KR20230039434A - Manufacturing methods of glass substrate structure and metallized substrate - Google Patents

Abstract

Disclosed is a method for manufacturing a glass substrate structure, including the steps of: forming an adhesion promoter layer on the surface of a glass substrate; forming a seed layer of a first metal on the surface of the adhesion promoter; and forming a bulk layer of a second metal on the seed layer through an autocatalytic reaction. Since the present invention does not use a noble metal catalyst, electroless plating can be performed inexpensively, and a wiring structure having excellent interlayer adhesion through a pre-dip process can be obtained.

Description

Manufacturing method of glass substrate structure and manufacturing method of wiring board {Manufacturing methods of glass substrate structure and metallized substrate}

The present invention relates to a method for manufacturing a glass substrate structure and a method for manufacturing a wiring board, and more particularly, to a method for manufacturing a glass substrate structure that can be manufactured at low cost and has excellent interlayer adhesion, and a method for manufacturing a wiring board.

Since conventional printed circuit boards have limitations in thermal stability and mechanical stability, there is a problem of warpage and a decrease in pattern accuracy due to this. Compared to printed circuit boards, the glass substrate has a significantly reduced warpage problem, but is expensive because electroless plating using an expensive catalyst is required. In addition, the conventional manufacturing method of the glass substrate structure has a problem in interlayer adhesion due to voids in the metal wiring layer, and improvement is required.

A first technical problem to be achieved by the present invention is to provide a method for manufacturing a glass substrate structure, such as a glass circuit board, which can be manufactured inexpensively and has excellent interlayer adhesion.

A second technical problem to be achieved by the present invention is to provide a manufacturing method of a wiring board that can be manufactured inexpensively and has excellent interlayer adhesion.

The present invention comprises the steps of forming an adhesion promoter (adhesion promoter) layer on the surface of the glass substrate in order to achieve the first technical problem; forming a seed layer of a first metal on the surface of the adhesion promoter; and forming a bulk layer of a second metal on the seed layer through an autocatalytic reaction.

In some embodiments, the manufacturing method of the glass substrate structure may further include acid treating a surface of the seed layer after forming the seed layer and before forming the bulk layer. can In some embodiments, the method of manufacturing the glass substrate structure may further include cleaning the surface of the seed layer with an alkali after the acid treatment and before the forming of the bulk layer.

In some embodiments, the adhesion promoter layer and the seed layer may each be formed by physical vapor deposition (PVD). In this case, the forming of the bulk layer may include 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 applying a bulking mixture containing from about 0.05 M to about 1.0 M of a complexing agent. In some embodiments, the bulk mixture may include about 10 ppm to about 1000 ppm by weight of a stabilizer. In some embodiments, the forming 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 such that the pH is between about 9 and about 11.

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

In some embodiments, the thickness of the bulk layer may be about 2.0 μm to about 10 μm.

The present invention comprises the steps of forming an adhesion promoter layer on the entire upper surface of a glass substrate in order to achieve the second technical problem; forming a seed layer of a first metal on the surface of the adhesion promoter; forming a mask layer having a pattern on the seed layer; etching the seed layer to form a patterned seed layer corresponding to the pattern; about 0.5 g/l to about 8 g/l of metal ions of the second metal to form a bulk layer of the second metal on the seed layer; about 0.01 M to about 1.0 M reducing agent; and from about 0.05 M to about 1.0 M of a complexing agent; and removing the mask layer.

In some embodiments, removing the mask layer may be performed after etching the seed layer and before applying the bulk mixture. A surface of the bulk layer may include a curved surface extending along the patterned seed layer.

In some embodiments, the applying of the bulk mixture is performed after the forming of the seed layer and before the etching of the seed layer, and in the forming of the mask layer on the seed layer, the A mask layer may be formed on the seed layer with the bulk layer interposed therebetween. In some embodiments, removing 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 a patterned seed layer using the bulk layer as an etch mask.

In some embodiments, the manufacturing method of the wiring board may further include acid treating a surface of the seed layer before applying the bulk mixture. In some embodiments, the method of manufacturing the wiring board may further include cleaning a surface of the seed layer with an alkali after the acid treatment and before the applying of the bulk mixture.

An average grain size of the bulk layer may be greater than that of the seed layer.

Another aspect of the present invention is to form an adhesion promoter layer on a surface of a glass substrate to a thickness of about 30 nm to about 150 nm by sputtering; forming a seed layer of a first metal on the surface of the adhesion promoter to a thickness of about 300 nm to about 700 nm by sputtering; acid-treating the surface of the seed layer with an aqueous solution of an inorganic acid; alkali cleaning the surface of the seed layer; and forming a bulk layer of a second metal to a thickness of about 2.0 μm to about 10 μm on the seed layer through an autocatalytic reaction. Forming the bulk layer may include 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 applying a bulk mixture containing about 0.05 M to about 1.0 M of a complexing agent, wherein the first metal and the second metal are each independently copper (Cu), tin (Sn) , At least one selected from the group consisting of nickel (Ni), iron (Fe), aluminum (Al), zinc (Zn), sodium (Na), calcium (Ca), and magnesium (Mg), wherein the first It provides a method of manufacturing a glass substrate structure, characterized in that the first metal and the second metal are selected such that the standard reduction potential of the metal is lower than or equal to the standard reduction potential of the second metal.

