TW505708B - Gold plating solution and plating method using the same - Google Patents

Abstract

This invention provides a gold plating solution which uses gold compounds such as gold salts or gold complex compounds as gold and contains a buffer agent, an organic gloss agent and a conduction salt; the solution is characterized by containing bis(1,2-ethyldiamine). Through the use of a non-cyanide gold plating solution with above-mentioned characteristics, solution stability in any gold plating bath is excellent without causing any change of physical properties of the deposited gold and without being decomposed during gold plating operation. The gold plating solution includes two aspects, the use of bis(1,2-ethyldiamine) gold complex as an ingredient and the use of a gold salt as an ingredient. When such a gold plating solution is used, hardness, purity, and crystal state of the deposited gold can be controlled; thus, it is an excellent gold plating solution not seen among conventional counterparts.

Description

505708 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to different and long-term golden methods. [Know-how] Gold plating is not only used for dining utensils. Because of its use in the electronics industry, gold electrocyanide baths have been used for a long time, but recently, due to the photoresist of semiconductor parts and the need for gold recording liquid Proposal. For example, as disclosed in J. Am, a non-cyanide gold chloride is used as a gold compound using a well-known manufacturing method and a solvent (diethyl ether). A new bis (1,2,-using the bis (1,2, Ethane can obtain beautiful appearance and can be controlled by electroplating, etc. In addition, it is widely used in ancient times. The immersion in the plating solution improves the Chem, the plating solution. The 'will be at room temperature of chlorine Ethylenediamine) A plating solution that does not contain sulfite ions, has excellent solution stability, and electroplating solutions using the gold plating solution have only been used for decoration or foreign foreign electrical characteristics, making it Almost all of them are toxic gold potassium cyanide all or drainage problems, to attack (attack) problems, so for non-cyanide, there have been various non-cyanide gold plating

Soc · 1951, vol · 73, P4722, using bis (1,2-ethanediamine) gold bis (1,2-ethanediamine) gold gaseous system auric acid, ethylene diamine (monohydrate) Made by reaction. The present inventors also produced a method of producing gold gaseous compounds and a gold plating solution of gold chloride as the plating solution and method of the layer, but the hardness, purity, and precipitation state of the crystals used in the gold plating bath, Also common

505708 V. Description of the invention (2) 1 ------------ Medium A: Used as gold salt. However, the use of Na3Au (S〇3) 2 gold, sulfite ions in the ^ / Valley 'night is very unstable, and due to the oxygen oxidized by the capacity or oxygen in the atmosphere, its concentration Naturally; the result is that the stability of the gold complex in the gold-electric ore liquid is reduced, and ^ α indicates that the physical properties of the electric truss are changed or the plating solution is decomposed. [Brief description of the drawings] A sem photograph of the structure of the precipitated particles on the surface of the gold plating layer shown in FIG. Figure 2 shows the relationship with the first! The figure also shows the precipitated structure on the surface of the gold plating layer. [Explanation of the invention] One inventor is to provide an electrolytic gold plating solution with better long-term stability and resistance to long-term workability by using a gold plating solution containing 丨, 2-ethylamine, and using the same Electroplating method of electrolytic gold plating solution. As a result of the research on non-cyanide electrolytic gold electricity, which is more practical in practice, the two founders have found a gold electricity mine as described in item 1 of the scope of patent application that can exert extremely excellent performance. — The gold electric ore liquid described in item 1 of the declared patent scope is a non-cyanide electrolytic gold electric money liquid. The electrolytic gold plating liquid uses gold compounds of gold salts or gold complexes as gold, It also contains a buffering agent, an organic gloss agent, and a conductive salt, and is characterized in that the above-mentioned electroplating solution is made of 1,2,2-ethanediamine. As a result of the use of the above-mentioned electro-mineral liquid, the content of the

