JPH0585637B2 - - Google Patents
Info
- Publication number
- JPH0585637B2 JPH0585637B2 JP58251196A JP25119683A JPH0585637B2 JP H0585637 B2 JPH0585637 B2 JP H0585637B2 JP 58251196 A JP58251196 A JP 58251196A JP 25119683 A JP25119683 A JP 25119683A JP H0585637 B2 JPH0585637 B2 JP H0585637B2
- Authority
- JP
- Japan
- Prior art keywords
- electroless plating
- transparent conductive
- conductive film
- plating
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000007772 electroless plating Methods 0.000 claims description 29
- 238000005530 etching Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- 229910003437 indium oxide Inorganic materials 0.000 claims description 14
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 101150003085 Pdcl gene Proteins 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 31
- 238000007747 plating Methods 0.000 description 20
- 239000004973 liquid crystal related substance Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- 239000011521 glass Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001432 tin ion Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、酸化インジウムあるいは酸化スズを
主成分として含む透明導伝膜上に、密着よく無電
解メツキ被膜を形成する方法に関している。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for forming an electroless plating film with good adhesion on a transparent conductive film containing indium oxide or tin oxide as a main component.
透明導伝膜上に無電解メツキ被膜を形成する場
合、次の２つの前処理方法があつた。
When forming an electroless plating film on a transparent conductive film, there are the following two pretreatment methods.
） SnCl2溶液に浸漬するセンシタイジング、
その後、PdCl2溶液に浸漬するアクテイベイテ
イングの前処理である。センシタイジングに於
ては、基板上にスズの２価イオンを吸着させ、
アクテイベイテイングに於ては、スズの２価イ
オンとパラジウムの２価イオンを反応させて、
金属パラジウムを析出させる方法である。) Sensitizing by immersion in SnCl2 solution,
This is followed by activating pretreatment by immersion in PdCl 2 solution. In sensitizing, divalent tin ions are adsorbed onto the substrate,
In activating, divalent tin ions and palladium divalent ions are reacted,
This is a method of depositing metal palladium.
また、
） としては、SnCl2とPdCl2の各液を混合す
ることによつて調整される触媒液も開発実用化
されている。このタイプの触媒液を使用する
と、ガラス，石英，水晶等にはまつたく無電解
メツキをすることができないが、ガラス，石
英，水晶等に金属酸化物被膜（透明導伝膜はこ
の中の１種である）を形成することで、無電解
メツキが可能となる現象を本発明者は以前に発
見している。 In addition, a catalyst solution prepared by mixing SnCl 2 and PdCl 2 solutions has also been developed and put into practical use. When this type of catalyst liquid is used, it is not possible to perform electroless plating on glass, quartz, crystal, etc., but metal oxide coating (transparent conductive film is one of them) The present inventor has previously discovered a phenomenon in which electroless plating is possible by forming seeds (seeds).
これによつて、ガラス，水晶，石英等上にパタ
ーンをもつた金属酸化物被膜を形成し、SnCl2及
びPdCl2の溶解液を使用することによつて、ガラ
ス，水晶，石英等への選択的な、金属酸化物被膜
層への無電解メツキが可能になつた。 By this, a metal oxide film with a pattern is formed on glass, crystal, quartz, etc., and by using a solution of SnCl 2 and PdCl 2 , it can be applied to glass, crystal, quartz, etc. Electroless plating on metal oxide film layers has become possible.
