KR100509865B1 - Surface Activation Method for Silver Electroless Plating - Google Patents
Surface Activation Method for Silver Electroless Plating Download PDFInfo
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- KR100509865B1 KR100509865B1 KR10-2003-0015226A KR20030015226A KR100509865B1 KR 100509865 B1 KR100509865 B1 KR 100509865B1 KR 20030015226 A KR20030015226 A KR 20030015226A KR 100509865 B1 KR100509865 B1 KR 100509865B1
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Abstract
본 발명은 은 무전해 도금(Ag electroless plating)을 위한 표면 활성화 방법에 관한 것으로서, 은 무전해 도금 전에 피도금재의 표면을 촉매로서 활성화시키는 방법에 있어서, 상기 촉매로서 금(Au)을 사용하는 것을 특징으로 하며, 이에 따라 접합성, 저항 측면 등에서 우수한 도금 특성을 나타내고, 박막의 배선용으로 사용시 신뢰도를 향상시키는 현저한 효과가 달성되게 된다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface activation method for Ag electroless plating, wherein a method of activating the surface of a plated material as a catalyst prior to silver electroless plating, wherein gold (Au) is used as the catalyst. As a result, a remarkable effect of exhibiting excellent plating characteristics in terms of bonding properties, resistance, and the like, and improving reliability in use for thin film wiring is achieved.
Description
본 발명은 은 무전해 도금(Ag electroless plating)을 위한 표면 활성화 방법에 관한 것이다. 더욱 상세하게는 은 무전해 도금 전에 피도금재의 표면을 활성화시키기 위한 촉매로서 종래의 팔라듐(Pd)이나 은(Ag) 대신에 금(Au)을 사용하여 이후 증착되는 은의 뭉침 현상을 방지함으로써, 배선용으로 사용 가능한 얇은 두께의 우수한 은 박막을 얻도록 하는 은 무전해 도금을 위한 표면 활성화 방법에 관한 것이다.The present invention relates to a surface activation method for Ag electroless plating. More specifically, by using gold (Au) instead of conventional palladium (Pd) or silver (Ag) as a catalyst for activating the surface of the plated material before silver electroless plating, it is possible to prevent the agglomeration of silver deposited subsequently. The present invention relates to a surface activation method for silver electroless plating to obtain an excellent thin film of thin thickness that can be used.
일반적으로, 은 무전해 도금(Ag electroless plating)은 도금 용액 내에서 환원제의 산화에 의해 발생된 전자를 이용하여 은 이온을 환원시켜 증착시키는 방법으로, 이러한 은 무전해 도금을 실시하기 위해서는 우선 표면에 환원제를 산화시키기 위한 촉매가 증착되어 있어야 한다.Generally, silver electroless plating is a method of reducing and depositing silver ions using electrons generated by oxidation of a reducing agent in a plating solution. A catalyst must be deposited to oxidize the reducing agent.
이러한 촉매로는 팔라듐(Pd)이나 은(Ag)이 통상적으로 사용되고, 치환반응을 통해 증착된다.As such a catalyst, palladium (Pd) or silver (Ag) is commonly used and is deposited through a substitution reaction.
그러나, 팔라듐이나 은을 사용하여 표면을 활성화시킨 후, 무전해 도금 방식으로 은을 증착하면, 도 1a, 1b, 2a 및 2b에서 보여지는 바와 같이, 증착된 은이 서로 뭉치는 현상(agglomeration)이 발생되게 된다.However, after activating the surface using palladium or silver, and depositing silver by electroless plating, as shown in FIGS. 1A, 1B, 2A, and 2B, agglomeration of the deposited silver occurs (agglomeration). Will be.
