TW202335328A - Methods of manufacutring glass substrate structure and metallized substrate - Google Patents

Abstract

A method of manufacturing a glass substrate structure includes: forming an adhesion promoter layer on a surface of a glass substrate; forming a seed layer of a first metal on a surface of the adhesion promoter layer; and forming a bulk layer of a second metal through an autocatalytic reaction on the seed layer.

Description

Methods of manufacturing glass substrate structures and metallized substrates

This case claims priority rights in accordance with the Patent Law of Korean Patent Application No. 10-2021-0122763 filed on September 14, 2021. The contents of the Korean Patent Application are the basis of this case and are incorporated into this article by reference in full. .

This case relates to a method of manufacturing a glass substrate structure and a method of manufacturing a metallized substrate, and more specifically, this case relates to a method of manufacturing a glass substrate structure and a method of manufacturing a metallized substrate, which methods can be manufactured and provided at an affordable price. Good interlayer adhesion.

Traditional printed circuit boards are limited by thermal and mechanical stability, and therefore suffer from warping and pattern accuracy degradation. Compared with traditional printed circuit boards, glass substrates significantly reduce the problem of warpage, but glass substrates are more expensive due to the need for electroless plating using expensive catalysts. In addition, the method of manufacturing a glass substrate according to the related art needs to be improved because there is an interlayer adhesion problem due to pores in the metal circuit layer.

The present invention provides a method for manufacturing a glass substrate structure, such as a glass circuit board, which can be manufactured cheaply and provides good interlayer adhesion.

The present invention provides a method for manufacturing a metallized substrate, which can be manufactured at an affordable price and provide good inter-layer adhesion.

Additional aspects will be set forth in part in the description which follows and will be, in part, understood from the description below, or may be learned by practice of the embodiments presented herein.

According to an aspect of the present invention, a method for manufacturing a glass substrate structure includes: forming an adhesion promoter layer on the surface of the glass substrate; forming a seed layer of the first metal on the surface of the adhesion promoter layer; and via autocatalysis The reaction forms a bulk layer of the second metal on the seed layer.

In some embodiments, the method may further include performing an acid treatment on the surface of the seed layer after forming the seed layer and before forming the bulk layer. In some embodiments, the method may further include performing alkali cleaning on the surface of the seed layer after performing the acid treatment and before forming the bulk layer.

In some embodiments, each of the adhesion promoter layer and the seed layer may be formed by physical vapor deposition (PVD). In some embodiments, forming the bulk layer may include applying a bulk mixture to the seed layer, the bulk mixture comprising about 0.5 g/l to about 8 g/l of metal ions of the second metal, about 0.01 M to about 1.0 M Reducing agent and complexing agent from about 0.05M to about 1.0M. In some embodiments, the bulk mixture may further comprise from about 10 ppm by weight to about 1000 ppm by weight of a stabilizer. In some embodiments, the formation of the bulk layer may be performed at a temperature of about 30°C to about 60°C. In some embodiments, the bulk mixture may further include a pH adjusting agent to adjust the pH to about 9 to about 11.

In some embodiments, the seed layer may include one or more selected from the group consisting of: copper (Cu), tin (Sn), nickel (Ni), iron (Fe), aluminum (Al), zinc (Zn), sodium (Na), calcium (Ca) and magnesium (Mg).

In some embodiments, the thickness of the bulk layer is from about 2.0 μm to about 10 μm.

According to other aspects of the present invention, a method for manufacturing a metallized substrate includes: forming an adhesion promoter layer on the entire upper surface of the glass substrate; forming a seed layer of the first metal on the surface of the adhesion promoter layer; forming A mask layer with a mask pattern is placed on the seed layer; etching the seed layer to form a seed pattern; applying a bulk mixture to the seed layer to form a bulk layer of a second metal on the seed layer, the bulk mixture Containing: about 0.5 g/l to about 8 g/l metal ions of the second metal, about 0.01 M to about 1.0 M reducing agent, and about 0.05 M to about 1.0 M complexing agent; and removing the mask layer.

In some embodiments, removal of the mask layer may be performed after etching the seed layer and before applying the bulk compound. In some embodiments, the surface of the bulk layer may include a curved surface extending along the seed pattern.

In some embodiments, applying the bulk mixture may be performed after forming the seed layer and before etching the seed layer, and forming a mask layer over the seed layer includes forming a mask over the seed layer with the bulk layer therebetween. layer. In some embodiments, removal of the mask layer may be performed after etching the seed layer.

In some embodiments, etching the seed layer may include etching the bulk layer using the mask layer as an etch mask, and forming the seed pattern using the etched bulk layer as an etch mask.

In some embodiments, the method may further comprise performing an acid treatment on the surface of the seed layer prior to applying the bulk mixture. In some embodiments, the method may further comprise performing an alkali wash on the surface of the seed layer after performing the acid treatment and before applying the bulk mixture.

In some embodiments, the average grain size of the bulk layer may be larger than the average grain size of the seed layer.

According to other aspects of the present invention, a method of manufacturing a glass substrate structure includes: forming an adhesion promoter layer with a thickness of about 30 nm to about 150 nm on the surface of the glass substrate by sputtering; forming a thickness of about 30 nm by sputtering. A seed layer of the first metal of about 300 nm to about 700 nm is placed on the surface of the adhesion promoter layer; performing acid treatment on the surface of the seed layer using an inorganic acid aqueous solution; performing alkali cleaning on the surface of the seed layer; and via An autocatalytic reaction forms a bulk layer of the second metal with a thickness of about 2.0 μm to about 10 μm on the seed layer. Forming the bulk layer includes applying a bulk mixture to the seed layer, the bulk mixture comprising about 0.5 g/l to about 8 g/l of a metal ion of the second metal, about 0.01 M to about 1.0 M of a reducing agent, and about 0.05 M to about 1.0 M of a reducing agent. About 1.0M complex agent, and the first metal and the second metal each independently include one or more groups selected from the following: copper (Cu), tin (Sn), nickel (Ni), iron (Fe) , aluminum (Al), zinc (Zn), sodium (Na), calcium (Ca) and magnesium (Mg), and the first metal and the second metal are selected so that the standard reduction potential of the first metal is less than or equal to the second metal the standard reduction potential.

Reference will now be made in detail to the embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals represent like elements throughout the specification. In this regard, embodiments of the invention may take different forms and should not be construed as limited to the description set forth herein. Therefore, by referring to the drawings, the embodiments are merely described below to illustrate aspects of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated items. Expressions such as "at least one of," when preceding a list of components, modify the entire list of components but do not modify the individual components of the list.

It will be understood that, although the terms "first, second, etc." may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. For example, a first element could be termed a second element, and similarly, a second element could be termed a first element, without departing from the teachings of the present invention.

The terminology used herein is only used to describe specific embodiments and is not intended to limit the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms unless the context clearly indicates otherwise. It will be further understood that when used in this specification, the terms "comprises" and/or "comprising" or "includes" and/or "including" designate stated features, integers , steps, operations, elements, components and/or the presence of the foregoing combinations, but does not exclude the existence or addition of one or more other features, regions, integers, steps, operations, elements, components and/or the foregoing combinations.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that such terms, such as those defined in commonly used dictionaries, are to be construed to have meanings consistent with their meaning in the relevant art and/or in the context of the present invention, and will not be construed unless expressly defined herein. These terms are interpreted as having an idealized or overly formal meaning.

As the embodiments may be modified, the order of processes may differ from that described. For example, two processes described as being performed sequentially may be performed substantially concurrently or in reverse order.

In the drawings, variations in shape may be anticipated based, for example, on manufacturing techniques and/or tolerances. Thus, embodiments should not be construed as limited to the particular shapes in the drawings but are instead constructed to include changes in shapes that occur, for example, during the manufacturing process. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. Furthermore, the term "substrate" as used herein may represent the substrate itself or a stacked structure including the substrate and certain layers or films formed on the surface of the substrate. The expression "surface of the substrate" may represent the exposed surface of the substrate itself or the outer surface of some layer or film formed on the substrate.

Figure 1 is a flow chart of a method for manufacturing a glass substrate structure according to an embodiment of the present invention. 2A to 2E are side cross-sectional views of a method of manufacturing a glass substrate structure according to the embodiment of FIG. 1 .

Referring to FIGS. 1 and 2A , the adhesion promoter layer 120 is formed on the glass substrate 110 (step S10 ).

The glass substrate 110 may include, for example, aluminosilicate, alkali-aluminosilicate, borosilicate, alkali-borosilicate, aluminoborosilicate Salt (aluminoborosilicate), alkali metal aluminum borosilicate (alkali-aluminoborosilicate), soda-lime (soda-lime) or other suitable glasses, but the invention is not limited thereto. Non-limiting examples of glass substrate 110 may include, for example, EAGLE ^XG® , Lotus ^™ , ^Willow® , Iris ^™ , and ^Gorilla® glasses from Corning Incorporated.

The glass substrate 110 may have a thickness of about 3 mm or less, for example, in the range of about 0.1 mm to about 2.5 mm, about 0.3 mm to about 2 mm, about 0.5 mm to about 1.5 mm, about 0.7 mm to about 1 mm, and inclusive. All ranges and subranges between ranges.

_Some non-limiting glass compositions may include between about 50 mol% and about 90 mol% _SiO2 , between 0 mol% and about 20 mol% _Al2O3 , between 0 mol% and About 20 mole % B ₂ O ₃ , between 0 mole % and about 20 mole % P ₂ O ₅ , and between 0 mole % and about 25 mole % R _x O, where R is lithium Any one or more of (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs) and x is 2 or R is zinc (Zn), magnesium (Mg), calcium (Ca ), strontium (Sr) or barium (Ba) and x is 1. In some embodiments, _RxO - _Al2O3 &gt;0; 0&lt; _RxO - _{Al2O3 &lt} ;15; x=2 and _R2O - _Al2O3 &_lt;15; _R2O -Al ₂ O ₃ ＜2 _; x=2 and _{R 2 O} –Al ₂ O ₃ –MgO＞-15 _; 0＜( _{R 3} )＜11, and -15＜(R ₂ O–Al ₂ O ₃ -MgO)＜11 and/or -1＜(R ₂ O–Al ₂ O ₃ )＜2 and -6＜(R ₂ O– Al ₂ O ₃ –MgO) <1. In some embodiments, the glass contains less than 1 ppm of each of cobalt (Co), nickel (Ni), and chromium (Cr). In some embodiments, the concentration of iron (Fe) is less than about 50 ppm, less than about 20 ppm, or less than about 10 ppm. In some embodiments, Fe+30Cr+35Ni<about 60 ppm, Fe+30Cr+35Ni<about 40 ppm, Fe+30Cr+35Ni<about 20 ppm, or Fe+30Cr+35Ni<about 10 ppm. In other embodiments, the glass may include between about 60 mol% to about 80 mol% SiO ₂ , between about 0.1 mol% to about 15 mol% Al ₂ O ₃ , between 0 mol% % to about 12 mole % B ₂ O ₃ and from about 0.1 mole % to about 15 mole % R _x O and from about 0.1 mole % to about 15 mole % R _x O , where R is One or more of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs) and x is 2 or R is zinc (Zn), magnesium (Mg), calcium (Ca ), strontium (Sr) or barium (Ba) and x is 1.

In other embodiments, the glass composition may include between about 65.79 mol% to about 78.17 mol% SiO ₂ , between about 2.94 mol% to about 12.12 mol% Al ₂ O ₃ , between about 0 mol% to about 11.16 mol% B ₂ O ₃ , between about 0 mol% to about 2.06 mol% Li ₂ O, between about 3.52 mol% to about 13.25 mol% Na ₂ O, from about 0 mol% to about 4.83 mol% K ₂ O, from about 0 mol% to about 3.01 mol% ZnO, from about 0 mol% to about 8.72 mol% MgO, from about 0 mol% to about 4.24 mol% CaO, from about 0 mol% to about 6.17 mol% SrO, from about 0 mol% to about 4.3 mol% BaO, and Between about 0.07 mole % and about 0.11 mole % SnO ₂ .

In additional embodiments, the glass substrate 110 may include glass having an _RxO / _Al2O3 ratio between 0.95 and _3.23 , where R is lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and one or more of cesium (Cs) and x is 2. In further embodiments, the glass may comprise an _RxO / _Al2O3 ratio between 1.18 and _5.68 , where R is lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and One or more of cesium (Cs) and x is 2 or R is zinc (Zn), magnesium (Mg), calcium (Ca), strontium (Sr) or barium (Ba) and x is 1. In yet other embodiments, the glass may comprise R _x O - Al ₂ O ₃ -MgO between -4.25 and 4.0, where R is lithium (Li), sodium (Na), potassium (K), rubidium One or more of (Rb) and cesium (Cs) and x is 2. In yet other embodiments, the glass may comprise between about 66 mol% to about 78 mol% SiO ₂ , between about 4 mol% to about 11 mol% Al ₂ O ₃ , between about 4 mol% to about 11 mol% B ₂ O ₃ , between about 0 mol% to about 2 mol% Li ₂ O, between about 4 mol% to about 12 mol% Na ₂ O, between about 0 mole % and about 2 mole % K ₂ O, between about 0 mole % and about 2 mole % ZnO, between about 0 mole % and about 5 mole % MgO, between about 0 mole % and about 2 mole % CaO, between about 0 mole % and about 5 mole % SrO, between about 0 mole % and about 2 mole % BaO, and Between about 0 mole % and about 2 mole % SnO ₂ .

In additional embodiments, the glass substrate 110 may comprise a glass material including: between about 72 mole % and about 80 mole % SiO ₂ , between about 3 mole % and about 7 mole % Al ₂ O _3. From about 0 mol% to about 2 mol% B ₂ O ₃ , from about 0 mol% to about 2 mol% Li ₂ O, from about 6 mol% to about 15 mol% % Na ₂ O, between about 0 mol % and about 2 mol % K ₂ O, between about 0 mol % and about 2 mol % ZnO, between about 2 mol % and about 10 mol % Molar % MgO, between about 0 mol % and about 2 mol % CaO, between about 0 mol % and about 2 mol % SrO, between about 0 mol % and about 2 mol % % BaO and between about 0 mole % and about 2 mole % SnO ₂ . In certain embodiments, the glass may include between about 60 mol% to about 80 mol% SiO ₂ , between about 0 mol% to about 15 mol% Al ₂ O ₃ , between about 0 mol% From about 15 mole % to about 15 mole % B ₂ O ₃ and from about 2 mole % to about 50 mole % R _x O , where R is lithium (Li), sodium (Na), potassium (K) , one or more of rubidium (Rb) and cesium (Cs) and x is 2 or R is zinc (Zn), magnesium (Mg), calcium (Ca), strontium (Sr) or barium (Ba) and x is 1, and Fe+30Cr+35Ni＜about 60ppm.

The adhesion promoter layer 120 is provided to improve the adhesion between the glass substrate 110 and the seed layer 130 formed later.

The adhesion promoter layer 120 may include, for example, metal, such as titanium (Ti), chromium (Cr), tungsten (W), molybdenum (Mo), tin (Sn), iron (Fe), cobalt (Co), nickel (Ni) ), palladium (Pd), gold (Au), silver (Ag), platinum (Pt), tantalum (Ta), hafnium (Hf), etc. or oxides of these metals.

The adhesion promoter layer 120 may be formed by physical vapor deposition (PVD). For example, the adhesion promoter layer 120 may be formed by methods such as sputtering, evaporation, and the like. In some embodiments, adhesion promoter layer 120 may be formed by sputtering.

The thickness of adhesion promoter layer 120 ranges from about 10 nm to about 200 nm. In some embodiments, the thickness of the adhesion promoter layer 120 ranges from about 10 nm to about 200 nm, from about 20 nm to about 190 nm, from about 30 nm to about 180 nm, from about 40 nm to about 170 nm, from about 50 nm to about 160 nm, from about 60 nm to about 60 nm. About 150 nm, about 70 nm to about 140 nm, about 80 nm to about 130 nm, or about 90 nm to about 120 nm or some range between the aforementioned values.

When the thickness of the adhesion promoter layer 120 is too thick, it is economically disadvantageous because the effect from the formation of the adhesion promoter layer 120 reaches saturation. When the thickness of the adhesion promoter layer 120 is too thin, the adhesion promoter layer 120 may not be sufficiently formed in some areas, thus causing the adhesion promotion effect to be deteriorated.

Referring to FIGS. 1 and 2B , the seed layer 130 is formed on the adhesion promoter layer 120 (step S20 ). The seed layer 130 may serve as a starting layer for forming the bulk layer that will later be formed.

The seed layer 130 includes a metal different from the metal of the adhesion promoter layer 120 , and may be, for example, one or more selected from the group consisting of: copper (Cu), tin (Sn), nickel (Ni) , iron (Fe), aluminum (Al), zinc (Zn), sodium (Na), calcium (Ca) and magnesium (Mg).

The seed layer 130 may be formed by PVD. For example, the seed layer 130 may be formed by methods such as sputtering, evaporation, and the like. In some embodiments, the seed layer 130 may be formed by sputtering.

The thickness of the seed layer 130 ranges from about 200 nm to about 1000 nm. In some embodiments, the thickness of the seed layer 130 ranges from about 200 nm to about 1000 nm, from about 240 nm to about 900 nm, from about 280 nm to about 800 nm, from about 300 nm to about 700 nm, from about 320 nm to about 650 nm, from about 340 nm to about 340 nm to about 700 nm. 600 nm and some range from about 350 nm to about 550 nm or the foregoing values.

Referring to FIGS. 1 and 2C , acid treatment (step S30 ) may be performed on the exposed surface of the seed layer 130 .

The acid treatment is performed to remove oxides present on the surface of the seed layer 130 and may be performed using an organic acid or an inorganic acid. In some embodiments, the acid treatment is performed by contacting a solution 160a of an organic acid or an inorganic acid with the surface of the seed layer 130.

The time range of acid treatment is about 10 seconds to about 10 minutes, about 20 seconds to about 8 minutes, about 30 seconds to about 6 minutes, about 40 seconds to about 5 minutes, about 50 seconds to about 4 minutes, about 1 minute to About 3 minutes or may be in some range between the aforementioned values. When the acid treatment time is too long, the effect from the acid treatment will reach saturation and the throughput will be reduced uneconomically. When the acid treatment time is too short, oxide removal may not be performed sufficiently.

Acid treatment can generally be performed at room temperature. For example, the temperature may be from about 10°C to about 45°C, from about 15°C to about 40°C, from about 20°C to about 37°C, from about 25°C to about 35°C, or between the foregoing values. Acid treatment is performed at certain ranges of temperatures.

Inorganic acids may include, for example, sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), nitric acid (HNO ₃ ), phosphoric acid (H ₃ PO ₄ ), sulfamic acid (SO ₃ HNH ₂ ), perchloric acid (HClO ₄ ), Chromic acid (H ₂ CrO ₄ ), sulfurous acid (H ₂ SO ₃ ), nitrous acid (HNO ₂ ) or a mixture of the above, but the present invention is not limited thereto.

Organic acids may include, for example, formic acid, acetic acid, trifluoro acetic acid, diacetic acid, imino diacetic acid, oxalic acid, lemon Citric acid, ascorbic acid, propionic acid, sorbic acid, succinic acid, fumaric acid, oleic acid, ethanol Glycolic acid, stearic acid, lactic acid, pyruvic acid, malonic acid, glutaric acid, malic acid ), mandelic acid, tartaric acid, palmitic acid, pamoic acid, maleic acid, hydroxymaleic acid, glutamic acid (glutamic acid), benzoic acid, acetoxybenzoic acid, salicylic acid, phenyl acetic acid, cinnamic acid, methanesulfonic acid ( methane sulfonic acid), ethane sulfonic acid, benzene sulfonic acid, toluene sulfonic acid, aniline sulfonic acid, naphthalene sulfonic acid, naphthalene disulfonic acid or a mixture of the foregoing, but the present invention is not limited thereto.

Acid treatment can be performed at a pH of about 0 to 3. In some embodiments, acid treatment may be performed at a pH of about 0 to 2.5, about 0 to 2.3, about 0 to 2.0, and about 0 to 1.7.

In order to adjust the pH of the acid treatment, the amount of inorganic acid or organic acid added can be adjusted. For example, the concentration of the inorganic acid or organic acid may range from about 0.5% to about 20% by weight, from about 1% to about 15% by weight, from about 2% to about 10% by weight, or somewhere in between the foregoing values. within some ranges.

When the concentration of the inorganic acid or organic acid is too high or the pH of the inorganic acid or organic acid is too low, the seed layer 130 may be damaged. When the concentration of the inorganic acid or organic acid is too low or the pH of the inorganic acid or organic acid is too high, oxide removal may be insufficiently performed.

Next, the surface of the seed layer 130 is rinsed to remove the inorganic acid or organic acid solution remaining on the surface of the seed layer 130 . For example, water such as deionized water is used to perform the rinse.

Referring to FIGS. 1 and 2D , a pre-impregnation process (step S40 ) may be performed on the exposed surface of the seed layer 130 .

A pre-impregnation process is performed to remove organic materials remaining on the surface of the seed layer 130 and may be performed using an alkaline solution 160b. In some embodiments, the prepreg process is performed by contacting the alkaline solution 160b with the surface of the seed layer 130 .

The pre-impregnation process can be performed for about 10 seconds to about 10 minutes, about 20 seconds to about 8 minutes, about 30 seconds to about 6 minutes, about 40 seconds to about 5 minutes, about 50 seconds to about 4 minutes, about 1 minutes to about 3 minutes or may be in some range between the aforementioned values. When the prepreg process takes too long, the effects from the prepreg process will be saturated and the throughput will be reduced uneconomically. When the pre-impregnation process time is too short, the removal of organic materials may be insufficiently performed.

The prepreg process is usually performed at room temperature. For example, the temperature may be from about 10°C to about 45°C, from about 15°C to about 40°C, from about 20°C to about 37°C, from about 25°C to about 35°C, or between the foregoing values. The prepreg process is performed at certain ranges of temperatures.

The alkaline solution may include, for example, NaOH aqueous solution, KOH aqueous solution, NH ₄ OH aqueous solution, Mg(OH) ₂ aqueous solution, Ca(OH) ₂ aqueous solution, Ba(OH) ₂ aqueous solution, Al(OH) ₃ aqueous solution or a combination of the foregoing, but The present invention is not limited to this.

The pre-impregnation process can be performed at a pH of about 9 to about 14. In some embodiments, the range may be from about 9.3 to about 13.7, from about 9.6 to about 13.4, from about 10 to about 13, from about 10.3 to about 12.7, from about 10.6 to about 12.4, from about 11 to about 12, or between the foregoing values. The pre-impregnation process is performed at certain ranges of pH.

In order to adjust the pH of the prepreg process, the concentration of the alkaline solution ranges from about 0.1% to about 2.0% by weight, from about 0.2% to about 1.8% by weight, from about 0.3% to about 1.6% by weight, and from about 0.4% to about 0.4% by weight. About 1.4% by weight, about 0.5% by weight to about 1.2% by weight, about 0.6% by weight to about 1.0% by weight, or can be in some range between the aforementioned values.

When the concentration of the alkaline solution is too high, the seed layer 130 may be damaged. When the concentration of the alkaline solution is too low, the removal effect of the organic material will be insufficient, and thus the adhesion of the subsequently formed bulk layer 140 will be deteriorated.

After the pre-impregnation process is completed, the surface of the seed layer 130 does not need to be rinsed.

Referring to FIGS. 1 and 2E , the bulk layer 140 is formed on the seed layer 130 (step S50 ). In some embodiments, bulk layer 140 may include the same metal as seed layer 130 . In some embodiments, bulk layer 140 may include a different metal than seed layer 130 .

In some embodiments, bulk layer 140 may be formed by electroless plating utilizing an autocatalytic reaction of seed layer 130 . An autocatalytic reaction can be performed using a reducing agent via the following chemical reaction equation.

M ^z+ (aq) + X ^z- (aq) → M ⁰ (s) + Z

In the chemical reaction formula, M represents a metal forming the bulk layer 140, ^Xz- represents a reducing agent, and Z represents an oxidation reaction byproduct. The reaction by-product, i.e., Z, can be a liquid, solid, or gas.

The metal M forming the bulk layer 140 may be the same as or different from the metal forming the seed layer 130 . The metal forming bulk layer 140 , that is, M, may include, for example, one or more selected from the group consisting of: Cu, Sn, Ni, Fe, Al, Zn, Na, Ca, and Mg. However, the metals forming the seed layer 130 and the bulk layer 140 may be selected such that the standard reduction potential of the metal forming the seed layer 130 is lower than or equal to the standard reduction potential of the metal forming the bulk layer 140 .

In some embodiments, the metal forming seed layer 130 and the metal forming bulk layer 140 may be different from each other. In some embodiments, the metal forming the seed layer 130 and the metal forming the bulk layer 140 may be the same metal. Even when the metal forming the seed layer 130 and the metal forming the bulk layer 140 are the same metal, since the methods of forming the seed layer 130 and the bulk layer 140 are different from each other, there is a gap between the seed layer 130 and the bulk layer 140 Observable interfaces can exist.

To form bulk layer 140, seed layer 130 may be immersed in the bulk mixture of an electroless plating bath. The bulk mixture may include ions of the metal M that form the bulk layer 140 and a reducing agent.

In order to provide ions of the metal M, the bulk mixture may comprise a salt of the metal M dissolved in the solvent. When the metal M is copper, examples of salts of the metal M may include copper sulfates, chlorides, nitrides, acetates, formates, the aforementioned hydrates, and the like, but the present invention is not limited thereto.

The concentration of metal M ions in the bulk mixture ranges, for example, from about 0.01M to about 0.5M. In some embodiments, the concentration of metal M ions ranges from about 0.01M to about 0.5M, about 0.015M to about 0.4M, about 0.02M to about 0.3M, about 0.025M to about 0.2M, about 0.03M to About 0.1M or in some range between the aforementioned values.

In some embodiments, the content of metal M in the bulk mixture may range from about 0.5 g/l to about 20 g/l, from about 0.8 g/l to about 17 g/l, from about 1 g/l to about 15 g/l. , about 1.3g/l to about 13g/l, about 1.5g/l to about 10g/l, about 2g/l to about 9g/l, about 2.2g/l to about 8g/l, about 2.5g/l to about 7 g/l, about 2.7 g/l to about 6.5 g/l, about 3 g/l to about 6 g/l, or may be in some range between the foregoing values. In some embodiments, when the metal M is copper, ions of the metal M may be provided such that the copper concentration in the bulk mixture ranges from about 0.5 g/l to about 10 g/l, from about 0.5 g/l to about 8 g/l. l or about 1 g/l to about 5 g/l.

Reducing agents may include, for example: sodium hypophosphite, formaldehyde, glyoxylic acid, hydrazine, dimethylamine borane, trimethylamine borane ), 4-methylmorpholine borane, sodium borohydride, potassium borohydride, glucose, sucrose, cellulose, sorbate Sugar alcohol (sorbitol), mannitol (mannitol), ascorbic acid (ascorbic acid), formic acid (formic acid), etc., but the present invention is not limited thereto.

The concentration of the reducing agent may range, for example, from about 0.01M to about 1M. In some embodiments, the concentration of the reducing agent may range, for example, from about 0.01M to about 0.9M, from about 0.02M to about 0.8M, from about 0.03M to about 0.7M, from about 0.04M to about 0.6M, from about 0.05M to About 0.5M, about 0.06M to about 0.4M, about 0.07M to about 0.35M, about 0.08M to about 0.3M, about 0.09M to about 0.25M, about 0.1M to about 0.2M or somewhere between the aforementioned values. within some ranges. When the reducing agent contains two or more reducing agents, the sum of the concentrations of all reducing agents falls within the aforementioned range.

When the concentration of the reducing agent is too high, the effect obtainable by the reducing agent becomes saturated and becomes uneconomical. When the concentration of the reducing agent is too low, the time to form the bulk layer 140 may be too long.

The bulk mixture may further comprise a complexing agent. Complexing agents may include, for example, sugar alcohols (e.g., xylitol, mannitol, and sorbitol), alkanolamines (e.g., triethanol amine), hydroxycarboxylic acids ( For example, lactic acid, citric acid, and tartaric acid), amino phosphonic acid, and aminopolyphosphonic acid (e.g., aminotrimethylenephosphine Aminotris (methylphosphonic acid), aminocarboxylic acid (e.g., oligoamino monosuccinic acid, polyamino monosuccinic acid, oligoamine oligoamino disuccinic acid, ethylenediamine-N,N'-disuccinic acid, polyamino disuccinic acid), Aminopolycarboxylic acid (e.g., nitrilotriacetic acid, ethylenediamine tetraacetic acid (EDTA)), N'-(2-hydroxyethyl)-ethylenediamine -N,N,N'-triacetic acid (N'-(2-hydroxyethyl)-Ethylenediamine-N,N,N'-triacetic acid (HEDTA)), cyclohexanediamine tetraacetic acid, diethyl diethylenetriamine pentaacetic acid, tetrakis-(2-hydroxypropyl)-ethylenediamine (Quadrol ^(R) ) or N,N,N',N'- Tetrakis(2-hydroxyethyl)ethylenediamine (N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine), any of the aforementioned salts or the aforementioned mixtures, but the present invention is not limited thereto.

The concentration of the complexing agent may range from about 0.001M to about 2M. In some embodiments, the concentration of the complexing agent may range from about 0.001M to about 2M, from about 0.005M to about 1.5M, from about 0.01M to about 1M, from about 0.02M to about 0.8M, from about 0.03M to about 0.6M. , about 0.05M to about 0.4M, about 0.07M to about 0.2M, or some range between the aforementioned values. When the complexing agent contains two or more reducing agents, the sum of the concentrations of all complexing agents falls within the aforementioned range.

The bulk mixture may further comprise a stabilizer. Stabilizers may be selected from the group consisting of, for example: mercaptobenzothiazole, thiourea, cyanide and/or ferrocyanide compounds, cobalt cyanide salts (cobalt cyanide salts), polyethylene glycol derivatives (polyethylene glycol derivatives), 4-nitrobenzoic acid (4-nitrobenzoic acid), 3,5-dinitrobenzoic acid (3,5-dinitrobenzoic acid), 2 ,4-dinitrobenzoic acid (2,4-dinitrobenzoic acid), 2-hydroxy-3,5-dinitrobenzoic acid (2-hydroxy-3,5-dinitrobenzoic acid), 2-acetylbenzoic acid (2-acetyl benzoic acid), 4-nitrophenol, 2,2′-bipyridyl, methylbutynol and propionitrile.

The concentration of the stabilizer may range from about 1 ppm by weight to about 10,000 ppm by weight. In some embodiments, the concentration of the stabilizer may range from about 2 ppm to about 8000 ppm by weight, from about 5 ppm to about 5000 ppm by weight, from about 10 ppm to about 3000 ppm by weight, from about 20 ppm to about 1000 ppm by weight. ppm by weight, from about 50 ppm by weight to about 800 ppm by weight, from about 100 ppm by weight to about 500 ppm by weight, or in some range between the foregoing values.

The bulk mixture may further comprise a pH adjuster. The pH adjuster may include, for example, NaOH aqueous solution, KOH aqueous solution, NH ₄ OH aqueous solution, Mg(OH) ₂ aqueous solution, Ca(OH) ₂ aqueous solution, Ba(OH) ₂ aqueous solution, Al(OH) ₃ aqueous solution or a mixture of the above . A pH adjuster may be added such that the pH of the bulk mixture ranges from about 8 to about 11.

In some embodiments, the pH of the bulk mixture ranges from about 8 to about 11, from about 8.5 to about 10.5, from about 9 to about 10, or in some range between the foregoing values.

During the formation of bulk layer 140, the temperature of the bulk mixture may range from about 10°C to about 75°C, about 15°C to about 70°C, about 20°C to about 65°C, about 25°C to about 60°C, about 30 °C to about 55°C, about 35°C to about 50°C, or some temperature range between the foregoing values.

When the temperature of the bulk mixture is too low, the reaction temperature will be lowered, so that the formation speed of the bulk layer 140 is reduced. When the temperature of the bulk mixture is too high, it becomes uneconomical.

The thickness of bulk layer 140 may range from about 2.0 μm to about 10 μm. In some embodiments, the thickness of the bulk layer 140 may range from about 2.0 μm to about 10 μm, from about 2.2 μm to about 8 μm, from about 2.4 μm to about 7 μm, from about 2.6 μm to about 6 μm, from about 2.8 μm to about 5 μm. , about 3.0 μm to about 4.5 μm or in some range between the aforementioned values.

The grain size of the seed layer 130 may be much smaller than the grain size of the bulk layer 140 .

In detail, the average grain size of the seed layer 130 may range from about 1 nm to about 150 nm, from about 2 nm to about 130 nm, from about 3 nm to about 100 nm, from about 5 nm to about 80 nm, from about 10 nm to about 50 nm, from about 20 nm to about 20 nm. About 40 nm or may be in some range between the aforementioned values.

In addition, the average grain size of the bulk layer 140 may range from about 0.2 μm to about 1.6 μm, from about 0.3 μm to about 1.5 μm, from about 0.4 μm to about 1.4 μm, from about 0.5 μm to about 1.3 μm, from about 0.6 μm to about 1.3 μm. About 1.2 μm, about 0.7 μm to about 1.1 μm, about 0.8 μm to about 1.0 μm, or may be in some range between the aforementioned values.

In conventional electroless plating, a catalyst layer containing metals such as palladium (Pd), silver (Ag) is formed on a substrate and then a bulk layer is formed through a chemical reaction by providing a plating solution on the catalyst layer. In contrast, in the method of manufacturing a glass substrate structure described with reference to Figures 2A to 2E, since a catalyst layer including a metal such as Pd is not provided, no catalyst layer is interposed between the glass substrate and the bulk layer.

3A to 3D are side cross-sectional views of a method of manufacturing a metallized substrate according to an embodiment of the present invention.

Referring to FIG. 3A , the adhesion promoter layer 120 and the seed layer 130 are sequentially formed on and above the glass substrate 110 . The foregoing formation is described in detail above with reference to Figures 1, 2A and 2B, and repeated descriptions thereof are omitted.

Referring to FIG. 3B , an etching mask pattern 150 may be formed on the seed layer 130 . The etching mask pattern 150 may be, for example, a photoresist pattern. The photoresist pattern (eg, photopolymer) can be negative photoresist or positive photoresist. In some embodiments, the etch mask pattern 150 may include carbon-based materials, such as amorphous carbon layer (ACL), silicon nitride, silicon oxide, and the like.

Referring to FIG. 3C , by sequentially etching the seed layer 130 and the adhesion promoter layer 120 using the etching mask pattern 150 as an etching mask, the seed layer pattern 130p and the adhesion promoter pattern 120p can be formed. Etching can be performed by known anisotropic etching methods.

Next, the etching mask pattern 150 can be removed. For example, the etch mask pattern 150 may be removed by dissolution in a solvent or by ashing in an oxidizing atmosphere.

Referring to FIG. 3D , an acid treatment and a prepreg process are performed on the surface of the seed layer pattern 130 p exposed by removing the etching mask pattern 150 , and thus the bulk layer 140 may be formed.

The acid treatment and pre-impregnation processes are described in detail with reference to Figures 1, 2C and 2D, and repeated descriptions thereof are omitted.

The bulk layer 140 may be formed via an autocatalytic reaction without a catalyst using the seed layer pattern 130p. The autocatalytic reaction mechanism is described in detail above with reference to Figures 1 and 2E, and its repeated description is omitted.

Since the bulk layer 140 grows quite isotropically, while growing in the vertical direction, that is, the Z direction, the bulk layer 140 can also grow in the horizontal direction, that is, the X direction and/or the Y direction. To a certain extent. However, growth in the vertical direction is faster than growth in the horizontal direction. In addition, since the growth of the bulk layer 140 is isotropic to a certain extent, the bulk layer 140 can grow to have a curved surface 142 .

In some embodiments, the seed layer pattern 130p may be a line-and-space pattern, and the curved surface 142 may extend along the seed layer pattern 130p.

4A to 4D are side cross-sectional views of methods of manufacturing metallized substrates according to other embodiments of the present invention.

Referring to FIG. 4A , the adhesion promoter layer 120 , the seed layer 130 and the bulk layer 140 are sequentially formed on and above the glass substrate 110 . The foregoing formation is as described in detail above with reference to FIGS. 1 to 2E, and repeated description thereof is omitted.

Referring to FIG. 4B , an etch mask pattern 150 may be formed on the bulk layer 140 . In other words, the etch mask pattern 150 may be formed on the seed layer 130 with the bulk layer 140 between the etch mask pattern 150 and the seed layer 130 .

The etching mask pattern 150 may be, for example, a photoresist pattern. The photoresist pattern, such as a photopolymer, can be negative photoresist or positive photoresist. In some embodiments, the etch mask pattern 150 may be a carbon-based material, such as ACL, silicon nitride, silicon oxide, etc.

Referring to FIG. 4C, by sequentially etching the bulk layer 140, the seed layer 130 and the adhesion promoter layer 120 using the etching mask pattern 150 as the etching mask, the bulk layer pattern 140p, the seed layer pattern 130p and the adhesion promoter layer can be formed. Accelerator pattern 120p. Etching can be performed by known anisotropic etching methods.

In some embodiments, the etch mask pattern 150 may be completely etched and disappear. Specifically, the etch mask pattern 150 may be completely etched before the bulk layer 140 or the seed layer 130 is fully etched. In this case, when the seed layer 130 is etched using the bulk layer 140 as an etching mask, the seed layer pattern 130p may be formed.