透明導伝膜上への無電解メツキは、液晶パネル
の端子メツキ等に応用されている。第１図は、液
晶パネルの正面図と断面図である。３及び３′は
透明導伝膜であり、３は、液晶パネルの端子部を
示している。従来、液晶パネルの端子部と液晶パ
ネルの端子との接触は、導電ゴムを用いて行われ
てきたが、液晶パネルの大容量化に伴い、端子密
度の増加、端子数の増加により、導電ゴムでは接
触不良が起りやすくなつてきた。接触不良をなく
すために、端子部のメタライズを行い、液晶パネ
ルとその駆動回路のハンダ付けが必要とされてき
た。３の端子部をメタライイズする場合、無電解
メツキ法，スパツタ法，蒸着法等の手段が検討さ
れたが低コトという観点から、無電解メツキ法が
使われている。無電解メツキで３の端子部をメタ
ライズする場合、）の方法をとれば、２の下基
板全面に金属被膜が形成されるため、その後のパ
ターニングが必要である。）の方法をとれば、
液晶パネルが完成した後、選択的に３の端子部に
メツキをつけることが可能である。透明導伝膜上
無電解メツキを行う場合、通常）の方法が用い
られる。 Electroless plating on transparent conductive films is applied to terminal plating of liquid crystal panels, etc. FIG. 1 is a front view and a sectional view of a liquid crystal panel. 3 and 3' are transparent conductive films, and 3 indicates a terminal portion of the liquid crystal panel. Conventionally, contact between the terminals of the liquid crystal panel and the terminals of the liquid crystal panel has been made using conductive rubber, but as the capacity of liquid crystal panels increases, the terminal density and number of terminals increase, so conductive rubber is used. Poor contact has become more likely to occur. In order to eliminate poor contact, it has been necessary to metalize the terminals and solder the liquid crystal panel and its drive circuit. When metallizing the terminal portion of No. 3, methods such as electroless plating, sputtering, and vapor deposition have been considered, but electroless plating has been used from the viewpoint of cost reduction. When metalizing the terminal portion of 3 by electroless plating, if method () is used, a metal film will be formed on the entire surface of the lower substrate of 2, and subsequent patterning will be required. ) method,
After the liquid crystal panel is completed, it is possible to selectively plate the terminals 3. When performing electroless plating on a transparent conductive film, the following method is usually used.
ここで、メタライズはパネル端子と、駆動回路
との実装を目的としているが、無電解メツキ被膜
の密着強度のバラツキが大きく、しばしば実装不
良が起るのが現状であつた。 Here, metallization is intended for mounting panel terminals and drive circuits, but the current situation is that the adhesion strength of the electroless plating film varies widely and mounting defects often occur.
本発明は、この無電解メツキ被膜と透明導伝膜
の密着強度のバラツキをなくし、密着性を向上さ
せるためにSnCl2及びPdCl2の溶解液に浸漬する
前に、透明導伝膜を還元エツチングすることを特
徴とする。
In order to eliminate variations in the adhesion strength between the electroless plating film and the transparent conductive film and improve the adhesion, the present invention performs reductive etching on the transparent conductive film before immersing it in a solution of SnCl 2 and PdCl 2 . It is characterized by
この無電解メツキ工程の概要を述べる。 An overview of this electroless plating process will be described.
１） ガラス，セラミツク，水晶等の基板に
CVDスパツタ，蒸着等によつてSnO2，In2O3
等の透明導伝膜を形成する。1) For substrates such as glass, ceramic, crystal, etc.
SnO 2 , In 2 O 3 by CVD sputtering, vapor deposition, etc.
Form a transparent conductive film such as
２） この基板を、透明導伝膜の還元性のエツチ
ング液の中に浸漬する。還元性のエツチング液
としては、Cr2+／Cr3+のドレツクス系エツチン
グ液が適当である。このレドツクス系エツチン
グ液は、たとえば
CrCl36H2O 100ｇ
HCl（35％） 500c.c.
H2O 500c.c.
を混合し、50cm2の面積をもつカーボン電極を２
本入れ、100A／cm2で連続電解を行つて得た。
HClの濃度は９％以上が望ましい。これ以下で
あると、エツチング液としての機能が非常に弱
くなる。また、CrCl3の濃度が低い場合は、エ
ツチング速度が遅くなる。このため0.5ｇ／
以上の濃度であるのが望ましい。2) This substrate is immersed in a reducing etching solution for the transparent conductive film. As the reducing etching solution, a Cr 2+ /Cr 3+ Drex etching solution is suitable. This redox-based etching solution is made by mixing, for example, 100 g of CrCl 3 6H 2 O, 500 g of HCl (35%), and 500 c.c. of H 2 O.
It was obtained by carrying out continuous electrolysis at 100 A/cm 2 .
