CN111349917A - Gold plating solution for semiconductor chip, gold plating method and nickel and gold plating method - Google Patents
Gold plating solution for semiconductor chip, gold plating method and nickel and gold plating method Download PDFInfo
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- CN111349917A CN111349917A CN201811581213.2A CN201811581213A CN111349917A CN 111349917 A CN111349917 A CN 111349917A CN 201811581213 A CN201811581213 A CN 201811581213A CN 111349917 A CN111349917 A CN 111349917A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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Abstract
The invention provides a gold plating solution, a gold plating method and a nickel and gold plating method for a semiconductor chip, wherein the gold plating solution comprises 4-10g/L of water-soluble gold salt, 12-20g/L of pH buffer, 4-8g/L of complexing agent, 30-45g/L of masking agent and water; nickel plating; performing gold plating using the gold plating method for the semiconductor chip; and (5) drying. The gold plating solution is stable, the gold plating method and the nickel-gold plating method are simple to operate, the gold plating process is uniform in speed, the gold layer bonding force is strong, and the gold plating layer thickness of the chip is uniform.
Description
Technical Field
The invention belongs to the technical field of semiconductor production processes, and particularly relates to a gold plating solution, a gold plating method and a nickel-gold plating method for a semiconductor chip.
Background
The nickel and gold plating layers have the advantages of low contact resistance, good conductivity, good weldability and strong corrosion resistance, so that the nickel and gold plating process is generally carried out in the production process of semiconductors in order to improve the welding effect and the conductivity of the wafers. The method of chemical nickel-gold plating is widely used due to simple operation and low cost, generally, a nickel layer with a certain thickness is deposited on the surface of a silicon wafer through reduction reaction, then a semiconductor material is immersed in gold plating solution, and a gold layer with a certain thickness is deposited through replacement reaction of nickel and gold on the surface of the silicon wafer.
The uniformity of the thickness of the nickel and gold layers obtained after the nickel and gold plating is finished can directly influence the welding effect and the appearance effect of the finally obtained semiconductor chip, but the gold plating rate of the gold plating solution used in the gold plating process in the prior art is not easy to control, so that the thickness of the gold plating layer on the surface of the chip is not uniform, the binding force of the gold layer is poor, and the gold plating solution in the same batch of the gold plating solution is often used for treating a plurality of batches of chips, and the concentration of the main salt in the gold plating solution is continuously reduced along with the treatment process, so that the concentration of the gold salt in the gold plating solution in the gold plating process of different batches of chips is different, the thickness of the gold plating layer on the surface of the chips in different batches is different, the performance of the finally obtained chips is poor.
Disclosure of Invention
The invention aims to provide a gold plating solution, a gold plating method and a nickel-gold plating method for a semiconductor chip, wherein the gold plating solution is stable, the gold plating process speed is uniform, the gold layer bonding force is strong, and the gold plating layer thickness of the chip is uniform.
In order to solve the technical problems, the invention adopts the technical scheme that: a gold plating solution for semiconductor chips comprises 4-10g/L of water-soluble gold salt, 12-20g/L of pH buffer, 4-8g/L of complexing agent, 30-45g/L of masking agent and water.
In the technical scheme, the pH value of the gold plating solution is preferably 5-7, and more preferably 5-6. The pH value of the gold plating solution is adjusted to be acidic, the potassium aurous cyanide can stably exist in a system with citric acid and the solution is acidic, cannot be separated out, and the cyanic acid generated in the gold plating process and the citric acid can generate hydrogen bonds to stably exist in the solution and cannot overflow in the form of harmful gas, so that the thickness of the gold plating layer on the surface of the chip is more uniform, and the color of the plating layer is golden and glossy.
The water-soluble gold salt refers to a water-soluble salt of gold, and in the technical scheme, the water-soluble gold salt is preferably one or a combination of more of potassium aurous cyanide, sodium gold sulfite, gold chloride trihydrate, hydrochloric acid and sodium aurous thiomalate, and more preferably, the water-soluble gold salt is potassium aurous cyanide.
Wherein, the pH buffering agent can gradually release acid or alkali in the gold plating process to keep the acidity of the gold plating solution, so that the acidity of the gold plating solution in which the chip is positioned in the gold plating process is uniform, thereby ensuring the uniform gold plating rate and obtaining the gold plating layer with uniform thickness. There are many types of pH buffers known in the art and may be used herein, for example, the pH buffer may be a combination of one or more of ammonium chloride, dipotassium hydrogen phosphate, sodium acetate and trisodium citrate.
The complexing agent is a compound capable of forming a complex with gold ions in the gold plating solution, and forms complexing agent-gold complex ions with the gold ions in the gold plating solution, and the complexing agent-gold complex ions continuously release free gold ions along with continuous consumption of the gold ions in the gold plating solution, so that the concentration of the free gold ions in the gold plating solution can be controlled to be kept stable, the reaction rate in the gold plating process is controlled, and the thickness uniformity of the gold plating layer in the gold plating process is higher. The complexing agent can be one or more of citric acid, soluble salt of citric acid, sodium sulfite, sodium thiosulfate and potassium sodium tartrate, and preferably, the complexing agent is a mixture of citric acid and the soluble salt of citric acid.
The masking agent is a compound capable of forming a complex with impurity ions in the gold plating solution, and the impurity ions in the gold plating solution can influence the stability of the gold plating solution and can influence the quality of a gold plating layer by replacing the gold ions to deposit on a chip in the gold plating process, so that the impurity ions in the gold plating solution and the complex formed by the impurity ions can stabilize the property of the gold plating solution by adding the masking agent, the impurity ions cannot deposit on the chip, and the quality of the gold plating layer is higher. The masking agent can be one or more of ethylenediamine tetraacetic acid or salt thereof, hydroxyethyliminodiacetic acid or salt thereof and diethyltriaminepentaacetic acid or salt thereof. Preferably, the masking agent is ethylenediaminetetraacetic acid or a salt thereof, preferably disodium ethylenediaminetetraacetate.
Another object of the present invention is to provide a method for plating gold on a semiconductor chip using the above gold plating solution.
In the technical scheme, the temperature of the gold plating solution in the gold plating process is preferably 60-100 ℃, and the temperature of the gold plating solution in the gold plating process is preferably 80-90 ℃.
In the technical solution, preferably, in the gold plating method, the same batch of gold plating solution is used for processing different batches of semiconductor chips, and the processing time of the different batches of semiconductor chips is increased in sequence. Because the concentration of the gold salt in the gold plating solution is continuously reduced in the process of processing different batches of semiconductor chips by the same gold plating solution, if the gold plating time is kept unchanged, the thickness of the gold plating layer of the semiconductor chips in different batches is inconsistent, therefore, when the semiconductor chips in different batches are processed, the thickness of the gold plating layer of the semiconductor chips in different batches tends to be consistent by sequentially increasing the gold plating time, and the utilization rate of the gold plating solution can be improved. Preferably, the processing time of each lot of semiconductor chips is increased by 60 to 90 seconds from the processing time of the last lot of semiconductor chips.
Still another object of the present invention is to provide a method for plating a semiconductor chip with nickel and gold, comprising: sequentially carrying out:
the method comprises the following steps of firstly, preprocessing the surface of a semiconductor chip, preferably, the first step comprises the steps of removing an oxide layer on the surface of the semiconductor chip, cleaning and activating the surface of the semiconductor chip in sequence;
secondly, nickel plating is carried out on the semiconductor chip;
thirdly, gold plating is carried out on the semiconductor chip by using the gold plating method of the semiconductor chip;
and fourthly, drying, preferably, the fourth step comprises slow hot water lifting and infrared drying.
The invention has the advantages and positive effects that: the gold plating solution for the semiconductor chip has stable property, the buffering agent ensures that the pH value of the gold plating solution is relatively constant in the gold plating process, and the complex continuously releases free gold ions along with the consumption of gold salt in the gold plating process, so that the concentration of the gold ions in the gold plating solution is stable in the gold plating process, the gold plating rate is stable, and the gold plating layer of the chip is uniform in thickness; the masking agent can complex impurity ions in the gold plating solution, and improve the stability of the gold plating solution and the gold plating quality of the chip. The gold plating method and the nickel-gold plating method for the chip are simple to operate, the thickness of the gold plating layer is uniform, and the utilization rate of the gold plating solution is high.
Drawings
Fig. 1 is a scanning electron microscope image of a semiconductor chip plated with nickel and gold in accordance with an embodiment of the present invention.
Detailed Description
The following further describes embodiments of the present invention with reference to specific examples:
example one
The method for plating nickel and gold on the semiconductor chip comprises the following steps:
firstly, semiconductor chip surface pretreatment: removing an oxide layer on the surface of the semiconductor chip, and soaking the semiconductor chip in nitric acid at 70-90 ℃ for 3-5 min; cleaning, namely performing pure water overflow cleaning on the obtained semiconductor chip at room temperature and performing ultrasonic cleaning; activating the surface of the semiconductor chip, and soaking the obtained semiconductor chip in the activating solution at room temperature for 3-5 min.
Step two, nickel plating is carried out on the obtained semiconductor chip: preparing nickel plating solution, wherein the nickel plating solution contains 0.4g/L of nickel chloride, 0.2g/L of sodium hypophosphite, 1.2g/L of ammonium chloride, 1.8g/L of citric acid, sodium citrate and ultrapure water; standing the prepared nickel plating solution for 24-36 hours to ensure that the nickel plating solution is fully and stably mixed; adding ammonia water into the nickel plating solution to adjust the pH value of the nickel plating solution to 8-9; soaking the semiconductor chip in the nickel plating solution at 80-90 ℃ for nickel plating, and when the same batch of nickel plating solution is used for processing different batches of chips, the processing time of the chips of different batches is sequentially increased by 30-90s so as to ensure that the nickel plating thickness of the chips of different batches is uniform.
Thirdly, gold plating is carried out on the nickel-plated semiconductor chip: preparing a gold plating solution, wherein the gold plating solution contains 4g/L potassium aurous cyanide, 12g/L ammonium chloride, 4g/L citric acid and sodium citrate, 30g/L disodium ethylene diamine tetraacetate and ultrapure water; standing the prepared gold plating solution for 24-36 hours to ensure that the gold plating solution is fully and stably mixed; adjusting the pH value of the gold plating solution to 5-6; soaking the semiconductor chip in the gold plating solution at 80-90 ℃ for gold plating, and when the same batch of nickel plating solution is used for processing different batches of chips, the processing time of the chips of different batches is sequentially increased by 60-90s so as to ensure that the nickel plating thickness of the chips of different batches is uniform.
Step four, drying: and (4) slowly pulling the gold-plated chip obtained in the third step by hot water and drying by infrared rays.
And fifthly, performing performance test on the obtained chip plated with nickel and gold, and performing scanning electron microscope test on the obtained chip plated with nickel and gold. The scanning electron microscope test result is shown in fig. 1, and the scanning electron microscope image shows that the thickness of the gold plating layer on the surface of the chip obtained by using the gold plating solution and the nickel-gold plating method of the invention to plate gold is uniform.
Example two
The method for plating nickel and gold on the semiconductor chip comprises the following steps:
firstly, semiconductor chip surface pretreatment: removing an oxide layer on the surface of the semiconductor chip, and soaking the semiconductor chip in nitric acid at 70-90 ℃ for 3-5 min; cleaning, namely performing pure water overflow cleaning on the obtained semiconductor chip at room temperature and performing ultrasonic cleaning; activating the surface of the semiconductor chip, and soaking the obtained semiconductor chip in the activating solution at room temperature for 3-5 min.
Step two, nickel plating is carried out on the obtained semiconductor chip: preparing nickel plating solution, wherein the nickel plating solution contains 0.4g/L of nickel chloride, 0.2g/L of sodium hypophosphite, 1.2g/L of ammonium chloride, 1.8g/L of citric acid, sodium citrate and ultrapure water; standing the prepared nickel plating solution for 24-36 hours to ensure that the nickel plating solution is fully and stably mixed; adding ammonia water into the nickel plating solution to adjust the pH value of the nickel plating solution to 8-9; soaking the semiconductor chip in the nickel plating solution at 80-90 ℃ for nickel plating, and when the same batch of nickel plating solution is used for processing different batches of chips, the processing time of the chips of different batches is sequentially increased by 30-90s so as to ensure that the nickel plating thickness of the chips of different batches is uniform.
Thirdly, gold plating is carried out on the nickel-plated semiconductor chip: preparing a gold plating solution, wherein the gold plating solution contains 10g/L potassium aurous cyanide, 20g/L ammonium chloride, 8g/L citric acid and sodium citrate, 45g/L disodium ethylene diamine tetraacetate and ultrapure water; standing the prepared gold plating solution for 24-36 hours to ensure that the gold plating solution is fully and stably mixed; adjusting the pH value of the gold plating solution to 5-6; soaking the semiconductor chip in the gold plating solution at 80-90 ℃ for gold plating, and when the same batch of nickel plating solution is used for processing different batches of chips, the processing time of the chips of different batches is sequentially increased by 60-90s so as to ensure that the nickel plating thickness of the chips of different batches is uniform.
Step four, drying: and (4) slowly pulling the gold-plated chip obtained in the third step by hot water and drying by infrared rays.
EXAMPLE III
The method for plating nickel and gold on the semiconductor chip comprises the following steps:
firstly, semiconductor chip surface pretreatment: removing an oxide layer on the surface of the semiconductor chip, and soaking the semiconductor chip in nitric acid at 70-90 ℃ for 3-5 min; cleaning, namely performing pure water overflow cleaning on the obtained semiconductor chip at room temperature and performing ultrasonic cleaning; activating the surface of the semiconductor chip, and soaking the obtained semiconductor chip in the activating solution at room temperature for 3-5 min.
Step two, nickel plating is carried out on the obtained semiconductor chip: preparing nickel plating solution, wherein the nickel plating solution contains 0.4g/L of nickel chloride, 0.2g/L of sodium hypophosphite, 1.2g/L of ammonium chloride, 1.8g/L of citric acid, sodium citrate and ultrapure water; standing the prepared nickel plating solution for 24-36 hours to ensure that the nickel plating solution is fully and stably mixed; adding ammonia water into the nickel plating solution to adjust the pH value of the nickel plating solution to 8-9; soaking the semiconductor chip in the nickel plating solution at 80-90 ℃ for nickel plating, and when the same batch of nickel plating solution is used for processing different batches of chips, the processing time of the chips of different batches is sequentially increased by 30-90s so as to ensure that the nickel plating thickness of the chips of different batches is uniform.
Thirdly, gold plating is carried out on the nickel-plated semiconductor chip: preparing a gold plating solution, wherein the gold plating solution contains 6g/L potassium aurous cyanide, 15g/L ammonium chloride, 6g/L citric acid and sodium citrate, 40g/L disodium ethylene diamine tetraacetate and ultrapure water; standing the prepared gold plating solution for 24-36 hours to ensure that the gold plating solution is fully and stably mixed; adjusting the pH value of the gold plating solution to 5-6; soaking the semiconductor chip in the gold plating solution at 80-90 ℃ for gold plating, and when the same batch of nickel plating solution is used for processing different batches of chips, the processing time of the chips of different batches is sequentially increased by 60-90s so as to ensure that the nickel plating thickness of the chips of different batches is uniform.
Step four, drying: and (4) slowly pulling the gold-plated chip obtained in the third step by hot water and drying by infrared rays.
Although the embodiments of the present invention have been described in detail, the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. A gold plating solution for semiconductor chips, characterized in that: comprises 4-10g/L of water-soluble gold salt, 12-20g/L of pH buffer, 4-8g/L of complexing agent, 30-45g/L of masking agent and water.
2. The gold plating liquid for semiconductor chips according to claim 1, characterized in that: the pH value of the gold plating solution is 5-7, and preferably, the pH value of the gold plating solution is 5-6.
3. The gold plating liquid for semiconductor chips according to claim 1 or 2, characterized in that: the water-soluble gold salt is one or a combination of more of potassium aurous cyanide, sodium gold sulfite, gold chloride trihydrate hydrochloric acid and sodium aurous thiomalate, and preferably, the water-soluble gold salt is potassium aurous cyanide.
4. The gold plating solution for semiconductor chips according to any one of claims 1 to 3, characterized in that: the pH buffering agent is one or more of ammonium chloride, dipotassium hydrogen phosphate, sodium acetate and trisodium citrate.
5. The gold plating solution for semiconductor chips according to any one of claims 1 to 4, characterized in that: the complexing agent is one or more of citric acid, soluble salt of citric acid, sodium sulfite, sodium thiosulfate and potassium sodium tartrate, and preferably, the complexing agent is a mixture of citric acid and the soluble salt of citric acid.
6. The gold plating solution for semiconductor chips according to any one of claims 1 to 5, characterized in that: the masking agent is one or a combination of more of ethylenediamine tetraacetic acid or salts thereof, hydroxyethyliminodiacetic acid or salts thereof and diethyltriamine pentaacetic acid or salts thereof, and preferably, the masking agent is ethylenediamine tetraacetic acid or salts thereof.
7. A method for gold plating a semiconductor chip using the gold plating solution as set forth in any one of claims 1 to 6.
8. The method of gold plating of a semiconductor chip of claim 7, wherein: the temperature of the gold plating solution in the gold plating process is 60-100 ℃, preferably 80-90 ℃.
9. The method of gold plating of a semiconductor chip according to claim 7 or 8, characterized in that: the processing time of the semiconductor chips of different batches is increased in sequence by using the same batch of gold plating solution, and preferably, the processing time of each batch of semiconductor chips is increased by 60-90 seconds compared with the processing time of the semiconductor chips of the previous batch.
10. A method for plating a semiconductor chip with nickel and gold is characterized in that: the method comprises the following steps: sequentially carrying out:
the method comprises the following steps of firstly, preprocessing the surface of a semiconductor chip, preferably, the first step comprises the steps of removing an oxide layer on the surface of the semiconductor chip, cleaning and activating the surface of the semiconductor chip in sequence;
secondly, nickel plating is carried out on the semiconductor chip;
a third step of gold-plating the semiconductor chip using the gold-plating method of the semiconductor chip according to any one of claims 7 to 9;
and fourthly, drying, preferably, the fourth step comprises slow hot water lifting and infrared drying.
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| CN201811581213.2A CN111349917A (en) | 2018-12-24 | 2018-12-24 | Gold plating solution for semiconductor chip, gold plating method and nickel and gold plating method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113151814A (en) * | 2021-02-05 | 2021-07-23 | 深圳市联合蓝海黄金材料科技股份有限公司 | Composition for cyanide-free electroless gold plating solution and application thereof, and cyanide-free electroless gold plating solution and application thereof |
| CN114717618A (en) * | 2022-04-26 | 2022-07-08 | 深圳市联合蓝海黄金材料科技股份有限公司 | Cyanide-free gold electroplating bath and application thereof, semiconductor gold-plated part and preparation method thereof |
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| CN114717618A (en) * | 2022-04-26 | 2022-07-08 | 深圳市联合蓝海黄金材料科技股份有限公司 | Cyanide-free gold electroplating bath and application thereof, semiconductor gold-plated part and preparation method thereof |
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