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WO2023051640A1 - 无氰电镀金镀液及其应用和电镀制金凸块的方法以及金凸块和电子部件 - Google Patents

无氰电镀金镀液及其应用和电镀制金凸块的方法以及金凸块和电子部件 Download PDF

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Publication number
WO2023051640A1
WO2023051640A1 PCT/CN2022/122268 CN2022122268W WO2023051640A1 WO 2023051640 A1 WO2023051640 A1 WO 2023051640A1 CN 2022122268 W CN2022122268 W CN 2022122268W WO 2023051640 A1 WO2023051640 A1 WO 2023051640A1
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WIPO (PCT)
Prior art keywords
gold
plating solution
electroplating
antimony
arsenic
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PCT/CN2022/122268
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English (en)
French (fr)
Inventor
王彤
任长友
邓川
刘鹏
Original Assignee
深圳市联合蓝海黄金材料科技股份有限公司
华为技术有限公司
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Application filed by 深圳市联合蓝海黄金材料科技股份有限公司, 华为技术有限公司 filed Critical 深圳市联合蓝海黄金材料科技股份有限公司
Priority to CN202280006145.5A priority Critical patent/CN116568871A/zh
Publication of WO2023051640A1 publication Critical patent/WO2023051640A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/11—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L24/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods
    • H01L2224/114—Manufacturing methods by blanket deposition of the material of the bump connector
    • H01L2224/1146—Plating
    • H01L2224/11462—Electroplating

Definitions

  • the invention relates to the field of semiconductor gold bump preparation, in particular to a cyanide-free electroplating gold plating solution and its application, a method for making gold bumps by electroplating, gold bumps prepared by the method, and electronic components with the gold bumps.
  • the most commonly used metal interconnect materials for semiconductors are aluminum, copper and gold.
  • Gold has excellent chemical stability, second only to silver and copper in terms of electrical and thermal conductivity. Gold will not be oxidized at room temperature or under heating conditions, and does not react with most chemical substances. It has good solderability, can be bonded by thermocompression, and has low contact resistance. Therefore, electroplating gold is widely used in electronic circuit boards, electronic connectors, semiconductor manufacturing and other fields.
  • Heat treatment is often performed after electroplating to increase the ductility of the gold plating.
  • gold is a metal with a low melting point, and recrystallization occurs during heat treatment, resulting in larger grain size and lower hardness.
  • the hardness of electroplated gold after heat treatment it can be divided into low hardness (40-60HV), medium hardness (70-90HV), and high hardness (90-120HV) electroplated gold.
  • the LCD driver chip is connected to the LCD through gold bumps.
  • the size of the gold bumps and the distance between the gold bumps need to be reduced.
  • the minimum width of gold bumps is reported to be 6 ⁇ m, and the bump pitch is 4 ⁇ m.
  • reducing the size of the gold bumps and the distance between adjacent ones will cause the gold bumps to be easily deformed during the thermocompression bonding process, resulting in the connection of adjacent bumps, resulting in short-circuit failure.
  • the bonding performance of electroplating gold is related to the hardness of electroplating gold.
  • the hardness of electroplating gold after heat treatment is generally controlled below 120HV.
  • CN104540983B discloses that the cyanide-free electroplating gold bath contains gold sulfite, conductive salt sulfite and sulfate, crystal regulator thallium compound, on this basis, further Adding any one or more of iridium, ruthenium, and rhodium compounds, the concentration of which is 1-3000 mg/L, can be used to prepare a gold-plated layer that still maintains high hardness after heat treatment.
  • the cyanide-free gold plating system uses the crystal regulator thallium compound to obtain a relatively rough coating, and the effective contact area is reduced during thermocompression bonding.
  • the purpose of the present invention is to overcome the problem that the hardness of gold bumps made by using cyanide-free gold plating technology after heat treatment is difficult to meet the requirements of semiconductor processing, provide cyanide-free electroplating gold plating solution and its application and electroplating method for making gold bumps and Gold bumps and electronic components.
  • the first aspect of the present invention provides a cyanide-free electroplating gold plating solution, wherein the plating solution comprises: gold source, conductive salt, buffer, additive and organic phosphonic acid, wherein the additive is selected from Compounds containing antimony and/or compounds containing arsenic.
  • the organic phosphonic acid is selected from at least one of methylene phosphonic acid, isocarbon diphosphonic acid, and carboxylic acid phosphonic acid, preferably selected from hydroxyethylidene diphosphoric acid (HEDP), ammonia trimethylene phosphonic acid (ATMP), ethylenediaminetetramethylenephosphonic acid (EDTMP); more preferably hydroxyethylidene diphosphonic acid and/or aminotrimethylenephosphonic acid.
  • HEDP hydroxyethylidene diphosphoric acid
  • ATMP ammonia trimethylene phosphonic acid
  • ETMP ethylenediaminetetramethylenephosphonic acid
  • the concentration of the organic phosphonic acid is 1-50g/L, preferably 4-30g/L.
  • the antimony-containing compound is selected from at least one of antimony oxides, antimony halides, antimony oxyhalides, antimonides, antimonates, organic antimonides, preferably selected from antimony sodium tartrate, tartaric acid At least one of antimony potassium, sodium antimonate, and potassium antimonate; preferably, the arsenic-containing compound is selected from at least one of arsenic oxides, arsenite, and arsenic-containing organic compounds, preferably selected from arsenous acid Sodium and/or Arsenic Trioxide.
  • the antimony-containing compound is calculated as antimony
  • the arsenic-containing compound is calculated as arsenic
  • the concentration of the antimony-containing compound in the plating solution is 1-100 mg/L, preferably 5-50 mg/L
  • the concentration of the arsenic-containing compound is 1-100 mg/L, preferably 5-50 mg/L.
  • the second aspect of the present invention provides an application of the cyanide-free electroplating gold plating solution provided by the present invention in semiconductor manufacturing.
  • the third aspect of the present invention provides a method for electroplating gold bumps, wherein the method includes: electroplating a semiconductor in the presence of the cyanide-free gold plating solution provided by the present invention, and forming gold bumps on the surface of the semiconductor.
  • the fourth aspect of the present invention provides a gold bump produced by the method provided by the present invention.
  • the fifth aspect of the present invention provides an electronic component having the gold bump provided by the present invention.
  • the present invention uses the provided cyanide-free electroplating gold plating solution to realize the preparation of high-hardness gold bumps on semiconductors, and the obtained gold bumps can still maintain high hardness (90-110HV) after heat treatment.
  • the deposition efficiency of the plating solution is high, greater than 99%, and the prepared gold plating layer has low roughness (less than 100nm) and high purity (99.99%).
  • the shape of the obtained gold bump is regular.
  • Fig. 1 is used for evaluating plating solution to fill level ability, illustrates the sectional schematic diagram of the test sample of the shape result that the plating solution that the present invention obtains prepares gold bump; Wherein, form bump opening size between two photoresists on the substrate It is 80 ⁇ m (length) ⁇ 20 ⁇ m (width) ⁇ 15 ⁇ m (depth), which is used to fill the plating solution. A 1.2 ⁇ m high passivation layer is set on the substrate to evaluate the filling ability of the plating solution.
