SJ/Z 3206.13-1989 General rules for emission spectroscopic analysis of semiconductor materials SJ/Z3206.13-1989 Standard download decompression password: www.bzxz.net

Guiding Technical Document of the Ministry of Electronics Industry of the People's Republic of China Semiconductor Material Emission Spectral Analysis Method SJ/Z3206.13--89
This standard applies to the general rules for emission spectrum analysis methods of semiconductor materials such as germanium, silicon, arsenic, antimony and antimony steel. Its contents include basic principles, instruments, preparation of standard solutions, sample processing methods, selection of spectral conditions, and related general provisions.
1 Introduction to standards
1.1 GB9259-88 Terminology of emission spectrum analysis 1.2 SJ/Z3206.3--89 Instruments and performance requirements for emission spectrum analysis 1.3 SJ/Z3206.11--89 General rules for emission spectrum quantitative analysis methods 1.4 SJ/Z3206.4--89 General rules for the use of spectral photosensitive plates 1.5 SJ/Z3206.14--89 General rules for spectrochemical analysis errors and experimental data processing methods 2 Basic principles
Before spectral excitation, the matrix elements in the semiconductor material are separated by chemical methods, the impurity elements are enriched and concentrated, and then the solution dry residue method or carbon powder adsorption method is used to select the killer elements for spectral quantitative determination. 3 The following situations require chemical treatment of the sample in advance: 3.1 The content of impurity elements in the sample is lower than the detection limit of direct spectroscopy (10-4~10-5%). If it is not separated and enriched, it cannot be measured.
3.2 The spectrum of the matrix element is relatively complex, which affects the measurement of the impurity element analysis line and the internal standard line. 3.3 The change of the matrix element composition has a significant effect on the spectral line intensity of the impurity element. 3.4 The matrix elements are highly toxic or radioactive, which will pollute the environment and harm human health during the excitation process. The impurity concentrate after separating the matrix is ​​excited with different excitation sources to produce the characteristic spectral lines of each impurity element. Then, according to the intensity or blackness of the spectral line, the content of each impurity element in the sample is obtained by the line of logR and logC or △S and logC. For the spectral quantitative analysis method, see SJ/Z3206.1189. 4 Instruments and working conditions
You can choose according to different instrument conditions and analysis requirements. The following only lists typical instrument parameters and working conditions.
4.1 Excitation source
4.1.1 Continuous AC arc: current 5~8A, exposure 40~60s. 4.1.2 Intermittent AC arc: arc pulse frequency 240Hz, pulse duration 1/10s, interval 1.5/10s. Ministry of Electronics Industry of the People's Republic of China issued on February 10, 1989 and approved for implementation on March 1, 1989
Current 8A, exposure 1min.
SJ/Z3206.13—89
4.1.3 DC arc: current 5201, exposure 20~60s, the upper electrode is the cathode, and the lower electrode is the hole-shaped anode. 4.1.4 High-voltage arc: voltage 10700V, inductance 1.5mH, capacitance 6000pf, exposure 2min. 4.1.5 Inductively coupled high frequency plasma (ICP): frequency 32MHz, power 3.5kW, high voltage 3000~4000V, positive current 0.8~14, grid current 100~200mA, irradiation 30~60s. 4.2 Sample introduction system
Can use carbon electrode, graphite electrode, copper electrode or solution direct atomization system-pneumatic atomizer, ultrasonic atomizer.
4.3 Spectroscopic system
Can use quartz prism spectrograph field grating spectrometer, reciprocal line dispersion rate 0.5~1nm/mm, wavelength range 200~600nm.
4.4 Detection system
Can use photographic devitrification photoelectric recording method. The photographic method requires the selection of spectral photosensitive plates according to specified conditions for development, fixing, drying and other treatments. Then use a microphotometer to measure the blackness of the spectral lines on the spectrum sheet. The photoelectric recording method uses a photomultiplier tube to transfer the light signal into an electrical signal, and the computer performs data processing. 5 Sample processing method
Sample processing is to separate and remove the matrix components in the flat conductor material, and the impurity elements are enriched and concentrated. There are two types of separation methods: separation of the matrix and separation of impurities. 5.1 Selection criteria for separation methods
5,1.1 Under the premise of ensuring that the impurity elements are not lost and fully enriched, the matrix elements should be separated as completely as possible to avoid affecting the determination of the impurity elements. 5.1.2 The impurity elements to be determined should be transferred to the enriched material in full or as much as possible, but contamination from the environment, containers, reagents and the operator himself should also be avoided. The recovery rate of impurity elements is required to be between 80% and 120%, and as close to 100% as possible.
5.1.3 Use as few chemical reagents (including types and quantities) as possible, and they should be easy to purify. It is required that the reagents used do not contain the impurities to be determined, so as to reduce the blank value. 5.1.4 Simple operation, fast trace, short cycle, low cost, and the sampling volume should be as small as possible. 5.2 Common separation methods for semiconductor material analysis Common separation methods for semiconductor material spectral analysis include volatilization, extraction, precipitation, ion exchange, electrolysis, etc. Table 1 shows the common separation methods for main conductive materials. 2
Matrix elements
Ga, As
Ga, As
Ga, As
In, P
In, P
In, Sb
In, Sb
In, As
Ga, P
SJ/Z3206.13—89
Semiconductor material matrix and impurity separation and enrichment methods Material types
Si, Sio,
SiHCIs||tt ||Ge, GeO
Ga, GaCls
Sb, SbCls
6 standard solution preparation
Separation object
Treat with HF+HNO,+HSO, volatilize with HF steam, volatilize with SiF
Heat and volatilize, residual SiO2 is treated with HF again and HC1, GeCl is used as a hair
Use various aldehydes in 6~12M HC1 to extract chlorides and use B (OH) to precipitate the impurities
Use H Cl, HBr, Br2 treatment, arsenic volatilization, cation exchange resin filter bed adsorption, heating volatilization, residual As2O, HBr treatment, arsenic volatilization, gallium with ether in 8MHC1, extraction with chloroform and disulfide
use dry Brs, HCI vapor, Ga, As halides detection, ether from hydrochloric acid or hydrobromic acid extraction with 8-hydroxyquinoline and chloroform extraction
use HBr and Br to volatilize bromide
extraction with chloroform and disulfide | |tt||Use acetaldehyde to extract sodium from 5MHBr
Use sodium sulfate to separate by coprecipitation
Use acetaldehyde to extract sodium from 5MHBr
Use di(2-ethylhexyl)phosphoric acid to extract arsenic from 8MHBr to volatilize as halide, and use di(2-ethylhexyl)phosphoric acid to extract arsenic from 7MHBr. Use nitrogen to extract diethylamino dithiocarboxylate. First, take the pure element or its compound of each impurity to be tested, dissolve it with acid or water, and prepare a 1mg/ml standard solution. Usually, the hydrochloric acid concentration in each solution is about 1M, which is stored in a polyethylene plastic bottle for standby use. Depending on the different detection limits of each impurity element and the actual content level, take a certain amount of standard solution, prepare a mixed mother liquor, and then dilute it step by step with 0.5M hydrochloric acid to prepare a set of standard series. Two typical examples of standard series for semiconductor material spectral analysis 3
SJ/Z3206.13-89
are shown in Tables 2 and 3. The grouping and concentration range in actual use can be adjusted appropriately, and the types of impurity elements can also be increased or decreased according to the analysis requirements.