505708 V. Description of the invention (3) 1,2-Ethyl diamine, so the solution stability is excellent regardless of any gold-electric ore bath, and the physical properties of the precipitated gold will not occur in the gold plating operation. Changes in the composition of the gold plating solution, such as changes or decomposition of the gold plating solution. The gold-electricity mineral liquid system includes the use of bis (1,2-ethanediamine) gold complex as a raw material and the use of gold salt as a raw material. As a result, a gold plating solution is formed. Contains 1,2-ethanediamine. If the above-mentioned gold plating solution is used, it is possible to control the hardness, purity, crystallization state, and the like of the deposited gold, and it becomes an excellent electrolytic gold electro-mineral liquid which has not been known in the past. The one described in Shen Qing's patent scope is a non-cyanide electrolytic gold electric money solution, in which the gold plating solution contains the gold concentration in the gold plating solution in the range of 2 g / l to 30 g / l. Bis d, 2-ethanediamine) gold complex in the amount of gold compound, 〇; [~ 2 · 5M of 1,2-ethanediamine sulfate, inorganic acid potassium salt as conductive salt An organic carboxylic acid as a buffering agent and a heterocyclic compound containing at least one hetero atom as a fluorene organic glossing agent. The non-cyanide electrolytic gold plating solution is prepared by using bis (1,2-ethanediamine) gold tincture as a raw material. In this context, the bis (1, 2, 2 = alkane-amine) gold complexes of gold compounds are those which can be expressed by Au (en, 3+ (en: I 2-ethane, two to =). Gold The content of the complex is such that the gold is within the range of 2 to 3 (^ / 1). ^ If the lower limit is 2 g / 1 or less, the gold precipitation rate will be reduced and ^ will be used in actual operations. If the limit value is 30g / 1, then there will be no change to ί5 and gold precipitation will easily occur. ® Here, this range is obtained for the purpose of the range of the operating environment value of the plate collection μ. /, L 2 of other constituent compounds 5. Ethyl diamine sulfate is used as the fifth, the description of the invention (4) to H1; 2-ethyl diamine sulfate is in the range of. &Quot;, and advances ::: ΐ ΐ: ◦. 1M or less The effect of the complexing agent cannot be exerted, and it cannot be dissolved if the upper limit value is 2 · 5M from the right. The potassium salt of inorganic acid can be potassium sulfate, potassium lice, and potassium nitrate as described in item 4 of the patent application scope. It is a substance that can be added as a conductive salt when it is a substance-based liquid. It is better to add it in the range of HOg / i. If it is within this limit, the following two or less, it is difficult to ensure the plating solution If it has sufficient conductivity, if the limit is 100 g / i or more, it will become insoluble in the solution. Organic carboxylic acid is used to perform the function as a buffering agent ==; 5 changes, in this case, organic As mentioned in the 5 items of the patent of Weiming Ming, it has acetic acid, formic acid, or stupidity. Ί: =: t is right and can be used to have the same effect as the surfactant. The amount of organic citric acid added is 2 〇 " If the value is less than 1g / 1, it will not be able to give full play to the buffer. If you add more than the upper limit of 200g / 1 or more, the effect of the delay will not increase. J 4Old you β β Further Heterocyclic compounds containing more than one heteroatom can be face-to-face! Sex agents have the same effect as gloss agents. The heterocyclic δ system is thlophene carboxylic acid as described in item 6 of the scope of the patent application. acid), phenanthroline 44-t-di-T: 111 " 01 me), Pyridine, bipyridyl acid or bipyridyl, etc., as the heteroatoms, and nitrogen-containing 7 / Cereal compounds, etc. Also, the added amount is in the range of O.hlOg / l 505708

= 軏 佳. If the right is below the lower limit value of 0.1 lg / 1, the effect as a glossing agent cannot be fully exerted; if it exceeds 10g / 1 # above the upper limit value, the effect of increasing glossiness will not be caused as a result. The invention described in item 3 of the scope of the patent application is a non-cyanide electrolytic gold plating solution. The electrolytic gold plating solution is composed of a gold salt, 1,2-ethanediamine, a buffering organic gloss agent, and a conductive salt. It is characterized in that the plating solution contains a trivalent gold salt as a gold supply source of 5 g / l to 30 g / l and 1,2-ethanediamine diamine at a concentration of 3.0 to 3.0 M. ,

This non-cyanide electrolytic gold electroplating bath is different from the electroplating bath described in item 2 of the scope of patent application in that it uses a gold salt as a source of gold supply. As a plating solution as described above, a general trivalent gold salt can be used. By using a trivalent gold salt, a wider range of raw materials can be used. At the same time, it is also free of sulfite ions, has a longer-term solution stability and is formed than the conventional gold sulfite plating solution. Considering the shape and the like of the electroplated coating, the result obtained by research is determined by judging that it is the most excellent for the total balance.

