TWI713669B - Electroless gold plating bath - Google Patents
Electroless gold plating bath Download PDFInfo
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- TWI713669B TWI713669B TW106100509A TW106100509A TWI713669B TW I713669 B TWI713669 B TW I713669B TW 106100509 A TW106100509 A TW 106100509A TW 106100509 A TW106100509 A TW 106100509A TW I713669 B TWI713669 B TW I713669B
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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
本發明之課題為提供可使鍍敷安定性、鍍敷後之外觀、及鍍敷速度全部提昇之新穎無電解金鍍敷浴。 The subject of the present invention is to provide a novel electroless gold plating bath that can improve plating stability, appearance after plating, and plating speed.
本發明之解決手段為一種無電解金鍍敷浴，其係含有水溶性金化合物、還原劑、錯合劑、及安定化劑，前述安定化劑係以下述式所表示的氰醇化合物。 The solution of the present invention is an electroless gold plating bath containing a water-soluble gold compound, a reducing agent, a complexing agent, and a stabilizer. The stabilizer is a cyanohydrin compound represented by the following formula.
式中，R1及R2係相同或相異，且意味著氫原子、矽烷基、或者可被取代基取代的烷基或芳香族基。 In the formula, R 1 and R 2 are the same or different, and mean a hydrogen atom, a silyl group, or an alkyl group or an aromatic group that may be substituted with a substituent.
Description
本發明係關於無電解金鍍敷浴。 The present invention relates to an electroless gold plating bath.
金係具有次高於銀、銅的電導電率，其以熱壓接所致之連接性等的物理性質優異，並且耐氧化性、耐藥品等的化學性質亦優異。因此，使用金之金鍍敷，於電子工業領域中，被廣泛使用作為印刷基板之電路、IC封裝之安裝部分或端子部分等的最終表面處理法。近年來，伴隨著電子零件的小型化、高密度化，適宜使用不需要導線而功能性等優異的無電解鍍敷法。 Gold has an electrical conductivity that is next higher than that of silver and copper, and it has excellent physical properties such as connectivity due to thermal compression bonding, and also excellent chemical properties such as oxidation resistance and chemical resistance. Therefore, gold plating using gold is widely used in the electronics industry as a final surface treatment method for printed circuit boards, mounting parts of IC packages, or terminal parts. In recent years, with the miniaturization and high density of electronic components, it is appropriate to use electroless plating methods that do not require wires and are excellent in functionality.
無電解鍍敷法，依據鍍敷方法而代表性地列舉下述之方法。 The electroless plating method typically includes the following methods depending on the plating method.
(1)於底層無電解鎳鍍敷皮膜上形成置換金鍍敷皮膜的無電解鎳/置換金法(Electroless Nickel Immersion Gold：ENIG) (1) Electroless Nickel Immersion Gold (Electroless Nickel Immersion Gold: ENIG) method of forming a replacement gold plating film on the bottom electroless nickel plating film
(2)於銅上直接形成置換金鍍敷皮膜的直接置換金法(Direct Immersion Gold：DIG) (2) Direct Immersion Gold (DIG) in which a replacement gold plating film is directly formed on copper
(3)於底層無電解鎳鍍敷皮膜與置換金鍍敷皮膜之 間設置無電解鈀鍍敷皮膜的無電解鎳/無電解鈀/置換金法(Electroless Nickel Electroless Palladium Immersion Gold：ENEPIG) (3) On the bottom of the electroless nickel plating film and the replacement gold plating film Electroless Nickel Electroless Palladium Immersion Gold (Electroless Nickel Electroless Palladium Immersion Gold: ENEPIG) with an electroless palladium plating film
此等方法係任一者皆可防止銅之擴散、提昇電路或端子之耐蝕性。尤其，使用無電解鈀鍍敷之ENEPIG法係作為使與線、無鉛焊料之連接可靠性進一步提昇的方法非常有用。 Any of these methods can prevent the diffusion of copper and improve the corrosion resistance of circuits or terminals. In particular, the ENEPIG method using electroless palladium plating is very useful as a method to further improve the connection reliability with wires and lead-free solder.
無電解金鍍敷浴係依據作為金供給源所使用的金鹽(水溶性金化合物)的種類而大致區分為氰浴與無氰浴(Non-Cyanide Bath)。其中，氰浴係含有含氰基(CN)之水溶性金化合物(例如氰化金鉀等之氰化金鹽等)。另一方面，無氰浴係含有不含氰基之水溶性金化合物(例如氯化金鈉等之氯化金鹽、亞硫酸金鈉等之亞硫酸金鹽等)。 The electroless gold plating bath is roughly divided into a cyanide bath and a non-cyanide bath (Non-Cyanide bath) depending on the type of gold salt (water-soluble gold compound) used as a gold supply source. Among them, the cyanide bath contains a water-soluble gold compound containing a cyano group (CN) (for example, cyanide gold salt such as potassium gold cyanide, etc.). On the other hand, cyanide-free baths contain water-soluble gold compounds that do not contain cyano groups (for example, gold chloride salts such as sodium gold chloride, gold sulfite salts such as sodium gold sulfite, etc.).
無電解金鍍敷浴，除了上述金鹽以外，亦含有還原劑、錯合劑、及安定化劑等之添加劑。其中，還原劑係為了將金鹽還原來析出金而添加。錯合劑主要是為了使金鍍敷液之金的溶解性安定化而添加。又，安定化劑係在鍍敷安定性、鍍敷後之外觀提昇、鍍敷皮膜形成速度(鍍敷速度)調整等的目的下添加。 The electroless gold plating bath contains additives such as reducing agents, complexing agents, and stabilizers in addition to the above-mentioned gold salts. Among them, the reducing agent is added in order to reduce the gold salt to precipitate gold. The complexing agent is mainly added to stabilize the solubility of gold in the gold plating solution. In addition, the stabilizer is added for the purpose of plating stability, appearance improvement after plating, and adjustment of plating film formation speed (plating speed).
尤其，於無電解金鍍敷浴中，必須對應於還原劑的種類來添加安定化劑，例如，在氰浴的情況，係使用毒物之KCN作為安定劑。然而，因為強的毒性，會對保管上、因廢棄導致之環境面的不良影響較大，而要求於 氰浴中，提供代替KCN的安定化劑。 In particular, in the electroless gold plating bath, a stabilizer must be added according to the type of reducing agent. For example, in the case of a cyanide bath, KCN, which is a poison, is used as a stabilizer. However, because of its strong toxicity, it will have a greater negative impact on the environment due to storage and disposal. In the cyanide bath, a stabilizer that replaces KCN is provided.
另一方面，在無氰浴的情況，作為安定化劑係可使用硫代二甘醇酸、巰基苯并噻唑、聚乙烯醇、甘醇酸、巰基琥珀酸等(例如專利文獻1~6)。 On the other hand, in the case of a cyanide-free bath, thiodiglycol acid, mercaptobenzothiazole, polyvinyl alcohol, glycolic acid, mercaptosuccinic acid, etc. can be used as stabilizers (for example, Patent Documents 1 to 6) .
[專利文獻1]日本特開2011-168837號公報 [Patent Document 1] Japanese Patent Application Publication No. 2011-168837
[專利文獻2]日本特開平6-145996號公報 [Patent Document 2] Japanese Patent Laid-Open No. 6-145996
[專利文獻3]日本特開平6-145997號公報 [Patent Document 3] Japanese Patent Laid-Open No. 6-145997
[專利文獻4]日本特開平6-280039號公報 [Patent Document 4] Japanese Patent Laid-Open No. 6-280039
[專利文獻5]日本特開2004-10964號公報 [Patent Document 5] JP 2004-10964 A
[專利文獻6]日本特開2005-194569號公報 [Patent Document 6] Japanese Patent Application Publication No. 2005-194569
然而，依據本發明者們之探討結果，得知上述專利文獻所記載之化合物，係作為安定化劑之效果不充分，而安定性、鍍敷後之外觀、鍍敷速度之任一點皆差。 However, based on the results of the inventors' investigation, it was found that the compound described in the above patent document is not sufficiently effective as a stabilizer, and is poor in stability, appearance after plating, and plating speed.
本發明係鑑於上述情事而完成者，其目的為提供無關於氰浴、無氰浴之種類，可使鍍敷安定性、鍍敷後之外觀、及鍍敷速度(以下，有時將此等彙整而稱為鍍敷能力)全部提昇之新穎無電解金鍍敷浴。 The present invention was completed in view of the above circumstances, and its purpose is to provide a stable plating, appearance after plating, and plating speed regardless of the type of cyanide bath or non-cyanide bath (hereinafter, sometimes such It is a novel electroless gold plating bath that has all been improved.
本發明之要旨係如下述1~4所述般。 The gist of the present invention is as described in 1 to 4 below.
1.一種無電解金鍍敷浴，其係含有水溶性金化合物、還原劑、錯合劑、及安定化劑，且前述安定化劑係以下述式所表示的氰醇化合物。 1. An electroless gold plating bath containing a water-soluble gold compound, a reducing agent, a complexing agent, and a stabilizer, and the stabilizer is a cyanohydrin compound represented by the following formula.
式中，R1及R2係相同或相異，且意味著氫原子、矽烷基、或者可被取代基取代的烷基或芳香族基。 In the formula, R 1 and R 2 are the same or different, and mean a hydrogen atom, a silyl group, or an alkyl group or an aromatic group that may be substituted with a substituent.
2.如上述1之無電解金鍍敷浴，其中，前述氰醇化合物係由丙酮氰醇、甲醛氰醇、苯甲醛氰醇、及1,1,1-三氟丙酮氰醇所成之群中選出的至少一種。 2. The electroless gold plating bath of 1 above, wherein the cyanohydrin compound is a group consisting of acetone cyanohydrin, formaldehyde cyanohydrin, benzaldehyde cyanohydrin, and 1,1,1-trifluoroacetone cyanohydrin At least one selected from among.
3.如上述1或2之無電解金鍍敷浴，其中，前述還原劑係由硼氫化合物、胺基硼烷化合物、硫脲、對苯二酚、抗壞血酸、肼、甲醛、及甲醛重亞硫酸鹽所成之群中選出的至少一種。 3. The electroless gold plating bath of 1 or 2 above, wherein the reducing agent is composed of borohydride compound, aminoborane compound, thiourea, hydroquinone, ascorbic acid, hydrazine, formaldehyde, and formaldehyde At least one selected from the group of sulfates.
4.如上述1或2之無電解金鍍敷浴，其中，作為前述還原劑而發揮作用的成分係包含：由甲醛、及甲醛重亞硫酸鹽所成之群中選出的至少一種、與以下述式 (1)或(2)所表示之胺化合物。 4. The electroless gold plating bath of 1 or 2 above, wherein the component that functions as the reducing agent includes: at least one selected from the group consisting of formaldehyde and formaldehyde bisulfite, and the following Formula The amine compound represented by (1) or (2).
‧R1-NH-C2H4-NH-R2‧‧‧(1) ‧R 1 -NH-C 2 H 4 -NH-R 2 ‧‧‧(1)
‧R3-(CH2-NH-C2H4-NH-CH2)n-R4‧‧‧(2) ‧R 3 -(CH 2 -NH-C 2 H 4 -NH-CH 2 ) n -R 4 ‧‧‧(2)
上述式(1)及(2)中，R1、R2、R3及R4係表示-OH、-CH3、-CH2OH、-C2H4OH、-CH2N(CH3)2、-CH2NH(CH2OH)、-CH2NH(C2H4OH)、-C2H4NH(CH2OH)、-C2H4NH(C2H4OH)、-CH2N(CH2OH)2、-CH2N(C2H4OH)2、-C2H4N(CH2OH)2或-C2H4N(C2H4OH)2，且可相同亦可相異，n為1~4之整數。 In the above formulas (1) and (2), R 1 , R 2 , R 3 and R 4 represent -OH, -CH 3 , -CH 2 OH, -C 2 H 4 OH, -CH 2 N(CH 3 ) 2 , -CH 2 NH(CH 2 OH), -CH 2 NH(C 2 H 4 OH), -C 2 H 4 NH(CH 2 OH), -C 2 H 4 NH(C 2 H 4 OH) , -CH 2 N(CH 2 OH) 2 , -CH 2 N(C 2 H 4 OH) 2 , -C 2 H 4 N(CH 2 OH) 2 or -C 2 H 4 N(C 2 H 4 OH ) 2 , and can be the same or different, n is an integer from 1 to 4.
依據本發明，可提供一種新穎的無電解金鍍敷浴，由於是使用鍍敷能力極優異的氰醇化合物作為安定化劑，因此無關於無電解金鍍敷浴的種類為氰浴、無氰浴，可使鍍敷安定性、鍍敷後之外觀、及鍍敷速度(統稱為鍍敷能力)全部提昇。 According to the present invention, a novel electroless gold plating bath can be provided. Since a cyanohydrin compound with excellent plating ability is used as a stabilizer, it is irrelevant to the types of electroless gold plating baths that are cyanide bath and non-cyanide bath. The bath can improve the stability of plating, appearance after plating, and plating speed (collectively called plating capacity).
本發明者們為了解決上述課題而再三進行探討。其結果，發現若使用以下述式所表示之氰醇化合物作為可使鍍敷安定性、鍍敷後之外觀、及鍍敷速度全部提昇 的安定化劑，則可達成所期望的目的，因而完成本發明。 In order to solve the above-mentioned problems, the inventors of the present invention have repeatedly studied. As a result, it was found that if the cyanohydrin compound represented by the following formula is used as the plating stability, the appearance after plating, and the plating speed are all improved The stabilizer can achieve the desired purpose, thus completing the present invention.
式中，R1及R2係相同或相異，且意味著氫原子、矽烷基、或者可被取代基取代的烷基或芳香族基。 In the formula, R 1 and R 2 are the same or different, and mean a hydrogen atom, a silyl group, or an alkyl group or an aromatic group that may be substituted with a substituent.
如此般，本發明之特徵在於，發現作為可使鍍敷安定性、鍍敷後之外觀、及鍍敷速度全部提昇的安定化劑，亦即，鍍敷能力優異的安定化劑，氰醇化合物係為有用之點。藉由氰醇化合物之使用而發揮優異的鍍敷能力之理由雖詳細內容並不清楚，但可推測，於分子內不僅是氰基(CN)亦具有羥基(OH)者係有效發揮作用。依據本發明，可推想，藉由CN基於鍍敷中游離而可發揮優異的鍍敷能力，但依據本發明者們之實驗結果得知僅單純地含有CN基而不含有OH基的化合物(例如丁二腈、乙腈)，係鍍敷能力所要求的三個特性中之安定性差(參照後述之比較例4、5)。 In this way, the present invention is characterized by the discovery of a cyanohydrin compound as a stabilizer that can improve the stability of plating, appearance after plating, and plating speed, that is, a stabilizer with excellent plating ability. It is a useful point. Although the details of the reason why the cyanohydrin compound exerts the excellent plating ability are not clear, it can be inferred that not only the cyano group (CN) but also the hydroxyl group (OH) in the molecule functions effectively. According to the present invention, it can be inferred that CN can exhibit excellent plating ability based on the freeing in plating. However, according to the experimental results of the present inventors, it is known that compounds containing only CN groups and not OH groups (such as Succinonitrile and acetonitrile) have poor stability among the three properties required for plating ability (refer to Comparative Examples 4 and 5 described later).
於本發明中，烷基係意味著碳數1~6之低級烷基、或者碳數7~10之中級烷基。上述烷基係可為直鏈狀、分支狀、環狀之任一者。上述烷基係包含無取代之烷 基、及可被取代基取代之烷基兩者。上述取代基係可列舉例如：氯、氟等之鹵素等。 In the present invention, the alkyl group means a lower alkyl group having 1 to 6 carbon atoms, or a middle alkyl group having 7 to 10 carbon atoms. The aforementioned alkyl group may be linear, branched, and cyclic. The above-mentioned alkyl group contains unsubstituted alkane Both a group and an alkyl group which may be substituted by a substituent. Examples of the above-mentioned substituent system include halogens such as chlorine and fluorine.
於本發明中，芳香族基係意味著具有芳香環之基。上述芳香環係可列舉例如：非苯系芳香環；苯環；萘環、蒽環；芘環等之縮合芳香環等。上述芳香族基係包含無取代之芳香族基、及可被取代基取代之芳香族基兩者。作為被取代基取代之芳香族基，係可列舉例如：上述之非苯系芳香環、芳香環、或者縮合芳香環之1個以上的碳原子被取代成氧原子、氮原子、硫原子等之雜原子的雜芳香環(吡咯環、吡啶環、噻吩環、呋喃環等)。 In the present invention, the aromatic group means a group having an aromatic ring. Examples of the above-mentioned aromatic ring system include non-benzene-based aromatic rings; benzene rings; naphthalene rings and anthracene rings; pyrene rings and other condensed aromatic rings. The above-mentioned aromatic group includes both an unsubstituted aromatic group and an aromatic group that may be substituted with a substituent. As the aromatic group substituted by a substituent, for example, one or more carbon atoms of the aforementioned non-benzene-based aromatic ring, aromatic ring, or condensed aromatic ring are substituted with oxygen atoms, nitrogen atoms, sulfur atoms, etc. Heteroatomic heteroaromatic ring (pyrrole ring, pyridine ring, thiophene ring, furan ring, etc.).
作為上述矽烷基係可列舉：前述之具有烷基之矽烷基(例如三甲基矽烷基等)、具有烷氧基之矽烷基等。上述烷氧基係意味著碳數1~6之低級烷氧基、或者碳數7~10之中級烷氧基。上述烷氧基係可為直鏈狀、分支狀、環狀之任一者。作為具有烷氧基之矽烷基係可列舉例如：二乙氧基矽烷基等。 Examples of the above-mentioned silyl group include the aforementioned silyl group having an alkyl group (for example, trimethylsilyl group, etc.), a silyl group having an alkoxy group, and the like. The aforementioned alkoxy group means a lower alkoxy group having 1 to 6 carbon atoms, or a middle alkoxy group having 7 to 10 carbon atoms. The above-mentioned alkoxy group may be linear, branched, and cyclic. Examples of the silyl group having an alkoxy group include diethoxysilyl group and the like.
作為使用於本發明之氰醇化合物，較佳係例如：丙酮氰醇、甲醛氰醇、及苯甲醛氰醇、1,1,1-三氟丙酮氰醇。此等係可單獨使用，亦可併用二種以上。以下顯示上述化合物之構造。 The cyanohydrin compound used in the present invention is preferably, for example, acetone cyanohydrin, formaldehyde cyanohydrin, benzaldehyde cyanohydrin, and 1,1,1-trifluoroacetone cyanohydrin. These systems can be used alone or in combination of two or more. The structure of the above compound is shown below.
以下，針對本發明之無電解金鍍敷浴進行說明。如前述般，本發明之無電解金鍍敷浴係含有水溶性金化合物、還原劑、錯合劑、及安定化劑，其特徵為使用上述氰醇化合物作為安定化劑之點。 Hereinafter, the electroless gold plating bath of the present invention will be described. As described above, the electroless gold plating bath of the present invention contains a water-soluble gold compound, a reducing agent, a complexing agent, and a stabilizer, and is characterized by using the above-mentioned cyanohydrin compound as a stabilizer.
為了使因氰醇化合物所致之鍍敷能力提昇作用有效發揮，於無電解金鍍敷浴中，氰醇化合物所佔之含量(單獨包含時為單獨之量，包含二種以上時為合計量)，較佳為0.0001~1mol/L，更佳為0.001~0.1mol/L。若未達0.0001mol/L，則無法得到所期望之效果。另一方面，若超過1mol/L，則鍍敷析出速度會降低。 In order to effectively exert the effect of improving the plating ability due to the cyanohydrin compound, the content of the cyanohydrin compound in the electroless gold plating bath (when included alone is a single amount, when two or more types are included, the total amount is ), preferably 0.0001 to 1 mol/L, more preferably 0.001 to 0.1 mol/L. If it is less than 0.0001mol/L, the desired effect cannot be obtained. On the other hand, if it exceeds 1 mol/L, the plating precipitation rate will decrease.
於本發明之無電解金鍍敷浴中，上述安定化 劑以外的要件並無特別限定，只要是在無電解鍍敷之領域中所通常使用者且不阻礙本發明之作用的範圍則無特別限定。以下，針對各要件，說明較佳的樣態。 In the electroless gold plating bath of the present invention, the above stabilized The requirements other than the agent are not particularly limited, and are not particularly limited as long as they are ordinary users in the field of electroless plating and do not hinder the scope of the effect of the present invention. Hereinafter, a better aspect will be explained for each requirement.
使用於本發明之水溶性金化合物，係可為不含有氰基(CN)的水溶性金化合物，亦可為含有氰基的水溶性金化合物。此等之種類並無特別限定，可使用在該技術領域中所通常所使用者。作為前者之例係可列舉例如：金之亞硫酸鹽、硫代硫酸鹽、硫氰酸鹽、硫酸鹽、硝酸鹽、甲磺酸鹽、四氨基錯合物、氯化物、溴化物、碘化物、氫氧化物、氧化物等。作為後者之例係可列舉例如：氰化金、氰化金鉀、氰化金鈉、氰化金銨等之氰化金鹽等。 The water-soluble gold compound used in the present invention may be a water-soluble gold compound not containing a cyano group (CN) or a water-soluble gold compound containing a cyano group. These types are not particularly limited, and can be used by users commonly used in the technical field. Examples of the former include: gold sulfite, thiosulfate, thiocyanate, sulfate, nitrate, methanesulfonate, tetraamino complex, chloride, bromide, and iodide , Hydroxide, oxide, etc. Examples of the latter include gold cyanide salts such as gold cyanide, potassium gold cyanide, sodium gold cyanide, and gold ammonium cyanide.
於鍍敷浴中，上述水溶性金化合物所佔之含量，以金基準計，較佳為0.0001~1mol/L，更佳為0.002~0.03mol/L。若低於上述範圍，則有鍍敷析出速度降低之虞，另一方面，若超過上述範圍，則有不利於經濟面的情況。 In the plating bath, the content of the aforementioned water-soluble gold compound is based on gold, preferably 0.0001 to 1 mol/L, more preferably 0.002 to 0.03 mol/L. If it is less than the above range, the plating precipitation rate may decrease. On the other hand, if it exceeds the above range, it may be disadvantageous in terms of economy.
使用於本發明之還原劑的種類，只要可發揮所期望之鍍敷能力者則無特別限定，可使用於該技術領域中所通常使用的還原劑。可列舉例如：氫化硼化合物、胺基硼烷化合物、硫脲、對苯二酚、抗壞血酸、肼、甲醛、甲醛重亞 硫酸鹽等。此等係可單獨添加，亦可併用二種以上。 The type of reducing agent used in the present invention is not particularly limited as long as it can exhibit the desired plating ability, and it can be used for reducing agents generally used in the technical field. Examples include: boron hydride compounds, aminoborane compounds, thiourea, hydroquinone, ascorbic acid, hydrazine, formaldehyde, formaldehyde Sulfate etc. These systems can be added alone, or two or more of them can be used in combination.
於本發明中，較佳係併用由甲醛、及甲醛重亞硫酸鹽所成之群中選出的至少一種(以下，有時稱為甲醛及/或甲醛重亞硫酸鹽)、與以下述式(1)或(2)所表示之胺化合物。 In the present invention, at least one selected from the group consisting of formaldehyde and formaldehyde bisulfite (hereinafter, sometimes referred to as formaldehyde and/or formaldehyde bisulfite) is preferably used in combination with the following formula ( The amine compound represented by 1) or (2).
‧R1-NH-C2H4-NH-R2‧‧‧(1) ‧R 1 -NH-C 2 H 4 -NH-R 2 ‧‧‧(1)
‧R3-(CH2-NH-C2H4-NH-CH2)n-R4‧‧‧(2) ‧R 3 -(CH 2 -NH-C 2 H 4 -NH-CH 2 ) n -R 4 ‧‧‧(2)
上述式(1)及(2)中，R1、R2、R3及R4係表示-OH、-CH3、-CH2OH、-C2H4OH、-CH2N(CH3)2、-CH2NH(CH2OH)、-CH2NH(C2H4OH)、-C2H4NH(CH2OH)、-C2H4NH(C2H4OH)、-CH2N(CH2OH)2、-CH2N(C2H4OH)2、-C2H4N(CH2OH)2或-C2H4N(C2H4OH)2，且可相同亦可相異。n為1~4之整數。 In the above formulas (1) and (2), R 1 , R 2 , R 3 and R 4 represent -OH, -CH 3 , -CH 2 OH, -C 2 H 4 OH, -CH 2 N(CH 3 ) 2 , -CH 2 NH(CH 2 OH), -CH 2 NH(C 2 H 4 OH), -C 2 H 4 NH(CH 2 OH), -C 2 H 4 NH(C 2 H 4 OH) , -CH 2 N(CH 2 OH) 2 , -CH 2 N(C 2 H 4 OH) 2 , -C 2 H 4 N(CH 2 OH) 2 or -C 2 H 4 N(C 2 H 4 OH ) 2 , and can be the same or different. n is an integer from 1 to 4.
可推測藉由將此等併用(共存)，而生成如下式所示般之甲醛-胺複合物，而發揮作為還原劑成分的作用。 It is presumed that by using these in combination (coexistence), a formaldehyde-amine complex as shown in the following formula is produced, and it functions as a reducing agent component.
‧在使用甲醛的情況 ‧When using formaldehyde
甲醛+胺化合物 →還原劑成分(甲醛-胺複合物) Formaldehyde + amine compound →Reducing agent component (formaldehyde-amine complex)
‧在使用甲醛重亞硫酸鹽的情況 ‧When using formaldehyde bisulfite
甲醛重亞硫酸鹽+胺化合物 →還原劑成分(甲醛-胺複合物)+亞硫酸 Formaldehyde bisulfite + amine compound →Reducing agent component (formaldehyde-amine complex) + sulfurous acid
作為上述甲醛重亞硫酸鹽係可列舉例如：甲 醛重亞硫酸鈉、甲醛重亞硫酸鉀、甲醛重亞硫酸銨等。 Examples of the formaldehyde bisulfite system include: Aldehydic sodium bisulfite, potassium formaldehyde bisulfite, ammonium formaldehyde bisulfite, etc.
上述併用樣態的詳細內容係於日本特開2008-169425號公報、日本特開2008-266668號公報中詳細敘述，因此，詳細內容只要參照上述公報即可。 The detailed content of the above-mentioned combination mode is described in Japanese Patent Laid-Open No. 2008-169425 and Japanese Patent Laid-Open No. 2008-266668. Therefore, the detailed content can be referred to the aforementioned publication.
於鍍敷浴中，上述甲醛及/或甲醛重亞硫酸鹽所佔之濃度(單獨包含時為單獨之濃度，包含兩者時為合計濃度)，較佳為0.0001~0.5mol/L，更佳為0.001~0.3mol/L。若低於上述範圍，則有底層鎳會腐蝕之虞，另一方面，若超過上述範圍，則有鍍敷浴變得不安定之虞。 In the plating bath, the concentration occupied by the above formaldehyde and/or formaldehyde bisulfite (when included alone is the concentration alone, when both are included, the total concentration), preferably 0.0001~0.5mol/L, more preferably It is 0.001~0.3mol/L. If it is less than the above range, the underlying nickel may corrode. On the other hand, if it exceeds the above range, the plating bath may become unstable.
於鍍敷浴中，上述胺化合物所佔之濃度，較佳為0.001~3mol/L，更佳為0.01~1mol/L。若低於上述範圍，則有析出速度降低之虞，另一方面，若超過上述範圍，則有鍍敷浴變得不安定之虞。 In the plating bath, the concentration of the above-mentioned amine compound is preferably 0.001 to 3 mol/L, more preferably 0.01 to 1 mol/L. If it is less than the above range, the precipitation rate may decrease. On the other hand, if it exceeds the above range, the plating bath may become unstable.
上述甲醛及/或甲醛重亞硫酸鹽之含量(單獨包含時為單獨之量，包含兩者時為合計量)、與上述胺化合物之含量的較佳之莫耳比，係甲醛及/或甲醛重亞硫酸鹽：胺化合物=1：30~3：1，更佳為1：10~1：1。若甲醛及/或甲醛重亞硫酸鹽比上述範圍多，則有鍍敷浴變得不安定之虞，另一方面，若上述胺化合物比上述範圍多，則有不利於經濟面的情況。 The content of the above formaldehyde and/or formaldehyde bisulfite (individual amount when included alone, and the total amount when both included), and the preferred molar ratio of the above amine compound content, is the weight of formaldehyde and/or formaldehyde Sulfite: Amine compound = 1:30~3:1, more preferably 1:10~1:1. If the amount of formaldehyde and/or formaldehyde bisulfite is more than the above range, the plating bath may become unstable. On the other hand, if the amount of the above amine compound is more than the above range, it may be economically disadvantageous.
使用於本發明之錯合劑的種類亦無特別限定，可使用無電解鍍敷浴中所使用之周知的錯合劑。可列舉例如：磷 酸、硼酸、檸檬酸、葡萄糖酸、酒石酸、乳酸、蘋果酸、乙二胺、三乙醇胺、乙二胺四乙酸、氮基三乙酸、二伸乙三胺五乙酸、羥乙基乙二胺三乙酸、三伸乙四胺六乙酸、1,3-丙二胺四乙酸、1,3-二胺-2-羥丙四乙酸、羥乙基亞胺二乙酸、二羥基甘胺酸、二醇醚二胺四乙酸、二羧甲基麩胺酸、羥亞乙基二磷酸、乙二胺四(亞甲基磷酸)、或者其鹼金屬(例如，鈉、鉀)鹽、鹼土類金屬鹽、銨鹽等。此等係可單獨使用，亦可併用二種以上。 The type of the complexing agent used in the present invention is also not particularly limited, and a well-known complexing agent used in an electroless plating bath can be used. Examples include: phosphorus Acid, boric acid, citric acid, gluconic acid, tartaric acid, lactic acid, malic acid, ethylenediamine, triethanolamine, ethylenediaminetetraacetic acid, nitrotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediamine Acetic acid, ethylenetetramine hexaacetic acid, 1,3-propylene diamine tetraacetic acid, 1,3-diamine-2-hydroxypropylene tetraacetic acid, hydroxyethyl imine diacetic acid, dihydroxyglycine, glycol Ether diamine tetraacetic acid, dicarboxymethyl glutamic acid, hydroxyethylene diphosphoric acid, ethylene diamine tetrakis (methylene phosphoric acid), or its alkali metal (for example, sodium, potassium) salt, alkaline earth metal salt, Ammonium salt and so on. These systems can be used alone or in combination of two or more.
於鍍敷浴中，上述錯合劑所佔之濃度(單獨包含時為單獨之量，包含兩者時為合計量)，較佳為0.001~1mol/L，更佳為0.01~0.5mol/L。若低於上述範圍，則有因所溶析的金屬而析出速度降低之虞，另一方面，若超過上述範圍，則有不利於經濟面的情況。 In the plating bath, the concentration of the above-mentioned complexing agent (individual amount when included alone, and the total amount when including both) is preferably 0.001 to 1 mol/L, more preferably 0.01 to 0.5 mol/L. If it is less than the above range, the precipitation rate may decrease due to the eluted metal. On the other hand, if it exceeds the above range, it may be economically disadvantageous.
本發明之無電解金鍍敷浴之pH較佳為5~10。若低於上述範圍，則有析出速度降低之虞，另一方面，若超過上述範圍，則有浴變得不安定之虞。pH調整劑之種類並無特別限定，可列舉在周知之鍍敷浴所使用者，例如：氫氧化鈉、氫氧化鉀、銨、硫酸、磷酸、硼酸等。 The pH of the electroless gold plating bath of the present invention is preferably 5-10. If it is less than the above range, the precipitation rate may decrease. On the other hand, if it exceeds the above range, the bath may become unstable. The type of pH adjuster is not particularly limited, and it can be used in well-known plating baths, such as sodium hydroxide, potassium hydroxide, ammonium, sulfuric acid, phosphoric acid, boric acid, and the like.
本發明之無電解金鍍敷浴之使用溫度較佳為40~90℃。若低於上述範圍，則有析出速度降低之虞，另一方面，若超過上述範圍，則有鍍敷浴變得不安定之虞。 The use temperature of the electroless gold plating bath of the present invention is preferably 40 to 90°C. If it is less than the above range, the precipitation rate may decrease. On the other hand, if it exceeds the above range, the plating bath may become unstable.
