KR20040107546A - an etching solution - Google Patents

an etching solution Download PDF

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Publication number
KR20040107546A
KR20040107546A KR1020030038373A KR20030038373A KR20040107546A KR 20040107546 A KR20040107546 A KR 20040107546A KR 1020030038373 A KR1020030038373 A KR 1020030038373A KR 20030038373 A KR20030038373 A KR 20030038373A KR 20040107546 A KR20040107546 A KR 20040107546A
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copper
chloride
sodium
weight
etching solution
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KR1020030038373A
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Korean (ko)
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이승희
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이승희
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Priority to KR1020030038373A priority Critical patent/KR20040107546A/en
Publication of KR20040107546A publication Critical patent/KR20040107546A/en

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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/16Acidic compositions
    • C23F1/18Acidic compositions for etching copper or alloys thereof
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/02Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067Etchants

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

PURPOSE: To provide an etchant composition for copper or copper alloy which improves productivity with almost no chlorine gas discharge and enhances quality of products also by increasing etching speed. CONSTITUTION: The etchant composition for copper or copper alloy comprises 0.1 to 10 wt.% of one or more oxidizing agents selected from sodium perchlorate, sodium chlorate and sodium hypochlorite; 5 to 15 wt.% of one or more inorganic chlorides selected from potassium chloride, sodium chloride and ammonium chloride; 5 to 15 wt.% of copper (II) chloride dihydrate; 6 to 10 wt.% of hydrochloric acid; and 50 to 80 wt.% of water, wherein the etchant composition has an acidity of 1.5 to 2.5N, specific gravity of 1.27 to 1.32 and copper concentration of 130 to 170 g/L.

Description

구리 또는 구리합금용 에칭액 조성물{an etching solution}Etching solution composition for copper or copper alloy

본 발명은 구리 또는 구리합금용 에칭액 조성물에 관한 것으로서, 보다 상세하게는 에칭속도가 빨라 생산성이 높으면서도 고품질의 제품을 얻을 수 있는 새로운 구성의 구리 또는 구리합금용 에칭액 조성물에 관한 것이다.The present invention relates to an etching solution composition for copper or copper alloy, and more particularly to an etching solution composition for copper or copper alloy of a new configuration that can produce a high-quality product with high productivity due to a high etching rate.

일반적으로 PCB나 리드프레임의 제조시에는 기판을 에칭하여 회로패턴을 형성한다. 이때에는 기판에 회로패턴형상으로 마스크를 인쇄하고 기판을 에칭액으로 에칭하여 회로패턴 이외의 부분을 에칭시켜 제거한다.In general, when manufacturing a PCB or lead frame, the substrate is etched to form a circuit pattern. At this time, a mask is printed on the substrate in the form of a circuit pattern, the substrate is etched with an etchant, and portions other than the circuit pattern are etched and removed.

한편, 에칭액 중에는 과산화수소를 주성분으로 하는 것이 주로 사용되어 있는데, 과산화수소를 주성분으로 하는 에칭액은 에칭속도가 다소 늦어 생산성이 낮을 뿐만 아니라 에칭과정에서 염소가스가 과다배출된다. 따라서 작업환경이 나빠지며, 환경오염도 유발되는 문제점이 있다.On the other hand, the etching liquid mainly contains hydrogen peroxide as the main component, but the etching liquid containing hydrogen peroxide as the main component has a low etch rate, resulting in low productivity and excessive chlorine gas discharge during the etching process. Therefore, the working environment is worse, there is a problem that also causes environmental pollution.

본 발명은 상기의 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 에칭속도가 빨라져서 생산성이 향상되며, 염소가스가 거의 배출되지 않을 뿐만 아니라 제품의 품질도 상승되는 새로운 구성의 구리 또는 구리합금용 에칭액 조성물을 제공하는 것이다.The present invention is to solve the above problems, the object of the present invention is to improve the productivity of the etching rate is faster, the chlorine gas is not discharged as well as the quality of the product of the new composition copper or copper alloy etching solution It is to provide a composition.