The concentration of HCl is preferably 9% or more. If it is less than this, the function as an etching solution becomes very weak. Furthermore, if the concentration of CrCl 3 is low, the etching rate will be slow. Therefore 0.5g/
It is desirable that the concentration be above.
この時のカソード反応は
Cr3+＋ｅ→Cr2+ …(1)
である。また、エツチング反応はSnO2を例に
とれば、
2Cr2+→3Cr3+＋2e …(2)
SnO2＋2H+＋2e→SnOT2O …(3)
SnO＋2HCl→SnCl2＋H2O …(4)
となると考えられる。 The cathode reaction at this time is Cr 3+ +e→Cr 2+ (1). Taking SnO 2 as an example, the etching reaction is as follows: 2Cr 2+ →3Cr 3+ +2e …(2) SnO 2 +2H + +2e→SnOT 2 O …(3) SnO+2HCl→SnCl 2 +H 2 O …(4) It is considered to be.
（参考例、金属表面処理技術
vol34，No.６ 1983 P286〜P289）
レドツクス系エツチング液への基板の浸漬時
間は、透明導伝膜が30Å以上エツチングするの
に必要な時間が望ましい。浸漬時間が短いと、
メツキ被膜密着強度の向上がみられない。ま
た、エツチング時間を長くしても、基板上に30
Å以上の透明導伝膜が残ることが必要である。(Reference example, Metal Surface Treatment Technology Vol. 34, No. 6, 1983, P286-P289) The immersion time of the substrate in the redox-based etching solution is preferably the time required to etch the transparent conductive film by 30 Å or more. If the soaking time is short,
No improvement in the adhesion strength of the plating film was observed. In addition, even if the etching time is increased, 30%
It is necessary that a transparent conductive film with a thickness of Å or more remains.
３） この基板を前述した）あるいは）の無
電解メツキの前処理を行い、無電解メツキ液の
中に浸漬し、透明導伝膜上に無電解メツキを形
成する。3) This substrate is subjected to the electroless plating pretreatment described in () or), and is immersed in an electroless plating solution to form electroless plating on the transparent conductive film.
無電解メツキ液としては、Ni−Ｐ，NiB，
Cu，Au，Ag等のメツキ浴があるが、最も密着
強度の大きいメツキ被膜はNi−Ｐメツキであ
る。 Electroless plating solutions include Ni-P, NiB,
There are plating baths of Cu, Au, Ag, etc., but the plating film with the highest adhesion strength is Ni-P plating.
４） この無電解メツキを200℃で１時間焼成し、
幅0.2mmのパターンを残してエツチングし、無
電解メツキ上にハンダコートし、第２図のよう
に裏面に銅層とハンダ層がついたフレキシブル
回路基板を熱圧着し、ハンダ接合した。このフ
レキシブル基板を引きはがす時に必要な力をこ
こででは無電解メツキ被膜の密着強度とした。4) This electroless plating is fired at 200℃ for 1 hour,
A pattern with a width of 0.2 mm was etched, and the electroless plating was coated with solder. A flexible circuit board with a copper layer and a solder layer on the back was thermocompressed and soldered as shown in Figure 2. The force required to peel off this flexible substrate was defined as the adhesion strength of the electroless plating film.
この密着強度は、Cr2+／Cr3+のレドツクス系
エツチング液の中に浸漬しない場合と比較し
て、平均約1.5倍の密着強度を示し、その密着
強度のバラツキは少なくなつた。 This adhesion strength was approximately 1.5 times higher on average than when the sample was not immersed in the Cr 2+ /Cr 3+ redox etching solution, and the variation in the adhesion strength was reduced.
実用的にはメツキ被膜の密着強度は液晶パネ
ルの端子のメタライズの場合、最低50ｇ／mmが
必要であり、本発明の方法を用いれば常にこの
値を得ることができる。 Practically speaking, the adhesion strength of a plating film must be at least 50 g/mm in the case of metallizing terminals of a liquid crystal panel, and this value can always be obtained using the method of the present invention.
以下実施例により本発明を詳細に述べる。 The present invention will be described in detail with reference to Examples below.
