CN114164465A - Sodium gold sulfite gold water and synthesis method and application thereof - Google Patents
Sodium gold sulfite gold water and synthesis method and application thereof Download PDFInfo
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- CN114164465A CN114164465A CN202111348340.XA CN202111348340A CN114164465A CN 114164465 A CN114164465 A CN 114164465A CN 202111348340 A CN202111348340 A CN 202111348340A CN 114164465 A CN114164465 A CN 114164465A
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Abstract
The invention relates to the field of cyanide-free gold plating solution, and discloses sodium gold sulfite gold water, a synthesis method and application thereof. The preparation method comprises the following steps: carrying out precipitation reaction on the chloroauric acid solution and ammonia water to obtain a bright orange-yellow precipitate product; wherein the concentration of the ammonia water is 10-15 wt%, and the end point pH of the precipitated product is 7.2-8.5; cleaning and filtering the precipitation product to obtain a gold fulminate precipitate; mixing the gold fulminate precipitate with water to prepare slurry, then carrying out initial reaction on the slurry and sulfite, and adjusting the final pH of the obtained reaction product to be more than 10 and not more than 11 to obtain an alkaline product; and carrying out re-reaction on the alkaline product to obtain the gold plating solution without the trivalent gold complex. The obtained colorless cyanide-free gold plating solution is not only transparent, namely colorless transparent gold sodium sulfite gold water, has good stability and overcomes the influence of impurities. The method can be applied to the processing of wafers and chips, in particular to the application of wafer gold electroplating.
Description
Technical Field
The invention relates to the field of cyanide-free gold plating solution preparation, and particularly relates to sodium gold sulfite gold water and a synthesis method and application thereof.
Background
Gold has found widespread use in integrated circuits due to its high temperature, tarnish resistance, and extremely high chemical resistance. Among them, the cyanide-free gold plating which is environmentally friendly and safe is a great demand for the current wafer gold plating. Although the technology of the industry has been greatly developed in recent years with the encouragement of the national policy to the cyanide-free gold plating industry, the stability of the gold plating solution needs to be improved to overcome the influence of simple gold impurities caused by poor processes for meeting the performance of wafer processing and chips.
The color of the ammonia type sodium gold sulfite gold plating solution in China at present is usually light yellow or yellow green. The color is an important index for judging whether the complexing reaction is complete or not, and whether the complexing reaction is complete or not determines the storage stability of the subsequent gold plating solution.
CN105568269A discloses a method for preparing cyanide-free gold-plating reagent sodium gold sulfite. The method comprises the steps of gold rolling, gold lump cleaning, gold dissolving, nitrate removing process, alkalization process, cleaning process, complex reaction and concentrated crystallization. Although the solid-liquid separation is carried out after the alkalization of the process, the gold hydroxide obtained after the alkali neutralization has poor stability, is inconvenient to wash and separate, has high gold content in filtrate and complex recovery process, and is easy to dehydrate and convert into gold oxide so as to decompose into simple gold, so that the utilization rate of gold is low.
CN101734708A discloses a preparation method of a sodium gold sulfite complex for cyanide-free gold plating. The method comprises the steps of gold dissolving, neutralizing, complexing and concentrating filtering, wherein the generated gold fulminate is coked in the actual operation process, so that the complexing reaction is incomplete, and yellow-green trivalent gold ions are remained. And the conversion rate of gold hydroxide generated in the alkalization process is not high, and the utilization rate of gold is not high.
In addition, the prior art aims to finally prepare the solid of the gold sodium sulfite, and the problem of the gold sodium sulfite and the gold water is not concerned, so that a production process of the colorless ammonia type gold sodium sulfite and gold water is needed.
Disclosure of Invention
The invention aims to solve the problem that the existing cyanide-free gold plating solution, such as sodium gold sulfite and gold water, is unstable and colored, and provides sodium gold sulfite and gold water, a synthesis method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for synthesizing gold sodium sulfite and gold water, wherein the method comprises:
carrying out precipitation reaction on the chloroauric acid solution and ammonia water to obtain a bright orange-yellow precipitate product; wherein the concentration of the ammonia water is 10-15 wt%, and the end point pH of the precipitated product is 7.2-8.5;
cleaning and filtering the precipitation product to obtain a gold fulminate precipitate;
mixing the gold fulminate precipitate with water to prepare slurry, carrying out initial reaction on the slurry and sulfite, and then adjusting the final pH of the obtained reaction product to be more than 10 and not more than 11 to obtain an alkaline product;
and carrying out re-reaction on the alkaline product to obtain the gold plating solution without trivalent gold ions.
