CN116087314A - Detection method for measuring impurity elements in high-purity silver (5N) - Google Patents
Detection method for measuring impurity elements in high-purity silver (5N) Download PDFInfo
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- CN116087314A CN116087314A CN202211724175.8A CN202211724175A CN116087314A CN 116087314 A CN116087314 A CN 116087314A CN 202211724175 A CN202211724175 A CN 202211724175A CN 116087314 A CN116087314 A CN 116087314A
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Abstract
The invention discloses a detection method for measuring impurity elements in high-purity silver (5N), which comprises the steps of dissolving a high-purity silver sample to be detected by nitric acid to obtain a solution to be detected, selecting 45 Sc、 115 In、 187 And Re is used as an internal standard element, a series of standard solution samples of each impurity element are analyzed by an inductively coupled plasma mass spectrometer according to the concentration from low to high, the mass percent content of the impurity element is obtained by calculating the concentration value of each element to be measured in the solution to be measured, wherein the concentration value is obtained by bringing the signal intensity ratio of a certain unknown element in high-purity silver (5N) of the solution to be measured to the working curve of the element. The method can simultaneously detect the content of 16 impurity elements in silver, has high accuracy, establishes a method for measuring the content of high-purity silver and impurity elements by an inductively coupled plasma mass spectrometry (ICP-MS) method, and has the characteristics of high analysis speed and high accuracy.
Description
Technical Field
The invention relates to the technical field of impurity element detection methods, in particular to a detection method for measuring impurity elements in high-purity silver (5N).
Background
The high-purity silver is an important raw material in the industries of electronics, electroplating, alloy manufacturing and the like, the content of impurity elements influences the electric, thermal, mechanical properties, processing technology and service life of the high-purity silver, along with the rapid development of the industries of chemical engineering, chemistry, catalysis and the like and the material disciplines, the market demand for the high-purity gold silver and electronic products thereof is continuously growing, the high-purity silver is widely applied to the semiconductor field, and the high-purity silver is deposited on the surface of a substrate by adopting a sputtering or vapor deposition technology through preparing a target material or an evaporation source material. The purity of silver has a great influence on the quality of the plated film, and a method for measuring impurity elements in high-purity silver (5N) is required.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a detection method for measuring impurity elements in high-purity silver (5N).
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention comprises the following steps:
a, dissolving a high-purity silver sample to be detected by nitric acid to obtain a solution to be detected:
b is selected from 45 Sc、 115 In、 187 Re is used as an internal standard element, a to-be-detected solution is analyzed by adopting an inductively coupled plasma mass spectrometer according to the concentration from low to high, so that a working curve Yn= aXn +b of corresponding impurities is obtained, and the linear correlation coefficient r of the corresponding impurities is required to be larger than 0.9990, wherein X represents the concentration of certain impurity element, Y represents the signal intensity ratio of the impurity element to the internal standard element under the concentration, and n represents one of magnesium, aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, cadmium, tin, antimony, tellurium, lead and bismuth;
c, analyzing the to-be-detected solution of the high-purity silver (5N) to obtain a signal intensity ratio Yu of an unknown element in the high-purity silver (5N) of the to-be-detected solution to an internal standard element, and bringing the signal intensity ratio Yu into a working curve of the element to obtain a concentration value Cn of each to-be-detected element in the to-be-detected solution;
substituting the concentration value Cn into a calculation formula to obtain the mass percent content value of magnesium, aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, cadmium, tin, antimony, tellurium, lead and bismuth, wherein the calculation formula is as follows:
ω n ＝(φ x ×V×N/m)×10 -7
wherein omega is n The trace impurity element mass percent (%), phi is the trace impurity element concentration (ug/L), and V is the constant volume (ml); m is the sample amount (g); n is the dilution multiple.
Further, the solution to be measured adopts a standard adding method, standard solutions of magnesium, aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, cadmium, tin, antimony, tellurium, lead and bismuth are diluted step by step, and internal standard solutions Sc, I n and Re are added into each standard and solution sample to be measured.