Since the present invention does not use a noble metal catalyst, electroless plating can be performed at low cost, and a wiring structure having excellent interlayer adhesion can be obtained through a pre-dip process.

1 is a flow chart showing a manufacturing method of a glass substrate structure according to an embodiment of the present invention.
Figures 2a to 2e are side cross-sectional views showing a manufacturing method of the glass substrate structure according to the embodiment.
3A to 3D are side cross-sectional views illustrating a method of manufacturing a wiring board according to an embodiment of the present invention.
4A to 4D are side cross-sectional views illustrating a method of manufacturing a wiring board according to another embodiment of the present invention.
5A to 5D are side cross-sectional views illustrating a method of manufacturing a wiring board according to another embodiment of the present invention.
6 is an enlarged scanning electron microscope (SEM) image of a cross section of a laminated structure manufactured by the method of manufacturing a wiring board according to an embodiment of the present invention.
7 is an enlarged SEM image of a cross section of a laminated structure manufactured by a method of manufacturing a wiring board according to another embodiment of the present invention.
8 is an SEM image showing an enlarged cross-section of a seed layer and a bulk layer in a laminated structure manufactured by a method of manufacturing a wiring board according to another embodiment of the present invention.
9 is a SEM image of a laminated structure manufactured in the same manner as in the embodiment of FIG. 8 except that a pre-dip process is not performed.
10 are images showing the surface of the bulk layer when the pre-dip process is performed and when the pre-dip process is not performed.

Hereinafter, preferred embodiments of the present invention concept will be described in detail with reference to the accompanying drawings. However, embodiments of the inventive concept may be modified in many different forms, and the scope of the inventive concept should not be construed as being limited due to the embodiments described below. The embodiments of the inventive concept are preferably interpreted as being provided to more completely explain the inventive concept to those with average knowledge in the art. The same sign means the same element throughout. Further, various elements and areas in the drawings are schematically drawn. Accordingly, the inventive concept is not limited by the relative size or spacing drawn in the accompanying drawings.

Terms such as first and second may be used to describe various components, but the components are not limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and conversely, a second element may be termed a first element, without departing from the scope of the inventive concept.

Terms used in this application are only used to describe specific embodiments, and are not intended to limit the concept of the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the expression "comprises" or "has" is intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features or It should be understood that the presence or addition of a number, operation, component, part, or combination thereof is not precluded.

Unless defined otherwise, all terms used herein, including technical terms and scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the concept of the present invention belongs. In addition, commonly used terms as defined in the dictionary should be interpreted as having a meaning consistent with what they mean in the context of the technology to which they relate, and in an overly formal sense unless explicitly defined herein. It will be understood that it should not be interpreted.

When an embodiment is otherwise implementable, a specific process sequence may be performed differently from the described sequence. For example, two processes described in succession may be performed substantially simultaneously, or may be performed in an order reverse to the order described.

In the accompanying drawings, variations of the shapes shown may be expected, eg depending on manufacturing techniques and/or tolerances. Therefore, the embodiments of the present invention should not be construed as being limited to the specific shape of the region shown in this specification, but should include, for example, a change in shape resulting from the manufacturing process. All terms “and/or” as used herein include each and all combinations of one or more of the recited elements. Also, the term "substrate" used herein may mean a substrate itself or a laminated structure including a substrate and a predetermined layer or film formed on a surface of the substrate. Also, in this specification, the term "surface of the substrate" may refer to an exposed surface of the substrate itself or an outer surface of a layer or film formed on the substrate.

1 is a flow chart showing a manufacturing method of a glass substrate structure according to an embodiment of the present invention. Figures 2a to 2e are side cross-sectional views showing a manufacturing method of the glass substrate structure according to the embodiment.

Referring to FIGS. 1 and 2A , an adhesion promoter layer 120 is formed on a glass substrate 110 .

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

The glass substrate 110 may be about 3 mm or less, for example, 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, or about 0.7 mm to about 1 mm. thickness, including all ranges and subranges therebetween.

Some non-limiting glass compositions include about 50 mole % to about 90 mole % SiO ₂ , about 0 mole % to about 20 mole % Al ₂ O ₃ , about 0 mole % to about 20 mole % B ₂ O ₃ , from about 0 mole % to about 20 mole % P ₂ O ₅ , and from about 0 mole % to about 25 mole % R _x O. wherein R is any one or more of Li, Na, K, Rb, Cs and x is 2, or R is Zn, Mg, Ca, Sr or Ba and x is 1. In some embodiments, R _x O - Al ₂ O ₃ >0; 0 < R _x O - Al ₂ O ₃ <15; x = 2 and R ₂ O - Al ₂ O ₃ <15; R ₂ O - Al ₂ O ₃ <2; x=2 and R ₂ O - Al ₂ O ₃ - MgO >-15; 0 < (R _x O - Al ₂ O ₃ ) < 25, -11 < (R ₂ O - Al ₂ O 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 each of Co, Ni, and Cr. In some embodiments, the concentration of Fe is less than about 50 ppm, less than about 20 ppm, or less than about 10 ppm. In other 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 comprises about 60 mole % to about 80 mole % SiO ₂ , about 0.1 mole % to about 15 mole % Al ₂ O ₃ , about 0 mole % to about 12 mole % B ₂ O ₃ , and about 0.1 mole % to about 15 mole % R _x O and about 0.1 mole % to about 15 mole % R _x O. wherein R is any one or more of Li, Na, K, Rb, Cs and x is 2, or R is Zn, Mg, Ca, Sr or Ba and x is 1.