For this purpose, trivalent gold salts are used as described in item 7 of the scope of the patent application to use bis (1,2-ethanediamine) gold trigas, gold hydroxide, potassium tetrahydroxide, and One or two or more components of qiaulic acid are preferred. The above-mentioned equivalent trivalent gold salts are not easily deteriorated even after being used for a long time when used as a plating solution, and therefore have long-term solution stability. The gold content is in the range of 5-30 g / l. If the lower limit value is 5 g / 1 or less, the gold precipitation rate becomes slow and is not suitable for practical operation; the upper limit value of 30 g / 1 is the limit of the soluble amount. Therefore, if the amount of gold is in

5. Description of the invention (6) '' -------- OK 可 :: Ϊ, the more the amount, the faster the precipitation. Therefore, within ^ 粑, the use value is selected according to the operating conditions corresponding to the purpose of use. \ 2-Ethylenediamine is used as a complexing agent. The amine sulfate is added in a range of 0.2 to 3.0 μ. If the lower limit is ^ 1, the effect as a complexing agent cannot be exerted; if the upper limit is exceeded, the presence of carbodiazepine is used by the ethanediamine, = liquid 2% = make: double (1, 2- Yiyuan Diamine) Gold wrong two liquid. Even in the case of the use of bis (1,2-ethylene diamine) gold because of the hexa-La female bis (, 2-ethanediamine) gold trichloride, two. "&Quot;, and σ have 1,2_ethanediamine, which makes it a more stable gold plating. These = :: t: liquids added with potency of potassium sulfate, potassium chloride, and potassium nitrate; ==== liquid; it can reach the recording liquid as a conductive salt with a lower limit of lg / 1 or less, which is It is difficult to ensure that the solution is in the ::::: solution if the upper limit is more than one, or 2 or more kinds of organic carboxylic acids, _acids, and boric acids, and one of the type of ° · 05M ^ 1 ou ^ nff acid, specifically, There is' ΊΓ: good. Here, organic enemies with a pH of 2 to 6. In addition, ir acid, • acid, succinic acid, lactic acid and tartaric acid can also use phosphoric acid and boric acid, which have a buffering effect.

_ 丨 _

Page 9 505708-V. Description of Invention (7). By buffering, rainbow & motion can be achieved. The addition amount is also usable = the pH of non-cyanide electrolytic gold power ore liquid changes to a total molar concentration of 0.05M-1. MJi is a kind of strict medicine, and it is better to make 0 0 5 M Ji (τ 'iii ^ t, dry range. If the lower limit value is less than 5M, the effect cannot be fully exerted. Do not increase the buffer therefore The effect of the agent is as follows: Step 9: For organic lubricating agents, such as the scope of application for patents Λ Λν phenanthroline, biphenyl, and the above oils: sound w. 1 or 2 The above ingredients. And, the added amount is preferably in the range of = ^ 5〇P 贤 1 () _ qing. Such a wide concentration: around "shows that the solubility of the above organic gloss agents will vary with the pH of the solution. If it is changed, if the right limit i50ppm or less, the effect of gloss d cannot be fully exerted, and if the right limit exceeds 10,000ppm or more, the improvement effect of gloss will not be improved because of this. Α Conductive conductive salts such as As described in item 10 of the scope of the patent application, compounds containing sulfate ions, hydrochloric acid ions, or nitrate ions can be used. That is, a compound using 1,2-ethanediamine can be dynamically supplied. 2-ethanediamine And the method of conducting ions is the most efficient and economical. Therefore, the use of ethanediamine It is preferable to add one or two or more components of the compound and the total molar concentration of the conductive ions in the range of 0.05M to 5.0M. If the lower limit of 忒 is 0.5M or less, It is difficult to ensure that the electroplating solution has sufficient conductivity, and if the upper limit value is 5 · OM or more, it cannot be dissolved in the melt.

