KR101571843B1

KR101571843B1 - Nano etching composition for improving the surface adhension

Info

Publication number: KR101571843B1
Application number: KR1020150089606A
Authority: KR
Inventors: 진정복; 이지현; 이진규
Original assignee: 진정복
Priority date: 2015-06-24
Filing date: 2015-06-24
Publication date: 2015-11-25

Abstract

The present invention relates to sulfuric acid; Hydrogen peroxide; Azole-based compounds; Cyclohexylamine; And the balance water; And the azole-based compound is selected from the group consisting of 5-aminotetrazole; And at least one selected from benzotriazole, pyrazole, 3-aminotriazole and sulfathiazole; The present invention relates to a nano-etching composition for use in soft etching when a printed circuit board is manufactured. In this case, the etching amount of the copper surface to be etched is reduced to minimize the loss of the copper film and improve the surface adhesion of the dry film to the copper substrate. .

Description

[0001] NANO ETCHING COMPOSITION FOR IMPROVING THE SURFACE ADHENSION [0002]

The present invention relates to an etching composition for soft etching performed during circuit formation in a manufacturing process of a printed circuit board, and more particularly, to a nano etching composition capable of improving the surface adhesion of a metal for a printed circuit board.

The technique of etching copper or copper alloy is used in a wide range of fields and is an indispensable technology in the manufacture of electronic and electric parts such as ornaments, resource recovery, semiconductor manufacturing, and printed wiring board manufacturing. Etching may be performed to remove contaminants or oxide films on the surface of copper or copper alloy, to planarize irregularities on the surface of copper or copper alloy, to form a protective film on the surface of copper or copper alloy, For dissolving and removing copper or copper alloy exposed portions which are not covered with a protective film, for dissolving copper or copper alloy on the substrate, for adhering a resist or the like for roughening the surface of copper or copper alloy And the like. Among them, soft etching is an etching method used for forming irregularities on the surface of copper to adhere a resist such as a dry film. In general, the etchant used to soft-etch is a hydrogen peroxide-sulfuric acid solution, which may additionally contain various additives to improve etching.

When a resist such as a photosensitive dry film is brought into close contact with a copper substrate by roughening the copper surface in the manufacture of a printed circuit board, the adhesion of the dry film to the copper substrate must be high enough to effectively form a circuit on the substrate. Accordingly, when the copper surface is etched using a soft etching solution to form irregularities, the surface area is widened, so that the adhesion of the resist such as the photosensitive dry film can be enhanced.

However, since the etching is performed several times in the process of manufacturing the printed circuit board, the etching amount of the copper surface is increased, which causes a problem that the thickness of the copper substrate film becomes thin. Further, in attaching the dry film to the copper substrate prior to the circuit formation of the printed circuit board, it is necessary to further improve the surface adhesion.

It is an object of the present invention to solve the above-mentioned problems, and it is an object of the present invention to provide a soft etching composition, which is formulated with a proper composition, and which, when used in the surface treatment of a copper substrate for attaching a dry film in a printed circuit board manufacturing process, Which is capable of reducing the etching amount and improving the surface adhesion force of the nano-etching composition.

According to one aspect of the present invention, sulfuric acid; Hydrogen peroxide; Azole-based compounds; Cyclohexylamine; And the balance water; Wherein the azole-based compound is selected from the group consisting of 5-aminotetrazole; And at least one selected from benzotriazole, pyrazole, 3-aminotriazole and sulfathiazole; .

Preferably, the nano-etching composition comprises 100 parts by weight of cyclohexylamine; 30 to 400 parts by weight of an azole-based compound; 1,500 to 2,500 parts by weight of sulfuric acid; 2,000 to 3,000 parts by weight of hydrogen peroxide; And the balance water; . &Lt; / RTI >

Preferably, the nanoetching composition may further comprise polyethylene glycol.

100 to 500 parts by weight of polyethylene glycol may be contained relative to 100 parts by weight of the cyclohexylamine.

The polyethylene glycol may have a number average molecular weight (Mn) of 100 to 5,000.

The benzotriazole may be contained in an amount of 200 to 600 parts by weight based on 100 parts by weight of the 5-aminotetrazole.

The pyrazole may be contained in an amount of 200 to 2,000 parts by weight based on 100 parts by weight of the 5-aminotetrazole.

