TW200839032A - Reduction-type electroless tin plating solution and tin plating films made by using the same - Google Patents

Abstract

The invention aims at providing a reduction-type electroless tin plating solution which is suppressed in the substitution reaction on a substrate copper or copper alloy and enables stable deposition and which is stable and good for practical use, and provides a reduction-type electroless tin plating solution characterized by comprising as the essential constituents a water-soluble tin compound, a water-soluble titanium compound, and an organic complexing agent containing trivalent phosphorus; a process for the production of tin plating films by using the tin plating solution; and tin plating films obtained by electroless plating with the solution.

Description

[Technical Field] The present invention relates to a reduced-type electroless tin plating bath, a tin film using the same, a method for producing the tin film, and a tin film obtained therefrom. [Prior Art] The electroless tin plating is applied to the terminal portion of an electronic component, and has been put into practical use as a replacement non-electrolytic tin liquid containing tin salt, organic sulfonic acid and sulfur urea as basic components. The replacement type non-electrolytic tin bath is such that the copper or copper alloy of the base material is dissolved in the form of metal ions to supply electrons to the tin ions in the plating solution to grow the tin film. Therefore, the fine pitched electrons in recent years are used. In the parts, if the electroless tin plating treatment is applied, the copper or copper alloy wiring may be broken and the thick tinplate version cannot be grown'. In order to solve this problem, Patent Document 1 discloses that the replacement type non-electrolytic chain tin liquid is modified, and instead of mineral acid such as hydrochloric acid or sulfuric acid, organic stone yellow acid and its divalent tin salt are used, and Sodium phosphite is used as a reducing agent to carry out the displacement reaction in parallel with the reduction reaction to reduce the inadvertent tin plating solution on the copper base material or the copper alloy; however, the copper base material or the copper alloy dissolves and cannot be achieved. A stage in which a tin film of a sufficient thickness is grown on fine pitch wiring in recent years. In addition, in Non-Patent Document 1, a reduction type of EDTA (Ethylenediaminetetraacetic Acid), NTA (Nitrilotriacetic Acid), and citric acid was used as a reducing agent, and sodium carbonate was used as a pH adjuster. Non-electrolytic tin plating solution; only it is easy to send 312XP / invention manual (supplement) /97-02/96147170 5 200839032 ^ abnormal precipitation of tin, plating solution is uneasy ^, difficult to work stably and so on. Patent Document 1: Japanese Laid-Open Patent Publication No. SHO63-230883 Non-Patent Document 1: Surface Technology, Book 44, Issue 11 (1 993) 102-107 Page 2 [Summary of the Invention] (Problems to be Solved by the Invention) The invention is proposed by the above prior art, and the object of the invention is that the Z inhibits the displacement reaction of the copper base material or the copper alloy, and the precipitation can be determined to be stable and stable (4) reduced non-electrolytic ore. Tin liquid. (Means for Solving the Problem) The results of deliberate research by the Mao Zemin and others in order to solve the above problems, see: by making him less soluble in water-soluble tin compounds, water-soluble titanation: rush, one and containing emulsification number The reduced-type non-electrolytic tin bath liquid which is a constituent component of the trivalent phosphorus organic compounding agent can suppress the substitution of the copper base material or the copper alloy, and has a stable deposition rate, and can achieve excellent plating properties. The present invention has been completed. That is, the present invention provides a reduced-type electroless tin plating bath containing at least a water-soluble tin compound as a water-repellent compound, a compounded titanium compound, and an organic complexing agent having an oxidation number of 3, as a constituent component. A method for producing a tin film is characterized in that non-electrochemical analysis of ore is carried out using the above-mentioned reduced type non-electrolytic tin bath. Further, the present invention provides a tin film which is characterized by non-electrolytic plating by using the above-described electroless tin plating solution. 312XP/Invention Manual (Supplement)/97-02/96147170 6 200839032 (Effect of the Invention) 豕本明明, can provide the suppression of the replacement of copper base metal or copper alloy:: dissolution of copper in the plating solution It can have a stable precipitation reaction, and the plating solution: It is also easy to break the wire even when the shape of the copper base material or the copper alloy is fine. The finely spaced electronic parts can also grow on copper or copper alloy. A tin film of sufficient thickness or the like can conform to a practical tin plating solution. [Embodiment] The present invention will be described below, but the present invention is not limited to the specific embodiments described above, and can be arbitrarily modified within the scope of the technical spirit of the present invention. The reduced type electroless tin plating bath of the present invention must contain a water-soluble tin compound. The water-soluble tin compound is not particularly limited as long as it can be used as a tin supply source, and is preferably selected from a mineral acid salt of tin, a carboxylate of tin, an alkanesulfonate of tin or an alkanolsulfonic acid. Among the groups consisting of salt, tin hydroxide and metastannic acid. These water-soluble tin compounds may be used alone or in combination of two or more. The valence (oxidation number) of the tin of the above-mentioned water-soluble tin compound can be either a divalent or a tetravalent one, and it is preferable to use a divalent value from the viewpoint of the deposition rate. That is, a stannous compound is preferred. Specific examples include inorganic salts of tin such as stannous chloride, tin chloride, stannous sulfate, tin sulfate, and tin pyrophosphate; stannous citrate, tin citrate, stannous oxalate, and oxalic acid. a carboxylate of tin such as tin; tin decane sulfonate, tin bismuth sulfonate, tin 2-ethane sulfonate, tin 1-propane sulfonate, 3-propene sulphuric acid tin, etc. 312XP/Invention Manual (Supplement) /97-02/96147170 7 200839032 Any alkane sulfonate of n-plating, B, 1-propylidene-burning tin; tin sterol sulfonate, hydroxyethane-hydrazine Hydrogen of tin such as tin sulfonate, hydroxy tin, tin hydroxide, etc., ore, performance and cost, and obtaining an alkanol sulfonate such as tin sulfonate, tin sulfonate, tin sulfonate, tin sulfonate, tin hydride Acid salt; stannous hydroxide, hydroxide, metastannic acid, and the like. Among these, it is preferable to consider stannous chloride or stannous sulfate in terms of the ease of analysis of the town. The content of the above-mentioned water-soluble tin compound in the reduced-type electroless tin plating bath of the present invention is not particularly limited, and the total amount of the reduced-type electroless tin plating solution is usually 0.5 g/L to 1 〇〇g/ as the metal tin. L is preferably 5 g/L to 3 〇g/L, and particularly preferably 10 g/L to 20 g/L. When the content of the metallic tin in the reduced-type electroless tin plating bath is too small, the precipitation rate of the tin film is too slow to be practical, and the content of the metallic tin in the reduced-type electroless tin plating bath is too large, and it is used as a tin source. The water-soluble tin compound may be difficult to dissolve.

The reduced type electroless tin plating solution of the present invention must contain a water-soluble compound. The water-soluble titanium compound is not particularly limited as long as it functions as a reducing agent, and specifically, it is preferably halogenated such as titanium trichloride, titanium triiodide or titanium tribromide. The reason for titanium, titanium sulfate, and the like is based on considerations such as plating performance and ease of availability. Regarding the valence number (oxidation number), the divalent titanium compound is unstable and easily oxidized to tetravalent, and the tetravalent titanium compound is not oxidized by itself, so that electrons cannot be supplied. Consider the price of 3. Such water-soluble chemistry 312XP/invention manual (supplement)/97-〇2/9614717() 8 200839032

The metal titanium is usually 0· 〇 lg / L 〜 l 〇 0g / L, preferably 〇 / L 2 L, particularly preferably lg / L ~ 10g / L. If the content of the water-soluble titanium compound in the reduced-type electroless tin plating bath is too small, the precipitation rate of the film is too slow to be practical, and if the content of the water-soluble titanium compound in the reduced-type electroless tin plating solution is too large, The tin source in the plating solution is abnormally precipitated, and the plating bath has poor stability and may not work stably. The reduced type electroless tin plating bath of the present invention must further contain an organic acid-containing complex having an oxidation number of 3%. The "organic complexing agent containing an oxidizing number of 3 valences" is not particularly limited, and specific examples thereof include nitrogen trisinophosphonic acid, ethylenediamine tetramethylene phosphonic acid, and diethylenetriamine pentaethylene. An amine-containing phosphonic acid such as linonic acid, /, anthracene-amine tetraphosphonium phosphonate, hexamethylenetriamine pentamethylphosphonic acid or the like; a hydroxyl group-containing phosphine such as 1-hydrocarbylethylene-M-diphosphonic acid An acid, a phenylphosphonic acid such as 3-nonoxyphosphoric acid; a benzylphosphonic acid such as 3-methylbenzylphosphonic acid or 4-cyanobenzylphosphonic acid; and the like. These "organic complexing agents containing the oxidized trivalent sarcophagus" may be used singly or in combination of two or more. In the reduced electroless tin plating bath of the present invention, the content of the above-mentioned "three-valent organic-based complexing agent containing oxidation number" is not particularly limited, and is usually lg/L for the entire reducing electroless tin plating solution. 5 〇〇 g / L, preferably i 〇 g / L ~ 2 〇〇 g / L, with 50 g / L ~ 150 g / L · is particularly good. If the content of the organic offset agent containing the oxidation number of 3 in the reduced-type electrolysis tin bath liquid is too small, the plating solution may be unstable and the effect of the compounding agent may not be exhibited; If it is too much, it will cause problems that are difficult to dissolve in water, etc. 'The effect of failing to improve as a wrong agent is not economical. 312XP/Invention Manual (Supplement)/97-02/96147170 9 200839032 The reduced-type electroless tin plating bath of the present invention may be appropriately contained in addition to the above-mentioned essential components to maintain a constant pH of the plating solution. a buffering agent, an antioxidant for preventing oxidation of a valence (oxidation number) of two valences to a tetravalent antioxidant, a pinhole for removing a tin-plated coating film, or a surfactant for defoaming a plating solution well It is used for a brightening agent for smoothing a tin plating film. The buffering agent which may be contained in the reducing type electroless tin plating bath of the present invention is not particularly limited as long as it is a well-known buffering agent, and examples thereof include inorganic acids such as succinic acid and phosphoric acid; Oxygen buffer such as malic acid. These may be used alone or in combination of two or more. The content of the buffering agent in the reduced-type non-electrolytic tin bath solution of the present invention is not limited to that of the temple, and is usually lg/L/L 110 g/L to 100 g/L for the ruthenium plating: if the content of the buffering agent is too small It will be difficult to play a buffer and the aspect of 'if too much' will fail to improve the buffer effect without paying for economic benefits. The reduced type electroless tin plating solution of the invention may be any known antioxidants, and is not particularly limited, and examples thereof include, for example, a compound, a squamous acid compound, a bismuth oxime, and pyrogallol or Wait for the salt and so on. These antioxidants: =: use, or 2 kinds of TM-. There is no second prototype electroless tin plating solution; if the content of the anti-oxidation effect agent is too small, there will be no moon, if too much, the reduced type electroless tin plating solution 312XP / invention manual bribe ) /9'〇2 axis 47170 10 200839032 The tin source in the case of abnormal precipitation. The stability of the ore-forming bath is poor, and there may be a surfactant that can be stably contained in the reduced-type non-electrolytic bond tin liquid of the month. As long as it is a well-known surfactant, it is not particularly limited, and a non-ionic interface can be used. An active agent, an anionic surfactant, an amphoteric surfactant or a cationic surfactant. These may be used alone or in combination of two or more. Eight kinds of f non-ionic surfactants can be exemplified by: (four) oxyacetic acid. "- often: alkoxy oxime butyl __ stone _ naphthol alkoxylate, styrenated phenol alkoxylate protection scale Nonionic surfactants; amine-type nonionic surfactants such as octylamine oxyacetate, hexamethylene oxime, linoleyl amine oxyalkyl ester, etc. "As an anionic surfactant, Ex.: sulphate salt of sodium lauryl sulfate, etc.; polyoxyethylene chito-based sulphur-asphyxiation, polyoxyethylene alkyl phenyl (tetra) acid salt; Wait. As the amphoteric surfactant, there may be mentioned: 2_10-alkyl group, hydrazine-methyl hydroxyethyl imidazolium betaine, hydrazine-stearyl-hydrazine, hydrazine-dimethyl-hydrazine-carboxymethyl; , lauryl dimethylamine oxide and the like. Soil Examples of the cationic surfactant include a lauryl group, a dimethyl dimethyl (tetra) vegetable, a lauryl base salt, and (d) (iv) salivary sulfhydryl amine acetate. Popularity or the like may be used alone or in combination of two or more kinds, preferably a nonionic surfactant or an amphoteric surfactant. In the reduced electroless tin plating bath of the present invention, the active agent (KOlg/L~20g/L is preferred), as long as the desired performance can be exerted, including 312XP/invention specification (supplement)/97· 〇2/9614717〇200839032 There is no particular limitation on the amount of the non-electrolytic tin bath of the present invention. The known brightening agent is not particularly limited, and may be exemplified as: 槺Private, W-based C, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The content of the gloss agent is preferably 〇.〇lg/L'g/L as long as the desired properties are exhibited, and the content is not particularly limited.

The above-mentioned ore-removing conditions of the reduced electroless tin plating bath of the present invention are not particularly limited, and it is particularly preferable as the temperature condition to be grasped and ah. Also, there is no special embarrassing time for the mining time! Minutes ~ 5 hours For better, 30 minutes to 3 hours is especially good. The thickness of the tin film obtained by non-electrochemical analysis of the reduced non-electrolytic tin bath of the present invention is not limited to (4), preferably 0 () 5, preferably m, preferably 0.5 / zm 5 / zm. . [Embodiment 1] Hereinafter, the present invention will be further described by way of examples and comparative examples, and the present invention is not limited by the scope of the invention. Further, the concentration value in the composition of the electroless plating solution is a concentration value obtained by the mass containing no crystal water in the case where the component contains crystal water. 5 pieces of 〇ldm2 pure copper plate of PAC200 (Murata product name) were used in the same manner, and degreased for 5 minutes at 5 (rc), followed by water washing. Then, ME0X (Murata) product name was used. Etching for 2 minutes at 3 ° C, followed by water washing. Next, using 1 312 312XP / invention manual (supplement) / 97-〇 2 / 96147170 12 200839032 % by weight of dilute sulfuric acid at 25 ° C After 30 seconds of acid washing, and then washing with water. Take the reduced electroless tin plating solution of the following composition, l〇〇mL, into a beaker. 'The above five copper plates were simultaneously immersed therein for 1 hour and 2 hours for plating treatment. The plating solution temperature in the plating treatment is 65. pH, pH is 6.5. [Composition of the electroless tin plating solution of Example 1] Tin sulfonate 10 g / L (calculated as metal tin)

Nitrogen trimethylene phosphonic acid (oxidation number 3 valence) 50g / L potassium citrate 30g / L

_ Three gasified titanium (20% by mass solution) 20 mL/L After the plating treatment, it was washed with water and dried, and evaluated by the following measurement method. The results are shown in Tables 1 and 2. [Method for Measuring Tin Film Thickness] The thickness of the tin film was measured by a usual method using a fluorescent X-ray analyzer SFT9255 (manufactured by Seiko Instruments, Inc.) on a pure copper plate on which a tin film was formed. Xin [Method for Measuring Copper Dissolution in Copper Electroplating Solution (Measured Concentration of Copper)]

Use ICP plasma luminescence spectrometer SPS3()(10) (SeikQ

The amount of copper eluted in the plating solution (manufactured by Instruments, Inc.) was measured by a usual method. / [Measurement method of bath decomposition] After the plating treatment, the appearance of the plating solution and the beaker wall was visually evaluated. [Example 2] The reduced type electroless tin plating solution in Example 1 was changed to the following composition 312XP / invention specification (supplement) / 97-02 / % 147170 13 200839032 The same measurement method as in Example 1 was carried out. Evaluation. The results are shown together in Tables 1 and 2. The plating treatment was carried out in the same manner as in Example 除 except that the temperature of the plating solution in the plating treatment was set to 7 Torr < t, and the pH was 6 5 . Then [the composition of the electroless tin plating solution of Example 2]

1 〇g/L (calculated as metal tin) Phosphonic acid (oxidation number 3) 50g/L 50g/L Tin sulfonate 1-hydroxyethylidene-1,11-2 potassium citrate

Di-titanium carbide (20% by mass solution) 40 mL/L [Example 3] The reduced-type electroless tin plating solution in Example 1 was changed to the following composition, and the plating solution in the plating treatment was temperature-determined. The plating treatment was carried out in the same manner as in Example 1 except that the ratio was 7 (rc and pH was 65). Then, the evaluation was carried out in the same manner as in Example 1. The results are shown together in Table 1. And Table 2. 肇 [Composition of the electroless tin plating solution of Example 3] Tin chloride Ug / L (based on metal tin)

3-decyloxybenzylphosphonic acid (oxidation number 3) 50g/L

Potassium citrate 50g/L

Titanium trichloride (20% by mass solution) 40mL/L

[Example 4] The reduced-type electroless tin plating solution in Example 1 was changed to the following composition, and the plating solution in the plating treatment was set to 70 ° C and the pH was 6 5 The plating treatment was carried out in the same manner as in Example 1. 312XP/Invention Manual (Supplement)/97-02/96147170 14 200839032 The results are shown together in the table. Evaluations 1 and Table 2 were carried out in the same manner as in Example 1. [Composition of electroless tin plating bath of Example 4]

10g / L (based on metal tin) 50g / L 50g / L 40mL / L sulfonium sulfonate sulfonyltrimethylene phosphonic acid (oxidation number 3 valence) dipotassium dichloride titanium dichloride (20% by mass solution) [ Comparative example 1]

The water-soluble compound of the reduced non-electric (tetra) tin solution in Example 1 was changed to sodium hypophosphite. The other composition was also changed to the following composition, and the temperature of the plating solution in the bell treatment was set to 85 t. A plating treatment was carried out in the same manner as in Example 1 except for PH A 6.5. Further, the plating treatment was carried out for 5 hours. Then, evaluation was carried out in the same manner as in Example 。. The results are shown together in Tables 1 and 2. [Composition of Electroless Tin Plating Bath of Comparative Example 1]

10 g/L (calculated as metal tin) 50 g/L 30 g/L 50 g/L tin sulfonate methanesulfonate (oxidation number 3 valence) potassium citrate sub-sodium sulphate [Comparative Example 2] Examples The water-soluble titanium compound of the reduced electroless tin plating bath in 1 is changed to sulfur urea, sodium hypophosphite, and the other composition is also changed to the following composition, and the plating solution in the plating treatment is set to 70°. c. The pH was 2.5, and the plating treatment was carried out in the same manner as in Example 1. In addition, 312XP / invention manual (supplement) / 97 · 〇 2 / 9614717 〇 15 200839032, plating treatment system for 3Q minutes. Then, the evaluation was carried out in the same manner as in the example. The results are shown together in Tables 1 and 2. [Comparative to the composition of the electroless tin plating bath of Example 2]

L〇g/L (as metal tin) 50g/L 75g/L 30g/L 50g/L methanesulfonate sulfonate thiourate potassium citrate sub-nanoate ► [Comparative Example 3] Example The oxidation number of the reducing type non-electrolytic tin bath in the first embodiment is changed to the nitrogen compound B: amine tetraacetic acid and nitrogen triacetic acid, and the other components are also changed to the following components, and The deposition treatment was carried out in the same manner as in Example 1 except that the temperature of the plating solution was 65 t: and the pH was 7 〇. Further, the plating treatment is performed for 5 hours. Then, the evaluation was carried out in the same manner as in Example i. The results are shown together in Tables 1 and 2. σ [Composition of electroless tin plating bath of Comparative Example 3] Tin chloride 1 )) π·/Τ / l〇g/L (in terms of metal tin)

Disodium edetate (nitrogen compound) 4〇g/L

Nitrogen triacetic acid (nitrogen compound) 20g/L

##瞻50g/L

Titanium trichloride (20% by mass solution) 40mL/L

[Comparative Example 4] The third-valent 312 XP/invention specification (supplement)/97-02/96147170 16 200839032 of the complexing agent of the reduced-type electroless tin plating solution in Example 2 was changed to an oxidation number of five-valent phosphorus. In the same manner as in Example 2 except that the temperature of the plating solution in the plating treatment was changed to 70 ° C and the pH was 6.5, the temperature was 7 (rc). Before the plating bath was decomposed, the plating treatment was not performed. [Comparison of the electroless tin plating solution of Comparative Example 4]

L〇g/L (calculated as metal tin) 50g/L 50g/L 40mL/L tin methane sulfonate pyrophosphate (oxidation number 5 price) citric acid unloading

Titanium dichloride (20% by mass solution) [Comparative Example 5] The trivalent phosphorus compound of the complexing agent of the reduced type electroless tin plating solution of Example 2 was changed to a phosphorus compound having a valence of 4, and In the plating treatment, the plating solution (10) was set to 70 C and the pH was 6.5. Otherwise, the plating treatment was carried out in the same manner as in Example 2 except that the temperature reached 7 〇χ: the plating bath was decomposed. The plating treatment was not performed.

10g/L (based on metal tin) 50g/L 50g/L 40mL/L

[Comparative Example 5 Composition of Electroless Tin Plating Bath Tin-phosphoric acid sulfonate (Oxidation Number 4) Potassium Citrate Di-titanium Dioxide (20% by mass solution) 312XP/Invention Manual (Supplement)/97Cre 614717 〇17 200839032

Seven r-i White T—Η 0· 003ppm or less (below the measured limit) The plating bath is not decomposed and stabilized for CO for 1 hour. White Τ—Η 0· 003ppm or less (below the measured limit) The plating bath is not decomposed and stabilized <N1 ¥ 1 >"< White r—Η 0· 003ppm or less (below the measured limit) The plating bath is not decomposed and stabilized. Example 1 T—Η Β r—Η 0· 003ppm or less (below the measured limit) The plating bath is not decomposed and stabilized. ^6 S? 璨 璨 Ϊ mSr $ T — Η 鹚 刼 ε € Comparative Example 5 1 tough sodium. It was impossible to measure due to failure to deposit plating. It could not be measured because it could not be demineralized. ^ Case: Comparative Example 4 刼剡珑.味姆-婵*5"璨 Unable to solve the key because of the failure to resolve the key! Disc wall 〇 1 to Aisy ^ Θ Book yell 剡 $ you scrape | κ · Comparative Example 3 1 hour B rH 4ppm plating bath undecomposed stability comparison example 2 30 minutes BT - Η 4 7 ppm plating bath undecomposed stability comparison example 1 2 hours ε & rH ο MW - slg -ffi plating bath undecomposed stability 0^ plating time tin film thickness s*s 5! τ—Η every S 璨3 001 0z, UH96/s-A6/ff }®)_s?is麟ΜΧΠ ε 200839032

Example 4 2 hours | B 03 0· 003 ppm or less (below the detection limit) The plating bath was not decomposed and stabilized. Example 3 2 hours B CN1 0. 003 ppm or less (below the measurement limit) The plating bath was not decomposed and stabilized Example 2 2 hours B (>3 0·003ppm or less (below the measured limit) The plating bath is not decomposed and stabilized in Example 1 2 hours white (NI 0-003ppm or less (below the measured limit) The plating bath is not decomposed and stabilized ^6 | The film of the tin film is thicker and thicker. iw § ηί 璨 attack rH Na Yu 鹱 W W ^ S s S Bad 3 Comparative Example 5 1 ^ ^ a Unable to measure due to failure to resolve the clock. ;-- ^ ^ * 蜮缈,|你^ ^ Comparative Example 4 Ή袈vg 贺0 荔,3⁄4 Θ 媸Vg 暂0 < Θ夺-_ Ή涂^ ^ ί ^ ^ ^ ^ Correction | κ ^ ^ ^ Comparative Example 3 Yu Li φ 5ϊ c=> ^ 7 — SB (NI ^ W ^ - 竣5 ^ c5 Book 瓌Ή珑 w ζ ^ ^ 2 Comparative Example 2 Β t co Ή 亨 “ -Μ白CO T—Η Ulj^ MW 竣5 书建t ^ i{¥ 絜Comparative example 1, LO Β TH .· ui|i ^ W - 竣S -ffi 遂ί ^ S you絜^6 S?絮时璩^ Ή Lingzang ni ηΆ 璨3 1— 13⁄4/余峰痛U ^ W ^ 鹱当刼白竣3 61 0£UH96/s, £6/ffsi)_s?i^徽/€κ<ΝΙε 200839032 [Measurement Results] #于贝知例1 In Example 2, Example 3, and Example 4, even if the tin oxide film was deposited to a film thickness, the elution of copper was below the detection limit, and it was found that the substitution reaction was well suppressed. In the case of 'only 5 hours, only 〇._.; 乂 2 and Comparative Example 3' were used to precipitate the tin film to 1 # m B, and copper was detected in the shovel. It is known that the film is deposited with the tin film. The substitution anti-f ^ ratio was compared with the case 4 and the comparative example 5 at a temperature of 7 (the mineral bath was decomposed before the TC, and the Μ + 1 - μ deuterium plating treatment could not be performed. From the results, it can be seen that the example: ? Example 3 and Example (4) Disk and copper were released. In Comparative Example 2 and Comparative Example 3, the substitution reaction was carried out in parallel with the original reaction, so that copper was dissolved. The thickness of the film was up to iJ2. In the case of /zm, in the implementation of i gate m2, the third embodiment and the fourth embodiment, 'the film thickness of the tin film is also increased by prolonging the separation to 2 times (the plating time is set to 2 hours). In order to prevent the decomposition of the ore solution, the clock solution is very stable, and the dissolution of copper is delayed. In other respects, in Comparative Example 2, even if the forging time W is even 2 hours, the plating time is even I is 4 times longer (even if the plating time is up to 4 hours), and it is not precipitated to 2 β -, and precipitated to 1. 3 // m. Comparative Example 3 is based on the analysis of =r)::r, so it is not in the first and second, and the reaction of the reaction to a good inhibition of the reduced precipitation reaction, and forging 312XP / invention book (supplement) / 97- 02/96147170 2〇200839032 The liquid is not practical and practical. In contrast, in the comparative example, the precipitation reaction cannot be sufficiently carried out & 2 /^。 In Comparative Example 2, the tin film was formed only to 1. 3 / ^. s, we believe that the copper surface is covered with a tin-bismuth film, causing the copper to no longer dissolve*, making it impossible to continue supplying electrons, causing the precipitation reaction to stop, and becoming the electroless plating solution with the replacement reaction as the main reaction mechanism. . Further, in Comparative Example 3, the plating solution was decomposed at 1 hour and 30 minutes, and thereafter no plating treatment was performed, and the plating solution was poor in stability and was not practical. Similarly, in Comparative Example 4 and Comparative Example 5, the plating bath was decomposed before the temperature reached the scratch, and it was not practical. In addition, in the case where electroless tin plating was performed on a thin copper wiring, in the case where the tin film was formed to a predetermined film thickness, the case of the non-electrolytic tin bath of Comparative Example 2 and Comparative Example 3 was dissolved to copper. There is a disconnection energy in the plating bath. (Industrial Applicability) The reduced electroless tin plating solution of the present invention is less likely to cause a copper substitution reaction with the substrate, so that elution of copper into the plating solution can be suppressed, and even a fine wiring can be used. The precipitation reaction is continuously performed under the line, and the plating solution itself is stable and practical, so it can be widely used for the use of tin ore which is generally represented by fine-pitched electronic parts. The present application is based on Japanese Patent Application No. 2006-352330, filed on Jan. 27, 2006, filed in木王 312XP / invention manual (supplement) /97-02/96147170