Page 505708

However, it is better to use this type of added sulphuric acid, hydrochloric acid and nitric acid to perform the addition formula as a means of adjusting the pH value. Then, the one described in item U of the scope of patent application is a non-gold plating method. This method uses the gold plating solution as described in the items 2, 3, 4, 5, or 6 of the scope of the patent application, which is characterized in that the pH value of the solution is 2 to 7, and the liquid temperature is 40 to 80 t: The electrolytic plating was performed under the conditions of a current density of 0 · 2 ~ 3 «5A / dm2. Here, the pH of the bath liquid will be in the range of pH 2 to 7 with the addition amount of the potassium salt of the inorganic acid. If it is within this range, the appearance of the deposited gold plating layer will not occur. abnormal. When it is necessary to adjust the pH, it is better to use potassium sulfate, potassium chloride, and potassium nitrate which do not affect the characteristics of the plating solution, or potassium salts of inorganic acids, or organic carboxylic acids such as acetic acid, formic acid, and stearic acid. Control the plating solution at a temperature of 40 ° C to 80 ° C. If it is below the lower limit, the precipitation speed will be slower if it is below, and it is not suitable for practical work. The photoresistance of the gold plating layer that affects the precipitation > the life of the valley solution is drastically reduced. The purpose is to control the current density during electrolysis to 0.2 to 3.5 A / dm2, and to consider the pH value and temperature of the above-mentioned plating solution so that the deposited gold plating layer serves the purpose properties. It is possible to use the above-mentioned gold electroplating solution and use the gold key method described herein. The amount of precipitated gold is higher than that of gold precipitated using the conventional gold electroplating solution, and f has fine precipitated crystals and also has hardness. Low characteristics. As soon as 舣 σ, the finer the crystal grains, the higher the hardness of the measured metal. But 砮

505708

To the fifth, the invention description (9) the use of the gold plating solution and the gold plating method of the present invention can simultaneously obtain fine crystal grains and low hardness precipitated gold, this feature is the same as the use of the plating solution and the method It's totally different. For example, in the conventional gold electric money bath using Na3Au (S03) 2, the sulfur contained in the plating solution is also precipitated in the precipitated gold, so the same effect as that of the gold particles is obtained, so that crystal grains are formed. Large, precipitated crystalline structure. In contrast, the microstructure obtained by the electroplating method of the present invention has high purity of the precipitated gold, so the crystal grains have a very fine density (bu 1 k) of gold, and thus a hard gold plating with a small transfer density within the crystal grains can be obtained. Floor. The above situation is as shown in Table 1. It is close to the high and low stones. Table 1 Vickers hardness of gold deposits. Comparison item of hardness The maximum value of the Vickers hardness of the conventional gold plating solution of this invention 69.1 77 .4 'Minimum 64.6 72.2 Average 66 1 7 1- " · —-—_ 75.1 Standard deviation 1 2.1 1. 9 (each Ή = 30) The measurement weight of the micro-dimensional hardness tester is increased lg

Then, the one described in item 12 of the patent application is a non-ambient electrolytic gold plating method, which uses non-cyanide electrolytic gold as described in item 3, 7, 8, 9 or 10 of the patent application. The electroplating solution is electrolyzed under the condition that the pH of the solution is 2 to 6, and the liquid temperature is 40 to 70 ° C, and the current density is 0.1 to 3. OA / dm2. Here, the pH of the solution is controlled within the range of pH 2 to 6, if

Page 12 505708 V. Description of the invention (10) If it is within this range, there will be no abnormality in the appearance of the deposited gold plating layer. When it is necessary to adjust the pH, it is better to use inorganic acid salts 'such as sulfuric acid, hydrochloric acid, and nitric acid', or acetic acid, formic acid, and benzoic acid, which are special organic slow acids, which do not affect the characteristics of the plating solution. Control the plating solution at a temperature of 40 to 70 ° C. If it is below the lower limit, the precipitation speed will be slower and it is not suitable for practical work. If it is above the upper limit, it will affect the temperature of the plating solution. The luster of the precipitated gold ore layer causes a sharp decrease in the life of the solution. The current density at the time of electrolysis is controlled to be in the range of: 1 to 3. A / dm2, which is a range in which good properties can be imparted on the deposited gold plating layer obtained by considering the pH value and temperature of the above-mentioned plating solution. That is, if the above gold plating solution and gold plating method are used, it can be obtained, as described in item i 丨 of the scope of application for patents, the nucleus has finer crystal grains and low hardness. And it has excellent long-term stability and can be used for a long time. For example, in a conventional gold plating bath using N ^ AiUSC »3) 2, since sulfur contained in the plating solution is also precipitated in the precipitated gold, the same effect as that of the dispersed gold particles is obtained, thus making Crystal grains form a large and hard = crystalline structure. In addition, as compared with the case where the electrolytic gold plating of the present invention is used as described above, the phenomenon of deterioration of the plating solution, such as gold precipitation, occurs in a short time, making it difficult to perform stable operations for a long time. The plating method using the conventional plating solution cannot achieve good accuracy when performing very fine-shaped scoop bump ore deposits, so the precipitation surface of the gold after plating will become rough, and the shape of the bumps will be skewed. Utilizing the invention