이와 같이, 3차원적으로 성장하거나 뭉침 현상이 일어나면, 얇은 박막 형태의 은을 얻을 수 없을 뿐만 아니라, 이렇게 증착된 은은 덩어리간 연결 상태도 미약하여 배선용으로 증착된 은을 사용하는 경우, 전기가 잘 통하지 않는다.As such, when three-dimensional growth or agglomeration occurs, not only a thin thin film of silver can be obtained, but the deposited silver also has a weak connection state between the agglomerates, and thus, when the silver deposited for wiring is used, Does not work
그러나, 초고밀도 집적 회로(ultra-large scale integration; ULSI)나 TFT-LCD(thin film transistor-liquid crystal display)에서 은을 배선용으로 사용하기 위해서는 얇은 박막 형태로 증착시키는 것이 필수적이다.However, in order to use silver for wiring in ultra-large scale integration (ULSI) or thin film transistor-liquid crystal display (TFT-LCD), it is essential to deposit thin films.
상기와 같은 문제점을 해결하기 위하여 본 발명은, 촉매로서 금(Au)을 사용하여 표면을 활성화시킴으로써 이후 증착되는 은의 뭉침 현상을 방지하여 배선용이나 은 전해 도금을 위한 시드층(seed layer)으로 사용할 수 있는 얇은 은 박막을 얻도록 하는 은 무전해 도금을 위한 표면 활성화 방법을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention can be used as a seed layer for wiring or silver electroplating by preventing the aggregation of silver deposited by activating the surface by using gold (Au) as a catalyst. It is an object of the present invention to provide a surface activation method for silver electroless plating to obtain a thin thin silver film.
본 발명의 상기 목적 및 기타 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
상기와 같은 목적을 달성하기 위하여 본 발명은, 은(Ag) 무전해 도금 전에 피도금재의 표면을 촉매로서 활성화시키는 방법에 있어서, 상기 촉매로서 금(Au)을 사용하는 것을 특징으로 하는 은 무전해 도금을 위한 표면 활성화 방법을 제공한다.In order to achieve the above object, the present invention provides a method of activating the surface of a plated material as a catalyst before silver (Ag) electroless plating, wherein the silver (Au) is used as the catalyst. Provided is a method of surface activation for plating.
바람직하게, 상기 촉매로서 금을 사용하기 위하여, 0.01~0.5g/ℓ 염화금 및 0.1~10㎖/ℓ 불산을 포함하는 금 활성화 용액에서 상기 피도금재의 표면을 반응시키게 된다.Preferably, in order to use gold as the catalyst, the surface of the plated material is allowed to react in a gold activation solution containing 0.01-0.5 g / l gold chloride and 0.1-10 ml / l hydrofluoric acid.
이하, 본 발명에 대하여 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따르면, 은 무전해 도금(Ag electroless plating)을 위한 촉매로서 금(Au)을 사용하며, 이러한 금의 물성을 다른 금속들과 비교하여 하기 표 1에 나타낸다.According to the present invention, silver (Au) is used as a catalyst for silver electroless plating, and the physical properties of such gold are shown in Table 1 below in comparison with other metals.
상기 표 1에 나타낸 바와 같이, 금은 다른 금속에 비해 은(Ag)과 결정 구조 및 격자 상수가 상당히 유사하고, 비저항도 은이나 구리(Cu)보다는 높지만 다른 금속들에 비해 훨씬 낮은 것을 알 수 있다.As shown in Table 1, gold has a very similar crystal structure and lattice constant with silver (Ag) than other metals, and has a higher resistivity than silver or copper (Cu), but much lower than other metals. .
이와 같이, 금은 은과 구조가 비슷하기 때문에 금 표면 위에서 은은 덩어리 형태인 3차원 성장을 하는 것이 아니라 막 형태인 2차원 형태로 성장할 수 있어, 종래의 뭉침 현상(agglomeration)이 발생되지 않게 되고, 이에 따라 두께를 낮추면서도 표면 거칠기가 상당량 감소되어 배선용으로 사용시 배선 역할을 원활히 수행할 수 있도록 한다.As such, since gold has a similar structure to silver, silver can grow on a gold surface in a two-dimensional form, instead of a lump-like three-dimensional growth, so that agglomeration does not occur in the related art. Accordingly, the surface roughness is significantly reduced while lowering the thickness so that the wiring role can be smoothly performed when used for wiring.
그리고, 금의 경우에는 대기 중에 노출되어도 산화되지 않기 때문에 은과 금 사이의 계면간 산화물에 의한 불순물 문제도 발생되지 않아 접합성과 저항 측면에서 상당한 개선 효과를 얻을 수 있게 된다.In addition, since gold is not oxidized even when exposed to the air, the impurity problem caused by the interfacial oxide between silver and gold does not occur, and a significant improvement in bonding and resistance can be obtained.
또한, 금의 상대적으로 낮은 비저항은 배선용으로 사용할 경우, 비저항에서 큰 제약 요소가 되지 않는 장점을 제공한다.In addition, the relatively low resistivity of gold offers the advantage of not being a significant constraint on resistivity when used for wiring.
나아가, 금은 환원 전위가 상대적으로 높기 때문에, 용이하게 피도금재 표면과의 치환 반응을 통해 금속 상태로 증착될 수 있는 장점이 있다.Furthermore, since gold has a relatively high reduction potential, there is an advantage that it can be easily deposited in a metal state through a substitution reaction with the surface of the plated material.
이하, 하기의 실시예를 통하여 본 발명을 더욱 상세히 설명하지만, 본 발명의 범위가 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.
[실시예]EXAMPLE
은 무전해 도금을 하기 위한 기판으로는 실리콘 위에 티타늄과 질화 티타늄이 각각 15㎚, 10㎚ 증착된 것을 사용하였다. 이러한 기판 위에 금을 증착하기 앞서, 표면 위에 존재하는 산화 티타늄을 제거하기 위해 1% 불산 용액에서 10분간 식각(etching)하였다.As substrates for silver electroless plating, titanium and titanium nitride were deposited on silicon at 15 nm and 10 nm, respectively. Prior to depositing gold on this substrate, it was etched in 1% hydrofluoric acid solution for 10 minutes to remove titanium oxide present on the surface.
그리고, 0.2g/ℓ 염화금, 5㎖/ℓ 50% 불산이 포함되어 있는 금 활성화 용액 내에서 기판을 1분 동안 반응시켰다. 그 결과로서, 도 3에 금을 증착시킨 질화 티타늄 표면에 대한 주사전자현미경(scanning electron microscopy; SEM) 사진을 나타내며, 이를 참조하면, 활성화 과정을 통해 증착된 금은 전 표면에 걸쳐 균일하게 증착되었음을 확인할 수 있고, 각각의 핵 크기는 대략 40㎚ 정도이었다.The substrate was reacted for 1 minute in a gold activation solution containing 0.2 g / l gold chloride and 5 ml / l 50% hydrofluoric acid. As a result, a scanning electron microscopy (SEM) image of the titanium nitride surface on which gold was deposited is shown in FIG. 3, and referring to this, gold deposited through the activation process was uniformly deposited over the entire surface. As confirmed, each nucleus size was approximately 40 nm.
이후, 이러한 표면 위에 은을 무전해 도금 방식으로 증착시켰다.Thereafter, silver was deposited on this surface by electroless plating.
도 4는 은 무전해 도금을 실시한 후의 표면(a)과 그 단면(b)에 대한 주사전자현미경 사진으로서, 표면을 살펴보면, 덩어리로 뭉쳐져 있는 현상을 발견할 수 없고, 균일한 막 형태로 도금층이 형성되었음을 확인할 수 있다. 그리고, 단면의 경우에도 팔라듐이나 은을 활성화시킨 경우와 달리 덩어리 사이의 경계면이 존재하지 않았다. 이때의 막 두께는 약 170㎚이었고, 비저항은 측정 결과 약 2.4μΩ·㎝로 매우 우수한 특성을 나타내었다.4 is a scanning electron micrograph of the surface (a) and its cross section (b) after silver electroless plating. Looking at the surface, it is not possible to find a phenomenon in which agglomerations are formed. It can be confirmed that formed. Also, in the case of the cross section, there was no interface between the lumps, unlike the case where palladium or silver were activated. At this time, the film thickness was about 170 nm, and the specific resistance was about 2.4 μΩ · cm, which was very excellent.