実施例 １
ソーダガラス上に、低温スパツタにより酸化イ
ンジウム膜を400Å形成した。Example 1 An indium oxide film with a thickness of 400 Å was formed on soda glass by low-temperature sputtering.
紫外線感光樹脂をスピンコート法により塗布
し、マスク露光，現像，塩酸によるエツチング
で、パターン幅0.2mm、長さ２cmの酸化インジウ
ムのパターンを形成した。 An indium oxide pattern with a pattern width of 0.2 mm and a length of 2 cm was formed by applying an ultraviolet photosensitive resin by spin coating, mask exposure, development, and etching with hydrochloric acid.
この基板を、
CrCl3・6H2O 20ｇ
HCl（35％） 300c.c.
H2O 700c.c.
の組成液中に表面積100cm2のカーボン電極を２本
入れ50mA／ｄm2で１時間連続電解を行い、
Cr2+／Cr3+のレドツクス系エンチング液とし、１
分間浸漬した。この時、酸化インジウム層は70Å
エツチングされた。 Two carbon electrodes with a surface area of 100 cm 2 were placed on this substrate in a solution containing 20 g of CrCl 3 6H 2 O (35%), 300 c.c. H 2 O, and 700 c.c. Perform electrolysis,
Cr 2+ /Cr 3+ redox-based enching liquid, 1
Soaked for minutes. At this time, the indium oxide layer is 70Å
Etched.
この後、所定の方法で調整された、日立化成社
製増感剤HS101Bに１分間浸漬し、水洗後、IN
−NaOH溶液に浸漬し、水洗後、所定の方法で
調整されたカニゼン社製無電解ニツケル−リンメ
ツキ液Ｓ−680の50℃浴の中に５分間浸漬した。
これによつて、酸化インジウム上に3000Åの無電
解ニツケル−リン被膜が形成された。水洗後、
200℃で１時間焼成した。この後、ニツケル・リ
ン被膜上にハンダバスにより15μmのハンダ層を
形成した。この基板とポリイミド上に銅層が形成
され、その上に12μmのハンダ層の形成されたフ
レキシブル回路基板を300℃で熱圧着した。この
方法でつくられた45コのサンプルの密着強度は第
３図のような分布を示した。 After that, it was immersed in Hitachi Chemical's sensitizer HS101B prepared according to a prescribed method for 1 minute, washed with water, and then
- After being immersed in a NaOH solution and washed with water, it was immersed for 5 minutes in a 50°C bath of electroless nickel-phosphorus plating solution S-680 manufactured by Kanigen Co., Ltd., which was prepared according to a predetermined method.
As a result, an electroless nickel-phosphorus film of 3000 Å was formed on the indium oxide. After washing with water,
It was baked at 200°C for 1 hour. Thereafter, a 15 μm solder layer was formed on the nickel phosphorus film using a solder bath. A copper layer was formed on this substrate and polyimide, and a flexible circuit board with a 12 μm solder layer formed thereon was thermocompression bonded at 300°C. The adhesion strength of 45 samples made using this method showed a distribution as shown in Figure 3.
これからわかるように、液晶パネルの端子上の
メツキとしては、メツキ被膜の密着強度は十分あ
ることがわかる。 As can be seen, the adhesion strength of the plating film is sufficient for plating on the terminals of a liquid crystal panel.
実施例 ２
石英ガラス上に、スパツタにより酸化インジウ
ム膜を500Å形成した。Example 2 An indium oxide film with a thickness of 500 Å was formed on quartz glass by sputtering.
実施例１と同様の方法で同一のパターンを形成
した。この基板を
CrCl3・6H2O 120ｇ
HCl（35％） 500c.c.
H2O 500c.c.