  • Figure 1a shows the passivation layer The opening is fully open, that is, the width of the formed gold bump is 20 ⁇ m, and there is no step in the middle; the width of the step formed by the passivation layer in Figure 1b is 12 ⁇ m, the width of the step formed by the passivation layer in Figure 1c is 8 ⁇ m, and the width of the step formed by the passivation layer in Figure 1d is The step width formed by the layer is 4 ⁇ m;
  • Fig. 2 is the 100 times enlarged picture of the profile of the gold bump corresponding to the various opening widths of Fig. 1 prepared in embodiment 5;
  • Fig. 3 is the 500 times enlarged picture of the profile of the gold bump corresponding to Fig. 1a, 1b opening prepared in embodiment 5;
  • Fig. 4 is a 500-fold enlarged picture of the profile of the gold bump corresponding to Fig. 1c and 1d openings prepared in Example 5;
  • Fig. 5 is a schematic diagram of sampling for determining the size of gold pillars and steps in the prepared gold bump. From Fig. 3 and Fig. 4, two adjacent gold bumps corresponding to the four kinds of opening widths are respectively selected to set up the detection area, which is divided into A area and B area, and display the detection points, the detection results are shown in Table 2.
  • the first aspect of the present invention provides a cyanide-free electroplating gold plating solution, wherein the plating solution comprises: a gold source, a conductive salt, a buffer, an additive and an organic phosphonic acid, wherein the additive is selected from antimony-containing compounds and/or or arsenic-containing compounds.
  • the cyanide-free electroplating gold plating solution contains organic phosphonic acid and specific additives, which can cooperate with other components to realize the preparation of high-hardness electroplating gold by using cyanide-free electroplating gold.
  • the cyanide-free electroplating gold plating solution provided is an aqueous solution, and also contains water as a solvent.
  • the organic phosphonic acid is selected from at least one of methylene phosphonic acid, isocarbon diphosphonic acid, and carboxylic acid phosphonic acid, preferably selected from hydroxyethylidene diphosphonic acid (HEDP ), amino trimethylene phosphonic acid (ATMP), ethylenediamine tetramethylene phosphonic acid (EDTMP); more preferably hydroxy ethylidene diphosphonic acid and/or amino trimethylene phosphonic acid.
  • HEDP hydroxyethylidene diphosphonic acid
  • ATMP amino trimethylene phosphonic acid
  • ETMP ethylenediamine tetramethylene phosphonic acid
  • the concentration of the organic phosphonic acid in the plating solution is 1-50 g/L.
  • the concentration of the organic phosphonic acid is greater than 50 g/L, the ability to complex with gold (I) becomes stronger, resulting in too dense electroplating film, which may cause poor welding.
  • the concentration of the organic phosphonic acid is less than 1 g/L, the plating solution becomes unstable and the plating layer becomes rough.
  • the concentration of the organic phosphonic acid is, for example, 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L L, 11g/L, 12g/L, 13g/L, 14g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L, 21g/L, 22g/L, 23g/L, 24g/L, 25g/L, 26g/L, 27g/L, 28g/L, 29g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, and the above Any value in the range composed of any two numerical values, preferably 4-30g/L.
  • the additive is the antimony-containing compound or the arsenic-containing compound.
  • the antimony-containing compound is selected from at least one of antimony oxides, antimony halides, antimony oxyhalides, antimonides, antimonates, organic antimonides, preferably selected from sodium antimony tartrate, potassium antimony tartrate, At least one of sodium antimonate and potassium antimonate;
  • the arsenic-containing compound is selected from at least one of arsenic oxides, arsenite, and arsenic-containing organic matter, preferably selected from sodium arsenite and/or or arsenic trioxide.
  • the antimony-containing compound is calculated as antimony
  • the arsenic-containing compound is calculated as arsenic
  • the concentration of the antimony-containing compound in the plating solution is 1-100 mg/L, more
  • the concentration of the antimony compound is, for example, 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L, 7mg/L, 8mg/L, 9mg/L, 10mg/L L, 11mg/L, 12mg/L, 13mg/L, 14mg/L, 15mg/L, 16mg/L, 17mg/L, 18mg/L, 19mg/L, 20mg/L, 21mg/L, 22mg/L, 23mg/L, 24mg/L, 25mg/L, 26mg/L, 27mg/L, 28mg/L, 29mg/L, 30
  • the concentration of the antimony-containing compound or the arsenic-containing compound when the concentration of the antimony-containing compound or the arsenic-containing compound is lower than 1 mg/L, the depolarization effect of the plating solution is not sufficient, resulting in reduced precipitation efficiency and reduced gold purity.
  • concentration of the antimony-containing compound or the arsenic-containing compound is greater than 100 mg/L, the roughness of the coating in the high current density area increases, and the appearance of the coating is uneven.
  • the weight ratio of (the antimony-containing compound or the arsenic-containing compound) to the organic phosphonic acid is preferably 1:10 -2500, preferably 1:100-1000, preferably for example 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, and any value in the range formed by any two values above, can provide better hardness and shape regularity of the gold bump after heat treatment.
  • the above weight ratio lower than 1:10 or higher than 1:2500 is not conducive to providing proper coordination and improving the hardness and shape regularity of the gold bump after heat treatment.
  • the gold source is selected from gold sulfate and/or sulfite, preferably at least one of sodium gold sulfite, potassium gold sulfite, and ammonium gold sulfite.
  • the amount of the gold source is such that the concentration of gold ions in the plating solution is 1-20 g/L.
  • the concentration of gold ions is less than 1g/L, the cathode precipitation efficiency is too low, and the electroplating solution becomes unstable at the same time, and gold is easy to precipitate in the plating solution instead of the surface of the cathode.
  • the concentration of gold ions is greater than 20g/L, although the stability of the electroplating solution and the appearance and physical properties of the coating have no effect, the gold is wasted due to the stripping of the plating solution after the plated sheet is completed, and the cost rises.
  • the preferred concentration of gold ions is, for example, 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, 11g/L , 12g/L, 13g/L, 14g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L, and any value in the range composed of any two of the above values , preferably 8-15g/L.
  • the conductive salt is selected from sulfite and/or sulfate, preferably selected from sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, sodium sulfate, potassium sulfate, At least one of ammonium sulfate and sodium bisulfate, preferably sodium sulfite and sodium sulfate.
  • the concentration of sodium sulfite is 10-120g/L; when it is less than 10g/L, the uniformity of electroplating will decrease, the hardness of the plating layer will be high, and even the plating solution may Decomposition occurs. When it is greater than 120g/L, the current density range in the high area becomes narrow and the coating becomes rough.
  • the concentration of sodium sulfite is preferably 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, 55g/L, 60g/L, 65g/L, 70g/L, 75g/L, 80g/L, 85g/L, 90g/L, 95g/L, 100g/L, 105g/L, 110g/L, 115g/L, 120g/L, and the above Any value in the range composed of any two numerical values, preferably 30-80g/L.
  • the concentration of sodium sulfate is 1-120g/L.
  • concentration of sodium sulfate is greater than 120g/L, the high current density range may be narrowed and the coating may become rough.
  • the concentration of sodium sulfate is preferably 1g/L, 5g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L , 55g/L, 60g/L, 65g/L, 70g/L, 75g/L, 80g/L, 85g/L, 90g/L, 95g/L, 100g/L, 105g/L, 110g/L, 115g /L, 120g/L, and any value in the range formed by any two of the above values, preferably 10-60g/L.
  • the buffering agent is selected from at least one of edetate, phosphate, tartrate, citrate, preferably selected from disodium edetate and/or disodium hydrogen phosphate.
  • the concentration of the buffer in the plating solution is 1-30 g/L.
  • concentration of the buffer is lower than 1g/L, sometimes the buffering capacity of the plating solution is insufficient and the appearance of the coating is uneven.
  • the buffer is greater than 30g/L, the current density range in the high area becomes narrow and the coating becomes rough.