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

In further embodiments, the glass substrate 110 may include a glass having an R _x O/Al ₂ O ₃ ratio of between 0.95 and 3.23. Here, R is any one or more of Li, Na, K, Rb, and Cs, and x is 2. In further embodiments, the glass may have an R _x O/Al ₂ O ₃ ratio between 1.18 and 5.68. wherein R is any one or more of Li, Na, K, Rb, Cs and x is 2, or R is Zn, Mg, Ca, Sr or Ba and x is 1. In still further embodiments, the glass can comprise R _x O - Al ₂ O ₃ - MgO between -4.25 and 4, where R is any one or more of Li, Na, K, Rb, Cs. and x is 2. In yet additional embodiments, the glass comprises about 66 mole % to about 78 mole % SiO ₂ , about 4 mole % to about 11 mole % Al ₂ O ₃ , about 4 mole % to about 11 mole % B ₂ O ₃ , about 0 mol% to about 2 mol% Li ₂ O, about 4 mol% to about 12 mol% Na ₂ O, about 0 mol% to about 2 mol% K ₂ O, about 0 mol % to about 2 mol% ZnO, about 0 mol% to about 5 mol% MgO, about 0 mol% to about 2 mol% CaO, about 0 mol% to about 5 mol% SrO, about 0 mol% to About 2 mol% BaO, and about 0 mol% to about 2 mol% SnO ₂ .

In additional embodiments, the glass substrate 110 comprises about 72 mol % to about 80 mol % SiO ₂ , about 3 mol % to about 7 mol % Al ₂ O ₃ , about 0 mol % to about 2 mol % B ₂ O ₃ , about 0 mol% to about 2 mol% Li ₂ O, about 6 mol% to about 15 mol% Na ₂ O, about 0 mol% to about 2 mol% K ₂ O, about 0 mol% to about 2 mol% ZnO, about 2 mol% to about 10 mol% MgO, about 0 mol% to about 2 mol% CaO, about 0 mol% to about 2 mol% SrO, about 0 mol % to about 2 mole % BaO, and about 0 mole % to about 2 mole % SnO ₂ . In certain embodiments, the glass comprises about 60 mole % to about 80 mole % SiO ₂ , about 0 mole % to about 15 mole % Al ₂ O ₃ , about 0 mole % to about 15 mole % B ₂ O ₃ , and from about 2 mol% to about 50 mol% R _x O, wherein R is any one or more of Li, Na, K, Rb, Cs and x is 2, or R is Zn , Mg, Ca, Sr, or Ba, where x is 1, and Fe + 30Cr + 35Ni < about 60 ppm.

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

The adhesion promoter layer 120 is, for example, titanium (Ti), chromium (Cr), tungsten (W), molybdenum (Mo), tin (Sn), iron (Fe), cobalt (Co), nickel (Ni) , metals such as palladium (Pd), gold (Au), silver (Ag), platinum (Pt), tantalum (Ta), hafnium (Hf), or the like, 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 a method such as sputtering or evaporation. In some embodiments, the adhesion promoter layer 120 may be formed by sputtering.

The adhesion promoter layer 120 may have a thickness of about 10 nm to about 200 nm. In some embodiments, the adhesion promoter layer 120 has a thickness of about 10 nm to about 200 nm, about 20 nm to about 190 nm, about 30 nm to about 180 nm, about 40 nm to about 170 nm, about 50 nm to about 160 nm, about 60 nm to about 150 nm, about 70 nm to about 140 nm, about 80 nm to about 130 nm, about 90 nm to about 120 nm, or any range between these values. there is.

If the thickness of the adhesion promoter layer 120 is too thick, the effect of forming the adhesion promoter layer 120 is saturated, which is economically unfavorable. If the thickness of the adhesion promoter layer 120 is too thin, the formation of the adhesion promoter layer 120 may be insufficient in some areas, and the effect of adhesion promotion may be reduced.

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

The seed layer 130 may be formed of a metal different from that of the adhesion promoter layer 120, for example, copper (Cu), tin (Sn), nickel (Ni), iron (Fe), or aluminum. It may be at least one selected from the group consisting of (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 sputtering or evaporation. In some embodiments, the seed layer 130 may be formed by sputtering.

The seed layer 130 may have a thickness of about 200 nm to about 1000 nm. In some embodiments, the seed layer 130 has a thickness of about 200 nm to about 1000 nm, about 240 nm to about 900 nm, about 280 nm to about 800 nm, about 300 nm to about 700 nm, about 320 nm. nm to about 650 nm, about 340 nm to about 600 nm, about 350 nm to about 550 nm, or any range in between.

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

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

The acid treatment time 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 any range between these numbers. If the acid treatment time is too long, the effect of the acid treatment is saturated and the throughput is reduced, which may be uneconomical. If the acid treatment time is too short, the removal of oxides may be insufficient.

The acid treatment may be generally performed at room temperature. For example, the acid treatment may be performed at about 10°C to about 45°C, about 15°C to about 40°C, about 20°C to about 37°C, about 25°C to about 35°C, or any range between these values. temperature can be performed.

Examples of the inorganic acid include 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 ), It may be chromic acid (H ₂ CrO ₄ ), sulfurous acid (H ₂ SO ₃ ), nitrous acid (HNO ₂ ), or a mixture thereof, but is not limited thereto.