の組成液中に表面積100cm2のカーボン電極を２本
入れ、100mA／ｄm2で１時間連続電極を行い、
Cr2+／Cr3+のレドツクス系エツチング液とし30秒
間浸漬した。この時、酸化インジウム層は100Å
エツチングされた。この後実施例１と同様の方法
でニツケル・リンメツキを行い、200℃１時間で
焼成後、実施例１と同様の密着試験を行い、同様
の結果を得た。 The same pattern was formed in the same manner as in Example 1. Two carbon electrodes with a surface area of 100 cm 2 were placed in a solution containing 120 g of CrCl 3 6H 2 O, 120 g of HCl (35%), and 500 c.c. conduct the electrode,
It was immersed in a Cr 2+ /Cr 3+ redox etching solution for 30 seconds. At this time, the indium oxide layer is 100Å
Etched. Thereafter, nickel plating was performed in the same manner as in Example 1, and after baking at 200°C for 1 hour, an adhesion test was performed in the same manner as in Example 1, and the same results were obtained.
実施例 ３
パイレツクスガラス上に、CVDにより酸化ス
ズ層を300Åつけた。Example 3 A tin oxide layer of 300 Å was deposited on Pyrex glass by CVD.
この基板を
CrCl3・6H2O 100ｇ
HCl（35％） 400c.c.
H2O 600c.c.
の組成液中に表面積100cm2のカーボン電極を２本
入れ、100mA／ｄm2で１時間連続電解を行い、
Cr2+／Cr3+のレドツクス系エツチング液とし１分
間浸漬した。この時酸化スズ層は80Åエツチング
された。 Two carbon electrodes with a surface area of 100 cm 2 were placed in a solution containing 100 g of CrCl 3 6H 2 O (35%), 400 c.c. H 2 O, and 600 c.c. of H 2 O, and continuously heated at 100 mA/dm 2 for 1 hour. Perform electrolysis,
It was immersed in a Cr 2+ /Cr 3+ redox etching solution for 1 minute. At this time, the tin oxide layer was etched by 80 Å.
この後、実施例１と同様の方法でニツケル・リ
ンメツキを行い、200℃１時間焼成した。 Thereafter, nickel plating was performed in the same manner as in Example 1, followed by firing at 200°C for 1 hour.
この後、実施例１と同様の方法でニツケルのパ
ターニングを行つた。ニツケルのエツチング液と
しては、
硝 酸 35部
リン酸 35部
硫 酸 ５部
酢 酸 ５部
水 20部
の混合液を用いた。 Thereafter, nickel was patterned in the same manner as in Example 1. As the nickel etching solution, a mixed solution of 35 parts of nitric acid, 35 parts of phosphoric acid, 5 parts of sulfuric acid, 5 parts of acetic acid, and 20 parts of water was used.
密着強度は、実施例１と同様の方法で測定し、
同様の結果を得た。 Adhesion strength was measured in the same manner as in Example 1,
Obtained similar results.
比較例 １
酸化インジウムを実施例１と同様の方法で、パ
ターニングを行い、Cr2+／Cr3+のレドツクス系エ
ツチング液を通さずに、実施例１と同様の方法で
無電解ニツケルメツキを行つた。Comparative Example 1 Indium oxide was patterned in the same manner as in Example 1, and electroless nickel plating was performed in the same manner as in Example 1 without passing through the Cr 2+ /Cr 3+ redox etching solution. .
200℃で１時間焼成後、密着強度を測定したと
ころ、第４図のような密着強度の分布が得られ
た。密着強度が20ｇ／mmのものもあり、実用的強
度がなかつた。 After baking at 200° C. for 1 hour, the adhesion strength was measured, and a distribution of adhesion strength as shown in FIG. 4 was obtained. Some had adhesion strength of 20 g/mm, which was insufficient for practical use.
比較例 ２
酸化インジウムを実施例１と同様の方法でパタ
ーニングを行い、Cr2／Cr3+のレドツクス系エツ
チング液の代りに、
塩 酸 10％
硝 酸 １％
の混合溶液で、40℃に加温した酸化インジウムの
エツチング液で、酸化インジウム層を100Åエツ
チングした。この後、実施例１と同様の方法でニ
ツケル・リンメツキを行い、200℃で１時間焼成
後実施例１と同様の方法で密着強度を測定した。Comparative Example 2 Indium oxide was patterned in the same manner as in Example 1, but instead of the Cr 2 /Cr 3+ redox etching solution, a mixed solution of 10% hydrochloric acid and 1% nitric acid was used at 40°C. The indium oxide layer was etched to a thickness of 100 Å using a warm indium oxide etching solution. Thereafter, nickel plating was performed in the same manner as in Example 1, and after baking at 200° C. for 1 hour, the adhesion strength was measured in the same manner as in Example 1.
