CN114324213A - Method and kit for determining ultra-trace metal impurities in high-silicon matrix solvent - Google Patents
Method and kit for determining ultra-trace metal impurities in high-silicon matrix solvent Download PDFInfo
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- 239000012535 impurity Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 62
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- 229910021654 trace metal Inorganic materials 0.000 title claims abstract description 17
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 46
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- 238000001514 detection method Methods 0.000 claims abstract description 12
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Abstract
The invention is applicable to the technical field of semiconductors, and provides a method for measuring ultra-trace metal impurities in a high-silicon matrix solvent. The method can accurately measure the metal impurities in the high silicon substrate solvent, does not use hydrofluoric acid, is simple and convenient to operate, avoids the safety problem caused by the hydrofluoric acid, and reduces the detection cost.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a method and a kit for determining ultra-trace metal impurities in a high-silicon substrate solvent.
Background
The integrated circuit industry is the basic industry of advanced manufacturing industry, and downstream application ends of the integrated circuit industry cover various industries such as automobiles, communication, electric appliances, computers, aerospace, military industry, photovoltaic industry and the like. Semiconductor raw materials are the cornerstones of the integrated circuit industry, and are used in all links of the integrated circuit production, for example, a mask plate, photoresist and various wet chemicals for cleaning are needed in the photoetching link, and silicon wafers, electronic gases and the like are needed in the etching link. With the continuous progress of the integrated circuit technology nodes, the requirements on the purity, the size and a series of physicochemical properties of the used raw materials are more and more strict. Among them, metal impurity control is an important part of semiconductor manufacturing processes.
In order to effectively control the metal impurities in the semiconductor, the solvent or reagent used in the production process needs to be strictly limited, for example, the impurity of silane is 10-12(ppt) level (purification technique and analytical method for gaseous and metallic impurities in high purity silane, Patrick a Taylor, Low temperature & specialty gases, 1996, No 3). In addition, high-matrix silicon exists in most of the solvents or reagents, and how to eliminate the influence of the high-matrix silicon and accurately measure the ultra-trace metal impurities in the high-matrix silicon is a technical difficulty in the semiconductor industry. Wherein, the milli-optical fiber is produced by using hydrofluoric acid4To eliminate the substrate interference caused by the silicon-based effect. On the basis, an inductively coupled plasma mass spectrometry (ICP-MS) detection method for 18 metal impurities including Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As and Pb in hexachlorodisilane [ a detection method for metal impurities in electronic specialty gas hexachlorodisilane products, proceedings of the university of China and south (Nature science edition), 12 months 2020 ] is established. However, in this method, hydrofluoric acid is addedMeanwhile, hydrofluoric acid reacts with a sample violently, is easy to splash, has extremely high danger, has high requirements on operators and protective equipment, and is easy to cause sample splash loss and inaccurate detection result; on the other hand, hydrofluoric acid is highly corrosive, a special corrosion-resistant system is required, and the purity of hydrofluoric acid itself is required to be high (such as an ultra-clean high-purity reagent), so that the detection cost is increased. In addition, the method has complex sample processing process, multiple operation steps and high risk of introducing pollution.
Disclosure of Invention
In order to solve the problems, the invention provides a method for measuring ultra trace metal impurities in a high silicon matrix solvent, which directly removes silicon in the high silicon matrix solvent through evaporation and reduces a step of removing silicon by hydrofluoric acid.
The invention is realized by the following technical scheme: a method for measuring ultra trace metal impurities in a high silicon matrix solvent comprises the steps of heating the high silicon matrix solvent to completely evaporate the high silicon matrix solvent, dissolving residual metal impurities, and detecting the metal impurities by using an atomic absorption spectrometry method, an inductively coupled plasma mass spectrometry method and the like. The heating temperature should be below the boiling point of the metal impurities and the same or higher than the boiling point of the high silicon substrate solvent.
Further, the heating of the high-silicon matrix solvent to evaporate the high-silicon matrix solvent comprises the following specific steps:
taking the high-silicon matrix solvent into a container, heating the container to completely evaporate the high-silicon matrix solvent, adding a diluent into the container, dissolving the remainder, and preparing a sample solution.
Still further, the method further comprises the steps of:
taking another container, and processing the rest of the container and the sample solution in parallel except that the high-silicon matrix solvent is not added to prepare a blank solution;
step (3) preparing a step concentration series standard solution of the metal impurities;
and (4) taking the blank solution, the standard solution and the sample solution to enter an inductively coupled plasma mass spectrometer for detection, calculating the concentration of the metal impurities in the sample solution according to a standard curve method, and calculating the content of the metal impurities in the high-silicon matrix solvent according to the sampling amount and the diluent amount.
By diluent is meant a liquid capable of dissolving the metal impurities and without introducing or with negligible interference, such as: 2% aqueous nitric acid.
In addition to the standard curve method according to step (4), quantitative calculation may be performed by an internal standard method or an external standard point method. Of course, the method of the present invention may also be used for the threshold method, that is, preparing a sample solution according to the step (1), preparing a standard solution with a threshold concentration, and comparing the measurement result of the sample solution with the measurement result of the standard solution with the threshold concentration to determine whether the metal impurity of the high silicon substrate solvent exceeds the threshold.
Further, the high silicon matrix solvent includes: hexachlorodisilane and trichlorosilane. The metal impurities are one or more of the following in combination: li (lithium), Na (sodium), K (potassium), Ti (titanium), Fe (iron), Ni (nickel), Zn (zinc), As (arsenic), Pb (lead), Ag (silver), Au (gold), Ba (barium), Be (beryllium), Bi (bismuth), Cd (cadmium), Ge (germanium), In (indium), Mo (molybdenum), Pt (platinum), Sb (antimony), Sn (tin), Sr (strontium), Ta (tantalum), Tl (thallium), W (tungsten), Zr (pickaxe). These 26 metal impurities were simultaneously determined in hexachlorodisilane as in inventive example 1.
Further, the method of the present invention is more suitable for the detection of gold impurities with a standard limit of ppt, such as 100ppt, in addition to the detection of metal impurities with a standard limit of ppm and ppb for high silicon matrix solvents.
It should be noted that the high silicon base solvent refers to a liquid solvent containing silicon which bonds with other elements to form compounds having a relatively low boiling point, such as hexachlorodisilane and trifluoroethyl silicon described above, but may be an organic solvent containing silane or a mixed solution containing such solvents (for example, chloroform containing trichlorosilane). The metal impurities in the high silicon matrix solvent are present in the form of simple substances and/or compound salts, and the boiling point of the metal impurities is generally far lower than that of the high silicon matrix solvent. When heating is carried out at a temperature of the boiling point of the solvent or higher, the solvent and/or the silane can be rapidly evaporated to form vapor to carry away the silicon; the metal impurities with high boiling point can remain at the bottom of the container, thereby achieving the purpose of removing silicon. Dissolving the metal impurities left at the bottom of the container by using a diluent, and detecting by ICP-MS. For example, hexachlorodisilane has a boiling point of 144-145.5 ℃; lithium has a boiling point of 1340 ℃ much higher than hexachlorodisilane. When lithium in hexachlorodisilane is measured, hexachlorodisilane is completely evaporated by heating at the temperature of 146 ℃, and then the rest lithium is dissolved by using a diluent for ICP-MS detection.
Still further, the above container should satisfy: no metal impurity interference is introduced or the introduced interference is negligible; (ii) is not reactive with the high silicon matrix solvent; the composite material can resist a certain temperature and cannot be melted in the heating process; and the corrosion resistance is certain, and the corrosion resistance cannot be caused by dilute acid (such as the 2% nitric acid aqueous solution). The container may be a PFA or PTFT container, such as a 50mL PFA bottle. Preferably, the container is provided with a cover, the high-silicon base solvent has a low boiling point and is likely to volatilize, and the container can be sealed by the cover before sampling into the container and heating in order to prevent volatilization of the high-silicon base solvent.
Further, the step (1), the step (2) and the step (3) are carried out in a clean bench to avoid environmental interference.
Further, in order to prevent air pollution caused by vapor formed after the evaporation of the high silicon substrate solvent, the vapor may be introduced into an absorption liquid or an activated carbon absorption device. The absorbing solution is a solution that can react with and retain a high silicon substrate solvent, and may be water when measuring metal impurities in hexachlorodisilane, for example. Hexafluorodisilane vapor is introduced into water, and hexafluorodisilane reacts with water to form silanol, thereby being retained by the water. The active carbon adsorption device contains active carbon, has a porous adsorption structure and can adsorb vapor formed by evaporation of a high silicon matrix solvent. Preferably, the container lid is provided with a vapor collecting device which can collect vapor evaporated from the container and is provided with or communicated with a conduit through which the vapor is introduced into the absorption liquid or the activated carbon absorption device.
In another aspect of the present invention, there is provided a kit for the determination of ultra trace metal impurities in a high silicon substrate solvent, the kit comprising: diluent and standard solutions of the step concentration series.
The kit is used for determining the ultra-trace metal impurities in the high-silicon matrix solvent, and the specific steps of using the kit to determine the ultra-trace metal impurities in the high-silicon matrix solvent comprise:
s1, putting the high-silicon matrix solvent into a container, heating the container to completely evaporate the high-silicon matrix solvent, adding a diluent into the container, and dissolving the remainder to prepare a sample solution;
s2, taking another container, and processing the rest of the container and the sample solution in S1 in parallel except that the high-silicon matrix solvent is not added to prepare a blank solution;
s3, taking the blank solution in the step S2, detecting the step concentration series standard solution in the kit and the sample solution in the step S1 in an inductively coupled plasma mass spectrometer, calculating the concentration of the metal impurities in the sample solution according to a standard curve method, and calculating the content of the metal impurities in the high-silicon matrix solvent according to the sampling amount and the diluent amount;
wherein the heating temperature in the step of S1 is lower than the boiling point of the metal impurity and the same as or higher than the boiling point of the high-silicon base solvent.
The kit comprises the reagents required by the method, and when the kit is used for experiments, only a sample solution and a blank solution are required to be prepared, so that the operation is simplified, and the pollution risk is reduced. Preferably, the kit is disposable. For example, a kit for use in the method for measuring metal impurities in hexafluorodisilane described in example 1 below, which kit consists of a 2% nitric acid aqueous solution and a standard solution. Wherein the standard solutions comprise the mixed standard solution described in example 1 and four series concentrations of standard solution ranging from 0 to 600 ppt. When the kit is used for carrying out the experiment of the embodiment 1, the liquid preparation operation can be reduced, and the pollution risk can be reduced.
The invention has the advantages that: the method adopts an evaporation method to remove silicon without using hydrofluoric acid, so that: the safety of the test is improved; secondly, the solvent is volatilized slowly and stably, so that the solvent cannot be splashed due to rapid reaction, damage accidents are caused, samples are lost, and the result accuracy is influenced; and thirdly, the sample only contacts the PFA bottle, and hydrofluoric acid is not required to be dripped by using a liquid transfer gun, so that the pollution which is difficult to control is avoided, and the test result is distorted. In addition, the method has good silicon removal effect, can reduce the silicon content in the sample to ppb level, greatly protects the sample introduction system of the inductively coupled plasma mass spectrometer, and prolongs the service life of the equipment. The method can increase the sample amount, thereby concentrating the metal impurities, achieving the accurate measurement of the ultra-trace metal impurities, reducing the requirement on the sensitivity of the instrument and reducing the test cost.
Drawings
FIG. 1 is a standard curve of lithium (Li) and sodium (Na) elements.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the prior art, silicon in a sample is removed by a hydrofluoric acid digestion method, and the sample is diluted to a proper concentration by a diluent and then tested on an inductively coupled plasma mass spectrometer. The invention directly removes silicon in the high silicon matrix solvent through evaporation.
Example one
The method for measuring the metal impurities In hexafluorodisilane comprises the steps of measuring the metal impurities including Ag (silver), As (arsenic), Au (gold), Ba (barium), Be (beryllium), Bi (bismuth), Cd (cadmium), Fe (iron), Ge (germanium), In (indium), K (potassium), Li (lithium), Mo (molybdenum), Na (sodium), Ni (nickel), Pb (lead), Pt (platinum), Sb (antimony), Sn (tin), Sr (strontium), Ta (tantalum), Ti (titanium), Tl (thallium), W (tungsten), Zn (zinc) and Zr (pickaxe), wherein the impurity limit is 100 ppt.
1. Solution preparation
Firstly, weighing 50g of hexachlorodisilane sample in a clean PFA bottle in a super clean bench, and accurately weighing to 0.0001 g. The PFA bottle was placed on a hot plate and heated at 180 ℃ until the solution in the PFA bottle was completely evaporated to dryness. Cooled to room temperature, and dissolved by adding 10mL of a diluent (2% aqueous nitric acid). 3 parts are prepared in parallel.
And (II) the blank solution is the same as the first solution except that no sample is added.
③ taking the stock solution of the mixed standard substance (prepared by mixing various commercial element standard substances, wherein the concentrations of Ag, As, Au, Ba, Be, Bi, Cd, Fe, Ge, In, K, Li, Mo, Na, Ni, Pb, Pt, Sb, Sn, Sr, Ta, Ti, Tl, W, Zn and Zr are all 100 mug/mL, namely 100ppb), and diluting the stock solution with a diluent to four series of concentrations with the concentration range of 0 to 600ppt (namely 0.6 ppb).
And fourthly, weighing 50g of hexachlorodisilane sample into a clean PFA bottle in a super clean bench by using the sample standard solution, accurately weighing the sample to 0.0001g, adding 50 mu L of mixed standard substance stock solution, and treating the rest of the mixed standard substance stock solution in the same way as the sample solution. 6 parts are prepared in parallel.
ICP-MS conditions
ICP-MS model PE 2000ICP-MS (PE, USA), the specific ICP-MS conditions are shown in tables 1 and 2 below.
It should be noted that in the course of experiments, the inventors found that Bi, Fe, K, Ti, Tl and Zn generated interference when the Standard reaction mode was adopted, and the amonia DRC (Ammonia gas) reaction mode was selected to eliminate the interference. Further, the inventors have optimized the flow rate of the reactant gas (Ammonia) of these several elements (as shown in table 2 below) so that it has the best response value.
TABLE 1 Instrument parameters
TABLE 2 method parameters
3. Results of the experiment
Taking the blank solution, the standard solutions with various concentrations, the sample solution and the sample, and adding the standard solution into the sample for ICP-MS detection.
And (3) taking the measurement results of the standard solutions with various concentrations As a standard curve, wherein the linear correlation coefficients of the to-Be-measured metal elements Ag, As, Au, Ba, Be, Bi, Cd, Fe, Ge, In, K, Li, Mo, Na, Ni, Pb, Pt, Sb, Sn, Sr, Ta, Ti, Tl, W, Zn and Zr are all larger than 0.999, and the method has good linearity In the concentration range of 0-0.6 ppb (for example, the standard curve of Li and Na is shown In figure 1).
The concentrations of the metal impurities in the sample solution and the sample standard solution are calculated according to a standard curve method, the content of the metal impurities is calculated according to the sampling amount and the diluent amount, the standard recovery rate is calculated, and the experimental result is shown in the following table 3.
TABLE 3 accuracy test results
As can be seen from table 3, the recovery rate of each metal element to be measured was in the range of 85.65% to 113.28% (satisfying the range of 85% to 115%), and the accuracy of the method was good.
In addition, the experimental process is performed by different experimenters on different days, the experimental results are consistent, and are not repeated herein, so that the precision of the method is good.
In conclusion, the method for measuring the metal impurities In the hexafluorodisilane has high precision, and can accurately detect the metal impurities (including Ag, As, Au, Ba, Be, Bi, Cd, Fe, Ge, In, K, Li, Mo, Na, Ni, Pb, Pt, Sb, Sn, Sr, Ta, Ti, Tl, W, Zn and Zr) In the hexafluorodisilane.
Example two
To further compare the prior art hydrofluoric acid desilication process with the evaporative desilication process of the present invention, the inventors used an organic solvent containing silane to measure the silicon content and the content of several metal impurities (K, Na, Zn) that are susceptible to environmental and human contamination, respectively.
The organic solvent containing the silane was taken and recorded as such. 3 sample solutions (same as example 1) were prepared as they were, and they were recorded as 1# sample, 2# sample and 3# sample after evaporation. In order to prevent the ICP-MS from being polluted by excessive silicon content, the Si (silicon) is detected by adopting ICP-OES (inductively coupled plasma emission spectrometer). Meanwhile, the inventor removes silicon by a hydrofluoric acid hydrolysis method, takes the original sample to prepare 3 parts of sample solution, records that after the sample No. 1 is treated by HF, after the sample No. 2 is treated by HF and after the sample No. 3 is treated by HF, the sample solution is subjected to ICP-OES to detect Si. And after the 1# sample is dried by distillation, the 2# sample is dried by distillation, the 3# sample is dried by distillation, the 1# sample is treated by HF, the 2# sample is treated by HF, and the 3# sample is treated by HF, and then the ICP-MS is used for detecting K, Na and Zn.
(1) The silicon content results are given in table 4 below. The silicon content (Si content) as it is was 34.70%, and the remaining Si contents were all less than 50ppb by the evaporation desiliconization method of the present invention, indicating that the method of the present invention can remove silicon in a high silicon substrate solvent. And (3) removing silicon by a hydrofluoric acid digestion method, wherein the content of residual silicon is in the range of 611.63-12083.95 ppb, which shows that the parallelism of silicon removal by the method is poor. Comparing the results of the two methods, the method for removing silicon by evaporation has more thorough effect and good parallelism.
TABLE 4 measurement results of silicon content
(2) The results of potassium (K), sodium (Na) and zinc (Zn) measurements are shown in table 5 below. As can be seen from the data in the following table, K, Na and Zn results in three samples measured by the evaporation desilication method of the invention have good parallelism; the K, Na and Zn results in three samples measured by a hydrofluoric acid desiliconization method are poor in parallelism, and after the 1# sample and the 3# sample are subjected to HF treatment, the two samples have larger abnormal data, which indicates that the samples are polluted in the preparation process. The comparison results show that: the evaporation desiliconization method reduces the operation process of adding hydrofluoric acid, has low pollution probability, and is more beneficial to measuring metal impurities which are easily polluted by environment or human factors.
TABLE 5 determination of Potassium, sodium and Zinc content
In conclusion, the method for determining the ultra-trace metal impurities in the high-silicon matrix solvent can accurately determine the ultra-trace metal impurities in the high-silicon matrix solvent; the silicon content in the high-silicon matrix solvent is reduced to ppb level, the damage of the high-silicon matrix to the instrument is avoided, and the silicon removing effect is better than that of the existing hydrofluoric acid silicon removing method, so that the method is more suitable for detecting the metal impurities in the high-silicon matrix solvent. In addition, the method reduces the operation steps and the pollution risk, and particularly has more reliable detection results for metal impurities which are easily polluted by environment or human factors.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The method for determining the ultra trace metal impurities in the high silicon matrix solvent is characterized in that the high silicon matrix solvent is heated to completely evaporate the high silicon matrix solvent, and the heating temperature is lower than the boiling point of the metal impurities and is the same as or higher than the boiling point of the high silicon matrix solvent.
2. The method according to claim 1, wherein the step of heating the high-silicon substrate solvent to complete evaporation of the high-silicon substrate solvent comprises:
taking the high-silicon matrix solvent into a container, heating the container to completely evaporate the high-silicon matrix solvent, adding a diluent into the container, dissolving the remainder, and preparing a sample solution.
3. The method of claim 2, further comprising the steps of:
taking another container, and processing the rest of the container and the sample solution in the step (1) in parallel except that the high-silicon matrix solvent is not added to prepare a blank solution;
step (3) preparing a step concentration series standard solution of the metal impurities;
step (4) taking the blank solution in the step (2), the step concentration series standard solution in the step (3) and the sample solution in the step (1) to enter an inductively coupled plasma mass spectrometer for detection; and calculating the concentration of the metal impurities in the sample solution according to a standard curve method, and calculating the content of the metal impurities in the high-silicon matrix solvent according to the sampling amount and the diluent amount.
4. The method of claim 3, wherein the parameters of the inductively coupled plasma mass spectrometer comprise: the radio frequency power is 1600W, the flow rate of the auxiliary gas is 1.2mL/min, the flow rate of the plasma gas is 18mL/min, a peak jump scanning mode is adopted, and the scanning times are 3; when bismuth, iron, potassium, titanium, thallium or zinc is detected, an ammonia gas reaction mode is adopted, the reactant gas flow of iron is 0.9mL/min, the reactant gas flow of potassium is 0.7mL/min, and the reactant gas flow of bismuth, titanium, thallium or zinc is 0.4 mL/min.
5. The method of claim 1, wherein the high-silicon matrix solvent comprises: hexachlorodisilane and trichlorosilane.
6. The method of claim 1, wherein the metallic impurities are a combination of one or more of the following: lithium, sodium, potassium, titanium, iron, nickel, zinc, arsenic, lead, silver, gold, barium, beryllium, bismuth, cadmium, germanium, indium, molybdenum, platinum, antimony, tin, strontium, tantalum, thallium, tungsten, and zirconium.
7. The method of claim 1, wherein the metal impurity limit is 100 ppt.
8. The method of claim 2, wherein step (1) further comprises passing the vapor formed by the evaporation of the high silicon substrate solvent to an absorption liquid or an activated carbon adsorption unit.
9. The method of claim 3, wherein said step (1), said step (2), and said step (3) are performed in a clean bench.
10. A kit for the determination of ultra trace metal impurities in a high silicon substrate solvent, said kit comprising: diluent and standard solution of step concentration series;
the kit is used for determining the ultra-trace metal impurities in the high-silicon matrix solvent, and the specific steps for determining the ultra-trace metal impurities in the high-silicon matrix solvent comprise:
s1, putting a high-silicon matrix solvent into a container, heating the container to completely evaporate the high-silicon matrix solvent, adding a diluent in the kit into the container, and dissolving the remainder to prepare a sample solution;
s2, taking another container, and processing the rest of the container and the sample solution in S1 in parallel except that the high-silicon matrix solvent is not added to prepare a blank solution;
s3, taking the sample solution in the step S1, the blank solution in the step S2 and the step concentration series standard solution in the kit, detecting the sample solution, the blank solution and the step concentration series standard solution in the kit by an inductively coupled plasma mass spectrometer, calculating the concentration of the metal impurities in the sample solution according to a standard curve method, and calculating the content of the metal impurities in the high-silicon matrix solvent according to the sampling amount and the diluent amount;
wherein the heating temperature in the step of S1 is lower than the boiling point of the metal impurity and the same as or higher than the boiling point of the high-silicon base solvent.
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