The organic acid is, for example, formic acid, acetic acid, trifluoro acetic acid, diacetic acid, imino diacetic acid, oxalic acid ), citric acid, ascorbic acid, propionic acid, sorbic acid, succinic acid, fumaric acid, oleic acid, glycolic acid ), stearic acid, lactic acid, pyruvic acid, malonic acid, glutaric acid, malic acid, mandelic acid, tartaric acid (tartaric acid), palmitic acid, pamoic acid, maleic acid, hydroxymaleic acid, glutamic acid, benzoic acid, acetoxybenzoic acid ( acetoxybenzoic acid, salicylic acid, phenyl acetic acid, cinnamic acid, methane sulfonic acid, ethane sulfonic acid, benzene sulfonic acid, toluene It may be toluene sulfonic acid, aniline sulfonic acid, naphthalene sulfonic acid, naphthalene disulfonic acid, or a mixture thereof, but is not limited thereto.

The acid treatment may be performed at a pH of about 0 to 3. In some embodiments, the acid treatment may be performed at a pH of about 0 to 2.5, about 0 to 2.3, about 0 to 2.0, or about 0 to 1.7.

In order to adjust the pH for the acid treatment, the addition amount of the inorganic acid or organic acid may be adjusted. For example, the concentration of the inorganic or organic acid is about 0.5 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 2 wt% to about 10 wt%, or any range between these values. can be

If the concentration of the inorganic acid or organic acid is too high or the pH is too low, the seed layer 130 may be damaged. If the concentration of the inorganic acid or organic acid is too low or the pH is too high, the removal of oxides may be insufficient.

Thereafter, the surface of the seed layer 130 may be rinsed to remove the inorganic acid or organic acid solution remaining on the surface of the seed layer 130 . The rinse can be with water, for example deionized water.

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

The pre-dip process is for removing organic matter present on the surface of the seed layer 130 and may be performed using an alkali solution. In some embodiments, the pre-dip process may be performed by contacting the surface of the seed layer 130 with an alkaline solution 160b.

The pre-dip process 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 1 minute. about 3 minutes, or any range of time between these values. If the time of the pre-dip process is too long, the effect of the pre-dip process is saturated and the throughput is reduced, which may be uneconomical. If the time of the pre-dip process is too short, removal of organic substances may be insufficient.

The pre-dip process may be generally performed at room temperature. For example, the pre-dip process may be performed at about 10°C to about 45°C, about 15°C to about 40°C, about 20°C to about 37°C, about 25°C to about 35°C, or any value in between. It can be performed at a range of temperatures.

The alkali solution may be, 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 these It may be a mixture of, but is not limited thereto.

The pre-dip process may be performed at a pH of about 9 to about 14. In some embodiments, the pre-dip process is about 9.3 to about 13.7, about 9.6 to about 13.4, about 10 to about 13, about 10.3 to about 12.7, about 10.6 to about 12.4, about 11 to about 12, or It can be performed under any range of pH between these values.

In order to adjust the pH for the pre-dip process, the concentration of the alkali solution is about 0.1 wt% to about 2.0 wt%, about 0.2 wt% to about 1.8 wt%, about 0.3 wt% to about 1.6 wt%, about 0.4 wt% to about 1.4 wt%, about 0.5 wt% to about 1.2 wt%, about 0.6 wt% to about 1.0 wt%, or any range in between.

If the concentration of the alkali solution is too high, the seed layer 130 may be damaged. If the concentration of the alkali solution is too low, the effect of removing organic matter is insufficient, and thus the adhesion of the bulk layer 140 to be formed later may deteriorate.

After the pre-dip process is completed, the surface of the seed layer 130 may not be rinsed.

Referring to FIGS. 1 and 2E , a bulk layer 140 is formed on the seed layer 130 (S50). In some embodiments, the bulk layer 140 may be made of the same type of metal as the seed layer 130 . In some embodiments, the bulk layer 140 may be formed of a different type of metal from that of the seed layer 130 .

In some embodiments, the bulk layer 140 may be formed by electroless plating by an automatic catalytic reaction using the seed layer 130 . The auto-catalytic reaction may be carried out according to the following reaction formula using a reducing agent.

M ^z+ (aq) + X ^z- (aq) → M ⁰ (s) + Z

Here, M is a metal constituting the bulk layer 140, X ^z- is a reducing agent, and Z is an oxidized reaction by-product. The reaction by-product (i.e., Z) may be a liquid or solid, or may be a gas.

The metal forming the bulk layer 140 may be the same as or different from the metal forming the seed layer 130 . The metal (ie, M) constituting the bulk layer 140 is, for example, copper (Cu), tin (Sn), nickel (Ni), iron (Fe), aluminum (Al), zinc (Zn), It may be at least one selected from the group consisting of sodium (Na), calcium (Ca), and magnesium (Mg). However, the seed layer 130 and the bulk layer (standard reduction potential) of the metal constituting the seed layer 130 is lower than or equal to the standard reduction potential of the metal constituting the bulk layer 140 ( 140) may be selected.

In some embodiments, a metal forming the seed layer 130 and a metal forming the bulk layer 140 may be different metals. In some other embodiments, the metal forming the seed layer 130 and the metal forming the bulk layer 140 may be the same metal. Even if the metal constituting the seed layer 130 and the metal constituting the bulk layer 140 are the same, since the method of forming the seed layer 130 and the bulk layer 140 is different, the seed layer 130 and the bulk layer 140 are formed differently. An observable interface may exist between the bulk layers 140 .