その結果は、第５図のような密着強度の分布が
得られ、密着強度が10ｇ／mmのものもあり、実用
的な強度はなかつた。 As a result, a distribution of adhesion strength as shown in Fig. 5 was obtained, and there were cases where the adhesion strength was 10 g/mm, which was not a practical strength.
以上説明した通り本願発明は、酸化インジウム
あるいは酸化スズを主成分として含む透明導伝膜
が表面に形成された基板をSnCl2及びPdCl2の溶
解液に浸漬した後、無電解メツキ液に浸漬させて
透明導伝膜上に無電解メツキ層を形成する無電解
メツキ方法において、前記溶解液に浸漬する前
に、透明導伝膜が表面に形成された基板を、
Cr2+／Cr3+の還元性のエツチング液の中に浸漬す
る、という構成により、透明導伝膜を均一に還元
エツチング液し、無電解メツキ被膜と透明導伝膜
との密着強度のバラツキをなくすことにより、密
着性が向上するという効果が得られるものであ
る。
As explained above, in the present invention, a substrate on which a transparent conductive film containing indium oxide or tin oxide as a main component is formed is immersed in a solution of SnCl 2 and PdCl 2 , and then immersed in an electroless plating solution. In the electroless plating method of forming an electroless plating layer on a transparent conductive film using
By immersing the transparent conductive film in a reducing etching solution of Cr 2+ /Cr 3+ , the transparent conductive film is uniformly etched, and variations in the adhesion strength between the electroless plating film and the transparent conductive film are eliminated. By eliminating this, the effect of improving adhesion can be obtained.
従つてこの発明によつて、透明導伝膜上に無電
解メツキを行う際、密着強度不足で実用化が困難
であつたもの、例えば、液晶パネル端子のメタラ
イズなどが、可能になり、その効果は極めて大き
い。 Therefore, this invention makes it possible to perform electroless plating on a transparent conductive film, which has been difficult to put into practical use due to insufficient adhesion strength, such as metallization of liquid crystal panel terminals, and its effects have been improved. is extremely large.
第１図、液晶パネルの正面図、断面図。
１：前面基板、２：背面基板、３，３′：透明
導伝膜、４：シール材、５：液晶組成物。
第２図、メツキ被膜の密着性試験方法。
６：ハンダコートされたメツキ被膜、７：フレ
キシブル回路基板、８：ハンダコートされた銅
層。
第３図、本発明のメツキ方法でつけられた、メ
ツキ被膜の密着性。第４図、従来のメツキ方法で
つけられたメツキ被膜の密着性。第５図、Cr2+／
Cr3+のレドツクス系エツチング液の代りに、
HCl，TNO3混合エツチング液を用いて酸化イン
ジウムのエツチングを行つた時のメツキ被膜の密
着性。
FIG. 1 is a front view and a sectional view of a liquid crystal panel. 1: Front substrate, 2: Back substrate, 3, 3': Transparent conductive film, 4: Sealing material, 5: Liquid crystal composition. Figure 2: Method for testing the adhesion of plating films. 6: Solder coated plating film, 7: Flexible circuit board, 8: Solder coated copper layer. FIG. 3 shows the adhesion of the plating film applied by the plating method of the present invention. Figure 4: Adhesion of plating film applied by conventional plating method. Figure 5, Cr 2+ /
Instead of Cr 3+ redox etching solution,
Adhesion of plating film when indium oxide is etched using HCl and TNO 3 mixed etching solution.
Claims (1)
して含む透明導伝膜が表面に形成された基板を
SnCl2及びPdCl2の溶解液に浸漬した後、無電解
メツキ液に浸漬させて透明導伝膜上に無電解メツ
キ層を形成する無電解メツキ方法において、前記
溶解液に浸漬する前に、透明導伝膜が表面に形成
された基板を、Cr2+／Cr3+の還元性のエツチング
液の中に浸漬することを特徴とする無電解メツキ
方法。1 A substrate on which a transparent conductive film containing indium oxide or tin oxide as a main component is formed.