Aminotriazole may be included in an amount of 20 to 100 parts by weight based on 100 parts by weight of the 5-aminotetrazole.

The sulfathiazole may be contained in an amount of 100 to 600 parts by weight based on 100 parts by weight of the 5-aminotetrazole.

The nanoetching composition may further comprise copper powder.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing a copper substrate (step a); And a step (b) of preparing a copper substrate having a surface irregularity by surface-treating the copper substrate with the nano-etching composition of claim 1; Is provided.

Step a: The copper substrate may be previously degreased and washed by washing with water.

And washing and drying the copper substrate after step b.

According to another aspect of the present invention, there is provided a method of manufacturing a printed circuit board including the nano etching method.

TECHNICAL FIELD The present invention relates to an etching composition for soft-etching a metal and, when used in the surface treatment of a copper substrate for attaching a dry film in a printed circuit board manufacturing process, reduces the amount of etching of the copper surface to be etched, And the surface adhesion of the dry film to the copper substrate can be improved.

FIG. 1 shows an SEM image of the surface of a sample etched with the nano-etching composition prepared according to Examples 1 to 4. FIG.
FIG. 2 is a SEM image of the surface of a sample etched with the nano-etching composition prepared according to Examples 5 to 9. FIG.
3 is an SEM image of the surface of a sample etched with the etching composition prepared according to Comparative Examples 1 to 3. FIG.

The invention is capable of various modifications and may have various embodiments, and particular embodiments are exemplified and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Furthermore, terms including an ordinal number such as first, second, etc. to be used below can be used to describe various elements, but the constituent elements are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

Also, when an element is referred to as being "formed" or "laminated" on another element, it may be directly attached or laminated to the front surface or one surface of the other element, It will be appreciated that other components may be present in the < / RTI >

The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, the nano-etching composition for improving the surface adhesion of the present invention will be described.

The present invention relates to sulfuric acid; Hydrogen peroxide; Azole-based compounds; Cyclohexylamine; And the balance water; Wherein the azole-based compound is selected from the group consisting of 5-aminotetrazole; And at least one selected from benzotriazole, pyrazole, 3-aminotriazole and sulfathiazole; .

Wherein the nano-etching composition comprises: 100 parts by weight of cyclohexylamine; 30 to 400 parts by weight of an azole-based compound; 1,500 to 2,500 parts by weight of sulfuric acid; 2,000 to 3,000 parts by weight of hydrogen peroxide; And the balance water; . &Lt; / RTI >

The nanoetching composition may further comprise polyethylene glycol.

The polyethylene glycol may be contained in an amount of 100 to 500 parts by weight based on 100 parts by weight of cyclohexylamine.

The polyethylene glycol may serve as a surfactant to remove oxides on the copper surface and lower the surface tension of the etchant.

The number average molecular weight of the polyethylene glycol may preferably be 120 to 4,000, more preferably 150 to 2,000.

The hydrogen peroxide is used as a main oxidizing agent for copper.

The sulfuric acid may serve as a co-oxidant for copper.

As the auxiliary oxidizing agent that can be used in place of the sulfuric acid, an inorganic acid, an organic acid, or a mixture thereof may be used alone or in combination. In addition to sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid may be used.

The azole compound may function as an etch inhibitor.

The cyclohexylamine can be used as an etching inhibitor like azole compounds to improve the surface roughness of the copper film by controlling the etching rate.

The nano-etching composition may further comprise copper powder.

The nano-etching method using the nano-etching composition of the present invention can be performed by the following process.

first. A copper substrate is prepared (step a).

A step of cleaning the copper substrate by degreasing and washing with water before step a may be further performed.

Next, the copper substrate is treated with the nano-etching composition of claim 1 By surface treatment Thereby producing a copper substrate having unevenness on its surface (step b).

After the step (b), the copper substrate may further be washed and dried.