  • the preferred concentration of the buffer is, for example, 1 g/L, 2 g/L, 3 g/L, 4 g/L, 5 g/L, 6 g/L, 7 g/L, 8 g/L, 9 g/L, 10 g/L, 11 g/L , 12g/L, 13g/L, 14g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L, 25g/L, 30g/L, and any two of the above Any value within the range of numerical composition, preferably 5-20 g/L.
  • the plating solution further includes a pH additive; preferably, the pH of the plating solution is 7-9.
  • the pH of the plating solution is lower than 7.0, the long-term stability of the plating solution deteriorates.
  • the pH of the plating solution is higher than 9.0, the photoresist dissolves or seepage occurs, and at the same time, the appearance of the plating layer is uneven because gold is difficult to restore.
  • the pH of the preferred plating solution is, for example, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7., 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, And any value in the range composed of any two of the above values, preferably 7.4-9.
  • pH adjuster sulfurous acid, sulfuric acid, etc. can be used as the acid, and sodium hydroxide, potassium hydroxide, ammonia water, etc. can be used as the base.
  • the plating solution may be prepared by putting the above-mentioned components into water and completely dissolving them.
  • the conductive salt, buffering agent and organic phosphonic acid can be completely dissolved by directly putting the corresponding compounds into water.
  • the gold source, arsenic-containing compound or antimony-containing compound can be added in the form of aqueous solution, but the actual dosage is calculated by gold element, arsenic and antimony respectively, and finally each component is completely dissolved.
  • the conductive salt, buffer, organic phosphonic acid and water can be mixed first to obtain a completely dissolved solution, and then the gold source, arsenic-containing compound or antimony-containing compound is added in the form of an aqueous solution to completely dissolve.
  • the dissolution process can be carried out at room temperature with stirring.
  • the pH value of the solution obtained by dissolving is also adjusted to meet the pH requirement of 7-9, preferably 7.4-9.
  • the requirements for pH adjustment are as described above and will not be repeated here.
  • volume adjustment of the obtained solution is also performed to obtain the final plating solution and meet the concentration requirements for each component.
  • the second aspect of the present invention provides an application of the cyanide-free electroplating gold plating solution provided by the present invention in semiconductor manufacturing.
  • the application may be in fields such as electronic circuit boards, electronic connectors, and semiconductor manufacturing.
  • the third aspect of the present invention provides a method for electroplating gold bumps, wherein the method includes: electroplating a semiconductor in the presence of the cyanide-free gold plating solution provided by the present invention, and forming gold bumps on the surface of the semiconductor.
  • the method includes: electroplating a semiconductor in the presence of the cyanide-free gold plating solution provided by the present invention, and forming gold bumps on the surface of the semiconductor.
  • it is suitable for preparing high-hardness gold bump products formed by photoresist technology on the surface of semiconductors, such as liquid crystal driver chips, CMOS image sensors, fingerprint sensors, etc. glass), COF (Chip on Film), COP (Chip on Plastics), etc. to realize the interconnection between chips and substrates.
  • the electroplating temperature is 40-70°C.
  • the temperature of electroplating is higher than 70°C, sometimes the plating solution will decompose, and at the same time, it will be difficult to manage the plating solution because the plating solution will be too fast.
  • the plating temperature is lower than 40° C., the deposition efficiency decreases, and the appearance of the plating layer may be uneven.
  • the current density of the electroplating is 0.1-2 A/dm 2 (ASD).
  • ASD A/dm 2
  • the current density of the electroplating is, for example, 0.1ASD, 0.2ASD, 0.3ASD, 0.4ASD, 0.5ASD, 0.6ASD, .07ASD, 0.8ASD, 0.9ASD, 1ASD, 1.1ASD, 1.2ASD, 1.3ASD, 1.4ASD, 1.5ASD, 1.7ASD, 1.8ASD, 1.9ASD, 2.0ASD, and any value in the range formed by any two values above, preferably 0.2-1.2ASD.
  • a gold bump prepared by the above method which has a regular shape and high hardness after heat treatment. It can reach above 98HV.
  • the present invention can also provide an electronic component with the above-mentioned gold bump or an electronic component manufactured by the above-mentioned method for preparing the gold bump.
  • Precipitation efficiency After electroplating, use the weighing method to calculate the precipitation efficiency of the plating solution.
  • the precipitation efficiency is the theoretical weight of the weight of electroplated gold divided by the electricity passed during the electroplating process and converted to monovalent gold.
  • Coating hardness Use a Vickers hardness tester to test the hardness of the coating, use a 10gf load to keep the measuring head on the surface of the coating for 10s, and test the hardness of the coating without heat treatment and after heat treatment at 270°C for 30 minutes.
  • Gold bump height In order to evaluate the leveling ability of the plating solution of the present invention, a graphic chip is designed according to actual needs, the area of the graphic chip is 30 ⁇ 30mm, and the surface cross-sectional structure of the silicon wafer is Si/SiO 2 /Al/Ti/ Au, using positive photoresist AZ4660 to form bump openings, the size of the opening is 80 ⁇ m (length) ⁇ 20 ⁇ m (width) ⁇ 15 ⁇ m (depth), the distance between the horizontal rows of adjacent bumps is 13 ⁇ m, and the distance between the vertical rows is 30 ⁇ m.
  • a passivation layer of 1.2 ⁇ m was designed on the aluminum electrode, and the opening widths were 4 ⁇ m, 8 ⁇ m and 12 ⁇ m (as shown in Figure 1).
  • NMP solvent to remove the photoresist to obtain the filling formed in the opening
  • Keyence VK-X3100 to measure the shape and height of the gold bump.
  • the calculated precipitation efficiency after electroplating is 99%. After electroplating, the surface of the coating is smooth and the color is uniform; the hardness of the coating is 147HV before heat treatment, and the hardness of the coating after heat treatment is 98HV.
  • the difference is that "20g of hydroxyethylidene diphosphoric acid” is added to replace “10g of hydroxyethylidene diphosphoric acid", "gold sodium sulfite aqueous solution with a gold element content of 12g” is added to replace “gold element content Replace "sodium arsenite solution with 0.01g arsenic content” with “8g sodium arsenite aqueous solution” and “sodium arsenite solution with 0.01g arsenic content”, replace "pH value 8.0” with "pH value 7.4" of the plating solution ”, to obtain plating solution-2.
  • the surface of the coating is smooth and uniform in color, the calculated precipitation efficiency is 99%, the hardness of the coating is 143HV before heat treatment, and the hardness of the coating after heat treatment is 101HV.
  • Example 1 According to the method of Example 1, the difference is that "4g of aminotrimethylene phosphonic acid” is added to replace “10g of hydroxyethylidene diphosphoric acid” and “10g of disodium hydrogen phosphate” is added to replace “10g of ethylenediaminetetraacetic acid Disodium", "gold sodium sulfite aqueous solution with a gold element content of 12g” replaced “gold sodium sulfite aqueous solution with a gold element content of 8g” and “sodium arsenite with arsenic content of 0.2g” replaced “arsenic content of 0.01g Sodium arsenite solution”, the "pH value of the plating solution is 8.5” is replaced by "pH value is 8.0", and the plating solution-3 is obtained.
  • the surface of the coating is smooth and uniform in color, the calculated precipitation efficiency is 100%, the hardness of the coating is 144HV before heat treatment, and the hardness of the coating after heat treatment is 107HV.
  • Example 1 According to the method of Example 1, the difference is that "30g of ammonia trimethylene phosphonic acid” is added to replace “10g of hydroxyethylidene diphosphoric acid” and "10g of disodium hydrogen phosphate” is added to replace “10g of ethylenediamine tetraacetic acid Disodium", "gold sodium sulfite aqueous solution with gold element content of 15g” replaced “gold sodium sulfite aqueous solution with gold element content of 8g” and “sodium arsenite with arsenic content of 0.2g” replaced “arsenic content of 0.01g Sodium arsenite solution”, the "pH value of the plating solution is 8.5” is replaced by "pH value is 8.0”, and the plating solution-4 is obtained.