In a second aspect of the present invention, the gold sodium sulfite gold water is a sulfite gold plating solution containing monovalent gold ions and does not contain trivalent gold ions.
The third aspect of the invention provides an application of the gold sodium sulfite gold water provided by the invention in wafer processing and chip manufacturing.
According to the technical scheme, the method provided by the invention considers the influences of the ammonia water concentration in the precipitation reaction and the end point pH of the precipitated product, and the initial reaction temperature T1And re-reaction of T2The final pH value of the reaction product is adjusted, so that colorless cyanide-free gold plating solution rather than only transparent cyanide-free gold plating solution, namely colorless transparent gold sodium sulfite gold water containing monovalent gold ions, is finally obtained, the stability is good, and the influence of impurities is overcome. The method can be applied to the processing of wafers and chips, in particular to the application of wafer gold electroplating.
Drawings
FIG. 1a is a photograph of a precipitated product obtained in example 1 of the present invention;
FIG. 1b is a photograph of a precipitated product obtained in comparative example 1 of the present invention;
FIG. 2a is a photograph of a gold sodium sulfite solution obtained in comparative example 1 of the present invention;
FIG. 2b is a photograph of the gold sodium sulfite solution obtained in example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a synthesis method of sodium gold sulfite and gold water, wherein the synthesis method comprises the following steps:
carrying out precipitation reaction on the chloroauric acid solution and ammonia water to obtain a bright orange-yellow precipitate product; wherein the concentration of the ammonia water is 10-15 wt%, and the end point pH of the precipitated product is 7.2-8.5;
cleaning and filtering the precipitation product to obtain a gold fulminate precipitate;
mixing the gold fulminate precipitate with water to prepare slurry, then carrying out initial reaction on the slurry and sulfite, and adjusting the final pH of the obtained reaction product to be more than 10 and not more than 11 to obtain an alkaline product;
and carrying out re-reaction on the alkaline product to obtain the gold plating solution without trivalent gold ions.
The synthesis method provided by the invention improves the conditions for preparing the sulfite gold plating solution from the chloroauric acid solution through ammonia water precipitation, cleaning filtration and complex reaction steps, and realizes the obtainment of colorless sulfite gold plating solution, such as gold sodium sulfite solution, gold potassium sulfite solution or gold ammonium sulfite solution, preferably gold sodium sulfite gold water. The sulfite gold plating solution does not contain trivalent gold ions, has better stability, and is more suitable for wafer processing and chip manufacturing.
In some embodiments of the present invention, ammonia is used as the precipitating agent, but the conditions of the precipitation reaction are modified to improve the precipitation effect and reduce the formation of insoluble matters, for example, the color of the precipitated product appears brown yellow when insoluble matters are formed. Controlling the concentration of the aqueous ammonia can achieve the effect of improving precipitation, for example, the concentration of the aqueous ammonia may be 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%, and any value in any two of the above numerical composition ranges. Preferably, the concentration of the aqueous ammonia is from 12 to 14 wt%, more preferably about 12.5 wt%. The ammonia water with the above concentration can be obtained by mixing and diluting concentrated ammonia water with water, such as deionized water. The color of the precipitated product thus obtained appeared orange-yellow. When the concentration of the aqueous ammonia is less than 10 wt%, there is a possibility that an unfavorable result of insufficient reaction may occur, resulting in the filtrate containing trivalent gold ions; when the concentration of the aqueous ammonia is higher than 15 wt%, the possibility of generating an insoluble substance by the precipitation reaction increases, which is not favorable for the subsequent complexation reaction.
Further, the end point pH of the precipitated product is within the above range, and the precipitation is complete and the amount of the poorly soluble substance is small, and for example, the end point pH of the precipitated product may be any value within the ranges of 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, and 8.5, and any two of the above ranges of numerical composition. More preferably, the end point pH of the precipitated product is from 7.9 to 8.1.
In the present invention, the process of the precipitation reaction may include: diluting the concentrated ammonia water to the concentration, adding the diluted concentrated ammonia water into the chloroauric acid solution to gradually generate orange-yellow gold fulminate precipitate, and continuously stirring until the pH value reaches the end point.
