KR20200092688A - Developing Solution Composition and Control system within Reactivity Surfactant for Prevent Scum in PCB Develop process - Google Patents
Developing Solution Composition and Control system within Reactivity Surfactant for Prevent Scum in PCB Develop process Download PDFInfo
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- KR20200092688A KR20200092688A KR1020190009893A KR20190009893A KR20200092688A KR 20200092688 A KR20200092688 A KR 20200092688A KR 1020190009893 A KR1020190009893 A KR 1020190009893A KR 20190009893 A KR20190009893 A KR 20190009893A KR 20200092688 A KR20200092688 A KR 20200092688A
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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Abstract
Description
본 발명은 인쇄회로기판(Printed Circuit Board, PCB)의 현상 공정 중에 발생하는 스컴의 생성을 억제하거나 방지하여 스컴으로 인한 쇼트를 포함하는 불량을 제거할 수 있는 PCB 현상공정에서 스컴 방지를 위한 반응성 계면활성제가 함유된 현상 조성물 및 이의 제어시스템에 관한 것이다. The present invention suppresses or prevents the generation of scum generated during the development process of a printed circuit board (PCB), thereby preventing a scum in a PCB development process that can remove defects including shorts caused by scum. It relates to a developing composition containing an active agent and a control system thereof.
일반적으로 인쇄회로기판(Printed Circuit Board, PCB)은 Photo-lithography 공정을 이용하여 제조하게 된다. Generally, a printed circuit board (PCB) is manufactured using a photo-lithography process.
예를 들면 기판에 드라이필름 레지스트(Dry Film Resist, DFR)를 이용하여 기판에 DFR을 라미네이션을 한다. For example, DFR is laminated to the substrate using a dry film resist (DFR) on the substrate.
DFR이 라미네이션 기판 된 기판을 DFR이 기판에 접착력과 안정화를 위해 열처리 또는 상온에서 15 ~ 30분 방치하며, 회로가 형성된 마스크를 이용하여 노광을 수행한다. The substrate on which the DFR is laminated is left for 15 to 30 minutes at a heat treatment or at room temperature for adhesion and stabilization to the substrate on which the DFR is laminated, and exposure is performed using a mask formed with a circuit.
마스크에는 빛이 통과하는 영역과 비 통과하는 영으로 구분되어 있어, 노광 중에 빛이 통과하여 DFR에 도달하면 광 개시반응을 통해 중합과 가교반응이 발생하게 되므로 중합과 가교반응이 발생한 영역과 미 노광부인 중합과 가교반응이 발생하지 않은 영역으로 나누어진다.The mask is divided into a region through which light passes and a non-passing region. When light passes through and reaches DFR during exposure, polymerization and cross-linking reaction occurs through a photo-initiation reaction, so that polymerization and cross-linking reaction occur and unexposed. It is divided into regions where no gynecological polymerization and crosslinking reaction have occurred.
반응이 발생한 영역과 발생하지 않은 영역은 알카리에서 용해도의 차이가 발생하고 발생된 용해도 차이를 이용하여 선택적으로 DFR 용해하는 과정을 현상공정이라고 하며, 통상 0.6 ~ 1.5 wt%의 탄산나트륨 또는 탄산가리 수용액이 사용된다.In the region where the reaction occurred and the region that did not occur, the process of selectively dissolving DFR using the difference in solubility in alkali and generating the difference in solubility is called a development process, and usually 0.6 to 1.5 wt% of sodium carbonate or aqueous carbonate Is used.
이때 미 반응된 DFR의 카르복실산과 탄산나트륨과의 비누화 반응을 통해 용해되고, 가교반응이 된 DFR의 경우에는 용해되지 않고 기판에 잔존하게 된다. At this time, the unreacted DFR is dissolved through the saponification reaction between carboxylic acid and sodium carbonate, and in the case of the crosslinked DFR, it does not dissolve and remains on the substrate.
다음 공정은 회로의 구리가 노출된 영역을 에칭으로 부식하여 회로를 형성하고 남아있는 DFR은 박리 용액에서 제거되어 회로를 형성하게 된다. The next step is to etch the circuit's copper-exposed areas by etching to form the circuit, and the remaining DFR is removed from the stripping solution to form the circuit.