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

In order to provide the ions of the metal M, the bulk mixture may include a salt of the metal M dissolved in a solvent. When the metal M is copper, examples of the salt of the metal M may include, but are not limited to, sulfate salts of copper, chlorides, nitrides, acetates, formates, and hydrates thereof.

The metal M ion in the bulk mixture may have a concentration of, for example, about 0.01 M to about 0.5 M. In some embodiments, the ion of the metal M is about 0.01 M to about 0.5 M, about 0.015 M to about 0.4 M, about 0.02 M to about 0.3 M, about 0.025 M to about 0.2 M, about 0.03 M to about 0.03 M about 0.1 M, or any range between these numbers.

In some embodiments, the amount of metal M in the bulk mixture is about 0.5 g/l to about 20 g/l, about 0.8 g/l to about 17 g/l, about 1 g/l to about 15 g /l, about 1.3 g/l to about 13 g/l, about 1.5 g/l to about 10 g/l, about 2 g/l to about 9 g/l, about 2.2 g/l to about 8 g/l , about 2.5 g/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 any range between these numbers. . In some embodiments, when the metal M is copper, the concentration of copper in the bulking mixture is about 0.5 g/l to about 10 g/l, about 0.5 g/l to about 8 g/l, or about Ions of metal M may be provided to have a concentration of 1 g/l to about 5 g/l.

The reducing agent, for example, sodium hypophosphite, formaldehyde, glyoxylic acid, hydrazine, dimethylamine borane, trimethylamine borane ( trimethylamine borane, 4-methylmorpholine borane, sodium borohydride, potassium borohydride, glucose, sucrose, cellulose , sorbitol, mannitol, ascorbic acid, formic acid, etc., but the present invention is not limited thereto.

The concentration of the reducing agent may be, for example, about 0.01 M to about 1 M. In some embodiments, the reducing agent is, for example, about 0.01 M to about 0.9 M, about 0.02 M to about 0.8 M, about 0.03 M to about 0.7 M, about 0.04 M to about 0.6 M, about 0.05 M to about 0.5 M, about 0.06 M to about 0.4 M, about 0.07 M to about 0.35 M, about 0.08 M to about 0.3 M, about 0.09 M to about 0.25 M, about 0.1 M to about 0.2 M, or between these values. may have a concentration in any range of When the reducing agent includes two or more reducing agents, the sum of the concentrations of all reducing agents is within the above range.

If the concentration of the reducing agent is too high, the effect obtainable from the reducing agent is saturated, which is economically unfavorable. If the concentration of the reducing agent is too low, the time required for forming the bulk layer 140 becomes excessively long.

The bulk mixture may further include a complexing agent. The complexing agents are, for example, sugar alcohols (such as xylitol, mannitol and sorbitol), alkanol amines (such as triethanol amine), hydroxycarboxylic acids (such as lactic acid, citric acid and tartaric acid), amino phosphonic acids and aminopolyphosphonic acids (such as aminotris(methylphosphonic acid)), aminocarboxylic acids (such as oligoamino monosuccinic acid, polyamino monosuccinic acid, such as oligoamino disuccinic acid, such as ethylenediamine-N,N'-di succinic acid, polyamino disuccinic acid), aminopolycarboxylic acids (such as nitrilotriacetic acid, ethylenediamine tetraacetic acid (EDTA), N'-(2-hydroxyethyl)-ethylenediamine-N,N,N'-triacetic acid (HEDTA), cyclohexanediamine tetraacetic acid, diethylenetriamine pentaacetic acid), tetrakis-(2-hydroxypropyl)-ethylenediamine ("Quadrol ^(R) ") and N,N,N',N'- tetrakis(2-hydroxyethyl) ethylenediamine, any salt thereof, or a mixture thereof, but the present invention is not limited thereto.

The concentration of the complexing agent may be about 0.001 M to about 2 M. In some embodiments, the complexing agent is from about 0.001 M to about 2 M, from about 0.005 M to about 1.5 M, from about 0.01 M to about 1 M, from about 0.02 M to about 0.8 M, from about 0.03 M to about 0.6 M M, from about 0.05 M to about 0.4 M, from about 0.07 M to about 0.2 M, or any concentration range between these numbers. When the complexing agent includes two or more reducing agents, the sum of the concentrations of all complexing agents is within the above range.

The bulk mixture may further include a stabilizer. The stabilizer is, for example, mercaptobenzothiazole, thiourea, cyanide and/or ferrocyanide compound, cobalt cyanide salt, polyethylene glycol derivatives , 4-nitrobenzoic acid, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid, 2-hydroxy-3 ,5-dinitrobenzoic acid (2-hydroxy-3,5-dinitrobenzoic acid), 2-acetyl benzoic acid (2-acetyl benzoic acid), 4-nitrophenol (4-nitrophenol), 2,2'-bipyridyl ( bipyridyl), methylbutynol and propionitrile.

The concentration of the stabilizer may be about 1 ppm by weight to about 10000 ppm by weight. In some embodiments, the stabilizer is in an amount of about 2 ppm to about 8000 ppm by weight, about 5 ppm to about 5000 ppm by weight, about 10 ppm to about 3000 ppm by weight, about 20 ppm to about 1000 ppm by weight , from about 50 ppm to about 800 ppm by weight, from about 100 ppm to about 500 ppm by weight, or any concentration range between these numbers.