The nano-etching of the present invention corresponds to a process corresponding to soft etching in the process of manufacturing a printed circuit board. Specifically, the printed circuit board process requires a process of attaching a dry film, which is an infrared photosensitive polymer film, to the substrate surface in order to pattern a circuit on a printed circuit board. At this time, the soft etching is a pretreatment process performed before the dry film adheres to the substrate to increase the adhesion of the dry film to the substrate. Therefore, when the soft etch is performed using a soft etchant, fine irregularities are formed on the copper surface to increase adhesion of the dry film to be patterned and to remove contaminants. In general, a solution containing hydrogen peroxide-sulfuric acid as a soft etchant is used, and an etching inhibitor and a stabilizer that adjust the etching rate can be added to the solution so that the etching can be effectively performed. Therefore, when the soft etching is performed using the nano-etching composition of the present invention, the adhesion of the dry film to the copper surface can be further improved by effectively forming irregularities on the surface of the copper substrate to widen the surface area.

The present invention provides a method of manufacturing a printed circuit board including the above-described nanoetching method.

Since the etching process related to circuit formation performed after the nanoetching is performed according to a conventionally known method, a description thereof will be omitted.

[Example]

Preferred embodiments of the nano-etching composition and the etching method using the nano-etching composition to be used in the present invention are described below, but the present invention is not limited thereto.

Example 1

0.25 g of 5-aminotetrazole, 1 g of benzotriazole, 0.1 g of 3-aminotriazole, 2 g of cyclohexylamine and 10 g of sulfuric acid (98%) were dissolved in 100 mL of water to prepare an etching additive. A mixed solution was prepared by adding an etching additive, sulfuric acid (98%), hydrogen peroxide and the remaining amount of water so that the concentration of the above etching additive, 5 wt% of sulfuric acid (98%) and hydrogen peroxide of 5 wt% 10 g of copper particles per liter of the solution were added to prepare a nano-etching composition.

Example 2

Except for using an etching additive containing 0.25 g of 5-aminotetrazole, 1 g of benzotriazole, 0.2 g of 3-aminotriazole, 2 g of cyclohexylamine and 10 g of sulfuric acid (98%) instead of the etching additive of Example 1 A nano-etching composition was prepared in the same manner as in Example 1.

Example 3

Except that an etching additive including 0.25 g of 5-aminotetrazole, 1 g of pyrazole, 2 g of cyclohexylamine and 10 g of sulfuric acid (98%) was used instead of the etching additive of Example 1, To prepare an etching composition.

Example 4

Except that an etching additive containing 0.25 g of 5-aminotetrazole, 2 g of pyrazole, 2 g of cyclohexylamine and 10 g of sulfuric acid (98%) was used instead of the etching additive of Example 1, To prepare an etching composition.

Example 5

Except for using an etching additive containing 0.25 g of 5-aminotetrazole, 4 g of pyrazole, 1 g of sulfathiazole, 2 g of cyclohexylamine, and 10 g of sulfuric acid (98%) instead of the etching additive of Example 1 To prepare a nano-etching composition.

Example 6

Except that the etching additive of Example 1 was replaced by 0.25 g of 5-aminotetrazole, 1 g of benzotriazole, 2 g of pyrazole, 0.1 g of 3-aminotriazole, 0.4 g of sulfur thiazole, 5 g of polyethylene glycol (weight average molecular weight Mw = 200) , 2 g of cyclohexylamine and 10 g of sulfuric acid (98%) was used instead of the etching additive.

Example 7

Except that the etching additive of Example 1 was replaced by 0.25 g of 5-aminotetrazole, 1 g of benzotriazole, 2 g of pyrazole, 0.1 g of 3-aminotriazole, 0.4 g of sulfur thiazole, 5 g of polyethylene glycol (weight average molecular weight Mw = 600) , 2 g of cyclohexylamine, and 10 g of sulfuric acid (98%) were used in place of the etching additive.

Example 8

Except that the etching additive of Example 1 was replaced by 0.25 g of 5-aminotetrazole, 1 g of benzotriazole, 2 g of pyrazole, 0.1 g of 3-aminotriazole, 0.4 g of sulfur thiazole, 5 g of polyethylene glycol (weight average molecular weight Mw = 800) , 2 g of cyclohexylamine, and 10 g of sulfuric acid (98%) were used in place of the etching additive.

Example 9

Except that an etching additive containing 0.25 g of 5-aminotetrazole, 1 g of benzotriazole, 2 g of cyclohexylamine, and 10 g of sulfuric acid (98%) was used instead of the etching additive of Example 1 To prepare a nano-etching composition.