위와 같은 공정을 DES(Developing Etching Stripping) 공정이라고 한다. 이때 회로를 형성하는 공정에서 초기에 시작되는 현상공정에서 용해된 DFR이 슬러리 및 스컴이 발생되고 발생된 스컴 등은 회로에 재 흡착되어 불량을 유발시키는 문제가 대두되고 있다. 또한 비누화 반응으로 인한 기포의 발생이 급격하게 발생하면서 공정에 불량을 유발하는 인자로 작용되고 있다.This process is called DES (Developing Etching Stripping) process. At this time, in the process of forming the circuit, DFR dissolved in the developing process that is started early, slurry and scum are generated, and the generated scum and the like are re-adsorbed to the circuit to cause defects. In addition, the generation of bubbles due to the saponification reaction is rapidly occurring, and is acting as a factor causing defects in the process.
뿐만 아니라 종래 공정에서는 발생된 기포를 억제하기 위해 소포제를 사용하여 문제를 해결하고 있으나 소포제를 과량 투입할 경우 현상액의 오염원과 스컴 발생을 촉진하는 문제를 내포하고 있으며, 현상액의 오염 및 스컴으로 인한 현상 탱크의 청소주기가 빨라 원가 상승의 문제도 가지고 있다.In addition, in the conventional process, a problem is solved by using an antifoaming agent to suppress the generated air bubbles. However, when an excessive amount of the antifoaming agent is added, it implies a problem of accelerating the generation of pollutants and scum in the developer, and the phenomenon caused by contamination and scum in the developer. As the cleaning cycle of the tank is fast, there is also a problem of cost increase.
따라서 본 발명의 목적은 현상용액에 반응성 계면활성제를 첨가하여 계면활성제의 소포성과 분산성을 용액 내에 부여함으로서 스컴 및 기포를 억제하면서 용액 내에서 DFR의 뭉침 현상을 저감시킬 수 있는 PCB 현상공정에서 스컴 방지를 위한 반응성 계면활성제가 함유된 현상 조성물 및 이의 제어시스템를 제공하는 것이다.Therefore, the object of the present invention is to add a reactive surfactant to the developing solution to impart defoaming and dispersibility of the surfactant into the solution, while suppressing scum and bubbles while reducing the aggregation of DFR in the solution. It is to provide a developing composition containing a reactive surfactant for prevention and a control system thereof.
상술한 문제점들을 해결하기 위한 수단으로서 본 발명의 PCB 현상공정에서 스컴 방지를 위한 반응성 계면활성제가 함유된 현상 조성물은, 탄산가리 또는 탄산나트륨 또는 탄산암모늄 중 선택된 어느 하나의 용액에 0.01 ~ 5%의 반응성 계면활성제가 함유되는 것이 특징이다.As a means for solving the above-described problems, the developing composition containing a reactive surfactant for preventing scum in the PCB development process of the present invention is 0.01 to 5% reactive to a solution selected from either carbonate or sodium carbonate or ammonium carbonate. It is characterized by containing a surfactant.
하나의 예로써, 상기 반응성 계면활성제는 PEI(Polyethyleneimine)를 포함하는 것이 특징이다.As an example, the reactive surfactant is characterized by including PEI (Polyethyleneimine).
한편 본 발명의 PCB 현상공정에서 스컴 방지를 위한 반응성 계면활성제가 함유된 현상 조성물의 제어시스템은 상기 언급한 현상 조성물을 pH로 제어하는 것이 특징이다.On the other hand, in the PCB development process of the present invention, the control system of the developing composition containing the reactive surfactant for preventing scum is characterized by controlling the above-mentioned developing composition to pH.
이와 같이 본 발명의 PCB 현상공정에서 스컴 방지를 위한 반응성 계면활성제가 함유된 현상 조성물 및 이의 제어시스템은 PEI(Polyethyleneimine) 및 아민을 포함하는 현상 조성물과 pH 제어를 통해 현상 조성물을 관리함으로써 분산성과 소포성을 가지고 있으며, 계면활성제가 함유되어 있어 현상의 형상이 잘 되고 칫수 구현을 정밀하게 할 수 있는 현상 용액으로서 사용이 가능한 장점이 있다.As described above, in the PCB development process of the present invention, a developer composition containing a reactive surfactant for preventing scum and a control system thereof manages the developer composition through PEI (Polyethyleneimine) and amine and the pH control to disperse and defoam. It has the property of being a surfactant and has the advantage of being able to be used as a developing solution that has a good shape of development and a precise dimension implementation because it contains surfactants.
도 1은 본 발명의 일 실시 예에 따른 현상 용액에서 PEI 유무에 따른 스컴의 발생 비교를 나타내는 사진.
도 2는 본 발명의 일 실시 예에 따른 PEI 1Wt% 함유한 현상 용액의 낙차 실험에 의한 기포발생 실험을 나타내는 사진.
도 3은 본 발명의 일 실시 예에 따른 PEI가 함유된 현상 용액으로 형성된 회로의 구현 사진.