Claims (1)

200839032 X. Application for Patent Fan Park·· 1. - The prototype non-electrolytic liquid is characterized by a water-soluble tin compound, a water-soluble titanium compound, and an organic complexing agent containing a dish of =, : as a constituent component. The number is W 2 · as in the reduction of the scope of the patent application, the water-soluble tin compound - demineralized tin liquid, the alkaliphate or the dalatite cover _ \ = mineral acid salt, a few acid salts, 1 3. A group consisting of two or more kinds of hydrazine emulsions and metastannic acid 3. The reduced type electroless tin plating solution of claim 2, wherein the water-soluble tin compound is stannous chloride, Tin chloride, tin sulphate, stannous citrate, tin citrate, stannous oxalate, ^ sulphate tin, tin succinate, tin succinate, propane, tin hydride, 3-propane sulfonic acid Tin, methanesulfonic acid-3-% knocking tin, antimony oxide stannous oxide, tin hydroxide or metastannic acid. 4. If you apply for a patent scope! The reduced non-electrolytic tin bath according to the item, wherein the water-soluble titanium compound is titanium halide or titanium sulfate. /, 5. The reduced type electroless tin plating solution of claim 4, wherein the titanium halide is titanium trichloride, titanium triiodide or titanium tribromide. 6. The reduced-type electroless tin plating bath according to any one of the above-mentioned claims, wherein the organic complexing agent having an oxidation number of trivalent is selected from the group consisting of amino group-containing methylene phosphonic acids, Any one or more of the group consisting of phosphinic acids, phenylphosphonic acids, and benzylphosphonic acids. 312XP/Invention Manual (Repair)/97-02/9614717〇200839032 7. The reduced-type electroless tin plating solution according to claim 6, wherein the amino group-containing methylene phosphonic acid is nitrogen trimethylene Phosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriamine pentamethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid or hexamethylenetriaminepentamethylenephosphonic acid. 8. The reducing type electroless tin plating solution according to claim 6 of the patent scope, wherein the hydroxyl group-containing phosphonic acid is hydroxyethylidene-M-diphosphonic acid. 9. The reducing type electroless tin plating solution of claim 6, wherein the phenylphosphonic acid is 3-methoxyphenylphosphonic acid. 10. For the reduced non-electrolytic tin bath according to item 6 of the patent application, preferably, the fresh-base phosphonic acid is 3-methyl-based phosphonic acid or 4-cyano-based acid. The 21st feature is characterized in that the method for manufacturing a non-12. tin film is applied for the application of five items, the item W_tin liquid, which is characterized by the reduction of six items of Shenli consumption. Non-electrolytic tin plating bath for non-electrical analysis. A 13.-type tin film, which is characterized in that it is subjected to non-electrolytic reaction by using a reduction type non-electrolytic chain tin liquid of the application of the second item of the fifth item, and is characterized in that Non-Electrolytic Analytical Plating by Reducing Electroless Tin Plating Solution of Application No. 6 ~ 312XP / Invention Manual (Replenishment) / 97-02/96147170 200839032 VII. Designation of Representative Representatives: (1) Designation of the Case The representative picture is: None (2) Simple description of the component symbol of this representative figure: None 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 312XP / invention manual (supplement) /97-02/96147170 4