Further, the method detection limit is based on 3 times of standard deviation.
Further, the flow rate of the atomizer is 1.2L/min, and the analog voltage is 1900; the flow rate of the auxiliary device is 0.8L/min, and the pulse voltage is 1000; the cooler flow is 15L/min, and the lens voltage is 10; the radio frequency power is RF1550W, the resolution is 0.8amu, the data acquisition mode is performed in a jumping mode, and the types of sampling cone and intercepting cone are nickel cone; the sample injection pump speed is 42r/min, and the flushing pump speed is 42r/min.
Further, the processing method comprises the steps of slicing the high-purity silver sample, adding nitric acid, and dissolving at a low temperature, wherein the dissolving temperature is less than 100 ℃ until no brown gas exists; and preparing a blank sample, and cooling and then fixing the volume.
Further, the preparation method of the standard solution comprises the steps of respectively transferring 0mL, 0.50mL, 1.00mL, 2.50mL, 5.00mL and 10.00mL of mixed standard solution containing magnesium, aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, cadmium, tin, antimony, tellurium, lead and bismuth into a polyethylene volumetric flask with the volume ratio of 100ug/L to 50mL, and uniformly mixing the solution to be detected containing 1g/L of silver matrix and nitric acid, wherein the solution to be detected is added according to the volume ratio of 5:1; the concentration is 0ug/L in sequence; 1ug/L;2ug/L;5ug/L;10ug/L;20ug/L.
Compared with the prior art, the invention has the beneficial effects that:
the method can simultaneously detect the content of 16 impurity elements in silver, has high accuracy, establishes a method for measuring the content of high-purity silver and impurity elements by an inductively coupled plasma mass spectrometry (ICP-MS) method, and has the characteristics of high analysis speed and high accuracy.
Drawings
FIG. 1 is a standard curve of the present invention ICP-MS for measuring tin in high purity silver (5N);
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully by reference to the accompanying drawings and technical solutions, in which it is shown, however, only some, but not all embodiments of the invention are shown.
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary only for explaining the present invention and are not to be construed as limiting the present invention.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless expressly stated otherwise, as understood by those skilled in the art. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It will be understood that when an element is referred to as being "connected" or "coupled" to another element, it can be directly connected or coupled to the other element or intervening elements may also be present. Further, "connected" or "coupled" as used herein may include wirelessly connected or coupled. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The inductively coupled plasma mass spectrometer (ICP-MS) used in the examples was equipped with a main quadrupole mass analyzer, a quadrupole collision cell, a quadrupole ion deflector, etc.
Examples:
the pretreatment of the test sample is performed in a pretreatment ultra-clean laboratory, and the measurement process is performed in a ten-thousand-level clean room.
Sample pretreatment
Pressing the sample into slices with the thickness of 1-2 mm, cutting the slices into slices with the thickness of 1-2 mm, putting the slices into a polytetrafluoroethylene beaker, cleaning the slices with 30ml of ethanol solution, slightly heating the slices on an electric hot plate for 3-5 min, pouring ethanol, repeatedly washing the silver slices with deionized water for 3-4 times, airing the slices, and taking out the slices for later use.
Accurately weighing 500mg silver flake (accurate to 0.01 mg), placing into 50ml polytetrafluoroethylene beaker, adding nitric acid, placing on electric hot plate, dissolving at low temperature, dissolving temperature < 100deg.C until no brown gas exists; and in the same step, preparing a blank sample, cooling, and then fixing the volume to a volumetric flask of 50ml for measurement.
Preparation of standard solution
Respectively transferring 0mL, 0.50mL, 1.00mL, 2.50mL, 5.00mL and 10.00mL of mixed standard solution containing magnesium, aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, cadmium, tin, antimony, tellurium, lead and bismuth into a volumetric flask with volume of 100ug/L to 50mL, adding 5mL of solution to be tested (silver matrix 1 g/L), adding 1mL of nitric acid (4.1.1), diluting with water to scale, and uniformly mixing; the concentration is 0ug/L in sequence; 1ug/L;2ug/L;5ug/L;10ug/L;20ug/L.