Page 13 505708 V. Description of the invention (11) The gold plating solution and gold plating method can obtain a gold electroplated layer in which gold is finely precipitated, so that a high-precision gold electric ore layer can be formed on a small-sized LSI bump. At the same time, the running cost of the gold-electric ore liquid can be reduced. Table 2 shows the results of long-term stability tests using the electrolytic gold plating solution of the present invention. In Table 1, the stability is the precipitation stability of the gold plating layer when the gold is 10 g / 1 after a current of 15 000 coulombs is passed in a 1 liter non-cyanide electrolytic gold plating solution ( Precipitation speed, precipitation deviation

(dispersion, precipitation hardness, etc.). Table 2 Item No. (lot No.) __ 1 2 3 4 5 6 Solution composition gold concentration g / ι 5 8 10 10 10 10 ΕηιηΜ 1 1 1 2 2 2 retarder M vinegar 0.3 Lemon ether 0.5 Phosphate, 0.1 mm. Oi Acetic acid 0.3 Acetic acid 0.3 Gloss $ ppm ①100 (2) 500 © 700 (2) 700 01000 02000 Plating strip # ΡΗ-4 5 4.5 3.8 3 6 Temperature 60 65 70 50 65 65 Current Density A / dm2 1 1 2 2 2 2 Appearance Wood Wood-Gloss Mou Glossy Glossy Glossy Glossy Glossy Glossiness Hv 100 70 70 70 70 70 Phenanthroline, ②2,2'-bipyridine ③2,24 -f-based pyridine (2,2-4-pi coline)

It shows the result of visual observation. It was increased by 1 t, and the total current of 15,000 kwh was passed through the ¾ gas-bond fluid. After adjusting the Kim Han-man to the original manganese, the change of the plating current during the measurement was recorded. Compared with the original electric forging conditions, if the current variation is within 5%, it is judged as "good". [Example]

Page 14

Hereinafter, the phenanthrene-cyanide electrolytic gold plating solution and the method using the same according to the present invention will be described in more detail through the best embodiment. Example 1 A bis (1,2-ethanediamine) gold complex of a gold compound is at a reaction temperature of 30 ° C. It is obtained by the following reaction. The reaction temperature at this time is preferably 15 = 60 ^ C. This is because if it is less than 15, the reaction will not proceed sufficiently and the yield will decrease; if it exceeds 60, it will cause a reduction reaction of gold ions to generate gold fine particles.

NaAuCl4 + 2en Au (en) 2Cl3 + NaCl # Use the bis (i, 2-ethanediamine) gold gaseous substance obtained thereby to reduce the non-cyanide gold plating solution. The composition of the non-cyanuric gold plating solution is as follows: JLUg / i 60g / l 60g / l 50g / 1 lg / 1 in the test pattern bis (1,2-ethanediamine) gold chloride (as gold ) 1,2-Ethylene diamine sulfate, potassium chloride, organic carboxylic acid (citric acid), heterocyclic compound (thiophenic acid, carbonic acid) Using this gold plating solution, gold plating is performed on the (test pattern) under the following electric mine conditions . pH value 5 〇 Electrolyte temperature β 〇. 〇 ^ 1 · 5 A / dm2 Electrolysis time Θ 0 minutes The physical properties of the gold plating layer formed under the above conditions were measured.

2169-2793-PFl.ptc Page 15 505708

V. Description of Invention (13)

The results are shown in Table 3. From Table 3, it can be seen that the Vickers hardness of the gold deposit is 66.7 on average. Furthermore, the scanning test electron microscope (SEM) was used to observe the test pattern after the gold plating, and the results are shown in Fig. 1. As can be seen from Fig. J, the obtained gold electric key surface Extremely smooth. Therefore, 'the bondability can be significantly increased by ensuring the smoothness of the electric money surface as described above. In addition, if the life of the electrolytic gold electric mineral liquid is converted by the time of electricity conversion, It is 3 hours. Example 2 The bis (1,2-ethanediamine) gold trigas compound used in the gold salt was obtained by the following reaction at a reaction temperature of 30 ° C. At this time The reaction and w degrees are 15-60. (: Better. This is because if the reaction method is fully performed if it is less than 15t, the yield will decrease; if it exceeds 60t, it will cause `` gold The reduction reaction of ions generates fine particles of gold.

NaAuCl4 + 2en Au (en) 2Cl3 + NaCl uses the bis (1,2-ethanediamine) gold trichloride obtained thereby to reduce the non-cyano gold plating solution. The composition of the non-cyano gold plating solution is as follows: bis (1,2-ethanediamine) gold trichloride (as gold) i0g / i 1,2-ethanediamine sulfate, / ·! 〆β… 1 00g / 1 buffering agent (citric acid) .t 5Og / 1 organic gloss agent (o-phenanthroline) ^ _ 100ppm ~ 〃 plating solution, gold plating on the test pattern under the following plating conditions .

pH 3e5Q

If you implement 8g / 1 at 66. 7 hours, carry out pH electrolyzing solution temperature, current density electrolysis time, if you have 72.1 hours, plating solution temperature 6 〇 ^ current density A / dm2 electrolysis time 75 minutes ^ under the above conditions The physical properties of the resulting gold plating layer were measured in the first place. It can be seen from Table 3 that the Vickers hardness of the gold plating layer is on average. If the life of the black electrolytic gold plating solution is converted to the time of energization, it is 3 500. The system uses gold hydroxide to control the concentration of gold into a two-cyanide electrolytic gold plating solution. The composition of the system is as follows: lice oxide gold (as gold) 8g / 1 1,2-ethanediamine dihydrochloride Buffering agent (boric acid) 30g / i Organic glossing agent (2, 2-bipyridine) 4jppm Using this gold electro-mineral liquid, the following electric jealousy is used. Γ ^ Under plating conditions, in test pattern "

4 · 3 5 5 ° C 1.2 A / dm2 75 minutes The gold produced under the above conditions was measured. The physical properties of a geoelectric forging layer were measured. The average Vickers hardness of the layer was ^. I ^. The poisonous life of edge electrolytic gold plating solution + ^ ^ ^ ^ J ". The electric power can be converted to 345 ° C. The conversion time is 345. V. Description of the invention (15) Example 4 In the gold salt, tetrahydroxyalloy potassium is used, and the concentration of gold is 1 Og / 1. The composition of the non-cyanide electrolytic gold bond solution is as follows: ~: 1, · tetrakismonium potassium (as gold) lOg / l not 1,2 ethyl amine_amine disulfate l20g / i buffer Agent (boric acid) 50 g / 1 organic gloss agent (2,2-bipyridine) 1200 ppm Using this gold plating solution, gold plating was performed under the following plating conditions. % And J 忒 pattern pH value Plating bath temperature Current density Electrolysis time 3. 60

6 5 ° C 1. 5 A / dm2 75 minutes 旲 J 2 The physical properties of the gold plating layer formed under the above conditions are determined, as shown in Table 2. As can be seen from Table 2, the dimension of the gold plating layer: 7 ^. The life of the electrolytic gold plating solution is converted into hours by time. Example 5 Gas gold acid was used in the gold salt. In addition, the gold concentration was controlled to 10 g / 1 °. The composition of the non-cyanide electrolytic gold plating solution was as follows: Chloroauric acid (as gold) 10 g / l 1,2-ethanediamine disulfate 150g / l buffering agent (boric acid) 40g / l organic gloss agent (2, 2-bipyridine) 1000ppm

Page 18 505708 ~ ------ 5. Description of the invention (16) ------- Using this gold plating solution, perform gold electricity It in the following.丨 pH value on the test pattern under plating conditions 3. 60 Electroplating bath temperature 60 ° C Current density 1 · 2 A / dm2 Electrolysis time 7 5 minutes = Gold electricity ore layer generated under the above conditions II =. See from Table 3! The Vickers hardness of the gold electric ore layer is flat "hours. Μ. The life of the solution of the gold plating solution is converted to 3 1 0 0 iL. Example 6 In the gold salt, potassium tetrahydroxy alloy and chloroauric acid are used. In addition, the total gold concentration is controlled to 10 g / i. The composition is as follows: The non-cyanide electrolytic gold plating solution is formulated with potassium tetrahydroxy alloy potassium (as gold) 5 g / 1 chloroauric acid (when As gold) 5g / 1 1,2-ethanediamine disulfate 120g / l Buffering agent (dipotassium hydrogen-filled) 30g / 1 Organic glossing agent (2, 2-dioxopyridine) 4 0 0 ppm Using this gold plating solution, gold plating was performed on the test pattern under the following plating conditions. PH value 6.0