本發明之無電解金鍍敷浴，係於上述之無電解鎳/置換金法(ENIG)、直接置換金法(DIG)、無電 解鎳/無電解鈀/置換金法(ENEPIG)之任一者皆可適用。例如，藉由使用本發明之無電解金鍍敷浴，使鈀鍍敷皮膜接觸於無電解金鍍敷浴，而可將鈀鍍敷皮膜表面進行無電解金鍍敷處理。於此情況中，可以例如5~60分鐘之接觸時間，形成厚度0.01~2μm之金鍍敷皮膜，可以例如0.002~0.03μm/分之析出速度將金鍍敷皮膜進行成膜。 The electroless gold plating bath of the present invention is based on the above-mentioned electroless nickel/displacement gold method (ENIG), direct replacement gold method (DIG), and electroless Any one of nickel removal/electroless palladium/replacement gold method (ENEPIG) is applicable. For example, by using the electroless gold plating bath of the present invention, the palladium plating film is brought into contact with the electroless gold plating bath, and the surface of the palladium plating film can be subjected to electroless gold plating treatment. In this case, a gold-plated film with a thickness of 0.01-2 μm can be formed with a contact time of, for example, 5 to 60 minutes, and the gold-plated film can be formed at a precipitation rate of, for example, 0.002 to 0.03 μm/min.
本發明之無電解金鍍敷浴，例如，可適宜使用於將印刷配線板、陶瓷基板、半導體基板、IC封裝等之電子零件的配線電路安裝部分或端子部分進行無電解金鍍敷處理的情況中。 The electroless gold plating bath of the present invention, for example, can be suitably used when electroless gold plating is performed on wiring circuit mounting parts or terminal parts of electronic parts such as printed wiring boards, ceramic substrates, semiconductor substrates, IC packages, etc. in.
本申請案係根據2016年5月12日所申請之日本專利申請第2016-96511號而主張優先權之利益者。2016年5月12日所申請之日本專利申請第2016-96511號之說明書的全部內容係用來參考而援用於本申請案中。 This application is based on Japanese Patent Application No. 2016-96511 filed on May 12, 2016 and claims the benefit of priority. The entire content of the specification of Japanese Patent Application No. 2016-96511 filed on May 12, 2016 is for reference and is incorporated in this application.
以下，雖列舉實施例來更具體地說明本發明，但本發明並不受下述實施例所限制，亦可在可適於前/後述之要旨的範圍內添加變更來實施，該等任一者皆包含於本發明之技術範圍內。 Hereinafter, although examples are given to explain the present invention more specifically, the present invention is not limited by the following examples, and can also be implemented by adding changes within the scope that can be adapted to the gist of the foregoing/later description. All of them are included in the technical scope of the present invention.
於本實施例中，為了調查氰醇化合物作為無電解金鍍敷浴之安定化劑有效發揮作用一事，而利用以下的方法來 調查安定性、外觀、及鍍敷皮膜形成速度(鍍敷速度)。 In this example, in order to investigate the effectiveness of the cyanohydrin compound as a stabilizer of the electroless gold plating bath, the following method was used to The stability, appearance, and plating film formation speed (plating speed) were investigated.
製作表1所記載之金鍍敷浴，裝入容器中，並昇溫至表1記載之各溫度後，以上述溫度保持24小時。表1中之溫度(保持溫度)不同的原因在於，依據還原劑的種類而Au之還原反應溫度不同之故。 The gold plating bath described in Table 1 was prepared, put into a container, and heated to each temperature described in Table 1, and then kept at the above temperature for 24 hours. The reason why the temperature (holding temperature) in Table 1 is different is that the Au reduction reaction temperature is different depending on the type of reducing agent.
藉由目視觀察保持上述溫度的期間之鍍敷液的狀態，調查浴分解的跡象之於容器之金析出的有無。將無金之析出者評估為○(安定性優異)，將觀察到金之析出者評估為×(安定性差)。 By visually observing the state of the plating solution while maintaining the above-mentioned temperature, the presence or absence of gold precipitation in the container was investigated for signs of bath decomposition. Those with no gold precipitation were evaluated as ○ (excellent in stability), and those with gold precipitation observed were evaluated as × (poor in stability).
將基板浸漬於表1之各鍍敷浴來施行金鍍敷，以目視觀察鍍敷外觀。詳細而言，準備上村工業(股)製BGA基板，依序施行表2記載之各步驟後，以目視觀察金鍍敷皮膜的外觀。表2之各步驟間，除了預浸漬與活化劑期間以外，充分進行水洗(水洗時間大約30秒~2分鐘)。其結果，將可得到均勻的外觀者評估為○(外觀優異)，將外觀不均勻，或者有不均者評估為×(外觀差)。 The substrate was immersed in each plating bath in Table 1 to perform gold plating, and the appearance of the plating was visually observed. Specifically, a BGA substrate manufactured by Uemura Kogyo Co., Ltd. was prepared, and after each step described in Table 2 was performed in sequence, the appearance of the gold plating film was visually observed. During each step in Table 2, except for the prepreg and activator period, fully wash with water (washing time is about 30 seconds to 2 minutes). As a result, those who can obtain a uniform appearance are evaluated as ○ (excellent in appearance), and those with uneven appearance or unevenness are evaluated as × (poor in appearance).
以與上述外觀之觀察方法相同地形成金屬鍍敷皮膜，對上述皮膜之厚度以螢光X射線膜厚計(Hitachi High- Tech Science(舊SII NanoTechnology)製之SFT-9550)進行測定。藉由將所得之金鍍敷皮膜的厚度除以該金鍍敷皮膜之形成時間而算出鍍敷速度(μm/hr)。於本實施例中，將鍍敷速度為0.15μm/hr以上者評估為○(鍍敷速度為快)，將鍍敷速度為未達0.15μm/hr者評估為×(鍍敷速度為慢)。 The metal plating film was formed in the same manner as the observation method of the above-mentioned appearance, and the thickness of the above-mentioned film was measured as the fluorescent X-ray film thickness (Hitachi High- SFT-9550 manufactured by Tech Science (formerly SII NanoTechnology) was measured. The plating rate (μm/hr) was calculated by dividing the thickness of the obtained gold plating film by the formation time of the gold plating film. In this example, the plating speed of 0.15 μm/hr or more is evaluated as ○ (the plating speed is fast), and the plating speed is evaluated as × (the plating speed is slow) if the plating speed is less than 0.15 μm/hr .