  • the surface of the coating is smooth and uniform in color, the calculated precipitation efficiency is 100%, the hardness of the coating is 139HV before heat treatment, and the hardness of the coating after heat treatment is 106HV.
  • the difference is that "10g of hydroxyethylidene diphosphoric acid, 10g of amino trimethylene phosphonic acid” is added to replace “10g of hydroxyethylidene diphosphate", "10g of disodium hydrogen phosphate” to replace “ 10g of disodium ethylenediaminetetraacetic acid", "gold sodium sulfite aqueous solution with gold element content 15g” replace “gold sodium sulfite aqueous solution with gold element content 8g” and "sodium arsenite with arsenic content 0.2g” Replace “sodium arsenite solution with arsenic content of 0.01g", replace “pH value of 8.0” with "pH value of the plating solution” to obtain plating solution-5.
  • the surface of the coating is smooth and uniform in color, the calculated precipitation efficiency is 99%, the hardness of the coating is 142HV before heat treatment, and the hardness of the coating after heat treatment is 101HV.
  • the surface of the coating is smooth and uniform in color, the calculated precipitation efficiency is 99%, the hardness of the coating is 142HV before heat treatment, and the hardness of the coating after heat treatment is 96HV.
  • the difference is that "20g of hydroxyethylidene diphosphoric acid” is added to replace “10g of hydroxyethylidene diphosphoric acid", "gold sodium sulfite aqueous solution with a gold element content of 12g” is added to replace “gold element content Replace "sodium arsenite solution with 0.01g arsenic content” with “8g sodium gold sulfite aqueous solution” and “antimony potassium tartrate with 0.01g antimony content”, and "pH value 7.4" of the plating solution replaces "pH value 8.0" , to obtain plating solution-7.
  • the surface of the coating is smooth and uniform in color, the calculated precipitation efficiency is 100%, the hardness of the coating is 140HV before heat treatment, and the hardness of the coating after heat treatment is 101HV.
  • Example 1 According to the method of Example 1, the difference is that "4g of aminotrimethylene phosphonic acid” is added to replace “10g of hydroxyethylidene diphosphoric acid", “10g of disodium hydrogen phosphate” is added to replace “10g of ethylenediamine tetraacetic acid Disodium”, “gold sodium sulfite aqueous solution with a gold element content of 12 g” replaced “gold sodium sulfite aqueous solution with a gold element content of 8 g” and "antimony potassium tartrate with an antimony content of 0.2 g" replaced “arsenic content of 0.01 g Sodium arsenate solution”, the "pH value of the plating solution is 8.5” is replaced by “pH value is 8.0”, and the plating solution-8 is obtained.
  • the surface of the coating is smooth and uniform in color, the calculated precipitation efficiency is 100%, the hardness of the coating is 147HV before heat treatment, and the hardness of the coating after heat treatment is 103HV.
  • Example 1 According to the method of Example 1, the difference is that "30g of ammonia trimethylene phosphonic acid” is added to replace “10g of hydroxyethylidene diphosphoric acid", “10g of disodium hydrogen phosphate” is added to replace “10g of ethylenediamine tetraacetic acid Disodium”, “gold sodium sulfite aqueous solution with a gold element content of 15g” replaced “gold sodium sulfite aqueous solution with a gold element content of 8g” and "antimony potassium tartrate with an antimony content of 0.2g” replaced “arsenic content of 0.01g Sodium arsenate solution”, the "pH value of the plating solution is 8.5” is replaced by “pH value is 8.0”, and the plating solution-9 is obtained.
  • the surface of the coating is smooth and uniform in color, the calculated precipitation efficiency is 100%, the hardness of the coating is 139HV before heat treatment, and the hardness of the coating after heat treatment is 110HV.
  • the difference is that "10g of hydroxyethylidene diphosphoric acid, 10g of amino trimethylene phosphonic acid” is added to replace “10g of hydroxyethylidene diphosphate” and "10g of disodium hydrogen phosphate” to replace “ 10g of disodium edetate", "gold sodium sulfite aqueous solution with 15g of gold element content” replace “gold sodium sulfite aqueous solution with 8g of gold element content” and "antimony potassium tartrate with 0.1g of antimony content” replace For “sodium arsenite solution with arsenic content of 0.01g", the "pH value of the plating solution is 8.5” is replaced by "pH value is 8.0”, and the plating solution-10 is obtained.
  • the surface of the coating is smooth and uniform in color, the calculated precipitation efficiency is 99%, the hardness of the coating is 138HV before heat treatment, and the hardness of the coating after heat treatment is 99HV.
  • Graphic sheet electroplating is carried out in a 1.7L Yamamoto plating vertical electroplating tank, and the plating solution is plating solution-1; the anode uses a platinum electrode, and the distance between the cathode and the anode is about 4cm. Use a scraper to move left and right on the surface of the cathode to promote the plating solution. exchange in photoresist.
  • the current intensity is 24mA (the current density is 0.5ASD), the electroplating temperature is 55°C, and the electroplating time is 35min.
  • the target height of gold bumps measured after electroplating was 12 ⁇ m.
  • the gold bumps made by the cyanide-free electroplating gold plating bath containing organic polyphosphoric acid as auxiliary complexing agent and single additive arsenic compound or antimony compound can be obtained by adopting the embodiment of the present invention. High hardness is still maintained after heat treatment, and the shape of gold bumps can also be kept regular. Compared with the prior art, the plating solution is better managed and the operating cost is lower.

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Abstract

本发明涉及半导体金凸块制备领域，公开了无氰电镀金镀液及其应用和电镀制金凸块的方法以及金凸块和电子部件。所述镀液包含：金源、导电盐、缓冲剂、添加剂和有机膦酸，其中，所述添加剂选自含锑化合物和/或含砷化合物。提供的无氰电镀金镀液能够实现在半导体上制备高硬度金凸块，得到的金凸块热处理后仍可保持高硬度(90-110HV)。该镀液的析出效率高，大于99％，制备的金镀层粗糙度低(小于100nm)，纯度高(99.99％)。且获得的金凸块的形状规则。

Description

无氰电镀金镀液及其应用和电镀制金凸块的方法以及金凸块和电子部件 技术领域
本发明涉及半导体金凸块制备领域，具体涉及一种无氰电镀金镀液及其应用和电镀制金凸块的方法以及该方法制得的金凸块和具有该金凸块的电子部件。
背景技术
最常用的半导体的金属互连材料是铝、铜和金。金具有极佳化学稳定性，导电导热方面仅次于银和铜。金常温或加热条件下不会被氧化，且与大部分化学物质都不发生反应，可焊性好，可热压键合，接触电阻低。因此，在电子线路板、电子连接器、半导体制造等领域广泛使用电镀金。
常常在电镀金后经过热处理以增加镀金的延展性。但是金是低熔点金属，在热处理过程中发生重结晶导致晶粒变大，硬度降低。根据热处理后电镀金的硬度，可分为低硬度(40-60HV)、中硬度(70-90HV)、高硬度(90-120HV)电镀金。随着液晶显示技术的发展，对于显示分辨率、刷新频率、亮度和对比度等要求越来越高，要求作为控制单元的液晶驱动芯片发挥更大性能。对于主流的COG、COF和COP技术，液晶驱动芯片通过金凸块连接到液晶显示器。因此，为了充分发挥液晶驱动芯片的性能，保证能够更多的输入输出单元，金凸块的尺寸以及金凸块之间的间距都需要减少。目前报道金凸块最小宽度6μm，凸块间距为4μm。但是减少金凸块尺寸及相邻间距，将导致热压键合的过程中，金凸块容易变形，造成相邻凸块连接，从而线路短接失效。
因此提出要提高金凸块的硬度解决上述问题，尤其是高硬度(90-120HV)的金凸块对于液晶显示技术是很重要的。其中，电镀金的键合性能和电镀金的硬度有关，硬度越高键合过程中需要的压力和温度越高，考虑到可能对器件性能的影响，一般控制电镀金热处理后的硬度在120HV以下。
目前采用无氰镀金替代氰化物镀金已成为发展趋势。但是，相比氰化物镀金，无氰镀金在热处理后硬度容易降低，难于制备高硬度的电镀金材料。
为了制备热处理后仍能保持高硬度的无氰电镀金，CN104540983B公开了无氰电镀金浴含有亚硫酸金盐、导电盐亚硫酸盐及硫酸盐、结晶调整剂铊化合物，在此基础上，进一步添加铱、钌、铑化合物的任何一种或一种以上，其浓度在1-3000mg/L，使用该电镀液可制备热处理后仍保持高硬度的镀金层。但是无氰镀金体系使用结晶调整剂铊化合物往往得到的镀层比较粗糙，热压键合时有效接触面积降低。
因此，为了无氰镀金体系满足金凸块的硬度和保持规则形状的要求，亟需解决的办法。
发明内容
本发明的目的是为了克服使用无氰镀金技术制得的金凸块在热处理后硬度，难以满足半导体加工要求的问题，提供无氰电镀金镀液及其应用和电镀制金凸块的方法以及金凸块和电子部件。
为了实现上述目的，本发明第一方面提供一种无氰电镀金镀液，其中，所述镀液包含：金源、导电盐、缓冲剂、添加剂和有机膦酸，其中，所述添加剂选自含锑化合物和/或含砷化合物。
优选地，所述有机膦酸选自亚甲基膦酸、同碳二膦酸、羧酸膦酸中的至少一种，优选选自羟基乙叉二磷酸(HEDP)、氨三亚甲基膦酸(ATMP)、乙二胺四亚甲基膦酸(EDTMP)中的至少一种；更优选为羟基乙叉二磷酸和/或氨三亚甲基膦酸。
优选地，所述镀液中，所述有机膦酸的浓度为1-50g/L，优选为4-30g/L。
优选地，所述含锑化合物选自锑的氧化物、锑的卤化物、锑的卤氧化物、锑化物、锑酸盐、有机锑化物中的至少一种，优选选自酒石酸锑钠、酒石酸锑钾、锑酸钠、锑酸钾中的至少一种；优选，所述含砷化合物选自砷的氧化物、亚砷酸盐、含砷有机物中的至少一种，优选选自亚砷酸钠和/或三氧化二砷。
优选地，所述含锑化合物以锑计，所述含砷化合物以砷计，所述镀液中，所述含锑化合物的浓度为1-100mg/L，优选为5-50mg/L；所述含砷化合物的浓度为1-100mg/L，优选为5-50mg/L。
本发明第二方面提供一种本发明提供的无氰电镀金镀液在半导体制造中的应用。
本发明第三方面提供一种电镀制金凸块的方法，其中，该方法包括：将半导体在本发明提供的无氰电镀金镀液存在下进行电镀，在半导体表面形成金凸块。
本发明第四方面提供一种本发明提供的方法制得的金凸块。
本发明第五方面提供一种具有本发明提供的金凸块的电子部件。
通过上述技术方案，本发明使用提供的无氰电镀金镀液能够实现在半导体上制备高硬度金凸块，得到的金凸块热处理后仍可保持高硬度(90-110HV)。该镀液的析出效率高，大于99％，制备的金镀层粗糙度低(小于100nm)，纯度高(99.99％)。且获得的金凸块的形状规则。
附图说明
图1是用于评估镀液填平能力，说明本发明获得的镀液制备金凸块的形状结果的测试样品的断面示意图；其中，在基底上两个光刻胶之间形成凸块开口尺寸为80μm(长)×20μm(宽)×15μm(深)，用于填充镀液，在基底上设置1.2μm高的钝化层用于评估镀液的填充能力，其中，图1a显示钝化层开口全开，即形成的金凸块的宽度为20μm，中间无台阶；图1b中钝化层形成的台阶宽度为12μm、图1c中钝化层形成的台阶宽度为8μm、图1d中钝化层形成的台阶宽度为4μm；
图2是实施例5制备得到的对应图1的多种开口宽度的金凸块的轮廓的100倍放大图片；
图3是实施例5制备得到的对应图1a、1b开口的金凸块的轮廓的500倍放大图片；
图4是实施例5制备得到的对应图1c、1d开口的金凸块的轮廓的500倍放大图片；
图5是测定制得的金凸块中金柱和台阶尺寸的取样的示意图，从图3和图4中对应4种开口宽度分别选相邻的两个金凸块设置检测区，分A区和B区，并显示检测点，检测结果见表2。
附图标记说明
1-对应图1a的开口制得的金凸块的俯视图
2-对应图1a的开口制得的金凸块的侧视轮廓图
3-对应图1b的开口制得的金凸块的俯视图
4-对应图1b的开口制得的金凸块的侧视轮廓图
5-对应图1c的开口制得的金凸块的俯视图
6-对应图1c的开口制得的金凸块的侧视轮廓图
7-对应图1d的开口制得的金凸块的俯视图
8-对应图1d的开口制得的金凸块的侧视轮廓图
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种无氰电镀金镀液，其中，所述镀液包含：金源、导电盐、缓冲剂、添加剂和有机膦酸，其中，所述添加剂选自含锑化合物和/或含砷化合物。
本发明中，无氰电镀金镀液含有有机膦酸和特定的添加剂，能够和其他组分一起协同，实现使用无氰电镀金能够制备高硬度电镀金。
本发明中，提供的无氰电镀金镀液为水溶液，还含有作为溶剂的水。
在本发明一些实施方式中，优选地，所述有机膦酸选自亚甲基膦酸、同碳二膦酸、羧酸膦酸中的至少一种，优选选自羟基乙叉二磷酸(HEDP)、氨三亚甲基膦酸(ATMP)、乙二胺四亚甲基膦酸(EDTMP)中的至少一种；更优选为羟基乙叉二磷酸和/或氨三亚甲基膦酸。
在本发明一些实施方式中，优选地，所述镀液中，所述有机膦酸的浓度为1-50g/L。本发明中，所述有机膦酸的浓度大于50g/L时，和金(I)的络合能力变强导致电镀膜过于致密化，可能产生焊接不良的问题。所述有机膦酸的浓度小于1g/L时，镀液变得不稳定，同时镀层变得粗糙。优选地，所述有机膦酸的浓度例如为1g/L、2g/L、3g/L、4g/L、5g/L、6g/L、7g/L、8g/L、9g/L、10g/L、11g/L、12g/L、13g/L、14g/L、15g/L、16g/L、17g/L、18g/L、19g/L、20g/L、21g/L、22g/L、23g/L、24g/L、25g/L、26g/L、27g/L、28g/L、29g/L、30g/L、35g/L、40g/L、45g/L、50g/L，以及上述任意两个数值组成的范围中的任意值，优选为4-30g/L。
在本发明一些实施方式中，优选地，所述添加剂为所述含锑化合物或所述含砷化合物。所述含锑化合物选自锑的氧化物、锑的卤化物、锑的卤氧化物、锑化物、锑酸盐、有机锑化物中的至少一种，优选选自酒石酸锑钠、酒石酸锑钾、锑酸钠、锑酸钾中的至少一种；优选，所述含砷化合物选自砷的氧化物、亚砷酸盐、含砷有机物中的至少一种，优选选自亚砷酸钠和/或三氧化二砷。
在本发明一些实施方式中，优选地，所述含锑化合物以锑计，所述含砷化合物以砷计，所述镀液中，所述含锑化合物的浓度为1-100mg/L，更优选地，所述含锑化合物的浓度例如为1mg/L、2mg/L、3mg/L、4mg/L、5mg/L、6mg/L、7mg/L、8mg/L、9mg/L、10mg/L、11mg/L、12mg/L、13mg/L、14mg/L、15mg/L、16mg/L、17mg/L、18mg/L、19mg/L、20mg/L、21mg/L、22mg/L、23mg/L、24mg/L、25mg/L、、26mg/L、27mg/L、28mg/L、29mg/L、30mg/L、31mg/L、32mg/L、33mg/L、34mg/L、35mg/L、36mg/L、37mg/L、38mg/L、39mg/L、40mg/L、41mg/L、42mg/L、43mg/L、44mg/L、45mg/L、46mg/L、47mg/L、48mg/L、49mg/L、50mg/L、60mg/L、70mg/L、80mg/L、90mg/L、100mg/L，以及上述任意两个数值组成的范围中的任意值，优选为5-50mg/L；所述含砷化合物的浓度为1-100mg/L，更优选地，所述含砷化合物的浓度例如为1mg/L、2mg/L、3mg/L、4mg/L、5mg/L、6mg/L、7mg/L、8mg/L、9mg/L、10mg/L、11mg/L、12mg/L、13mg/L、14mg/L、15mg/L、16mg/L、17mg/L、18mg/L、19mg/L、20mg/L、21mg/L、22mg/L、23mg/L、24mg/L、25mg/L、、26mg/L、27mg/L、28mg/L、29mg/L、30mg/L、31mg/L、 32mg/L、33mg/L、34mg/L、35mg/L、36mg/L、37mg/L、38mg/L、39mg/L、40mg/L、41mg/L、42mg/L、43mg/L、44mg/L、45mg/L、46mg/L、47mg/L、48mg/L、49mg/L、50mg/L、60mg/L、70mg/L、80mg/L、90mg/L、100mg/L，以及上述任意两个数值组成的范围中的任意值，优选为5-50mg/L。本发明中，所述含锑化合物或所述含砷化合物的浓度低于1mg/L时，镀液的去极化效果不足够，导致析出效率降低，金的纯度下降。所述含锑化合物或所述含砷化合物的浓度大于100mg/L时，高电流密度区镀层粗糙度增加，镀层外观不均匀。特别地，当本发明的无氰电镀金镀液中包含了上述添加剂和有机膦酸，优选(所述含锑化合物或所述含砷化合物)与所述有机膦酸的重量比为1:10-2500，优选为1:100-1000，优选例如为1:100、1:200、1:300、1:400、1:500、1:600、1:700、1:800、1:900、1:1000，以及上述任意两个数值组成的范围中的任意值，能够提供更好的金凸块热处理后硬度和形状规则性。上述重量比低于1:10或高于1:2500都不利于提供合适的配合作用，提高金凸块热处理后硬度和形状规则性。
在本发明一些实施方式中，优选地，所述金源选自金的硫酸盐和/或亚硫酸盐，优选为亚硫酸金钠、亚硫酸金钾、亚硫酸金铵中的至少一种。
在本发明一些实施方式中，优选地，所述金源的用量使得所述镀液中金离子的浓度为1-20g/L。本发明中，金离子的浓度小于1g/L时，阴极析出效率过低，同时电镀液变得不稳定在镀液中而非阴极表面容易析金。金离子的浓度大于20g/L时，虽然对于电镀液的稳定性和镀层的外观、物理性质没有影响，但是由于镀片完成后镀液的带出造成金的浪费，成本上升。优选金离子的浓度例如为1g/L、2g/L、3g/L、4g/L、5g/L、6g/L、7g/L、8g/L、9g/L、10g/L、11g/L、12g/L、13g/L、14g/L、15g/L、16g/L、17g/L、18g/L、19g/L、20g/L，以及上述任意两个数值组成的范围中的任意值，优选为8-15g/L。
在本发明一些实施方式中，优选地，所述导电盐选自亚硫酸盐和/或硫酸盐，优选选自亚硫酸钠、亚硫酸钾、亚硫酸铵、亚硫酸氢钠、硫酸钠、硫酸钾、硫酸铵、硫酸氢钠中的至少一种，优选为亚硫酸钠和硫酸钠。
在本发明一些实施方式中，优选地，所述镀液中，亚硫酸钠的浓度为10-120g/L；不足10g/L时，电镀的均匀性会下降，镀层的硬度偏高，甚至电镀液可能发生分解。大于120g/L时，高区电流密度区间变窄导致镀层变粗糙。优选亚硫酸钠的浓度例如为10g/L、15g/L、20g/L、25g/L、30g/L、35g/L、40g/L、45g/L、50g/L、55g/L、60g/L、65g/L、70g/L、75g/L、80g/L、85g/L、90g/L、95g/L、100g/L、105g/L、110g/L、115g/L、120g/L，以及上述任意两个数值组成的范围中的任意值，优选为30-80g/L。硫酸钠的浓度为1-120g/L。硫酸钠的浓度大于120g/L时可能会造成高度电流密度区间变窄导致镀层变粗糙。优选硫酸钠的浓度例如为1g/L、5g/L、10g/L、15g/L、20g/L、25g/L、30g/L、35g/L、40g/L、45g/L、50g/L、55g/L、60g/L、65g/L、70g/L、75g/L、80g/L、85g/L、90g/L、95g/L、100g/L、105g/L、110g/L、115g/L、120g/L，以及上述任意两个数值组成的范围中的任意值，优选为10-60g/L。
在本发明一些实施方式中，优选地，所述缓冲剂选自乙二胺四乙酸盐、磷酸盐、酒石酸盐、柠檬酸盐中的至少一种，优选选自乙二胺四乙酸二钠和/或磷酸氢二钠。
在本发明一些实施方式中，优选地，所述镀液中，所述缓冲剂的浓度为1-30g/L。缓冲剂的浓度低于1g/L时，有时镀液的缓冲能力不足导致镀层外观不均匀，缓冲剂的大于30g/L时，高区电流密度区间变窄导致镀层变粗糙。优选缓冲剂的浓度例如为1g/L、2g/L、3g/L、4g/L、5g/L、6g/L、7g/L、8g/L、9g/L、10g/L、11g/L、12g/L、13g/L、14g/L、15g/L、16g/L、17g/L、18g/L、19g/L、20g/L、25g/L、30g/L，以及上述任意两个数值组成的范围中的任意值，优选 为5-20g/L。
在本发明一些实施方式中，优选地，其中，所述镀液还包括pH添加剂；优选地，所述镀液的pH为7-9。镀液的pH低于7.0时，镀液的长期稳定性变差。镀液的pH高于9.0时，光刻胶溶解或者发生渗镀，同时由于金难于还原导致镀层外观不均匀。优选镀液的pH例如为7.0、7.1、7.2、7.3、7.4、7.5、7.6、7.、7.8、7.9、8、8.1、8.2、8.3、8.4、8.5、8.6、8.7、8.8、8.9、9.0，以及上述任意两个数值组成的范围中的任意值，优选为7.4-9。作为pH调节剂，作为酸可以选用亚硫酸、硫酸等，作为碱可以选用氢氧化钠、氢氧化钾、氨水等。
本发明中，所述镀液可以的制备方法是将上述各组分投入水中完全溶解后获得。其中，导电盐、缓冲剂、有机膦酸可以是将相应的化合物直接投入水中进行完全溶解。金源、含砷化合物或含锑化合物可以是以水溶液的形式加入，但分别以金元素、砷、锑计算实际的用量，最后各组分完全溶解。优选地，可以先将导电盐、缓冲剂、有机膦酸与水混合得到完全溶解的溶液，然后将金源、含砷化合物或含锑化合物以水溶液形式加入，完全溶解。溶解过程可以在常温下进行，伴随搅拌。溶解得到的溶液还进行pH值调节，满足pH为7-9，优选为7.4-9。pH值调节的要求如上所述，不再赘述。进一步地，还进行得到溶液的体积调整，以得到最终的所述镀液且满足对各组分的浓度要求。
本发明第二方面提供一种本发明提供的无氰电镀金镀液在半导体制造中的应用。
在本发明一些实施方式中，优选地，应用可以是用于电子线路板、电子连接器、半导体制造等领域。
本发明第三方面提供一种电镀制金凸块的方法，其中，该方法包括：将半导体在本发明提供的无氰电镀金镀液存在下进行电镀，在半导体表面形成金凸块。优选例如适用于在半导体表面制备通过光刻胶技术形成的高硬度金凸块产品，例如液晶驱动芯片、CMOS图像传感器、指纹传感器等，可通过倒装技术TAB(Tape Automated Bonding)、COG(Chipon glass)、COF(Chip on Film)、COP(Chip on Plastics)等实现芯片和基板之间的互连。
在本发明一些实施方式中，优选地，所述电镀的温度为40-70℃。电镀的温度高于70℃时，有时镀液会发生分解，同时因为镀液会发太快电镀液管理困难。电镀的温度低于40℃时，析出效率降低，有时镀层外观不均匀。优选例如为40℃、45℃、50℃、51℃、52℃、53℃、54℃、55℃、56℃、57℃、58℃、59℃、60℃、65℃、70℃，以及上述任意两个数值组成的范围中的任意值，优选为50-60℃。
在本发明一些实施方式中，优选地，所述电镀的电流密度为0.1-2A/dm 2(ASD)。电流密度超出上述区间时，有时可能发生镀液的分解或者镀层外观的不均匀。优选所述电镀的电流密度例如为0.1ASD、0.2ASD、0.3ASD、0.4ASD、0.5ASD、0.6ASD、.07ASD、0.8ASD、0.9ASD、1ASD、1.1ASD、1.2ASD、1.3ASD、1.4ASD、1.5ASD、1.7ASD、1.8ASD、1.9ASD、2.0ASD，以及上述任意两个数值组成的范围中的任意值，优选为0.2-1.2ASD。
还提供一种上述方法制得的金凸块，具有规则的形状和高的热处理后硬度。可以达到98HV以上。
更进一步地，本发明还能够提供一种具有上述金凸块的电子部件或由上述金凸块制备方法制得的电子部件。
以下将通过实施例对本发明进行详细描述。
测试方法：
析出效率：电镀完毕后，采用称重法计算镀液的析出效率，析出效率为电镀金的重量除 于电镀过程中通过的电量全部转为一价金的理论重量。
镀层硬度：使用维氏硬度计测试镀层的硬度，使用10gf负荷将测定压头在镀层表面保持10s，测试未热处理以及在270℃进行了30min热处理后的镀层硬度。
金凸块高度：为了评估本发明的镀液的填平能力，根据实际需求设计了图形片，图形片的面积为30×30mm，硅晶片的表面断面结构为Si/SiO 2/Al/Ti/Au，使用正光刻胶AZ4660形成凸块开口，开口尺寸为80μm(长)×20μm(宽)×15μm(深)，相邻凸块横排之间的距离为13μm，纵排之间的距离为30μm。在铝电极上设计了1.2μm的钝化层，开口宽度分别为4μm、8μm和12μm(如图1所示)。电镀后使用NMP溶剂去除光刻胶，获得填充在开口中形成的，使用基恩士VK-X3100测量金凸块的形状和高度。
实施例1
在1L的烧杯中，加入60g的亚硫酸钠、30g的硫酸钠、10g的羟基乙叉二磷酸和10g的乙二胺四乙酸二钠，添加去离子水600mL，搅拌完全溶解后，加入金元素含量为8g的亚硫酸金钠水溶液和砷含量0.01g的亚砷酸钠溶液，添加去离子水调整镀液的体积到1L和调节pH值为8.0，得到镀液-1。
加热镀液-1到55℃。电镀使用铂金钛网为阳极，预镀金处理过的黄铜片为阴极，阴极面积为2×2cm，调整电流密度为0.5ASD，电镀100min，得到镀金件。
电镀结束计算析出效率为99％，电镀后镀层表面光滑、色泽均匀；镀层在热处理前硬度为147HV，在热处理后镀层的硬度为98HV。
实施例2
按照实施例1的方法，不同的是，加入“20g的羟基乙叉二磷酸”替换“10g的羟基乙叉二磷酸”、“金元素含量为12g的亚硫酸金钠水溶液”替换“金元素含量为8g的亚硫酸金钠水溶液”和“砷含量0.01g的亚砷酸钠”替换“砷含量0.01g的亚砷酸钠溶液”，镀液的“pH值为7.4”替换“pH值为8.0”，得到镀液-2。
电镀后镀层表面光滑、色泽均匀，计算析出效率为99％，镀层在热处理前硬度为143HV，在热处理后镀层的硬度为101HV。
实施例3
按照实施例1的方法，不同的是，加入“4g的氨三亚甲基膦酸”替换“10g的羟基乙叉二磷酸”和“10g的磷酸氢二钠”替换“10g的乙二胺四乙酸二钠”、“金元素含量为12g的亚硫酸金钠水溶液”替换“金元素含量为8g的亚硫酸金钠水溶液”和“砷含量0.2g的亚砷酸钠”替换“砷含量0.01g的亚砷酸钠溶液”，镀液的“pH值为8.5”替换“pH值为8.0”，得到镀液-3。
电镀后镀层表面光滑、色泽均匀，计算析出效率为100％，镀层在热处理前硬度为144HV，在热处理后镀层的硬度为107HV。
实施例4
按照实施例1的方法，不同的是，加入“30g的氨三亚甲基膦酸”替换“10g的羟基乙叉二磷酸”和“10g的磷酸氢二钠”替换“10g的乙二胺四乙酸二钠”、“金元素含量为15g的亚硫酸金钠水溶液”替换“金元素含量为8g的亚硫酸金钠水溶液”和“砷含量0.2g的亚砷酸钠”替换“砷含量0.01g的亚砷酸钠溶液”，镀液的“pH值为8.5”替换“pH值为8.0”，得到镀液-4。
电镀后镀层表面光滑、色泽均匀，计算析出效率为100％，镀层在热处理前硬度为139HV， 在热处理后镀层的硬度为106HV。
实施例5
按照实施例1的方法，不同的是，加入“10g的羟基乙叉二磷酸、10g氨三亚甲基膦酸”替换“10g的羟基乙叉二磷酸”、“10g的磷酸氢二钠”替换“10g的乙二胺四乙酸二钠”、“金元素含量为15g的亚硫酸金钠水溶液”替换“金元素含量为8g的亚硫酸金钠水溶液”和“砷含量0.2g的亚砷酸钠”替换“砷含量0.01g的亚砷酸钠溶液”，镀液的“pH值为8.5”替换“pH值为8.0”，得到镀液-5。