Bath temperature 4 5 ° C Current density 1. 0 A / dm2

Page 19 505708 5. Description of the invention (17) Electrolysis time 75 minutes The physical properties of the gold plating layer formed under the above conditions were measured. The results are shown in Table 3. As can be seen from Table 3, the average Vickers hardness of the gold plating layer was 67 · 0. The life of this electrolytic gold plating solution is 3280 hours in terms of the conduction time. Comparative Example In order to compare the efficiency between the non-cyanide electrolytic gold plating solution of the present invention and the conventional non-cyanide electrolytic gold plating solution, Na3Au (s〇3) 2 was used as the gold salt, and the reduction was performed by electroplating. The above steps are similarly applied with two gold platings on the test pattern as a comparative example. The composition of the conventional non-cyano gold electrolytic gold plating solution is as follows: 10 g / l 20 g / 1 120 g / l 〇lg / l

Na3Au (S03) 2 (as au)

Na2S03

Na2HP04 it uses this solution and is plated with gold in the following. The temperature of the plating solution was measured at 65x under the condition of no inquiry: Current density nc Electrolysis time 60J /, 2 The measurement was made under the above conditions: = physical properties of the coating, the results are shown in Table 3 The life and gold, Vickers hardness averaged 75.1. Go further 1. From Table 3, it can be seen that the gold plating layer

505708 V. Description of the invention (18) If the service life is converted by the time of energization, it is 丨 〇 〇 ～ 2 〇 〇 00 hours. As a result, the ratio of the conventional electrolytic gold electrolysis liquid to the non-cyano gold electrolytic gold electroplating liquid phase of the present invention is relatively short. Example 1 Example 2 Example 3 Life of plating solution [hours] 3100 -3500 T450 Vickers hardness iHvi 66 7 " 66.7 Example 4 黉 Shi J 5 3300 72,1 T3. 0 Visual appearance X Ze_gloss 笠Gloss Example 6 Comparative Example 3100 32 80 1790 70.5 67,0ΤδΤΓ _ Semi-Gloss Semi-Gloss Semi-Gloss Semi-Gloss

Furthermore, a scanning electron microscope (SEM) was used to observe the test pattern after gold plating as shown in the comparative example, and the results are shown in FIG. 2. By comparing FIG. 1 and FIG. 2 above, it can be seen that compared with the gold plating surface obtained when the non-cyano gold plating solution of the present invention is used, the gold plating obtained by using a conventional electrolytic gold plating solution The surface is noticeably less smooth. [Effect of the invention]

By using the non-cyanuric gold plating solution of the present invention, it is possible to provide a gold plating solution with excellent solution stability and no change in the physical properties of the precipitated gold or the decomposition of the gold plating solution during the gold plating operation. At the same time, the purpose of reducing the operating cost of the electrolytic gold plating can be achieved. In addition, by including 1,2-ethanediamine in the Rongjin plating solution, the hardness, purity, and state of the precipitated crystals can be controlled. Therefore, it is suitable for forming fine patterns, and Ensures proper adhesion:

Page 21

Claims (1)