In some embodiments of the invention, it is preferred that the precipitation reaction temperature is 50 to 70 ℃, such as 50 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 70 ℃ and any value in any two of the above numerical composition ranges, preferably 55 to 65 ℃, more preferably 60 ℃. The progress of the precipitation reaction between the chloroauric acid solution and the ammonia water of the diluted concentration can be promoted more effectively.
In some embodiments of the invention, the precipitation product may contain the gold fulminate precipitate, water, and the species that carry the gold chloroauric acid solution and aqueous ammonia into the precipitation reaction, such as chloride ions, excess aqueous ammonia. Preferably, the process of cleaning and filtering comprises: and repeatedly adding water to filter cakes obtained by filtering the precipitation products, washing and filtering, wherein the concentration of chloride ions in the final filtrate is less than 100 mass ppm. The concentration of chloride ions in the final filtrate can be determined by a chloride ion concentration detector. The finally obtained filter cake is the precipitate of the fulminate gold. The cleaning and filtering realize the removal of excessive ammonia water and residual chloride ions on the surface of the gold fulminate precipitate. The concentration of chloride ions in the final filtrate indicates that the filter cake (i.e. the gold fulminate precipitate) obtained at the same time is qualified.
In some embodiments of the invention, the washing temperature is preferably 55-75 deg.C, and may be, for example, 55 deg.C, 56 deg.C, 57 deg.C, 58 deg.C, 59 deg.C, 60 deg.C, 61 deg.C, 62 deg.C, 63 deg.C, 64 deg.C, 65 deg.C, 66 deg.C, 67 deg.C, 68 deg.C, 69 deg.C, 70 deg.C, 71 deg.C, 72 deg.C, 73 deg.C, 74 deg.C, 75 deg.C, and any of the two ranges of values, preferably 60-70 deg.C. The washing may be carried out by first heating the washing water to the washing temperature, then adding the filter cake thereto, and stirring the mixture. The water amount is not specially limited, and the condition that the washing is qualified can be met when the concentration of chloride ions in the filtrate obtained by final washing meets the condition, and the washing is finished to obtain solid gold fulminate precipitate.
In some embodiments of the invention, the gold fulminate precipitate is further subjected to a complexation reaction. However, in order to obtain a better complexing reaction, it is preferable to carry out the reaction stepwise, i.e., as described above, the initial reaction is carried out first, the final pH of the reaction product is adjusted to obtain an alkaline product, and the alkaline product is finally re-reacted.
In the present invention, the gold fulminate precipitate is first slurried with water to carry out the initial reaction. Preferably, the solid content of the gold fulminate precipitate in the slurry is 14 to 18 wt%, and may be, for example, 14 wt%, 14.5 wt%, 15 wt%, 15.5 wt%, 16 wt%, 16.5 wt%, 17 wt%, 17.5 wt%, 18 wt%, and any value in any two of the above ranges, preferably 16 wt%. The solid content of the fulminate gold is too high, so that the gold is easily separated out in the subsequent complexing reaction process.
In some embodiments of the present invention, preferably, the process of the initial reaction comprises: the slurry is first heated to an initial reaction temperature T1，T1At 45-65 deg.C, for example, 45 deg.C, 46 deg.C, 47 deg.C, 48 deg.C, 49 deg.C, 50 deg.C, 51 deg.C, 52 deg.C, 53 deg.C, 54 deg.C, 55 deg.C, 56 deg.C, 57 deg.C, 58 deg.C, 59 deg.C, 60 deg.C, 61 deg.C, 62 deg.C, 63 deg.C, 64 deg.C, 65 deg.C, and any value in any two of the above numerical composition ranges, preferably 50-60 deg.C, and then adding sulfite to the slurry. Control T1In the above range, the conversion of the trivalent gold complex into the monovalent gold complex is facilitated. If T is1Below 45 ℃ this may lead to incomplete complexation; if T is1Above 65 c, this would likely result in accelerated oxidation of sulfite by oxygen in the air. Wherein the sulfite may be added in the form of a salt or in the form of a solution to participate in the initial reaction, preferably a saturated solution of sulfite. During the initial reaction, the gold fulminate precipitate in the slurry did not dissolve. Preferably, the initial reaction time is from 8 to 12min, preferably from 9 to 11 min. The initial reaction is complete and sulfite addition to the slurry is complete.