도 1은 에칭이 제대로 이루어진 PCB의 구리라인을 보인 단면도1 is a cross-sectional view showing a copper line of the PCB properly etched

도 2의 a와 b는 에칭이 제대로 이루어지지 않은 PCB의 구리라인을 보인 단면도Figure 2a and b is a cross-sectional view showing the copper line of the PCB is not properly etched

본 발명에 따르면, 과염소산나트륨, 염소산나트륨 또는 차아염소산나트륨 중에서 하나 또는 그 이상으로 선택되는 산화제와, 염화칼륨, 염화나트륨 또는 염화암모늄 중에서 하나 또는 그 이상으로 선택되는 무기염화합물과, 염화제이구리와, 염산과 물을 포함하며, 산도가 1.5~2.5N, 비중이 1.27~1.32, 구리농도가 130~170g/L 인 것을 특징으로 하는 구리 또는 구리합금용 에칭액 조성물이 제공된다.According to the present invention, an oxidizing agent selected from one or more of sodium perchlorate, sodium chlorate or sodium hypochlorite, an inorganic salt selected from one or more of potassium chloride, sodium chloride or ammonium chloride, copper chloride and hydrochloric acid And water, an acidity of 1.5 to 2.5N, specific gravity of 1.27 to 1.32 and a copper concentration of 130 to 170 g / L, an etching solution composition for copper or copper alloy is provided.

본 발명의 다른 특징에 따르면, 상기 산화제는 0.1~10중량%, 염산은 6~10중량%, 무기염화물은 5~15중량%, 염화제이구리는 5~15중량%, 물은 50~80중량%로 이루어진 것을 특징으로 하는 구리 또는 구리합금용 에칭액 조성물이 제공된다.According to another feature of the present invention, the oxidizing agent is 0.1 to 10% by weight, hydrochloric acid is 6 to 10% by weight, inorganic chloride is 5 to 15% by weight, copper chloride is 5 to 15% by weight, water is 50 to 80% by weight There is provided an etching solution composition for copper or copper alloy, which is made of%.

1One

이하, 본 발명의 바람직한 실시예를 통해 본 발명을 구체적으로 설명하면 다음과 같다. 본 발명은 산화제와 무기염화합물과 염산과 물로 이루어진 구리 또는 구리합금용 에칭액 조성물이다. 이때 상기 산화제는 과염소산나트륨, 염소산나트륨 또는 차아염소산나트륨 중에서 하나 또는 그 이상으로 선택되며, 무기염화합물은 염화칼륨, 염화나트륨 또는 염화암모늄 중에서 하나 또는 그 이상으로 선택된다. 이러한 본 발명에 의한 에칭액은 산도가 1.5~2.5N이다. 에칭액의 산도는 HCl에 의해 결정되는데, 산도가 2.5N 보다 높은 경우에는 제품 즉, PCB의 품질이 저하될 우려가 높아진다. 즉, PCB의 회로는 도 1에 도시된 바와 같이, 회로를 이루는 구리라인이 상하 동일한 폭을 가지도록 에칭되어야 하나, 에칭이 제대로 되지 않거나 또는 과도하게 에칭된 경우에는 도 2의 a와 같이, 회로를 이루는 구리라인이 하측으로 갈수록 그 면적이 넓어져서 그 단면이 대략 사다리꼴형상을 이루거나 또는 도 2의 b와 같이, 회로를 이루는 구리라인의 양측면이 내측으로 함몰되는 언더컷형상이 발생된다. 그리고 이와 같이 구리라인이 도 2의 a와 같이, 하향으로 갈수록 넓어져서 기판과 접하는 면적이 넓어지면 근접되는 구리라인과 접하게 되어 쇼트가 발생되며, 도 2의 b와 같이 언터컷형상이 발생되면 단선이 되는 등 PCB의 불량이 발생된다. 이와 같이 에칭액의 산도가 2.5N 보다 높은 경우에는 과도하게 에칭되어 도 2의 b와 같은 언더컷현상이 발생된다. 그리고 에칭액의 산도가 1.5N 보다 낮은 경우에는 에칭이 진행됨에 따라 염화제일구리(CuCl)가 생성되어 침전이 생기며, 이에 따라 에칭액의 점도가 상승되어 애칭액의 사용이 불가하게 된다.Hereinafter, the present invention will be described in detail through preferred embodiments of the present invention. The present invention is an etching liquid composition for copper or copper alloy composed of an oxidizing agent, an inorganic salt compound, hydrochloric acid and water. In this case, the oxidizing agent is selected from one or more of sodium perchlorate, sodium chlorate or sodium hypochlorite, the inorganic chlorine compound is selected from one or more of potassium chloride, sodium chloride or ammonium chloride. The etching solution according to the present invention has an acidity of 1.5 to 2.5 N. The acidity of the etching solution is determined by HCl. When the acidity is higher than 2.5N, there is a high possibility that the quality of the product, that is, the PCB, is degraded. That is, the circuit of the PCB should be etched so that the copper lines constituting the circuit have the same widths up and down as shown in FIG. 1, but when the etching is not performed properly or is excessively etched, as shown in FIG. As the copper line forming the lower side becomes wider, the cross section becomes substantially trapezoidal, or as shown in b of FIG. 2, an undercut shape in which both side surfaces of the copper line forming the circuit are recessed inward. As described above, the copper line is widened toward the lower side as shown in a of FIG. 2, and when the area in contact with the substrate is widened, the copper line is in contact with the adjacent copper line, and a short is generated. PCB defects are generated. In this way, when the acidity of the etching solution is higher than 2.5N, the etching is excessively etched, and the undercut phenomenon as shown in b of FIG. 2 occurs. When the acidity of the etching solution is lower than 1.5N, as the etching proceeds, cuprous chloride (CuCl) is generated and precipitation occurs, thereby increasing the viscosity of the etching solution and making it impossible to use the etching solution.

또한, 상기 에칭액은 비중이 1.27~1.32이다. 에칭액의 비중은 구리농도에 의해 가장 큰 영향을 받는데, 비중이 1.32 보다 높은 경우에는 전술한 바와 같은 이유로 제품의 품질이 저하될 우려가 높으며, 비중이 1.27 보다 낮은 경우에는 에칭속도가 느려져서 생산성이 저하될 뿐만 아니라 품질저하도 우려된다.In addition, the etching liquid has a specific gravity of 1.27 to 1.32. The specific gravity of the etching solution is most affected by the copper concentration.If the specific gravity is higher than 1.32, there is a high possibility that the quality of the product will be deteriorated for the same reason as described above. In addition, quality deterioration is a concern.

또, 상기 에칭액은 구리의 농도가 130~170g/L이다. 이러한 구리의 농도는 전술한 비중과 직접적인 관계를 갖는 것으로, 구리의 농도가 상기 수준보다 높은 경우에는 비중이 1.32 보다 높은 경우와 같이, 제품의 품질저하가 우려되며, 구리의 농도가 상기 수준 보다 낮은 경우에는 비중이 1.27보다 낮은 경우와 같이, 에칭속도의 저하 및 품질저하가 우려된다.In addition, the etching solution has a copper concentration of 130 to 170 g / L. This concentration of copper has a direct relationship with the above-described specific gravity, and if the concentration of copper is higher than the above level, such as when the specific gravity is higher than 1.32, deterioration of the product is concerned, and the concentration of copper is lower than the above level. In this case, as in the case where the specific gravity is lower than 1.27, there is a concern that the etching rate decreases and the quality deteriorates.

이상과 같이 에칭액이 상기 수준의 산도와 비중, 구리농도를 유지할 수 있도록 각 성분들의 혼합량이 조절된다. 바람직하게는 산화제는 0.1~10중량%, 염산은 6~10중량%, 무기염화물은 5~15중량%, 염화제이구리는 5~15중량%, 물은 70~80중량% 정도로 혼합된다. 그리고 에칭과정에서도 에칭액을 소정간격으로 모니터하여 에칭액이 상기 수준의 산도과 비중, 구리농도를 유지할 수 있도록 각 성분들이 수시로 첨가된다.As described above, the amount of mixing of the components is controlled so that the etching solution maintains the acidity, specific gravity, and copper concentration of the above levels. Preferably, the oxidizing agent is 0.1 to 10% by weight, hydrochloric acid is 6 to 10% by weight, inorganic chloride is 5 to 15% by weight, copper chloride is 5 to 15% by weight, water is mixed about 70 to 80% by weight. In the etching process, the etching solution is monitored at predetermined intervals so that each component is added at any time so that the etching solution maintains the above acidity, specific gravity, and copper concentration.

이상에서와 같이 본 발명에 의하면, 에칭속도가 빨라져서 생산성이 향상되며, 염소가스가 거의 배출되지 않을 뿐만 아니라 제품의 품질도 상승되는 새로운 구성의 구리 또는 구리합금용 에칭액 조성물이 제공된다. 이러한 본 발명에 의한 에칭액을 사용하여 구리 또는 구리합금을 에칭하는 경우에는 염소가스의 배출이 거의 없으면서도 에칭속도가 빨라져서 생산성향상과 더불어 원가가 절감된다.As described above, according to the present invention, there is provided a etching composition for the copper or copper alloy of a new configuration in which the etching rate is increased, the productivity is improved, and chlorine gas is not almost discharged, and the quality of the product is also increased. In the case of etching copper or copper alloy using the etching solution according to the present invention, the etching speed is increased while generating little chlorine gas, thereby improving productivity and reducing costs.

Claims (2)

과염소산나트륨, 염소산나트륨 또는 차아염소산나트륨 중에서 하나 또는 그 이상으로 선택되는 산화제와, 염화칼륨, 염화나트륨 또는 염화암모늄 중에서 하나 또는 그 이상으로 선택되는 무기염화합물과, 염화제이구리와, 염산과 물을 포함하며, 산도가 1.5~2.5N, 비중이 1.27~1.32, 구리농도가 130~170g/L 인 것을 특징으로 하는 구리 또는 구리합금용 에칭액 조성물.An oxidizing agent selected from one or more of sodium perchlorate, sodium chlorate or sodium hypochlorite, an inorganic chlorine compound selected from one or more of potassium chloride, sodium chloride or ammonium chloride, copper chloride, hydrochloric acid and water; Acidity 1.5-2.5N, specific gravity 1.27-1.32, copper concentration 130-170g / L The etching liquid composition for copper or copper alloys characterized by the above-mentioned. 제1항에 있어서, 상기 산화제는 0.1~10중량%, 염산은 6~10중량%, 무기염화물은 5~15중량%, 염화제이구리는 5~15중량%, 물은 50~80중량%로 이루어진 것을 특징으로 하는 구리 또는 구리합금용 에칭액 조성물.According to claim 1, wherein the oxidizing agent is 0.1 to 10% by weight, hydrochloric acid is 6 to 10% by weight, inorganic chloride is 5 to 15% by weight, copper chloride is 5 to 15% by weight, water is 50 to 80% by weight Etching liquid composition for copper or copper alloy, characterized in that made.
KR1020030038373A 2003-06-13 2003-06-13 an etching solution KR20040107546A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103764874A (en) * 2011-08-31 2014-04-30 东友Fine-Chem股份有限公司 Etchant liquid composition for a metal layer, including copper and titanium
CN109097777A (en) * 2018-09-29 2018-12-28 惠州大亚湾海科发实业有限公司 Wiring board acid environment protection etching solution
CN116641053A (en) * 2023-06-21 2023-08-25 惠州昊化电子材料有限公司 Acidic etching solution and preparation method thereof

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Publication number Priority date Publication date Assignee Title
KR20010044026A (en) * 2000-03-08 2001-06-05 홍성현 Etching composition for copper or copper alloy and method for etching copper or copper alloy using the same
JP2001262373A (en) * 2000-03-24 2001-09-26 Yoshikazu Kobayashi Cupric chloride etching liquid composition
KR20030006809A (en) * 2001-07-16 2003-01-23 (주)오알켐 Composite in order to recycle etchant which can continuously operate and supply, and the supply method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010044026A (en) * 2000-03-08 2001-06-05 홍성현 Etching composition for copper or copper alloy and method for etching copper or copper alloy using the same
JP2001262373A (en) * 2000-03-24 2001-09-26 Yoshikazu Kobayashi Cupric chloride etching liquid composition
KR20030006809A (en) * 2001-07-16 2003-01-23 (주)오알켐 Composite in order to recycle etchant which can continuously operate and supply, and the supply method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103764874A (en) * 2011-08-31 2014-04-30 东友Fine-Chem股份有限公司 Etchant liquid composition for a metal layer, including copper and titanium
CN109097777A (en) * 2018-09-29 2018-12-28 惠州大亚湾海科发实业有限公司 Wiring board acid environment protection etching solution
CN109097777B (en) * 2018-09-29 2021-08-20 惠州大亚湾海科发实业有限公司 Acidic environment-friendly etching solution for circuit board
CN116641053A (en) * 2023-06-21 2023-08-25 惠州昊化电子材料有限公司 Acidic etching solution and preparation method thereof

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