Starting up and igniting
Opening argon, and confirming that the pressure of the instrument with a pressure reducing valve is (85-100 ps I) when the reaction gas or the collision gas is required to be used; opening an instrument exhaust system, and confirming that the instrument exhaust wind speed is 7-9 m/s; opening an instrument switch and a radio frequency generator switch, opening a computer, starting instrument operation software, and initializing an instrument;
opening the instrument control interface, vacuumizing, and waiting for vacuum Ready (suggesting that the vacuum value reaches 2×10e) -6 Torr, spot torch sample); opening the circulating water machine to confirm that the circulating water machine works normally; check and confirm the sample injection system (torch tube, atomizer chamber, atomizer,Pump tube, etc.) whether the peristaltic pump tube is properly installed and connected, the peristaltic pump tube is properly wound; the plasma torch is ignited, forming a stable plasma torch.
The instrument operating parameters are detailed in table 1.
Table 1 main operating parameters of inductively coupled plasma mass spectrometer
Selection of assay isotopes
In the process of measuring the impurity element of the high-purity silver (5N), in order to reduce the interference among elements, improve the accuracy and precision of the elements and ensure that the detection limit of the elements meets the requirement, proper measurement isotopes are required to be selected, the basic principle of high abundance and no interference is adopted, and the isotopes which have no mass spectrum interference and have higher abundance are preferentially selected; secondly, selecting isotopes which have less interference and can be corrected; if several disturbances are serious, isotopes are selected which are less abundant but do not interfere.
The isotopes chosen according to the nature of the elements to be tested in this experiment are shown in table 2.
TABLE 2 isotopic abundance and mass number of each impurity element
The method for editing the internal standard-standard addition method mainly comprises the steps of inputting Ar or He working modes, isotopes of impurity elements to be detected, concentration values of all standard points on a working curve and the like, wherein the standard series of the working curve is 0ug/L;1ug/L;2ug/L;5ug/L;10ug/L;20ug/L;
sample measurement
Then analyzing a series of standard solution samples of each impurity element according to the concentration from low to high so as to obtain a working curve Yn= aXn +b of the corresponding impurity, wherein the linear correlation coefficient r of the working curve Yn= aXn +b is required to be larger than 0.9990, X represents the concentration of certain impurity element, Y represents the signal intensity ratio of the impurity element to an internal standard element under the concentration, and n represents one of magnesium, aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, cadmium, tin, antimony, tellurium, lead and bismuth;
then analyzing the to-be-measured solution of the high-purity silver (5N) to obtain a signal intensity ratio Yu of an unknown element in the high-purity silver (5N) of the to-be-measured solution to an internal standard element, and bringing the signal intensity ratio Yu into a working curve of the element to obtain a concentration value Cn of each to-be-measured element in the to-be-measured solution; the concentration values of magnesium, aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, cadmium, tin, antimony, tellurium, lead and bismuth are obtained in sequence.
Standard curve and method detection limit
The experiment was performed in parallel for 6 times, with the detection limit of the method being 3 times standard deviation. The standard curve correlation coefficient of each element is 0.9992-0.9999, which is larger than 0.9990, and the linearity is good; the method can be used for sample analysis, the detection limit is 0.009ug/L to 0.24ug/L, and the standard curve and the detection limit of each trace impurity element are shown in Table 3; the working curve is exemplified by tin, as shown in fig. 1, the linear equation of which is y=0.371x+0.061, and the linear correlation coefficient is r=0.9994;
TABLE 3 Standard Curve and method detection Limit for impurity elements in high purity silver (5N)
Precision and recovery test
Trace impurity elements in a high-purity silver (5N) sample are measured according to an experimental method, a standard adding recovery experiment and a precision experiment (n=6) are carried out, the recovery rate is 84% -105%, the precision is 2.1% -16.7%, and the measurement results are shown in Table 4. The method has high accuracy and good precision, and the inspection result shows the reliability of the method.
TABLE 4 precision of the addition of the standard recovery test and analysis
The method fills the technical blank of detecting the high-purity silver (99.999%), can detect the content of 16 impurity elements in the silver simultaneously, has high accuracy, establishes a method for measuring the content of the high-purity silver and the impurity elements by an inductively coupled plasma mass spectrometry (ICP-MS), supplements the blank of measuring the high-purity silver, has the characteristics of high analysis speed and high accuracy, and provides technical support for quality detection of the high-purity silver.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. A detection method for measuring impurity elements in high purity silver (5N), comprising the steps of:
a, dissolving a high-purity silver sample to be detected by nitric acid to obtain a solution to be detected:
b is selected from 45 Sc、 115 In、 187 Re is used as an internal standard element, and a series of standard solution samples of each impurity element are analyzed by adopting an inductively coupled plasma mass spectrometer according to the concentration from low to high, so that the worker of the corresponding impurity is obtainedMaking a curve yn= aXn +b, wherein the linear correlation coefficients r of the curve yn= aXn +b are all required to be larger than 0.9990, X represents the concentration of an impurity element, Y represents the signal intensity ratio of the impurity element to an internal standard element under the concentration, and n is one of magnesium, aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, cadmium, tin, antimony, tellurium, lead and bismuth;
c, analyzing the to-be-detected solution of the high-purity silver (5N) to obtain a signal intensity ratio Yu of an unknown element in the high-purity silver (5N) of the to-be-detected solution to an internal standard element, and bringing the signal intensity ratio Yu into a working curve of the element to obtain a concentration value Cn of each to-be-detected element in the to-be-detected solution;
substituting the concentration value Cn into a calculation formula to obtain the mass percentage of magnesium, aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, cadmium, tin, antimony, tellurium, lead and bismuth, wherein the calculation formula of the mass percentage is as follows:
ω n ＝(φ x ×V×N/m)×10 -7
wherein omega is n The trace impurity element mass percent (%), phi is the trace impurity element concentration (ug/L), and V is the constant volume (ml); m is the sample amount (g); n is the dilution multiple.
2. The method for detecting impurity elements In high-purity silver (5N) according to claim 1, wherein the solution to be detected adopts a standard addition method, the standard solutions are diluted step by step, and the internal standard solutions Sc, in and Re are added to each standard and solution sample to be detected.
3. The method for detecting an impurity element in high purity silver (5N) according to claim 1, wherein the method has a detection limit based on a standard deviation of 3 times.
4. The method for detecting an impurity element in high purity silver (5N) according to claim 1, wherein the atomizer flow rate is 1.2L/min, and the analog voltage is 1900; the flow rate of the auxiliary device is 0.8L/min, and the pulse voltage is 1000; the flow rate of the cooler is 15L/min, and the lens voltage is 10; the radio frequency power is RF1550W, the resolution is 0.8amu, the data acquisition mode is performed in a jumping mode, and the types of sampling cone and intercepting cone are nickel cone; the sample injection pump speed is 42r/min, and the flushing pump speed is 42r/min.
5. The method for detecting impurity elements in high-purity silver (5N) according to claim 1, wherein the processing method comprises the steps of slicing a high-purity silver sample, adding nitric acid, and dissolving at a low temperature until no brown gas exists, wherein the dissolution temperature is less than 100 ℃; and preparing a blank sample, and cooling and then fixing the volume.
6. The method for detecting impurity elements in high-purity silver (5N) according to claim 1, wherein the method for preparing the standard solution comprises the steps of respectively transferring 0mL, 0.50mL, 1.00mL, 2.50mL, 5.00mL, 10.00mL of mixed standard solution containing magnesium, aluminum, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, cadmium, tin, antimony, tellurium, lead and bismuth into a volumetric flask of 100ug/L to 50mL, and mixing the mixed standard solution containing 1g/L of silver matrix and nitric acid according to a volume ratio of 5:1; the concentration is 0ug/L in sequence; 1ug/L;2ug/L;5ug/L;10ug/L;20ug/L.
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