Further, it is preferable that the sulfite is used in an amount of 250-350 parts by weight, for example, 250 parts by weight, 260 parts by weight, 270 parts by weight, 280 parts by weight, 290 parts by weight, 300 parts by weight, 310 parts by weight, 320 parts by weight, 330 parts by weight, 340 parts by weight, 350 parts by weight, and any of the above two numerical composition ranges, preferably 280-320 parts by weight, more preferably 300 parts by weight, with respect to 100 parts by weight of gold contained in the slurry. The saturated solution of sulfite is calculated according to the amount of sulfite contained. The amount of sulfite is sufficient to convert trivalent gold ions to monovalent gold ions and to coordinate sulfite with monovalent ions.
In some embodiments of the present invention, preferably, the sulfite is at least one selected from sodium sulfite, potassium sulfite, and ammonium sulfite, preferably sodium sulfite.
In the present invention, after the initial reaction is completed, the pH of the obtained reaction product is initially adjusted. In some embodiments of the present invention, preferably, the adjusting comprises: adding dilute sulfuric acid to the reaction product, and when the end pH of the reaction product is reached, stopping adding dilute sulfuric acid, completing the adjustment 1. In the present invention, when the end pH of the reaction product is reached, the gold fulminate precipitate in the reaction product starts to dissolve, and the reaction product obtained by the initial reaction gradually changes into the alkaline product. And controlling the final pH value of the reaction product within the range can be favorable for controlling the dissolution of the gold fulminate precipitate and for subsequent re-reaction to obtain the colorless sodium gold sulfite solution. The reaction product has too high a termination pH value, so that the system has slow reaction and the conversion of trivalent gold into monovalent gold is insufficient. The final pH of the reaction product is too low, which easily causes the poor stability of the product sodium gold sulfite solution, and generates simple substance gold particles. The reaction product may have a terminal pH of greater than 10, for example, a pH of 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11, and any of the two compositional ranges above, preferably the reaction product has a terminal pH of 10.4 ≦ pH ≦ 1.
In the present invention, the end point pH of the precipitated product and the end point pH of the reaction product are both pH values reflecting the respective whole after the precipitated product and the reaction product are respectively uniform.
In some embodiments of the present invention, preferably, the concentration of the dilute sulfuric acid is 4 to 6 wt%, preferably 4.5 to 5.5 wt%. The concentration of the dilute sulfuric acid used can be just advantageous for controlling the gradual transition of the reaction products during the conditioning.
In some embodiments of the invention, the re-reaction is performed last, allowing all the gold fulminate precipitate in the alkaline product to continue to dissolve. Preferably, the process of re-reacting comprises: heating the alkaline product to a re-reaction temperature T2And is combined withAt T2Reacting for more than 10 hours at constant temperature. In the present invention, it is preferable to control the re-reaction temperature T2With said initial reaction temperature T1Related, the technical effects that the gold precipitate of the fuluric acid is completely dissolved, and the obtained gold plating solution does not contain trivalent gold ions can be obtained. The composition and content of gold ions in the gold plating solution can be determined by ultraviolet spectroscopy. In the gold plating solution obtained in the present application, the gold ions contain only monovalent gold ions, and the content can be 30-60g/L, such as 30g/L, 31g/L, 32g/L, 33g/L, 34g/L, 35g/L, 36g/L, 37g/L, 38g/L, 39g/L, 40g/L, 41g/L, 42g/L, 43g/L, 44g/L, 45g/L, 46g/L, 47g/L, 48g/L, 49g/L, 50g/L, 51g/L, 52g/L, 53g/L, 54g/L, 55g/L, 56g/L, 57g/L, 58g/L, 59g/L, 60g/L, and any of the two numerical ranges above, preferably 40 g/L. Preferably, T2＞T1Preferably T2Ratio T15-10 ℃ higher, e.g., 5 ℃, 6 ℃, 7 ℃, 8 ℃, 9 ℃, 10 ℃ higher, and any value in any two of the above ranges of values; preferably, T2Is 55-75 deg.C, such as 55 deg.C, 56 deg.C, 57 deg.C, 58 deg.C, 59 deg.C, 60 deg.C, 61 deg.C, 62 deg.C, 63 deg.C, 64 deg.C, 65 deg.C, 66 deg.C, 67 deg.C, 68 deg.C, 69 deg.C, 70 deg.C, 71 deg.C, 72 deg.C, 73 deg.C, 74 deg.C, 75 deg.C, and any value in any two of the above-mentioned numerical composition ranges, preferably 60-70 deg.C. The invention completes the whole complexation reaction process under the above-defined preferred conditions, and can better realize that the colorless sulfite gold plating solution is finally obtained, preferably gold sodium sulfite gold water, which only contains monovalent gold ions and does not contain trivalent gold ions.
In some embodiments of the present invention, preferably, the preparation method further comprises: the chloroauric acid solution is obtained by dissolving metal gold by aqua regia and removing nitrate by hydrochloric acid. Specifically, any form of metal gold, such as blocks, sheets and the like, can be added into the king water and heated until the gold is completely dissolved, so as to obtain chloroauric acid solution; then, the chloroauric acid solution is concentrated, and the concentration method can be heating, evaporating and concentrating to 500 g/L; and (3) carrying out nitrate removal on the concentrated solution, namely dropwise adding concentrated hydrochloric acid into the concentrated solution, simultaneously allowing yellow nitrogen oxides to escape from the concentrated solution until the yellow nitrogen oxides do not escape, adding water into the residue to obtain the chloroauric acid solution after the nitrate removal is finished, and then using purified water to fix the volume to 100 g/L.
In some embodiments of the present invention, the concentration of the chloroauric acid solution is preferably 100 g/L.
According to the preparation method provided by the invention, ammonia water used in the precipitation reaction is controlled to be diluted ammonia water, the end point pH of a precipitation product obtained in the precipitation reaction is controlled within a limited concentration range, the defect of generating insoluble matters can be overcome, the subsequent complex reaction is facilitated, and the problem that trivalent gold ions are mixed in the obtained sulfite gold plating solution (such as gold sodium sulfite gold water) to influence the stability of the solution is avoided; meanwhile, the final pH value of the reaction product of the initial reaction obtained in the complexation reaction is adjusted, which is also helpful for reducing the impurity ions remained in the final sulfite gold plating solution (i.e. gold sodium sulfite and gold water).
Further, the preparation method provides an initial reaction temperature T1And the re-reaction temperature T2Has T in between2＞T1The method is more beneficial to complete reaction of the gold fulminate precipitate and the sulfite and dissolution of the gold fulminate precipitate, avoids residual impurity gold ions, and better provides the effect of obtaining colorless and transparent sulfite gold plating solution.
In a second aspect of the present invention, the gold sodium sulfite gold water is a sulfite gold plating solution containing monovalent gold ions and does not contain trivalent gold ions. Preferably a colorless and transparent solution of gold sodium sulfite (i.e., gold sodium sulfite and gold water).
Further in some embodiments of the present invention, preferably, the gold sodium sulfite water is prepared by the synthesis method provided in the invention. By the same method, colorless and transparent gold potassium sulfite solution or colorless and transparent gold ammonium sulfite solution can be obtained.
The third aspect of the invention provides an application of the gold sodium sulfite gold water in wafer processing and chip manufacturing.
In particular, it may be an application on wafer plating with gold.
The present invention will be described in detail below by way of examples. Wherein, the content of gold ions in the prepared colorless and transparent sodium gold sulfite water is determined by ultraviolet spectroscopy.
Example 1
Gold dissolution: putting 20g of gold tablets into a beaker, adding aqua regia and heating until gold is completely dissolved;
nitrate removal by hydrochloric acid: concentrating the gold solution, dropwise adding concentrated hydrochloric acid until yellow nitrogen oxide does not escape, diluting with purified water to a constant volume of 200mL after nitrate removal is finished, and obtaining a chloroauric acid solution with the concentration of 100 g/L;
ammonia water precipitation: diluting concentrated ammonia water with purified water (ammonia water concentration is 12.5 wt%), adding into chloroauric acid solution for precipitation reaction at 60 deg.C, gradually generating precipitate, and stirring until the final pH value of the precipitate is 7.9 to obtain bright orange yellow precipitate (shown in FIG. 1 a);
cleaning and filtering: transferring the precipitate product to a Buchner funnel, repeatedly stirring and cleaning the precipitate for 8 times by using 500mL of 65 ℃ hot water, cleaning excessive ammonia water and chloride ions remained on the surface of the gold fulminate until the concentration of the chloride ions in the filtrate is less than 100 mass ppm, and obtaining the gold fulminate precipitate;
and (3) complexing reaction: transferring the washed gold fulminate precipitate to a 1L beaker, adding purified water to a constant volume of 500mL to prepare a slurry (the solid content of the gold fulminate precipitate is 18 wt%), heating the slurry to 58 ℃ and adding 56g of sodium sulfite (corresponding to 280 parts by weight of sodium sulfite relative to 100 parts by weight of gold) to perform an initial reaction for 10 min; then adding a 5 wt% dilute sulfuric acid solution into the obtained reaction product to adjust the pH to 10.60, at the moment, dissolving the gold fulminate precipitate, and stopping adding the dilute sulfuric acid to obtain an alkaline product;
and heating the alkaline product to 65 ℃, and continuing to dissolve and react the gold fulminate precipitate for more than 10 hours at constant temperature to obtain colorless gold sodium sulfite gold water, wherein the colorless gold sodium sulfite gold water contains univalent gold complexes and does not contain trivalent gold complexes. The appearance is shown in fig. 2 b.
Example 2
Gold dissolution: putting 20g of gold tablets into a beaker, adding aqua regia and heating until gold is completely dissolved;
nitrate removal by hydrochloric acid: concentrating the gold solution, dropwise adding concentrated hydrochloric acid until yellow nitrogen oxide does not escape, diluting with purified water to a constant volume of 200mL after nitrate removal is finished, and obtaining a chloroauric acid solution with the concentration of 100 g/L;
ammonia water precipitation: diluting concentrated ammonia water with purified water (ammonia water concentration is 14 wt%), adding into chloroauric acid solution for precipitation reaction at 55 deg.C, gradually generating precipitate, and stirring until the final pH value of the precipitate is 8.1 to obtain bright orange yellow precipitate (similar to the result in FIG. 1a, not shown);
cleaning and filtering: transferring the precipitate product to a Buchner funnel, repeatedly stirring and cleaning the precipitate for 8 times by using 500mL of 60 ℃ hot water, cleaning excessive ammonia water and chloride ions remained on the surface of the gold fulminate until the concentration of the chloride ions in the filtrate is less than 100 mass ppm, and obtaining the gold fulminate precipitate;
and (3) complexing reaction: transferring the washed gold fulminate precipitate to a 1L beaker, adding purified water to a constant volume of 500mL to prepare a slurry (the solid content of the gold fulminate precipitate is 16 wt%), heating the slurry to 50 ℃ and adding 60g of sodium sulfite (corresponding to 300 parts by weight of sodium sulfite relative to 100 parts by weight of gold) to perform 11min to terminate the initial reaction; then adding 5.5 wt% of dilute sulfuric acid solution into the obtained reaction product to adjust the pH to 10.4, at the moment, dissolving the gold fulminate precipitate, and stopping adding the dilute sulfuric acid to obtain an alkaline product;
heating the alkaline product to 60 ℃, and continuing to dissolve and react the gold fulminate precipitate for more than 10 hours at constant temperature to obtain colorless gold sodium sulfite gold water, wherein the colorless gold sodium sulfite gold water contains univalent gold complexes and does not contain trivalent gold complexes. The appearance is similar to that shown in fig. 2b and is not shown.
Example 3
Gold dissolution: putting 20g of gold tablets into a beaker, adding aqua regia and heating until gold is completely dissolved;
nitrate removal by hydrochloric acid: concentrating the gold solution, dropwise adding concentrated hydrochloric acid until yellow nitrogen oxide does not escape, diluting with purified water to a constant volume of 200mL after nitrate removal is finished, and obtaining a chloroauric acid solution with the concentration of 100 g/L;
ammonia water precipitation: diluting concentrated ammonia water with purified water (ammonia water concentration is 12 wt%), adding into chloroauric acid solution for precipitation reaction at 65 deg.C, gradually generating precipitate, and stirring until the final pH value of the precipitate is 8.0 to obtain bright orange yellow precipitate (similar to the result in FIG. 1a, not shown);
cleaning and filtering: transferring the precipitate product to a Buchner funnel, repeatedly stirring and cleaning the precipitate for 8 times by using 500mL of 70 ℃ hot water, cleaning excessive ammonia water and chloride ions remained on the surface of the gold fulminate until the concentration of the chloride ions in the filtrate is less than 100 mass ppm, and obtaining the gold fulminate precipitate;
and (3) complexing reaction: transferring the washed gold fulminate precipitate to a 1L beaker, adding purified water to a constant volume of 500mL to prepare a slurry (the solid content of the gold fulminate precipitate is 14 wt%), heating the slurry to 60 ℃ and adding 64g of sodium sulfite (corresponding to 320 parts by weight of sodium sulfite relative to 100 parts by weight of gold) to carry out 9min to terminate the initial reaction; adding 4.5 wt% of dilute sulfuric acid solution into the obtained reaction product, adjusting the pH to 11.0, dissolving the gold fulminate precipitate, and stopping adding the dilute sulfuric acid to obtain an alkaline product;
heating the alkaline product to 70 ℃, and continuing to dissolve and react the gold fulminate precipitate for more than 10 hours at constant temperature to obtain colorless gold sodium sulfite gold water, wherein the colorless gold sodium sulfite gold water contains univalent gold complexes and does not contain trivalent gold complexes. The appearance is similar to that shown in fig. 2b and is not shown.