Table 2 Standard series elements for determining trace impurities in semiconductor materials
Series number
Series number
Al, Pb, Fe
Cr, Zn
Ni, Ti, Mn
Table 3 Standard series for determining trace impurities in semiconductor materials Al, Cu, Ag
7 Spectral analysis of impurity concentrates
7.1 The way impurities enter the excitation zone
Ti, Mg, Mn,
Bi, Mo
Sn, Cr, Fe, Cd,
Co, Ni, Zn, Ca, Pb
In (internal standard)
In (internal standard)
The impurity concentrate after chemical separation is transferred to the spectral electrode and then excited by the excitation source; or the concentrated solution is directly sprayed into the spectral excitation area by the atomization device. The basic methods are as follows: 1.1 Solution dry residue (residue) method
The impurity concentrate after separation of the matrix is ​​evaporated to about 0.1~0.2ml, and 0.1ml internal standard solution, use a plastic dropper to transfer all the solution to a pair (or one) of flat-head graphite electrodes coated with 1% polystyrene benzene solution as a sealant, dry under an infrared lamp, and wait for spectrum photography. Make three parallel copies of each sample, and do a blank test at the same time. The firmness of impurity residues on the electrode has a great influence on the accuracy and detection limit of spectral analysis. Generally, the total amount of substances loaded on the surface of a pair of electrodes is not more than 1mg. If the load is too large, a sparse layer will be formed on the surface of the electrode. When the discharge is excited, the impurities will be radiated and lost. The solution dry residue method generally uses an AC arc! Or spark excitation, excitation conditions see 3.1.7.1.2 Carbon powder adsorption method
Add a few drops of 1M plate acid solution and 0.1n1 internal standard solution to the impurity concentrate, heat and rotate under an infrared lamp to completely dissolve the residue on the wall, transfer the solution to a small quartz beaker containing 40mg high-purity phosphorus powder with a plastic dropper, then wash the wall with a few drops of water and transfer it to the carbon powder. Dry the carbon powder under an infrared lamp, mix it thoroughly, and then put it into a perforated graphite electrode for spectrum photography. The graphite electrode has a hole diameter of 3.5mm and a hole depth of 5mm. Proof, ① The carbon powder used in this method must not contain the impurities to be measured. ② The carbon powder adsorption method generally uses DC arc excitation. 7.1.3 Solution direct atomization method
When using ICP as the excitation source, the impurity concentrate is diluted to a certain volume with 1M hydrochloric acid solution, and then the sample solution is atomized by a pneumatic atomizer or an ultrasonic atomizer and sprayed into a desolventizing device. After heating and cooling, the solvent is removed, and the impurities enter the plasma torch in the form of extremely fine aerosols and are excited. A certain height of the plasma torch is intercepted for irradiation.
7.1.4 While the sample is being processed, the standard series is made into a spectral electrode according to the solution dry residue method or powder adsorption method, or the standard series is sprayed into the plasma torch in the same way as the sample. Then, the standard and the sample are spectrographically photographed under the same conditions.
7.2 Selection of spectral conditions
Depending on the different instrument conditions and analysis requirements, the following items should be selected to obtain the best analysis results. 7.2.1 Type of excitation source and its working parameters. 7.2.2 Type of spectrograph, including working wavelength range, illumination system, slit width, step dimmer, neutral optics, filters, etc.
7.2.3 Type and size of electrodes.
7.2.4 Pre-burning time and noise time.
7.2.5 Type of photosensitive plate and developing and fixing conditions. 7.2.6 Wavelength of analytical line pair.
7.3 Photometry and data processing
Use the S scale (or W scale, P scale) of the microphotometer to measure the blackness value of each element cumulative spectral line in the standard sample and the analytical sample, take the average value of three parallel measurements, draw the △S (or W, △P) and logC working curve or logR and logC working curve, find out the absolute content of each impurity element in the analytical sample and blank from the curve, and take the average value of three parallel samples. The percentage of each impurity element in the sample is calculated by the following formula: X% -- C*-Co 1.....
Wherein: Cx and Co are the impurity contents in the sample and blank respectively obtained from the working curve, g, and G is the sample mass, g.
The wavelengths of the spectral lines of each impurity element selected for photometry are shown in Table 4. In order to avoid interference from the spectral lines of matrix elements or high-content impurity elements, spectral lines of other wavelengths can sometimes be selected. -5-
8 General provisions
Wavelength nm
8.1 Purification of water and chemical reagents
SJ/Z3206.13—89
Table 4 Spectral line wavelength table for semiconductor material analysis Elements
Ia (internal standard)
In (internal standard)
In (internal standard)
Wavelength nm
Wavelength nm
Since the impurity content required to be measured in semiconductor materials is generally within the ppb range, the purity of water and chemical reagents used in the analysis process should be higher than that of the analysis sample. In order to meet this requirement, water and reagents must be purified in advance. Water and acids are generally purified by distillation, including sub-boiling distillation, isothermal distillation, rectification, etc., and organic solvents are also purified by distillation. Solid high-purity reagents can be purified by recrystallization, extraction, complexation, electrolysis, sublimation and other methods. The purified reagents must be qualified in the blank test before they can be used. 8.2 Selection of container materials
Pudao's glass instruments are not suitable for the analysis of semiconductor materials due to their high impurity content and poor corrosion resistance. The only container materials suitable for semiconductor analysis are polytetrafluoroethylene, polyethylene, transparent quartz and platinum. 8.3 Cleaning of containers
The importance of container cleaning is no less than the correct analysis operation. Unclean containers will cause the entire analysis operation to fail. The following is a general cleaning method. Soak the plastic or quartz container in aqua regia for one day, and then soak it in 6N high-purity hydrochloric acid for several days. After taking it out, rinse it with a large amount of high-purity water with a resistivity greater than 10MQ. ctn, and then dry it in a clean laminar flow hood. After taking out the quartz instrument from the hydrochloric acid, it can also be cleaned in 5-10% dilute hydrofluoric acid for 10 minutes, and then rinsed with a large plate of water and dried.