이상에서 설명한 바와 같이 본 발명에 의한 은 무전해 도금을 위한 표면 활성화 방법은, 접합성, 저항 측면 등에서 우수한 도금 특성을 나타내고, 박막의 배선용으로 사용시 신뢰도를 향상시키는 현저한 효과가 있는 유용한 발명인 것이다.As described above, the surface activation method for silver electroless plating according to the present invention is a useful invention that exhibits excellent plating characteristics in terms of bonding properties, resistance, and the like, and has a remarkable effect of improving reliability when used for wiring of thin films.
상기에서 본 발명은 기재된 구체예를 중심으로 상세히 설명되었지만, 본 발명의 범주 및 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다. While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.
도 1a는 종래의 팔라듐(Pd)을 촉매로 하여 은 무전해 도금을 실시한 표면을 보여 주는 주사전자현미경 사진이다.1A is a scanning electron micrograph showing a surface of silver electroless plating using a conventional palladium (Pd) as a catalyst.
도 1b는 종래의 팔라듐(Pd)을 촉매로 하여 은 무전해 도금을 실시한 표면의 단면(b)을 보여 주는 주사전자현미경 사진이다.FIG. 1B is a scanning electron micrograph showing a cross section (b) of a surface subjected to silver electroless plating using a conventional palladium (Pd) as a catalyst.
도 2a는 종래의 은(Ag)을 촉매로 하여 은 무전해 도금을 실시한 표면을 보여 주는 주사전자현미경 사진이다.FIG. 2A is a scanning electron micrograph showing a surface of silver electroless plating using a conventional silver (Ag) as a catalyst.
도 2b는 종래의 은(Ag)을 촉매로 하여 은 무전해 도금을 실시한 표면의 단면을 각각 보여 주는 주사전자현미경 사진이다.FIG. 2B is a scanning electron micrograph showing a cross section of a surface subjected to silver electroless plating using a conventional silver (Ag) as a catalyst.
도 3은 본 발명에 따라 금(Au) 활성화 용액을 통해 촉매로서 금을 증착시킨 질화 티타늄 표면을 보여 주는 주사전자현미경 사진이다.3 is a scanning electron micrograph showing a titanium nitride surface on which gold was deposited as a catalyst through a gold (Au) activation solution in accordance with the present invention.
도 4a는 본 발명에 따라 금(Au)을 촉매로 하여 은 무전해 도금을 실시한 표면을 보여 주는 주사전자현미경 사진이다.4A is a scanning electron micrograph showing a surface of silver electroless plating using gold (Au) as a catalyst according to the present invention.
도 4b는 본 발명에 따라 금(Au)을 촉매로 하여 은 무전해 도금을 실시한 표면의 단면을 보여 주는 주사전자현미경 사진이다.4B is a scanning electron micrograph showing a cross section of a surface subjected to silver electroless plating using gold (Au) as a catalyst according to the present invention.
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|---|---|---|---|---|
| JPH07316826A (en) * | 1994-05-12 | 1995-12-05 | Glaverbel Sa | Method of forming silver coating film on glass substrate |
| JP2001335858A (en) * | 2000-05-26 | 2001-12-04 | Ishikawajima Harima Heavy Ind Co Ltd | Method for treating high activity material |
| KR20030017694A (en) * | 2001-08-21 | 2003-03-04 | 삼성전자주식회사 | Method for forming metal interconnections using electroless plating |
-
2003
- 2003-03-11 KR KR10-2003-0015226A patent/KR100509865B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07316826A (en) * | 1994-05-12 | 1995-12-05 | Glaverbel Sa | Method of forming silver coating film on glass substrate |
| JP2001335858A (en) * | 2000-05-26 | 2001-12-04 | Ishikawajima Harima Heavy Ind Co Ltd | Method for treating high activity material |
| KR20030017694A (en) * | 2001-08-21 | 2003-03-04 | 삼성전자주식회사 | Method for forming metal interconnections using electroless plating |
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| KR20040080464A (en) | 2004-09-20 |
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