Example 4
The process of example 1 was followed except that the heated slurry to 58 ℃ was replaced with "heated slurry to 65 ℃". Colorless sodium gold sulfite gold water is obtained.
However, the complex reaction process is slow, the reduction reaction of monovalent gold ions is easier to occur in the reaction process, and the obtained product gold sodium sulfite gold water may contain simple substance gold impurities.
Example 5
The procedure of example 1 was followed except that "aqueous ammonia concentration of 10% by weight" was used instead of "aqueous ammonia concentration of 12.5% by weight". Colorless sodium gold sulfite gold water is obtained.
However, in the process of preparing the gold fulminate by ammonia water precipitation, the concentration of the ammonia water is relatively dilute, the complexing efficiency of ammonia molecules and trivalent gold ions is relatively low, and a small amount of trivalent gold ions are contained in filtrate in subsequent solid-liquid separation, so that the utilization rate of the noble metal gold is low.
Example 6
The procedure of example 1 was followed except that "aqueous ammonia concentration of 15 wt%" was used instead of "aqueous ammonia concentration of 12.5 wt%". Colorless sodium gold sulfite gold water is obtained.
However, in the process of preparing the gold fulminate, the concentration of the system is overlarge, insoluble matters containing gold are generated in the process of adding ammonia water, and the insoluble matters do not react with sodium sulfite in the subsequent complexing reaction, so that the utilization of noble metal gold is influenced.
Example 7
The process according to claim 1, except that "the end point pH of the precipitated product is 7.9" is replaced by "the end point pH of the precipitated product is 7.2". Colorless sodium gold sulfite gold water is obtained.
However, the final pH of the precipitated product is 7.2, the complex reaction is possibly insufficient due to the small using amount of ammonia water, and the filtrate in the subsequent solid-liquid separation contains yellow-green trivalent gold ions, so that the utilization rate of gold is reduced.
Example 8
The process according to claim 1, except that "the end point pH of the precipitated product is 7.9" is replaced by "the end point pH of the precipitated product is 8.5". Colorless sodium gold sulfite gold water is obtained.
However, the precipitated product contains more ammonium ions, resulting in an increase in the baume of the precipitated product.
Example 9
The process according to claim 1, except that "the stop pH is 10.60" is replaced by "the stop pH is 11". Colorless sodium gold sulfite gold water is obtained.
However, the termination pH is high and the rate of the complexation reaction is slow, which may result in the reduction of gold ions to elemental gold impurities.
Comparative example 1
Gold dissolution: putting 20g of gold tablets into a beaker, adding aqua regia and heating until gold is completely dissolved;
nitrate removal by hydrochloric acid: concentrating the gold solution, dropwise adding concentrated hydrochloric acid until yellow nitrogen oxide does not escape, diluting with purified water to a constant volume of 200mL after nitrate removal is finished, and obtaining a chloroauric acid solution;
ammonia water precipitation: adding concentrated ammonia (about 25 wt%) into chloroauric acid solution for precipitation reaction at 60 deg.C, gradually generating precipitate and stirring until pH is 10.0 to obtain brown yellow precipitate (shown in FIG. 1 b);
cleaning and filtering: transferring the precipitate product to a Buchner funnel, repeatedly stirring and cleaning the precipitate for 8 times by using 500mL of 65 ℃ hot water, cleaning excessive ammonia water and chloride ions remained on the surface of the gold fulminate until the concentration of the chloride ions in the filtrate is less than 100 mass ppm, and obtaining the gold fulminate precipitate;
and (3) complexing reaction: transferring the washed gold fulminate precipitate to a 1L beaker, adding purified water to a constant volume of 500mL to prepare slurry (the solid content of the gold fulminate precipitate is 18 wt%), heating the slurry to 55 ℃, and adding 56g of sodium sulfite (which is equivalent to 280 parts by weight of sodium sulfite relative to 100 parts by weight of the gold fulminate precipitate) to perform 10min to terminate the initial reaction; adding a 5 wt% dilute sulfuric acid solution into the obtained reaction product, adjusting the pH value of the reaction product to be 10.60, dissolving the gold fulminate precipitate, and stopping adding the dilute sulfuric acid to obtain an alkaline product;
heating the alkaline product to 65 ℃, and continuing to react for more than 10 hours to obtain light yellow green gold sodium sulfite solution, wherein trivalent gold ions are detected. The appearance is shown in fig. 2 a.