Referring to Figure 4D, the etching mask pattern 150 is removed. For example, the etch mask pattern 150 may be removed by dissolution in a solvent or by ashing in an oxidizing atmosphere.

5A to 5D are side cross-sectional views of methods of manufacturing metallized substrates according to other embodiments of the present invention.

Referring to FIG. 5A , the adhesion promoter layer 120 and the seed layer 130 are sequentially formed on and above the glass substrate 110 . The foregoing formation is described in detail above with reference to Figures 1, 2A and 2B, and repeated descriptions thereof are omitted.

Referring to FIG. 5B , an etching mask pattern 150 may be formed on the seed layer 130 . The etching mask pattern 150 may be, for example, a photoresist pattern. The photoresist pattern, such as a photopolymer, can be negative photoresist or positive photoresist. In some embodiments, the etch mask pattern 150 may be a carbon-based material, such as ACL, silicon nitride, silicon oxide, etc.

Referring to FIG. 5C , a bulk layer 140 may be formed to fill the gaps of the etching mask pattern 150 .

In order to form the bulk layer 140, first, an acid treatment and a prepreg process are performed on the surface of the seed layer 130 exposed through the gap. The acid treatment and pre-impregnation processes are described in detail with reference to Figures 1, 2C and 2D, and repeated descriptions thereof are omitted.

In some embodiments, before forming the etch mask pattern 150 , an acid treatment and a pre-dip process are performed on the surface of the seed layer 130 . In other words, after performing acid treatment and prepreg process on the surface of the seed layer 130 in FIG. 5A, the etching mask pattern 150 in FIG. 5B can be formed.

The bulk layer 140 may be formed via an autocatalytic reaction without a catalyst using the seed layer pattern 130p. The autocatalytic reaction mechanism is described in detail above with reference to Figures 1 and 2E, and its repeated description is omitted.

Referring to Figure 5D, the etching mask pattern 150 is removed. For example, the etch mask pattern 150 may be removed by dissolution in a solvent or by ashing in an oxidizing atmosphere.

Next, the exposed seed layer 130 and adhesion promoter layer 120 can be removed using the bulk layer 140 as an etch mask. In some embodiments, the exposed seed layer 130 and adhesion promoter layer 120 may be removed via anisotropic etching. In some embodiments, since the exposed seed layer 130 and adhesion promoter layer 120 have thin thickness, the seed layer 130 and adhesion promoter layer 120 may be removed through isotropic etching.

FIG. 6 is a scanning electron microscope (SEM) image of an enlarged cross-sectional view of a stacked structure manufactured by a method of manufacturing a metallized substrate according to an embodiment of the present invention.

Referring to FIG. 6 , it is observed that the adhesion promoter layer 120 , the seed layer 130 and the bulk layer 140 are formed on and above the glass substrate 110 . Although the seed layer 130 and the bulk layer 140 are both formed of copper, since the formation methods are different from each other, the interface between the seed layer 130 and the bulk layer 140 can be observed.

Furthermore, it was observed that the bulk layer 140 was formed very thick (approximately 4 μm) by electroless plating. Since the metal thickness (about 0.02 μm to about 0.5 μm) formed in general electroless plating is very thin compared to the aforementioned thickness, the electroless plated metal cannot be used alone as wiring due to high resistance, and needs to be routed through electroless plating. The extra stack is plated on top of it. In comparison, since the bulk layer 140 of the metallized substrate fabricated according to embodiments of the present invention is very thick, the bulk layer 140 can be used alone as a wiring.

Figure 7 is an SEM image of an enlarged cross-sectional view of a stacked structure manufactured by a method of manufacturing a metallized substrate according to other embodiments of the present invention.

Referring to FIG. 7 , both the seed layer 130 and the bulk layer 140 are formed of copper. The seed layer 130 is formed to have a thickness of approximately 550 nm by sputtering, and the bulk layer 140 is formed to have a thickness of 3.75 μm by an electroless plating method according to an embodiment of the present invention.

Since the grain sizes of the seed layer 130 and the bulk layer 140 are very different from each other, the interface between the seed layer 130 and the bulk layer 140 can be noticed. It can be seen that most of the grain sizes of the seed layer 130 are much smaller than 200 nm. Furthermore, it can be observed that the grains of the bulk layer 140 typically have dimensions of several hundred nanometers or larger.

Figure 8 is an SEM image of an enlarged cross-sectional view of the seed layer 130 and the bulk layer 140 in a stacked structure manufactured by a method of manufacturing a metallized substrate according to other embodiments of the present invention; Figure 9 is an SEM image of the Figure 8 is an SEM image of a stacked structure manufactured by the same method as the embodiment but without performing the pre-preg process.

Referring to FIG. 8 , it is observed that the seed layer 130 with relatively small grains and the bulk layer 140 with relatively large grains are formed in sequence, and the seed layer 130 and the bulk layer 140 are in close contact with each other, and in the seed layer 130 There are no holes in the interface with bulk layer 140 .

Referring to FIG. 9 , it is observed that a plurality of consecutive holes are formed in the interface between the seed layer 130 and the bulk layer 140 . Since these holes will deteriorate the adhesion between the seed layer 130 and the bulk layer 140 , the bulk layer 140 will be separated from the seed layer 130 .

Figures 10A and 10B are respectively surface images of the bulk layer 140 with and without the pre-impregnation process.

Referring to FIG. 10A , it is observed that when the prepreg process is performed, the surface of the electroless plated bulk layer 140 is formed smooth. In contrast, referring to FIG. 10B , it is observed that when the prepreg process is not performed, a plurality of bubbles are formed in the surface of the electroless plated bulk layer 140 . It is assumed that the formation of bubbles is due to the holes described with reference to Figure 9.

Since the present invention does not use a precious metal catalyst, it can perform electroless plating at an affordable price, and thus obtain a wiring structure with excellent interlayer adhesion through the prepreg process.

It is to be understood that the embodiments described herein are to be considered in a descriptive sense and not for purposes of limitation. Features or aspects that are described in each embodiment should generally be considered as available for other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the drawings, those of ordinary skill in the art will understand that, without departing from the spirit and scope of the disclosure as defined by the following claims, executable forms and Various variations in details.