Platinum instruments can be cleaned with hot concentrated hydrochloric acid.
8.4 Storage of standard solutions
The following factors that may cause the concentration of standard solutions to change with storage time must be considered: 8.4.1 Evaporation of solvents.
8.4.2 Adsorption of trace elements on the wall of the storage container and dissolution of impurities in the container. SJ/Z3206.13—89
8.4.3 Chemical changes such as precipitation and colloid formation occur under storage conditions. The following storage conditions are generally adopted:
a. Use polytetrafluoroethylene or polyethylene bottles to store standard solutions and sample solutions. b. The solution is an acidic medium with a pH of less than 2 to make the impurities contained relatively stable. C. It is more appropriate to use old bottles that have been used to store dilute solutions of certain elements for a long time than new bottles. Containers that have stored solutions with too high concentrations should not be used to store dilute solutions.
d. The validity period of standard solutions stored under the above conditions is one month. Storage at low temperatures can appropriately extend the validity period.
e. The best way is to use a concentrated solution and gradually dilute it before use to prepare a dilute solution. 8.5 Sampling technology
8.5.1 Liquid samples can be measured with a quartz or plastic measuring cylinder or pipette. First open the container, shake it well, rinse the bottle mouth with the sample, and then rinse the quartz measuring cylinder with the sample. After discarding these two parts of liquid, formal sampling can be carried out. 8.5.2 Powders or particles can be sampled with a quartz spoon. Grinding should be avoided as much as possible to avoid contamination. When grinding is necessary, the material of the mortar should be selected to be thicker than the sample and does not contain the impurity elements to be measured. 8.5.3 After mechanical cutting of large solid samples, first use a solvent to wash away surface contamination, then use an appropriate cleaning agent to clean, and finally rinse with high-purity water and dry. 8.6 Blank value control
The size and stability of the blank value directly affect the reliability of the analysis results. The main factors causing blank detection are dust in the air, impurities in the reagents, container contamination and the operator himself, which must be reduced or avoided as much as possible. Using a chemical room or a clean workbench can effectively reduce the blank value. The relationship between the blank value and the fluctuation of the blank value and the detection limit can be expressed by the following formula: DL- X +36..........
Wherein: DL detection limit,
mean value of blank value;
6-standard deviation of blank value.
. (2)
When analyzing semiconductor materials, blank tests must be performed simultaneously under the same conditions. For high-accuracy analysis, the blank value is required to be less than one-tenth of the content of the measured element. In general, the blank value should not exceed at least one-half of the content of the measured element.
8.7 Allowable error
The lower the concentration of the measured element, the worse the accuracy and precision. Therefore, the standard of constant analysis cannot be used to require micro-analysis. In the analysis of the ppb order of magnitude, a relative standard deviation within 50% is appropriate. Additional remarks:
This standard was proposed by the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. This standard was drafted at the expense of the 55th Institute and the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. The main drafters of this standard are Huang Wenyu and Zhao Changchun.1n1 internal standard solution, heat and rotate under infrared lamp to completely dissolve the residue on the wall, transfer the solution to a small quartz beaker containing 40mg high-purity phosphorus powder with a plastic dropper, wash the wall with a few drops of water and transfer it to the carbon powder. Dry the carbon powder under infrared lamp, mix it thoroughly, and then put it into the perforated graphite electrode for spectrum recording. The graphite electrode has a hole diameter of 3.5mm and a hole depth of 5mm. ① The carbon powder used in this method shall not contain the impurities to be measured. ② The carbon powder adsorption method generally uses DC arc excitation. 7.1.3 Solution direct atomization method
When using ICP as the excitation source, dilute the impurity concentrate with 1M hydrochloric acid solution to a certain volume, then atomize the sample solution with a pneumatic atomizer or ultrasonic atomizer and spray it into the desolventizing device. After heating and cooling, the solvent is removed, and the impurities enter the plasma torch in the form of extremely fine aerosols and are excited. Intercept a certain height of the plasma torch for irradiation.