电镀后镀层表面光滑、色泽均匀，计算析出效率为99％，镀层在热处理前硬度为142HV，在热处理后镀层的硬度为101HV。
实施例6
按照实施例1的方法，不同的是，加入“锑含量0.01g的酒石酸锑钾”替换“砷含量0.01g的亚砷酸钠溶液”，得到镀液-6。
电镀后镀层表面光滑、色泽均匀，计算析出效率为99％，镀层在热处理前硬度为142HV，在热处理后镀层的硬度为96HV。
实施例7
按照实施例1的方法，不同的是，加入“20g的羟基乙叉二磷酸”替换“10g的羟基乙叉二磷酸”、“金元素含量为12g的亚硫酸金钠水溶液”替换“金元素含量为8g的亚硫酸金钠水溶液”和“锑含量0.01g的酒石酸锑钾”替换“砷含量0.01g的亚砷酸钠溶液”，镀液的“pH值为7.4”替换“pH值为8.0”，得到镀液-7。
电镀后镀层表面光滑、色泽均匀，计算析出效率为100％，镀层在热处理前硬度为140HV，在热处理后镀层的硬度为101HV。
实施例8
按照实施例1的方法，不同的是，加入“4g的氨三亚甲基膦酸”替换“10g的羟基乙叉二磷酸”、“10g的磷酸氢二钠”替换“10g的乙二胺四乙酸二钠”、“金元素含量为12g的亚硫酸金钠水溶液”替换“金元素含量为8g的亚硫酸金钠水溶液”和“锑含量0.2g的酒石酸锑钾”替换“砷含量0.01g的亚砷酸钠溶液”，镀液的“pH值为8.5”替换“pH值为8.0”，得到镀液-8。
电镀后镀层表面光滑、色泽均匀，计算析出效率为100％，镀层在热处理前硬度为147HV，在热处理后镀层的硬度为103HV。
实施例9
按照实施例1的方法，不同的是，加入“30g的氨三亚甲基膦酸”替换“10g的羟基乙叉二磷酸”、“10g的磷酸氢二钠”替换“10g的乙二胺四乙酸二钠”、“金元素含量为15g的亚硫酸金钠水溶液”替换“金元素含量为8g的亚硫酸金钠水溶液”和“锑含量0.2g的酒石酸锑钾”替换“砷含量0.01g的亚砷酸钠溶液”，镀液的“pH值为8.5”替换“pH值为8.0”，得到镀液-9。
电镀后镀层表面光滑、色泽均匀，计算析出效率为100％，镀层在热处理前硬度为139HV，在热处理后镀层的硬度为110HV。
实施例10
按照实施例1的方法，不同的是，加入“10g的羟基乙叉二磷酸、10g氨三亚甲基膦酸”替换“10g的羟基乙叉二磷酸”和“10g的磷酸氢二钠”替换“10g的乙二胺四乙酸二钠”、“金 元素含量为15g的亚硫酸金钠水溶液”替换“金元素含量为8g的亚硫酸金钠水溶液”和“锑含量0.1g的酒石酸锑钾”替换“砷含量0.01g的亚砷酸钠溶液”，镀液的“pH值为8.5”替换“pH值为8.0”，得到镀液-10。
电镀后镀层表面光滑、色泽均匀，计算析出效率为99％，镀层在热处理前硬度为138HV，在热处理后镀层的硬度为99HV。
以上实施例中涉及条件和结果见表1。
表1
Figure PCTCN2022122268-appb-000001
实施例11
金凸块的制备
图形片电镀是在1.7L的山本镀垂直电镀槽体中进行，镀液为镀液-1；阳极使用铂电极，阴极和阳极的距离约4cm，使用刮杆在阴极表面左右移动以促进镀液在光刻胶中的交换。电流强度为24mA(电流密度为0.5ASD)，电镀温度为55℃，电镀时间35min。电镀后测量金凸块的目标高度为12μm。
如图2-3所示，在图形片上没有发生漏镀的情况，没有相邻金凸块之间因为光刻胶的溶解或破裂而发生凸块相互连接。金凸块的形状比较规则，在金凸块表面没有观察到金瘤或针孔。金凸块表面比较平整，没有倾斜。如图5和表2数据所示，通过统计在图形片上对角线两个区域的金凸块高度，金凸块高度为12.28±0.39μm，镀金表面高度差为1.15±0.10μm，符合技术要求规格。
表2
Figure PCTCN2022122268-appb-000002
通过表1和2的结果可以看出，采用本发明的实施例使用含有有机多磷酸为辅助络合剂和单一添加剂砷化合物或锑化合物的无氰电镀金镀液制得的金凸块，能够在热处理后仍保持高硬度，且金凸块的形状还能保持规则。相比已有技术，镀液更加好管理，运行成本更低。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (11)

  1. 一种无氰电镀金镀液，其特征在于，所述镀液包含：金源、导电盐、缓冲剂、添加剂和有机膦酸，其中，所述添加剂选自含锑化合物和/或含砷化合物。
  2. 根据权利要求1所述的镀液，其特征在于，所述有机膦酸选自亚甲基膦酸、同碳二膦酸、羧酸膦酸中的至少一种；
    和/或，所述镀液中，所述有机膦酸的浓度为1-50g/L。
  3. 根据权利要求1或2所述的镀液，其特征在于，所述含锑化合物选自锑的氧化物、锑的卤化物、锑的卤氧化物、锑化物、锑酸盐、有机锑化物中的至少一种；
    和/或，所述含砷化合物选自砷的氧化物、亚砷酸盐、含砷有机物中的至少一种；
    和/或，所述含锑化合物以锑计，所述含砷化合物以砷计，所述镀液中，所述含锑化合物的浓度为1-1000mg/L；所述含砷化合物的浓度为1-1000mg/L。
  4. 根据权利要求1-3中任意一项所述的镀液，其中，所述金源选自金的硫酸盐和/或亚硫酸盐；
    和/或，所述金源的用量使得所述镀液中金离子的浓度为1-20g/L。
  5. 根据权利要求1-4中任意一项所述的镀液，其中，所述导电盐选自亚硫酸盐、亚硫酸氢盐、硫酸盐、硫酸氢盐中的至少一种；
    和/或，所述镀液中，亚硫酸钠的浓度为10-120g/L；硫酸钠的浓度为1-120g/L。
  6. 根据权利要求1-5中任意一项所述的镀液，其中，所述缓冲剂选自乙二胺四乙酸盐、磷酸盐、酒石酸盐、柠檬酸盐中的至少一种；
    和/或，所述镀液中，所述缓冲剂的浓度为1-30g/L。
  7. 根据权利要求1-6中任意一项所述的镀液，其中，所述镀液还包括pH添加剂；
    和/或，所述镀液的pH为7-9。
  8. 一种权利要求1-7中任意一项所述的无氰电镀金镀液在半导体制造中的应用。
  9. 一种电镀制金凸块的方法，其特征在于，该方法包括：
    将半导体在权利要求1-7中任意一项所述的无氰电镀金镀液存在下进行电镀，在半导体表面形成金凸块；
    和/或，所述电镀的温度为40-70℃；
    和/或，所述电镀的电流密度为0.1-2A/dm 2。
  10. 一种权利要求9所述的方法制得的金凸块。
  11. 一种具有权利要求10所述的金凸块的电子部件。
PCT/CN2022/122268 2021-09-30 2022-09-28 无氰电镀金镀液及其应用和电镀制金凸块的方法以及金凸块和电子部件 WO2023051640A1 (zh)

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CN113832509B (zh) * 2021-09-30 2022-08-26 深圳市联合蓝海黄金材料科技股份有限公司 用于在镍镀层上电镀金的镀液和在镍镀层上电镀金的方法和镀金件
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