Comparative Example 1

4 wt% of sulfuric acid (98%), and 5 wt% of hydrogen peroxide to prepare a mixed solution, and 10 g of copper particles per 1 L of the mixed solution were added to prepare a nano-etching composition.

Comparative Example 2

A nano-etching composition was prepared in the same manner as in Example 1, except that an etching additive containing 2 g of cyclohexylamine and 10 g of sulfuric acid (98%) was used instead of the etching additive of Example 1.

Comparative Example 3

Except that an etching additive containing 0.25 g of 5-aminotetrazole, 2 g of cyclohexylamine, and 10 g of sulfuric acid (98%) was used instead of the etching additive of Example 1, and the nano-etching composition was prepared in the same manner as in Example 1 .

Table 1 and Table 2 summarize the component contents of the etching compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 of the present invention. Table 1 summarizes the components of the etching additive contained in the etching composition, and Table 2 summarizes the components of the total etching composition.

division

Etching additive
5-Aminotetrazole (g)
Benzotriazole (g)
Pyrazole (g)

3-Aminotriazole (g)
Sulfur thiazole (g)
Polyethylene glycol (g)
Cyclohexylamine (g)

Sulfuric acid (g)

Hydrogen peroxide (g)

200 (Mn) 600 (Mn) 1,000 (Mn) Example 1 0.25 One - 0.1 - - - - 2 10 - Example 2 0.25 One - 0.2 - - - - 2 10 - Example 3 0.25 - One - - - - - 2 10 - Example 4 0.25 - 2 - - - - - 2 10 - Example 5 0.25 - 4 - One - - - 2 10 - Example 6 0.25 One 2 0.1 0.5 5 - - 2 10 - Example 7 0.25 One 2 0.1 0.5 - 5 - 2 10 - Example 8 0.25 One 2 0.1 0.5 - - 5 2 10 - Example 9 0.25 One - - - - - - 2 10 - Comparative Example 1 - - - - - - - - - - - Comparative Example 2 - - - - - - - - 2 10 - Comparative Example 3 0.25 - - - - - - - 2 10 -

division
Etching composition Etching additive (wt%) 98% sulfuric acid (wt%) Hydrogen peroxide (wt%) Copper particles (g / L)
water Example 1 5 3 5 10 Residual water Example 2 5 3 5 10 Residual water Example 3 5 3 5 10 Residual water Example 4 5 3 5 10 Residual water Example 5 5 3 5 10 Residual water Example 6 5 3 5 10 Residual water Example 7 5 3 5 10 Residual water Example 8 5 3 5 10 Residual water Example 9 5 3 5 10 Residual water Comparative Example 1 0 4 5 10 Residual water Comparative Example 2 5 3 5 10 Residual water Comparative Example 3 5 3 5 10 Residual water

[Test Example]

Test Example 1: Scanning Electron Microscope, SEM ) Surface analysis of specimen after etching through image

A specimen with thickness of 17 ㎛ and width of 10 ㎝ x 10 ㎝ was prepared.

FIGS. 1 and 2 show SEM images of the surface of a sample etched with the etching compositions of Examples 1 to 4 and Examples 5 to 9, respectively, and FIG. 3 shows the SEM image of the sample etched with the compositions of Comparative Examples 1 to 3 SEM image of the surface. It can be seen that the surface of the etched sample using the compositions of Examples 1 to 9 was relatively more irregular than the surface of the etched sample using the compositions of Comparative Examples 1 to 3. Therefore, the nano-etching composition prepared by the technique of the present invention is considered to be effective for increasing the roughness of the copper surface.

In addition, since the etching composition of the present invention commonly contains an azole compound, it is judged to affect the formation of surface roughness, and the surface roughness and adhesion can be controlled by suitably controlling the composition of the azole compound contained in the etching composition .

Test Example 3: Guri city convenience Measurement of etching amount

A copper specimen (15 cm × 10 cm long) was etched for 60 seconds with the etching compositions of Example 1 and 9 and Comparative Examples 1 to 3, and the amount of etching was measured and shown in Table 3 below.

Specifically, the copper specimen was etched with a spray etching apparatus, washed with water, dried, and then weighed. The etching amount was calculated by using the following equation (1).

[Formula 1]

Etching amount (μm) = (weight of specimen before etching - weight (g) of specimen after etching) x 10,000 / {width of specimen x length (cm) x 2 (both sides) x specific gravity of copper}

Referring to Table 3 below, it can be seen that the etching amounts of the copper samples etched with the etching compositions of Examples 1 to 9 are smaller than the etching amounts of the copper wiring portions etched with the etching compositions prepared according to Comparative Examples 1 to 3. Therefore, when the etching composition of the present invention is used, loss of the copper surface can be reduced more than that of the conventional etching composition, so that nano-etching (soft etching) can be effectively performed.

Test Example 4: Measurement of adhesion according to surface profile

In order to comparatively measure the surface adhesion, the copper specimen was etched using the etching compositions of Examples 1 to 9 and Comparative Examples 1 to 3, respectively, so that the surface etching amount of the copper wire (15 cm by 10 cm in width) was 0.3 μm . The adhesion of the dry film to the etched surface of the copper foil was measured using a tensile strength measuring instrument, and the results are shown in Table 3 below.

A 3M tape having a width of 18 mm and a length of 10 cm was attached to each of the etched copper wire pieces, and then the tape was separated with a tensile strength measuring instrument having a cross speed of 50 mm / min. Respectively.

The copper wire treated with the etching compositions of Comparative Examples 1 to 3 had surface adhesion of 416.4 to 600.7 g / f. In contrast, the surface adhesion force of the copper wire treated with the etching composition of Example 8 was 1,030 g / f, which was twice as high as the surface adhesion force of the copper wire treated with the etching composition of Comparative Example 3. Therefore, it was confirmed that when the copper substrate is soft-etched using the nano-etching composition of the present invention, the adhesion of the surface of the copper substrate can be improved as compared with the etching compositions of Comparative Examples 1 to 3.

Test results of Test Examples 3 and 4 are summarized in Table 3 below.

Etching amount (60 seconds) Adhesion (g / f) (based on an etching amount of 0.3 mu m) Example 1 0.35 670 Example 2 0.17 650 Example 3 0.34 650.5 Example 4 0.32 800.3 Example 5 0.35 1,020 Example 6 0.28 1,005 Example 7 0.3 1,025 Example 8 0.32 1,030 Example 9 0.46 805.6 Comparative Example 1 1.1 416.4 Comparative Example 2 0.6 473.3 Comparative Example 3 0.48 600.7

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is possible.

Claims

100 parts by weight of cyclohexylamine;
30 to 400 parts by weight of an azole-based compound;
1,500 to 2,500 parts by weight of sulfuric acid;
2,000 to 3,000 parts by weight of hydrogen peroxide; And
Residual water; / RTI >
The azole-
5-aminotetrazole; And
At least one selected from benzotriazole, pyrazole, 3-aminotriazole and sulfathiazole; &Lt; / RTI >

delete

The method according to claim 1,
Wherein the nanoetching composition further comprises polyethylene glycol. &Lt; RTI ID = 0.0 > 8. < / RTI >

The method of claim 3,
And 100 to 500 parts by weight of polyethylene glycol relative to 100 parts by weight of the cyclohexylamine.

The method of claim 3,
Wherein the polyethylene glycol has a number average molecular weight (Mn) of 100 to 5,000.

The method according to claim 1,
Wherein the benzotriazole is contained in an amount of 200 to 600 parts by weight based on 100 parts by weight of the 5-aminotetrazole.

The method according to claim 1,
Wherein the pyrazole is contained in an amount of 200 to 2,000 parts by weight based on 100 parts by weight of the 5-aminotetrazole.

The method according to claim 1,
Wherein the 3-aminotriazole is contained in an amount of 20 to 100 parts by weight based on 100 parts by weight of the 5-aminotetrazole.

The method according to claim 1,
Wherein the sulfathiazole is contained in an amount of 100 to 600 parts by weight based on 100 parts by weight of the 5-aminotetrazole.

The method according to claim 1,
Wherein the nano-etching composition further comprises copper powder.

Preparing a copper substrate (step a); And
(B) preparing a copper substrate having a surface unevenness by surface-treating the copper substrate with the nano-etching composition of claim 1; To
Containing nano-etching method.

12. The method of claim 11,
Further comprising the step of cleaning the copper substrate by degreasing and washing with water before step a.

12. The method of claim 11,
And washing and drying the copper substrate after step (b).

A method of manufacturing a printed circuit board comprising the nano-etching method of claim 11.