도 4는 본 발명의 일 실시 예에 따른 pH 제어 회로도.1 is a photograph showing a comparison of occurrence of scum according to the presence or absence of PEI in the developing solution according to an embodiment of the present invention.
Figure 2 is a photograph showing a bubble generation experiment by a drop experiment of a developing solution containing PEI 1Wt% according to an embodiment of the present invention.
Figure 3 is an implementation picture of a circuit formed of a PEI-containing developer solution according to an embodiment of the present invention.
4 is a pH control circuit diagram according to an embodiment of the present invention.
이하, 본 발명의 구성 및 작용을 첨부된 도면에 의거하여 좀 더 구체적으로 설명한다. 본 발명을 설명함에 있어서, 본 명세서 및 청구범위에 사용된 용어나 단어는 발명자가 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the configuration and operation of the present invention will be described in more detail based on the accompanying drawings. In describing the present invention, terms or words used in the present specification and claims are based on the principle that the inventor can properly define the concept of terms in order to best describe his or her invention. It must be interpreted as a meaning and concept consistent with the technical idea of.
본 발명은 PEI를 함유하는 현상용액 조성물로서 탄산가리, 탄산나트륨 또는 탄산암모늄 용액에 0.01 ~ 5%의 PEI를 포함하는 현상용액 조성물이다. The present invention is a developer composition containing PEI in an amount of 0.01 to 5% in a solution of sodium carbonate or ammonium carbonate as a developer composition containing PEI.
상기 현상용액 조성물에 탄산가리 또는 탄산나트륨 또는 탄산암모늄 중 어느 하나를 혼합하여 사용할 수 있다.Either carbonate or sodium carbonate or ammonium carbonate may be mixed with the developer solution composition.
상기 탄산염 등의 농도는 0.05 ~ 1.5Wt%가 바람직하다. 0.05 Wt%보다 낮을 경우에는 현상 속도가 급격하게 저하되는 문제점을 함유하고, 1.5Wt%보다 높을 경우 가교된 DFR이 용해되는 문제가 있다.The concentration of the carbonate, etc. is preferably 0.05 ~ 1.5Wt%. When it is lower than 0.05 Wt%, the development rate is rapidly lowered, and when it is higher than 1.5 Wt%, the crosslinked DFR is dissolved.
상기 첨가하는 PEI의 종류는 다양한 종류를 사용할 수 있으며, Polyethylenimine, linear, Polyethylenimine hydrochloride, Hexamethyleneimine, N-Methylethylenediamine, 1,3-Diamino-2-propanol 인 것이 바람직하다. Various types of PEI to be added may be used, and it is preferable that they are Polyethylenimine, linear, Polyethylenimine hydrochloride, Hexamethyleneimine, N-Methylethylenediamine, 1,3-Diamino-2-propanol.
상기 반응성 계면활성제는 0.1 ~ 5 wt%인 것이 바람직하고, 0.05 ~ 3 Wt% 인 것이 더욱 바람직하다. 여기서 0.01wt% 보다 낮을 경우 소포성과 반응성이 떨어져 효과가 반감이 되고, 5Wt% 보다 높을 경우 소포성과 반응성 특성효과의 차이가 없으며, 점성이 올라가는 문제가 발생한다.The reactive surfactant is preferably 0.1 to 5 wt%, and more preferably 0.05 to 3 Wt%. Here, if it is lower than 0.01wt%, the effect is half-reduced due to defoaming and reactivity, and when it is higher than 5Wt%, there is no difference between defoaming and reactivity characteristics, and a problem arises in that viscosity increases.
현상의 온도는 20 내지 50℃ 범위인 것이 바람직하고, 여기서, 현상용액의 온도는 20 내지 50℃ 범위에서 온도가 낮은 때에는, 현상속도가 급격하게 저하되는 문제가 발생할 수 있으며, 온도가 높을때에는 가교된 DFR의 용해가 발생할 수 있다. The temperature of the development is preferably in the range of 20 to 50°C, where the temperature of the developing solution is in the range of 20 to 50°C, when the temperature is low, a problem that the development rate may drop rapidly may occur, and when the temperature is high, crosslinking Dissolution of the DFR may occur.
한편 본 발명은 상술한 현상 방법과 제어시스템을 제공한다.Meanwhile, the present invention provides the above-described developing method and control system.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세히 설명하기로 한다.Hereinafter, examples will be described in detail to specifically describe the present invention.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해 될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며, 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The present invention can be better understood by the following examples, the following examples are for illustrative purposes of the present invention and are not intended to limit the protection scope defined by the appended claims.