—88117RRR —88117RRR 6. Apply for a patent _ Amendment: Health · .. Taxi salt or gold tincture 'The electrolytic gold electricity money system uses a gold gloss agent and a value of 逡 Lin 1 ΛΑ as gold, and contains a buffer, organic Heart = pass is characterized in that the non-cyanide electrolytic gold electric ore liquid containing 2 of the above item 1 is contained in the above-mentioned electric forging solution, and the gold concentration in the electroplating solution is changed to 2 g / 1 to 30 g / 丨Gold compound of bis (1,2-ethanediamine) gold complex, 0.1-2.5M of 1,2-ethanediamine sulfate, potassium salt of inorganic acid as conductive salt,. As buffer Organic carboxylic acid agents, and heterocyclic compounds containing one or more heteroatoms as organic gloss agents. 3. The non-cyanide electrolytic gold plating solution as described in item 1 of the scope of patent application, wherein the gold plating solution contains: so that the gold concentration in the gold plating solution becomes within the range of 5g / i ~ 30g / i The amount of valent gold salt, ethanediamine from 0.2M to 3.0M, buffer, organic gloss agent and conductive salt. 4. The non-cyanide electrolytic gold plating solution as described in item 2 of the scope of the patent application, wherein the inorganic acid potassium salt as the conductive salt is 100 g / l of potassium sulfate, potassium chloride or potassium nitrate. 5. The non-cyanide electrolytic gold plating solution as described in item 2 of the scope of patent application, wherein the organic carboxylic acid as the buffering agent is acetic acid, formic acid or benzoic acid having a carboxyl group of 200 g / l. 2169-2793-PFl.ptc Page 22 505708 __ Case No. 88117558 缶 Λ-^ Amendment VI. Patent Application Range 6 · Non-cyanide electrolytic gold electroplating solution as described in item 2 of the patent application range, which serves as an organic gloss The heterocyclic compound containing one or more kinds of heteroatoms of the agent is thiophenecarboxylic acid, o-phenanthroline, pyridine, pyridinesulfonic acid, or bipyridine from 0.1 to 10 g / l. 7. The non-cyanide electrolytic gold plating solution as described in item 3 of the scope of patent application, wherein the trivalent gold salt is selected from the group consisting of bis (1, ethanediamine) gold chloride, gold hydroxide, potassium tetrahydroxide alloy, and chlorine One or more types of auric acid. 8. The non-cyanic electrolytic gold key bond liquid as described in item 3 of the scope of the patent application, wherein the buffering agent is one or more of organic dibasic acid, dishic acid, and boric acid selected from a pK value of 2 to 6. And its total mole concentration is o.mlj 0Μ 〇9. The non-cyanide electrolytic gold plating solution as described in item 7 of the scope of patent application, wherein the buffering agent is an organic slow acid selected from a ρK value of 2 to 6, Phosphoric acid and boric acid have one or more than one component, and the total molar concentration thereof is from 0.05M to 1M. And ... · 10 · — A kind of non-cyanide electrolytic gold plating solution as described in the scope of application for patent No. 3, 7, 8 or 9, characterized in that:, the organic gloss agent is selected from phenanthrene, dipyridine, Among the derivatives of o-phenanthroline and the derivatives of bipyridine, one or two or more components, and the total molar concentration thereof is 50 ppm to 1,000 ppm. 11. A non-cyanide electrolytic gold plating solution as described in the scope of patent application No. 3, 7, 8 or 9, characterized in that: '' The conductive salt is one selected from the compounds capable of supplying sulfate ion, hydrochloric acid ion, and nitrate ion. Or 2 or more ingredients, I ^ total mole concentration 505708 _ Case No. 881Π5M Amendment 6 The scope of application for patents is from 0.05M to 5.0M. The plating solution is specially described in the non-cyano electrolytic gold electro-acid ionization described in item 10 of the 'Patent Patent Wai' :::: 21 05Μ〜5. 0Μ。 Sulfate ions, hydrochloric acid ions, and nitrate I ions can be supplied in one or two of the compound is 0.05M ~ 5. 0M. For the above components, and / or the total mole concentration is a patented non-gold plating method, which uses a gold plating solution as described in item 5 or 6 of the application, the solution is 2 to 7, the liquid temperature is 40, and the flow is 0. Under the conditions of electrolytic plating. 14. · A non-cyanide electrolytic gold electroplating method, the method = the non-ambient electrolytic gold electroplating as described in the range 3, 7, 8 or "; the pH of the Luo solution is 2 ~ 6, the liquid temperature is The electrolytic plating was performed under conditions of 40 to 700 c and a current density of 0.1 to 3.0 A / dm 2. 'lj · A non-cyanide electrolytic gold electroplating method, which uses the non-cyanide electrolytic gold recording solution as described in item 10 of the application, where the M value of the solution is 2 ~ 6, and the liquid temperature is 40 ~ 7 (TC, current density is 0, 1 pieces for electrolytic plating. LUA / dm Article 16 ·-a non-rat electrolytic gold electric seam method, the non-cyanide electrolytic gold electricity / 所述 described in item 11 of the patent scope Use as application ^ ^ „, ^ 40 ^ 70 Γ: 3 ot ;: electrolytic plating under conditions. · 〇A / dm Article 1 7 ·-a non-cyanide electrolytic gold plating method, the party's patent scope is the first The non-cyanide electrolytic gold thunder wheel described in item 2 uses the same as the application of lice solution gold plating 竦, in the pH of the solution 505708 _Case No. 88117558_ Years and Months Revision_ VI. The scope of the patent application is 2 ~ 6, the liquid temperature is 40 ~ 70 ° C, and the current density is 0:! ~ 3.0A / dm2. 2169-2793-PFl.ptc Page 25