In an electroless plating method in which a transparent conductive film is immersed in a solution of SnCl 2 and PdCl 2 and then immersed in an electroless plating solution to form an electroless plating layer on the transparent conductive film, the transparent An electroless plating method characterized by immersing a substrate on which a conductive film is formed in a reducing etching solution of Cr 2+ /Cr 3+ .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25119683A JPS60141874A (en) | 1983-12-28 | 1983-12-28 | Electroless plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25119683A JPS60141874A (en) | 1983-12-28 | 1983-12-28 | Electroless plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60141874A JPS60141874A (en) | 1985-07-26 |
| JPH0585637B2 true JPH0585637B2 (en) | 1993-12-08 |
Family
ID=17219108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25119683A Granted JPS60141874A (en) | 1983-12-28 | 1983-12-28 | Electroless plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60141874A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0196384A (en) * | 1987-10-08 | 1989-04-14 | Seiko Instr & Electron Ltd | Method for plating transparent conductive film pattern |
| US9064985B2 (en) * | 2006-11-01 | 2015-06-23 | Bar-Ilan University | Nickel-cobalt alloys as current collectors and conductive interconnects and deposition thereof on transparent conductive oxides |
| JP4840707B2 (en) * | 2009-01-02 | 2011-12-21 | 末則 山下 | Golf putting practice equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4949013A (en) * | 1972-05-25 | 1974-05-13 | ||
| JPS5125226A (en) * | 1974-08-25 | 1976-03-01 | Nippon Soken | SHOTOTSUKENCHISOCHI |
| JPS5794563A (en) * | 1980-12-02 | 1982-06-12 | Seiko Epson Corp | Electroless plating method |
-
1983
- 1983-12-28 JP JP25119683A patent/JPS60141874A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4949013A (en) * | 1972-05-25 | 1974-05-13 | ||
| JPS5125226A (en) * | 1974-08-25 | 1976-03-01 | Nippon Soken | SHOTOTSUKENCHISOCHI |
| JPS5794563A (en) * | 1980-12-02 | 1982-06-12 | Seiko Epson Corp | Electroless plating method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60141874A (en) | 1985-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6127052A (en) | Substrate and method for producing it | |
| KR900003152B1 (en) | Method for forming capacitive circuit on circuit board | |
| EP0083458B1 (en) | Method of partially metallising electrically conductive non-metallic patterns | |
| US4666078A (en) | Electroless plated terminals of display panel | |
| JP3173873B2 (en) | Method for selectively providing a pattern of a substance other than glass on a glass substrate by electroless metal coating | |
| JPS585984B2 (en) | Pretreatment method for electroless plating | |
| JPH022948B2 (en) | ||
| JPH0585637B2 (en) | ||
| JPH11330652A (en) | Board and manufacture thereof | |
| JP3348705B2 (en) | Electrode formation method | |
| KR100798870B1 (en) | Conductive metal plated polyimide substrate including coupling agent and method for producing the same | |
| JPS60245781A (en) | Plating method onto transparent conductive film pattern | |
| JPS59149326A (en) | Production of liquid crystal panel | |
| JPH06260759A (en) | Manufacture of printed circuit board | |
| JPS63891B2 (en) | ||
| JPS60245782A (en) | Plating method onto transparent conductive film pattern | |
| JPH0661619A (en) | Production of circuit board | |
| JPH05125552A (en) | Method for plating transparent conductive film with gold | |
| JPS5856386A (en) | Method of producing printed circuit board | |
| JP3929782B2 (en) | Wiring board manufacturing method | |
| JPS60121616A (en) | Method of forming transparent conductive film | |
| JPS5879842A (en) | Electroless plating of glass and ceramic | |
| JPH01169811A (en) | Electrode structure | |
| JP3255769B2 (en) | How to plate on insulator | |
| JPH0437967B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |