPLE 2
	EXAMPLE 1	1~2 μm	90.5%	98.1%
	EXAMPLE 2	1~10 μm	94.1%	99.3%
	EXAMPLE 3	15~20 μm	92.2%	98.6%

	TABLE 2
	SURFACE	SPECTRAL
	ROUGHNESS	REFLECTANCE
	Ry	@400 nm	@700 nm
	COMPARATIVE	0.41 μm	83.4%	97.4%
	EXAMPLE 1
	COMPARATIVE	0.47 μm	79.0%	95.7%
	EXAMPLE 2
	EXAMPLE 1	0.79 μm	90.5%	98.1%
	EXAMPLE 2	1.93 μm	94.1%	99.3%
	EXAMPLE 3	1.27 μm	92.2%	98.6%

By using a spectrophotometer (U 4000 by Hitachi, Ltd.), spectral reflectances of the silver plated layers of the Examples 1 to 3 and the Comparative Examples 1 and 2 for visible lights of wavelengths 400 nm and 700 nm were measured. As shown in Table 1, the spectral reflectances of the silver plated layers of the Examples 1 to 3 are higher than those of the silver plated layers of the Comparative Examples 1 and 2. Accordingly, it is possible to manufacture a silver plated layer of a high reflectance by controlling a grain site of the outermost surface of the silver plated layer to about 0.5 to 30 μm, preferably 1 to 10 μm. By setting surface roughness of the substrate material to 0.5 μm or more, a high reflectance can be realized by limiting a film thickness of the silver plated layer to a minimum.

[Film Thickness]

Silver plated layers of Examples 4 to 7 were formed by using methods below, and changes in reflectance accompanying changes in film thickness of the silver plated layers were measured.

EXAMPLE 4

According to the Example 4, a substrate including a copper plated layer was dipped in a low cyan bath of a silver concentration of 65 g/l, a free cyanide concentration 2 g/l and a brightening agent concentration of 0 ml/l When a temperature was 30° C., and a current density was set to 2 A/dm², a deposition speed was 128 μm/minute, and the substrate was subjected to electrosilvering by changing time to obtain a silver plated layer of the Example 4 with a different film thickness on the copper plated layer.

EXAMPLE 5

According to the Example 5, a substrate including a copper plated layer was dipped in a low cyan bath of a silver concentration of 65 g/l, a free cyanide concentration of 2 g/l, and a brightening agent concentration of 10 ml/l. When a temperature was 30° C., and a current density was set to 2 A/dm², a deposition speed was 128 μm/minute, and the substrate was subjected to electrosilvering by changing time to obtain a silver plated layer of the Example 5 with a different film thickness on the copper plated layer.

EXAMPLE 6

According to the Example 6, first, a substrate including a copper plated layer was dipped in Watts bath (Sulnic As T, C. Uyemura & Co., Ltd.) containing no commercial sulfur. The substrate was subjected to electric nickel plating to form a nickel plated layer on the copper plated layer. Then, the substrate was dipped in a low cyan bath of a silver concentration of 65 g/l, a free cyanide concentration of 2 g/l, and a brightening agent concentration 10 ml/l. When a temperature was 30° C., and a current density was to 2 A/dm², a deposition speed was 128 μm/minute, and the substrate was subjected to electrosilvering by changing time to obtain a silver plated layer of the Example 6 with a different film thickness on the nickel plated layer.

EXAMPLE 7

According to the Example 7, a substrate including a copper plated layer was dipped in watts bath of a nickel sulfate concentration of 300 g/l, a nickel chloride concentration 45 g/l and a boric acid concentration of 3 μg/l. The substrate was subjected to electric nickel plating to form a nickel plated layer on the copper plated layer. Then, the substrate was dipped in a low cyan bath of a silver concentration of 65 g/l, a free cyanide concentration of 2 g/l, and a brightening agent concentration of 10 ml/l. When a temperature was 30° C., and a current density was set to 2 A/dm², a deposition speed was 1.28 μm, and the substrate was subjected to electrosilvering by changing time to obtain a silver plated layer of the Example 7 with a different film thickness on the nickel plated layer.

[Evaluation]

By using a spectrophotometer (U 4000 by Hitachi, Ltd.), spectral reflectances of the silver plated layers of the Examples 4 to 7 for a visible light of a wavelength 400 nm after changes in film thickness of the silver plated layers were measured. As shown in FIG. 7, when a substrate material is copper (Examples 4 and 5), a high reflectance is obtained when the silver plated layer is 1 μm or more. When a substrate material is nickel (Examples 6 and 7), a high reflectance is obtained when the silver plated layer is 4 μm or more. Additionally, comparison between the Examples 6 and 7 shows that a higher reflectance can be realized when the nickel plated layer contains no sulfur

[Heating]

Silver plated layers of Examples 8 to 10 were formed by methods described below. Spectral reflectances of the silver plated layers of the Examples 8 to 10 for lights of wavelength are as of 300 to 800 nm were measured.

EXAMPLE 8

According to the Example 8, the silver plated layer of the Example 1 was subjected to ref lowing at a temperature of 320° C. in a nitrogen atmosphere of a residual oxygen concentration of 500 ppm for 30 seconds to obtain a silver plated layer of the Example 8.

EXAMPLE 9

According to the Example 9, the silver plated layer of the Example 1 was directly used as the silver plated layer of the Example 9.

EXAMPLE 10

According to the Example 10, the silver plated layer of the Example 1 was subjected to ref lowing at a temperature of 150° C. in a nitrogen atmosphere of a residual oxygen concentration of 500 ppm for 1 hour to obtain a silver plated layer of the Example 10.

[Evaluation]

By using a spectrophotometer (U 4000 by Hitachi, Ltd.), spectral reflectances of the Examples 8 to 10 for wavelength are as of 300 to 800 nm were measured. As shown in FIG. 8, the silver plated layer is subjected to reflowing at 300° C. in a nitrogen atmosphere for 1 minute (Example 8), especially a reflectance for a light of a wavelength 400 to 500 nm is increased, and a reflectance for the light of the wavelength 400 nm is 90% or more. This is because heating reduces a grain size of the silver plated layer.

[Type of Bath]

Silver plated layers of Examples 11 and 12 and Comparative Examples 3 and 4 were formed by methods described below. Spectral reflectances of the silver plated layers of the Examples 11 and 12 and the Comparative Examples 3 and 4 for lights of wavelength are as of 300 to 800 nm were measured.

EXAMPLE 11

According to the Example 11, a substrate including a copper plated layer was dipped in a low cyan bath of a silver concentration of 65 g/l, a free cyanide concentration 2 g/l and a brightening agent concentration of 0 ml/l. The substrate was subjected to electrosilvering at a temperature 30° C. for 190 seconds by setting a current density to 2 A/dm² to obtain a silver plated layer of the Example 11 on the copper plated layer of a film thickness of 4 μm.

EXAMPLE 12

According to the Example 12, a substrate including a copper plated layer was dipped in a low cyan bath of a silver concentration of 65 g/l, a free cyanide concentration of 2 g/l, and a brightening agent concentration of 10 ml/l. The substrate was subjected to electrosilvering at a temperature 30° C. for 190 seconds by setting a current density to 2 A/dm² to obtain a silver plated layer of the Example 12 on the copper plated layer of a film thickness of 4 μm.

COMPARATIVE EXAMPLE 3

According to the Comparative Example 3, a substrate including a copper plated layer was dipped in a high cyan bath of a silver concentration of 40 g/l, a free cyanide concentration of 120 g/l, a potassium carbonate concentration of 30 g/l, and a brightening agent concentration of 30 ml/l. The substrate was subjected to electrosilvering at a temperature 25° C. for 190 seconds by setting a current density to 2 A/dm² to obtain a silver plated layer of the Comparative Example 3 on the copper plated layer of a film thickness of 4 μm.

COMPARATIVE EXAMPLE 4

According to the Comparative Example 4, a substrate including a copper plated layer was dipped in a non-cyan bath of a silver concentration of 30 g/l, and a brightening agent concentration of 1.5 ml/l. The substrate was subjected to electric nickel plating at a temperature of 25° C. for 380 seconds by setting current density to 1 A/dm² to obtain a silver plated layer of the Comparative Example 4 on the nickel plated layer of a film thickness of 4 μm.

[Evaluation]

By using a spectrophotometer (U 4000 by Hitachi. Ltd.), spectral reflectances of the silver plated layers of the Examples 11 and 12 and the Comparative Examples 3 and 4 for lights of wavelengths 300 nm and 800 nm were measured. As shown in FIG. 9, when the silver plated layer is formed by a low-cyan bath containing no brightening agent (Example 11), the silver plated layer exhibits a higher reflectance.

Claims

1. A silver layer formed by electrosilvering a substrate material, wherein a grain size of an outermost surface is within a range of 0.5 μm or more to 30 μm or less.

2. The silver layer according to claim 1, wherein a silver plated layer has a film thickness of 1 μm or more, and the substrate material is copper.

3. The silver layer according to claim 1, wherein a silver plated layer has a film thickness of 4 pan or more, and the substrate material is nickel.

4. The silver layer according to claim 2, wherein surface roughness of the substrate material is 0.5 μm or more.

5. The silver layer according to claim 3, wherein the nickel contains no sulfur.

6. A method for manufacturing the silver layer according to claim 1, comprising the steps of: heating the silver plated layer at a temperature of 200° C. or more for 30 seconds or more after the electrosilvering.

7. A method for manufacturing the silver layer according to claim 1, comprising the steps of: carrying out the electrosilvering by low-cyan bathing.

8. A LED mounted substrate comprising, the silver layer according to claim 1 as a reflective surface.

9. A method for manufacturing the LED mounted substrate according to claim 8, comprising the steps of: forming a conductive layer on a substrate surface;patterning the conductive layer to form a circuit pattern;forming a copper plated layer on the circuit pattern;forming a nickel plated layer on the copper plated layer; andforming a silver plated layer on the nickel plated layer.