Comparative example 2
According to the method of comparative example 1, except that the final pH of the reaction product was 10.00 and the final pH of the reaction product was 10.60 in place of that, a gold sodium sulfite solution was obtained, which was found to contain trivalent gold ions.
As can be seen from the results of the examples and the comparative examples, the examples adopting the method provided by the invention can obtain obviously better effect, and obtain colorless and transparent gold sodium sulfite gold water containing univalent gold ions and no trivalent gold ions.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A synthesis method of gold sodium sulfite gold water is characterized by comprising the following steps:
carrying out precipitation reaction on the chloroauric acid solution and ammonia water to obtain a bright orange-yellow precipitate product; wherein the concentration of the ammonia water is 10-15 wt%, and the end point pH of the precipitated product is 7.2-8.5;
cleaning and filtering the precipitation product to obtain a gold fulminate precipitate;
mixing the gold fulminate precipitate with water to prepare slurry, then carrying out initial reaction on the slurry and sulfite, and adjusting the final pH of the obtained reaction product to be more than 10 and not more than 11 to obtain an alkaline product;
and carrying out re-reaction on the alkaline product to obtain the gold plating solution without trivalent gold ions.
2. The synthesis method according to claim 1, wherein the concentration of the ammonia water is 12-14 wt%; the end point pH of the precipitated product is 7.9-8.1;
and/or the precipitation reaction temperature is 50-70 ℃.
3. The synthesis method according to claim 1 or 2, characterized in that the process of washing and filtering comprises: repeatedly adding water into a filter cake obtained by filtering the precipitation product for cleaning and filtering again, wherein the concentration of chloride ions in the final filtrate is less than 100 mass ppm;
and/or the cleaning temperature is 55-75 ℃.
4. The synthesis method according to claim 3, wherein the slurry has a solid content of the gold fulminate precipitate of 14-18 wt%.
5. The synthesis method according to any one of claims 1 to 4, wherein the initial reaction comprises: the slurry is first heated to an initial reaction temperature T1，T1At 45-65 ℃, then adding sulfite into the slurry;
and/or the amount of sulfite is 250-350 parts by weight relative to 100 parts by weight of gold contained in the slurry;
and/or, the sulfite is selected from at least one of sodium sulfite, potassium sulfite and ammonium sulfite;
and/or the initial reaction time is 8-12 min.
6. The synthesis method according to any one of claims 1 to 5, wherein the reaction product has a terminal pH of 10.4. ltoreq. pH 11;
and/or, the process of adjusting comprises: adding dilute sulfuric acid to the reaction product, and stopping adding dilute sulfuric acid when the final pH of the reaction product is reached to finish the adjustment;
and/or the concentration of the dilute sulfuric acid is 4-6 wt%.
7. The method of any one of claims 1 to 6, wherein the re-reacting comprises: heating the alkaline product to a re-reaction temperature T2And at T2Reacting for more than 10 hours at constant temperature.
8. The method of synthesis of claim 7, wherein T is2＞T1；
And/or, T2Ratio T1The height is 5-10 ℃;
and/or, T2Is 55-75 ℃.
9. The gold sodium sulfite gold water is characterized in that the gold sodium sulfite gold water is a sulfite gold plating solution containing monovalent gold ions and does not contain trivalent gold ions;
and/or the gold sodium sulfite gold water is prepared by the synthesis method of any one of claims 1 to 8.
10. Use of the sodium gold sulfite solution of claim 9 in wafer processing and chip fabrication.
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