將此等之結果記載於表3。於本實施例中，將以上述方式所評估之安定性、外觀、及鍍敷速度全部為○者判定為鍍敷能力優異，任一者為×者判定為鍍敷能力差。 The results are shown in Table 3. In this example, the stability, appearance, and plating speed evaluated in the above-mentioned manner were all determined to be excellent in plating ability, and any one was determined to be poor in plating ability.
由表3，可如下述般地考察。 From Table 3, it can be considered as follows.
實施例1、4(使用氰浴)、實施例2、3(使用無氰浴)，係使用氰醇化合物作為安定化劑的例子，其安定性、外觀、及鍍敷速度任一者皆良好，鍍敷能力極優異。亦即，氰醇化合物作為無電解金鍍敷浴之安定化劑極有用，得知上述效果係無關於氰浴、無氰浴的種類皆可有效發揮。 Examples 1, 4 (using a cyanide bath), Examples 2, 3 (using a non-cyanide bath), are examples of using a cyanohydrin compound as a stabilizer, and its stability, appearance, and plating speed are all good , The plating ability is extremely excellent. That is, the cyanohydrin compound is extremely useful as a stabilizer for the electroless gold plating bath, and it is known that the above-mentioned effect can be effectively exerted regardless of the type of the cyanide bath and the non-cyanide bath.
相對於此，比較例1(使用氰浴)、比較例3(使用無氰浴)，係皆無添加安定化劑的例子，其安定性降低。 In contrast, Comparative Example 1 (using a cyanide bath) and Comparative Example 3 (using a non-cyanide bath) are examples in which a stabilizer is not added, and the stability is reduced.
比較例2、6(皆使用無氰浴)，係使用以往之安定化劑的例子，於比較例2中係觀察到外觀不良及鍍敷速度之降低。於比較例6中係安定性降低。 Comparative Examples 2 and 6 (both using a cyanide-free bath) are examples of using conventional stabilizers. In Comparative Example 2, poor appearance and reduction in plating speed were observed. In Comparative Example 6, the stability of the system was reduced.
比較例4、5(皆使用氰浴)，係使用具有CN基但不具有OH基之丁二腈、乙腈作為安定化劑的例子，任一者皆無法得到所期望之安定性。 Comparative Examples 4 and 5 (both using a cyanide bath) are examples in which succinonitrile and acetonitrile having CN groups but not OH groups are used as stabilizers, and neither of them can achieve the desired stability.
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| TW201807253A TW201807253A (en) | 2018-03-01 |
| TWI713669B true TWI713669B (en) | 2020-12-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW106100509A TWI713669B (en) | 2016-05-12 | 2017-01-06 | Electroless gold plating bath |
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| Country | Link |
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| JP (1) | JP6901847B2 (en) |
| CN (1) | CN107365985A (en) |
| TW (1) | TWI713669B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3517651B1 (en) | 2018-01-26 | 2020-09-02 | ATOTECH Deutschland GmbH | Electroless gold plating bath |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246955A (en) * | 2006-03-14 | 2007-09-27 | Okuno Chem Ind Co Ltd | Electroless gold-plating bath |
| TW200842203A (en) * | 2007-01-11 | 2008-11-01 | Uyemura C & Co Ltd | Method for maintaining plating capacity in electroless gold plating bath |
| TW201114945A (en) * | 2009-04-21 | 2011-05-01 | Uyemura & Co Ltd | Electroless gold plating bath |
| TW201137185A (en) * | 2010-03-12 | 2011-11-01 | Univ Leuven Kath | Liquid metal salts |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3589916A (en) * | 1964-06-24 | 1971-06-29 | Photocircuits Corp | Autocatalytic gold plating solutions |
| JP5526458B2 (en) * | 2006-12-06 | 2014-06-18 | 上村工業株式会社 | Electroless gold plating bath and electroless gold plating method |
| JP5013077B2 (en) * | 2007-04-16 | 2012-08-29 | 上村工業株式会社 | Electroless gold plating method and electronic component |
| JP5504467B2 (en) * | 2008-03-25 | 2014-05-28 | 独立行政法人理化学研究所 | Photoreduction processing of 3D nano metal structures |
| JP6722037B2 (en) * | 2016-05-12 | 2020-07-15 | 上村工業株式会社 | Method for maintaining and controlling plating ability of electroless gold plating bath |
-
2016
- 2016-12-12 JP JP2016240473A patent/JP6901847B2/en active Active
-
2017
- 2017-01-06 TW TW106100509A patent/TWI713669B/en not_active IP Right Cessation
- 2017-03-03 CN CN201710124004.4A patent/CN107365985A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246955A (en) * | 2006-03-14 | 2007-09-27 | Okuno Chem Ind Co Ltd | Electroless gold-plating bath |
| TW200842203A (en) * | 2007-01-11 | 2008-11-01 | Uyemura C & Co Ltd | Method for maintaining plating capacity in electroless gold plating bath |
| TW201114945A (en) * | 2009-04-21 | 2011-05-01 | Uyemura & Co Ltd | Electroless gold plating bath |
| TW201137185A (en) * | 2010-03-12 | 2011-11-01 | Univ Leuven Kath | Liquid metal salts |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017206766A (en) | 2017-11-24 |
| TW201807253A (en) | 2018-03-01 |
| JP6901847B2 (en) | 2021-07-14 |
| CN107365985A (en) | 2017-11-21 |
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