The bulk mixture may further include a pH adjusting agent. The pH adjusting agent is, 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 mixtures thereof can include The pH adjusting agent may be added to bring the pH of the bulk mixture to a range of about 8 to about 11.

In some embodiments, the bulk mixture can have a pH of about 8 to about 11, about 8.5 to about 10.5, about 9 to about 10, or any range in between.

While the formation of the bulk layer 140 is performed, the bulk mixture is 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 any range between these values.

If the temperature of the bulk mixture is too low, the reaction rate is lowered and the formation rate of the bulk layer 140 may be slowed down. Too high a temperature of the bulk mixture is economically disadvantageous.

The bulk layer 140 may have a thickness of about 2.0 μm to about 10 μm. In some embodiments, the bulk layer 140 has a thickness of about 2.0 μm to about 10 μm, about 2.2 μm to about 8 μm, about 2.4 μm to about 7 μm, about 2.6 μm to about 6 μm, about 2.8 μm to about 2.8 μm. about 5 μm, about 3.0 μm to about 4.5 μm, or any range between these numbers.

The grain size of the seed layer 130 is much smaller than that of the bulk layer 140 .

Specifically, the average size of the crystal grains of the seed layer 130 is about 1 nm to about 150 nm, about 2 nm to about 130 nm, about 3 nm to about 100 nm, about 5 nm to about 80 nm, about 10 nm. to about 50 nm, about 20 nm to about 40 nm, or any range between these numbers.

In addition, the average size of the crystal grains of the bulk layer 140 is about 0.2 μm to about 1.6 μm, about 0.3 μm to about 1.5 μm, about 0.4 μm to about 1.4 μm, about 0.5 μm to about 1.3 μm, about 0.6 μm to about 0.6 μm. 1.2 μm, about 0.7 μm to about 1.1 μm, about 0.8 μm to about 1.0 μm, or any range between these numbers.

In conventional electroless plating, a catalyst layer containing a metal such as palladium or silver is first formed on a substrate, and a plating solution is provided on the catalyst layer to form a bulk layer through a chemical reaction. However, in the manufacturing method of the glass substrate structure described with reference to FIGS. 2A to 2E , since a catalyst layer containing a metal such as palladium is not used, the catalyst layer is not interposed between the glass substrate and the bulk layer.

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

Referring to FIG. 3A , an adhesion promoter layer 120 and a seed layer 130 are sequentially formed on a glass substrate 110 . Since this has been described in detail with reference to FIGS. 1, 2a, and 2b, a detailed description thereof will be 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 is a photosensitive polymer and may be a negative photoresist or a positive photoresist. In some embodiments, the etching mask pattern 150 may be a carbon-based material such as an amorphous carbon layer (ACL), silicon nitride, or silicon oxide.

Referring to FIG. 3C , the seed layer 130 and the adhesion promoter layer 120 are sequentially etched using the etching mask pattern 150 as an etching mask to obtain a seed layer pattern 130p and an adhesion promoter pattern 120p. can form The etching may be performed by a known anisotropic etching method.

Thereafter, the etching mask pattern 150 may be removed. The etching mask pattern 150 may be removed, for example, by dissolving in a solvent or by ashing in an oxidizing atmosphere.

Referring to FIG. 3D , an acid treatment and a pre-dip process are performed on the surface of the pattern 130p of the seed layer revealed by the removal of the etching mask pattern 150, and the bulk layer 140 is formed. can form

Since the acid treatment and the pre-dip process have been described in detail with reference to FIGS. 1, 2c, and 2d, further description is omitted here.

The bulk layer 140 may be formed by an automatic catalytic reaction using the pattern 130p of the seed layer without a catalyst. Since the mechanism of the automatic catalytic reaction has been described in detail with reference to FIGS. 1 and 2e, further description is omitted here.

Since the bulk layer 140 is to some extent isotropic, it grows to some extent in the horizontal direction (ie, the X direction and/or the Y direction) while growing in the vertical direction (ie, the Z direction). However, growth in the vertical direction may be faster than in the horizontal direction. Also, since the growth of the bulk layer 140 is somewhat isotropic, it can grow to have a curved surface 142 .

In some embodiments, the pattern 130p of the seed layer is a line-and-space pattern, and the curved surface 142 extends along the pattern 130p of the seed layer. It can be.

4A to 4D are side cross-sectional views illustrating a method of manufacturing a wiring board according to another embodiment of the present invention.

Referring to FIG. 4A , an adhesion promoter layer 120 , a seed layer 130 , and a bulk layer 140 are sequentially formed on a glass substrate 110 . Since this has been described in detail with reference to FIGS. 1 to 2e, a detailed description thereof will be omitted.

Referring to FIG. 4B , an etching mask pattern 150 may be formed on the bulk layer 140 . That is, the etching mask pattern 150 may be formed on the seed layer 130 with the bulk layer 140 interposed therebetween.

The etching mask pattern 150 may be, for example, a photoresist pattern. The photoresist pattern is a photosensitive polymer and may be a negative photoresist or a positive photoresist. In some embodiments, the etching mask pattern 150 may be a carbon-based material such as an amorphous carbon layer (ACL), silicon nitride, or silicon oxide.

Referring to FIG. 4C , the bulk layer 140, the seed layer 130, and the adhesion promoter layer 120 are sequentially etched using the etching mask pattern 150 as an etching mask to form a pattern 140p of the bulk layer. , the seed layer pattern 130p and the adhesion promoter pattern 120p may be formed. The etching may be performed by a known anisotropic etching method.

In some embodiments, the etching mask pattern 150 may be exhausted by the anisotropic etching. In particular, the etching mask pattern 150 may be completely exhausted before the bulk layer 140 or the seed layer 130 is sufficiently etched. In this case, the seed layer 130 may be etched using the bulk layer 140 as an etch mask, thereby forming the seed layer pattern 130p.

Referring to FIG. 4D , the etching mask pattern 150 is removed. The etching mask pattern 150 may be removed, for example, by dissolving in a solvent or by ashing in an oxidizing atmosphere.

5A to 5D are side cross-sectional views illustrating a method of manufacturing a wiring board according to another embodiment of the present invention.

Referring to FIG. 5A , an adhesion promoter layer 120 and a seed layer 130 are sequentially formed on a glass substrate 110 . Since this has been described in detail with reference to FIGS. 1, 2a, and 2b, a detailed description thereof will be 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 is a photosensitive polymer and may be a negative photoresist or a positive photoresist. In some embodiments, the etching mask pattern 150 may be a carbon-based material such as an amorphous carbon layer (ACL), silicon nitride, or silicon oxide.

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

In order to form the bulk layer 140, first, an acid treatment and a pre-dip process may be performed on the surface of the seed layer 130 exposed through the gap. Since the acid treatment and the pre-dip process have been described in detail with reference to FIGS. 1, 2c, and 2d, further description is omitted here.

In some embodiments, the acid treatment and the pre-dip process may be performed on the surface of the seed layer 130 before forming the etching mask pattern 150 . That is, after performing an acid treatment and a pre-dip process on the surface of the seed layer 130 of FIG. 5A, the etching mask pattern 150 of FIG. 5B may be formed.

The bulk layer 140 may be formed by an automatic catalytic reaction using the pattern 130p of the seed layer without a catalyst. Since the mechanism of the automatic catalytic reaction has been described in detail with reference to FIGS. 1 and 2e, further description is omitted here.

Referring to FIG. 5D , the etching mask pattern 150 is removed. The etching mask pattern 150 may be removed, for example, by dissolving in a solvent or by ashing in an oxidizing atmosphere.

Thereafter, the exposed seed layer 130 and the adhesion promoter layer 120 may be removed using the bulk layer 140 as an etching mask. In some embodiments, the exposed seed layer 130 and the adhesion promoter layer 120 may be removed through anisotropic etching. In some embodiments, since the exposed seed layer 130 and the adhesion promoter layer 120 are thin, they may be removed through isotropic etching.

6 is an enlarged scanning electron microscope (SEM) image of a cross section of a laminated structure manufactured by the method of manufacturing a wiring board 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 the glass substrate 110 . Although both the seed layer 130 and the bulk layer 140 are copper, an interface is observed between the seed layer 130 and the bulk layer 140 because of different formation methods.

It is also observed that the bulk layer 140 is formed quite thick (about 4 μm) by electroless plating. Since the thickness of metal formed in conventional electroless plating is much thinner than this (about 0.02 μm to about 0.5 μm), it is difficult to use it as a wire due to its high resistance alone, and additional lamination is required through electrolytic plating thereon. However, since the bulk layer 140 of the wiring board manufactured according to the exemplary embodiment of the present invention is considerably thick, it may be used alone as a wiring.

7 is an enlarged SEM image of a cross section of a laminated structure manufactured by a method of manufacturing a wiring board according to another embodiment of the present invention.

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

Since the seed layer 130 and the bulk layer 140 have a large difference in grain size, an interface between them can be identified. It can be seen that the size of the majority of grains in the seed layer 130 is much smaller than 200 nm. In addition, it is observed that crystal grains of the bulk layer 140 generally have a size of hundreds of nm or more.

8 is an SEM image showing enlarged cross-sections of the seed layer 130 and the bulk layer 140 in the laminated structure manufactured by the method of manufacturing a wiring board according to another embodiment of the present invention. 9 is a SEM image of a laminated structure manufactured in the same manner as in the embodiment of FIG. 8 except that a pre-dip process is not performed.

Referring to FIG. 8 , a seed layer 130 having relatively small crystal grains and a bulk layer 140 having relatively large crystal grains are sequentially formed, and the It is observed that the seed layer 130 and the bulk layer 140 are in close contact without voids at the interface.

Referring to FIG. 9 , it is observed that several voids are formed in a line at the interface between the seed layer 130 and the bulk layer 140 . Since these voids deteriorate adhesion between the seed layer 130 and the bulk layer 140 , the bulk layer 140 may be separated from the seed layer 130 .

10 are images showing the surface of the bulk layer when the pre-dip process is performed (a) and when the pre-dip process is not performed (b).

Referring to (a) of FIG. 10 , when the pre-dip process is performed, it is observed that the surface of the electroless plated bulk layer is formed smoothly. On the other hand, referring to (b) of FIG. 10 , it was observed that a number of blisters were formed on the surface of the electroless plated bulk layer if the pre-dip process was not performed. This is estimated to be due to the void described with reference to FIG. 9 .

As described above, the embodiments of the present invention have been described in detail, but those of ordinary skill in the art to which the present invention pertains, without departing from the spirit and scope of the present invention defined in the appended claims. Various modifications of the present invention may be practiced. Accordingly, changes in future embodiments of the present invention will not deviate from the technology of the present invention.

Claims (21)

Forming an adhesion promoter layer on the surface of the glass substrate;
forming a seed layer of a first metal on the surface of the adhesion promoter; and
forming a bulk layer of a second metal on the seed layer through an autocatalytic reaction;
Method of manufacturing a glass substrate structure comprising a. According to claim 1,
The manufacturing method of the glass substrate structure, characterized in that it further comprises the step of acid-treating the surface of the seed layer after the step of forming the seed layer and before the step of forming the bulk layer. According to claim 2,
The manufacturing method of the glass substrate structure, characterized in that it further comprises the step of alkali cleaning the surface of the seed layer after the step of acid treatment and before the step of forming the bulk layer. According to claim 1,
The method of manufacturing a glass substrate structure, characterized in that the adhesion promoter layer and the seed layer are formed by physical vapor deposition (PVD), respectively. According to claim 4,
Forming the bulk layer comprises:
from about 0.5 g/l to about 8 g/l of the metal ion of the second metal;
from about 0.01 M to about 1.0 M reducing agent; and
from about 0.05 M to about 1.0 M complexing agent;
Method for producing a glass substrate structure comprising the step of applying a mixture for bulk containing. According to claim 5,
The bulk mixture is a method for manufacturing a glass substrate structure, characterized in that it comprises about 10 wtppm to about 1000 wtppm of the stabilizer. According to claim 5,
Forming the bulk layer is a method of manufacturing a glass substrate structure, characterized in that carried out at a temperature of about 30 ℃ to about 60 ℃. According to claim 5,
The method for producing a glass substrate structure, characterized in that the bulk mixture further comprises a pH adjusting agent so that the pH is from about 9 to about 11. According to claim 1,
The seed layer is made of copper (Cu), tin (Sn), nickel (Ni), iron (Fe), aluminum (Al), zinc (Zn), sodium (Na), calcium (Ca), and magnesium (Mg). Method for manufacturing a glass substrate structure, characterized in that at least one selected from the group consisting of. According to claim 1,
The method of manufacturing a glass substrate structure, characterized in that the thickness of the bulk layer is about 2.0 ㎛ to about 10 ㎛. forming an adhesion promoter layer on the entire upper surface of the glass substrate;
forming a seed layer of a first metal on the surface of the adhesion promoter;
forming a mask layer having a pattern on the seed layer;
etching the seed layer to form a patterned seed layer corresponding to the pattern;
about 0.5 g/l to about 8 g/l of metal ions of the second metal to form a bulk layer of the second metal on the seed layer; from about 0.01 M to about 1.0 M reducing agent; and from about 0.05 M to about 1.0 M of a complexing agent; and
removing the mask layer;
Method for manufacturing a metallized substrate comprising a. According to claim 11,
The method of manufacturing a wiring board, characterized in that the removing of the mask layer is performed after the etching of the seed layer and before the applying of the bulk mixture. According to claim 12,
The method of manufacturing a wiring board, characterized in that the surface of the bulk layer comprises a curved surface extending along the patterned seed layer. According to claim 11,
The step of applying the mixture for bulking is performed after the step of forming the seed layer and before the step of etching the seed layer,
In the step of forming the mask layer on the seed layer, the mask layer is formed on the seed layer with the bulk layer interposed therebetween. 15. The method of claim 14,
The method of manufacturing a wiring board, characterized in that the removing of the mask layer is performed after the etching of the seed layer. 15. The method of claim 14,
Etching the seed layer comprises:
etching the bulk layer using the mask layer as an etching mask; and
forming a patterned seed layer using the bulk layer as an etching mask;
A method for manufacturing a wiring board comprising a. According to claim 11,
The manufacturing method of the wiring board, characterized in that it further comprises the step of acid-treating the surface of the seed layer prior to the step of applying the bulk mixture. 18. The method of claim 17,
The manufacturing method of the wiring board, characterized in that it further comprises the step of alkali cleaning the surface of the seed layer after the step of acid treatment and before the step of applying the bulk mixture. According to claim 11,
The manufacturing method of the wiring board, characterized in that the average grain size of the bulk layer is larger than the average grain size of the seed layer. forming an adhesion promoter layer on the surface of the glass substrate to a thickness of about 30 nm to about 150 nm by sputtering;
forming a seed layer of a first metal on the surface of the adhesion promoter to a thickness of about 300 nm to about 700 nm by sputtering;
acid-treating the surface of the seed layer with an aqueous solution of an inorganic acid;
alkali cleaning the surface of the seed layer; and
forming a bulk layer of a second metal to a thickness of about 2.0 μm to about 10 μm on the seed layer through an autocatalytic reaction;
including,
Forming the bulk layer comprises:
from about 0.5 g/l to about 8 g/l of the metal ion of the second metal;
from about 0.01 M to about 1.0 M reducing agent; and
from about 0.05 M to about 1.0 M complexing agent;
Applying a bulking mixture containing
The first metal and the second metal are each independently copper (Cu), tin (Sn), nickel (Ni), iron (Fe), aluminum (Al), zinc (Zn), sodium (Na), calcium ( Ca), and magnesium (Mg), wherein the first metal has a standard reduction potential lower than or equal to the standard reduction potential of the second metal. and wherein the second metal is selected. 21. The method of claim 20,
Method for manufacturing a glass substrate structure, characterized in that the catalyst layer is not interposed between the glass substrate and the bulk layer.

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