110:Glass substrate 120: Adhesion promoter layer 120p: Adhesion promoter pattern 130:Seed layer 130p: Seed layer pattern 140:Block layer 140p:Block layer pattern 142:Surface 150: Etch mask pattern 160a: Solutions of organic or inorganic acids 160b:Alkaline solution S10: Steps S20: Steps S30: Steps S40: Steps S50: Steps

The foregoing and other aspects, features and advantages of certain embodiments of the present invention will be more clearly understood from the following embodiments combined with the accompanying drawings, in which:

Figure 1 is a flow chart of a method for manufacturing a glass substrate structure according to an embodiment of the present invention;

Figures 2A to 2E are side cross-sectional views of a method of manufacturing a glass substrate structure according to the embodiment of Figure 1;

Figures 3A to 3D are side cross-sectional views of a method of manufacturing a metallized substrate according to an embodiment of the present invention;

4A to 4D are side cross-sectional views of methods of manufacturing metallized substrates according to other embodiments of the present invention;

5A to 5D are side cross-sectional views of methods of manufacturing metallized substrates according to other embodiments of the present invention;

Figure 6 is a scanning electron microscope (SEM) image of an enlarged cross-sectional view of a stacked structure manufactured by a method of manufacturing a metallized substrate according to an embodiment of the present invention;

Figure 7 is an SEM image of an enlarged cross-sectional view of a stacked structure manufactured by a method of manufacturing a metallized substrate according to other embodiments of the present invention;

Figure 8 is an SEM image of an enlarged cross-sectional view of a seed layer and a bulk layer in a stacked structure manufactured by a method of manufacturing a metallized substrate according to other embodiments of the present invention;

Figure 9 is an SEM image of a stacked structure fabricated by the same method as the embodiment of Figure 8 but without performing a pre-dip process; and

Figures 10A and 10B are respectively surface images of the bulk layer when the pre-impregnation process is performed and when the pre-impregnation process is not performed.

Domestic storage information (please note in order of storage institution, date and number) without Overseas storage information (please note in order of storage country, institution, date, and number) without

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S50: Steps

Claims (21)

A method of manufacturing a glass substrate structure, the method comprising: Forming an adhesion promoter layer on a surface of a glass substrate; Forming a first metal seed layer on a surface of the adhesion promoter layer; and A second metal bulk layer is formed on the seed layer through an autocatalytic reaction. The method of claim 1, further comprising: performing an acid treatment on a surface of the seed layer after forming the seed layer and before forming the bulk layer. The method of claim 2, further comprising: performing alkali cleaning on the surface of the seed layer after performing the acid treatment and before forming the bulk layer. The method of claim 1, wherein each of the adhesion promoter layer and the seed layer is formed by physical vapor deposition (PVD). The method of claim 4, wherein forming the bulk layer includes applying a bulk mixture to the seed layer, the bulk mixture comprising: about 0.5 g/l to about 8 g/l of metal ions of the second metal; about 0.01M to about 1.0M of a reducing agent; and A mixture of about 0.05M to about 1.0M. The method of claim 5, wherein the bulk mixture further includes about 10 ppm to about 1000 ppm by weight of a stabilizer. The method of claim 5, wherein the forming of the bulk layer is performed at a temperature of about 30°C to about 60°C. The method of claim 5, wherein the bulk mixture further includes a pH adjusting agent to adjust the pH to about 9 to about 11. The method of claim 1, wherein the seed layer includes one or more groups selected from the following: copper (Cu), tin (Sn), nickel (Ni), iron (Fe), aluminum ( Al), zinc (Zn), sodium (Na), calcium (Ca) and magnesium (Mg). The method of claim 1, wherein the bulk layer has a thickness of about 2.0 μm to about 10 μm. A method of manufacturing a metallized substrate, the method comprising: Forming an adhesion promoter layer on an entire upper surface of a glass substrate; Forming a first metal seed layer on a surface of the adhesion promoter layer; forming a mask layer with a mask pattern on the seed layer; Etching the seed layer to form a patterned seed layer; Applying a bulk mixture to the seed layer to form a bulk layer of a second metal on the seed layer, the bulk mixture comprising: about 0.5 g/l to about 8 g/l of the second metal Metal ions; a reducing agent from about 0.01M to about 1.0M; and a complexing agent from about 0.05M to about 1.0M; and Remove this mask layer. The method of claim 11, wherein removing the mask layer is performed after etching the seed layer and before applying the bulk mixture. The method of claim 12, wherein a surface of the bulk layer includes a curved surface extending along the seed pattern. The method of claim 11, wherein applying the bulk mixture is performed after forming the seed layer and before etching the seed layer; and Forming the mask layer on the seed layer includes forming the mask layer over the seed layer, and the bulk layer is located between the seed layer and the mask layer. The method of claim 14, wherein after etching the seed layer, removing the mask layer is performed. The method of claim 14, wherein etching the seed layer includes: Use the mask layer as an etch mask to etch the bulk layer; and A patterned seed layer is formed using the etched bulk layer as an etch mask. The method of claim 11, further comprising: performing an acid treatment on a surface of the seed layer before applying the bulk mixture. The method of claim 17, further comprising: performing an alkali wash on the surface of the seed layer after performing the acid treatment and before applying the bulk mixture. The method of claim 11, wherein an average grain size of the bulk layer may be larger than an average grain size of the seed layer. A method of manufacturing a glass substrate structure, the method comprising: Forming an adhesion promoter layer with a thickness of about 30 nm to about 150 nm on a surface of a glass substrate by sputtering; Forming a first metal seed layer with a thickness of about 300 nm to about 700 nm on a surface of the adhesion promoter layer by sputtering; performing an acid treatment on a surface of the seed layer using an aqueous inorganic acid solution; performing an alkali wash on the surface of the seed layer; and Forming a second metal bulk layer with a thickness of about 2.0 μm to about 10 μm on the seed layer through an autocatalytic reaction, wherein forming the bulk layer includes applying a bulk mixture to the seed layer, the bulk mixture comprising: about 0.5 g/l to about 8 g/l of metal ions of the second metal; about 0.01M to about 1.0M of a reducing agent; and a mixture of about 0.05M to about 1.0M, and The first metal and the second metal each independently include one or more groups selected from the following: copper (Cu), tin (Sn), nickel (Ni), iron (Fe), aluminum (Al) , zinc (Zn), sodium (Na), calcium (Ca) and magnesium (Mg), and the first metal and the second metal are selected so that a standard reduction potential of the first metal is less than or equal to the second metal a standard reduction potential. The method of claim 20, wherein a catalyst layer is not inserted between the glass substrate and the bulk layer.