실시예로서 탄산나트륨 또는 탄산가리를 물에 0.5 wt%, 1 Wt%, 1.5 Wt%의 농도로 용액을 각각 제조한다. 이때 상온에서 200RPM으로 교반하여 분말을 완전히 용해한다. 여기에 다양한 PEI를 0.1 W%, 0.5W%, 1Wt%, 3Wt%, 5Wt%를 첨가하여 PEI를 첨가하지 않은 시료와 제조하였다. As an example, a solution of sodium carbonate or calcium carbonate in water at a concentration of 0.5 wt%, 1 Wt%, and 1.5 Wt% is prepared, respectively. At this time, the mixture was stirred at 200 RPM at room temperature to completely dissolve the powder. Various PEIs were added to 0.1 W%, 0.5 W%, 1 Wt%, 3 Wt%, and 5 Wt% to prepare samples without PEI.
제조된 시료에 DFR 1.0M2/L 양으로 용해하였다. 교반기를 이용하여 5시간 이상 충분하게 DFR을 용해하였다. 용해된 시료는 불투명한 푸른색을 나타내었다. 제조된 시료는 pH를 2가 될 때까지 염산을 투입하여 용액의 변화를 관찰 한다. 스컴의 발생유무를 관찰하고 여과하여 무게로 스컴의 발생을 평가하였다. The sample was dissolved in an amount of 1.0 M2/L DFR. DFR was dissolved sufficiently for 5 hours or more using a stirrer. The dissolved sample showed an opaque blue color. The prepared sample is observed by changing the solution by adding hydrochloric acid until the pH is 2. The occurrence of scum was observed and filtered to evaluate the occurrence of scum by weight.
하기 표 1은 탄산 종류 및 PEI에 따른 슬러지 발생 유무를 나타낸다. Table 1 below shows the presence or absence of sludge generation according to the type of carbonic acid and PEI.
도 1은 스컴 발생 유/무 사진으로, 도 1에 도시된 바와 같이 PEI를 첨가하지 않은 시료의 경우에는 DFR 뭉쳐 스컴이 발생된 것을 확인 할 수 있었다. 1 is a picture of whether or not scum is generated, and as shown in FIG. 1, in the case of a sample without PEI, it was confirmed that scum was generated by agglomeration of DFR.
한편 제조된 현상용액은 기포 발생실험을 수행하였다. 결과는 도 2에 나타낸 것과 같이 기포가 발생하지 않은 것을 알 수 있었다. Meanwhile, the prepared developing solution was subjected to a bubble generation experiment. As a result, it was found that no bubbles were generated as shown in FIG. 2.
또한 제조된 현상용액을 이용하여 Line/Space가 55/55 um의 회로를 이용하여 현상을 하였고, 도 3에 보여지고 있는 것처럼 현상이 잘 형성되어 있는 것을 확인되었다.In addition, the developed solution was used to develop the line/space using a 55/55 um circuit, and it was confirmed that the phenomenon was well formed as shown in FIG. 3.
또한 PEI가 함유된 용액의 pH 측정결과 농도에 의해 pH가 변화하는 것을 확인하였고, 실험한 농도에서 pH가 선형적으로 움직이는 것을 확인하였고, 이를 이용하여 pH 제어장치를 설계하였다. 도 4는 pH 제어를 위한 간단한 도면을 나타 내었다.In addition, as a result of measuring the pH of the solution containing PEI, it was confirmed that the pH was changed by the concentration, and it was confirmed that the pH moved linearly at the tested concentration, and a pH control device was designed using this. 4 shows a simple diagram for pH control.
이상 설명한 내용을 통해 당업자라면 본 발명의 기술사상을 일탈하지 아니하는 범위에서 다양한 변경 및 수정 가능함을 알 수 있을 것이다. 따라서, 본 발명의 기술적 범위는 명세서의 상세한 설명에 기재된 내용으로 한정되는 것이 아니라 특허청구범위에 의해 정해져야만 할 것이다.Through the above description, those skilled in the art will appreciate that various changes and modifications can be made without departing from the technical idea of the present invention. Therefore, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.
Claims (3)
A development composition containing a reactive surfactant for preventing scum in a PCB development process, characterized in that 0.01 to 5% of a reactive surfactant is contained in a solution selected from either carbonate or sodium carbonate or ammonium carbonate.
상기 반응성 계면활성제는 PEI(Polyethyleneimine)를 포함하는 것을 특징으로 하는 PCB 현상공정에서 스컴 방지를 위한 반응성 계면활성제가 함유된 현상 조성물.
According to claim 1,
The reactive surfactant comprises a PEI (Polyethyleneimine) development composition containing a reactive surfactant for preventing scum in the PCB development process, characterized in that.
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