7.1.4 While the sample is being processed, the standard series is made into a spectral electrode by the solution dry residue method or the powder adsorption method, or the standard series is sprayed into the plasma torch in the same way as the sample. Then, the standard and sample are spectrographically photographed under negotiated conditions.
7.2 Selection of spectral conditions
Depending on the different instrument conditions and analysis requirements, the following items should be selected to obtain the best analysis results. 7.2.1 Type of excitation source and its operating parameters. 7.2.2 Type of spectrograph, including the wavelength range of operation, illumination system, slit width, step dimmer, neutral optics, filters, etc.
7.2.3 Type and size of electrodes.
7.2.4 Pre-burning time and noise time.
7.2.5 Type of photosensitive plate and conditions of development and fixing. 7.2.6 Wavelength of analytical line pairs.
7.3 Photometry and data processing
Use the S scale (or W scale, P scale) of the microphotometer to measure the black value of each element in the standard sample and the analytical sample, take the average value of three parallel measurements, draw the △S (or W, △P) and logC working curve or logR and logC working curve, find out the absolute content of each impurity element in the analytical sample and the blank from the curve, and take the average value of three parallel samples. Calculate the percentage of each impurity element in the sample according to the following formula: X% -- C*-Co 1.....
Where: Cx, Co are the impurity contents in the sample and blank found from the working curve, g, G--sample mass, g.
The wavelengths of the spectral lines of each impurity element selected for photometry are shown in Table 4. In order to avoid the interference of the spectral lines of matrix elements or high-content impurity elements, spectral lines of other wavelengths can sometimes be selected. -5-
8 General provisions
Wavelength nm
8.1 Purification of water and chemical reagents
SJ/Z3206.13—89
Table 4 Spectral line wavelength table for semiconductor material analysis Elements
Ia (internal standard)
In (internal standard)
In (internal standard)
Wavelength nm
Wavelength nm
Since the impurity content required to be measured in semiconductor materials is generally within the ppb range, the purity of water and chemical reagents used in the analysis process should be higher than that of the analysis sample. In order to meet this requirement, water and reagents must be purified in advance. Water and acids are generally purified by distillation, including sub-boiling distillation, isothermal distillation, rectification, etc., and organic solvents are also purified by distillation. Solid high-purity reagents can be purified by recrystallization, extraction, complexation, electrolysis, sublimation and other methods. The purified reagents must be qualified in the blank test before they can be used. 8.2 Selection of container materials
Pudao's glass instruments are not suitable for the analysis of semiconductor materials due to their high impurity content and poor corrosion resistance. The only container materials suitable for semiconductor analysis are polytetrafluoroethylene, polyethylene, transparent quartz and platinum. 8.3 Cleaning of containers
The importance of container cleaning is no less than the correct analysis operation. Unclean containers will cause the entire analysis operation to fail. The following is a general cleaning method. Soak the plastic or quartz container in aqua regia for one day, and then soak it in 6N high-purity hydrochloric acid for several days. After taking it out, rinse it with a large amount of high-purity water with a resistivity greater than 10MQ. ctn, and then dry it in a clean laminar flow hood. After taking out the quartz instrument from the hydrochloric acid, it can also be cleaned in 5-10% dilute hydrofluoric acid for 10 minutes, and then rinsed with a large plate of water and dried.
Platinum instruments can be cleaned with hot concentrated hydrochloric acid.
8.4 Storage of standard solutions
The following factors that may cause the concentration of standard solutions to change with storage time must be considered: 8.4.1 Evaporation of solvents.
8.4.2 Adsorption of trace elements on the wall of the storage container and dissolution of impurities in the container. SJ/Z3206.13—89
8.4.3 Chemical changes such as precipitation and colloid formation occur under storage conditions. The following storage conditions are generally adopted:
a. Use polytetrafluoroethylene or polyethylene bottles to store standard solutions and sample solutions. b. The solution is an acidic medium with a pH of less than 2 to make the impurities contained relatively stable. C. It is more appropriate to use old bottles that have been used to store dilute solutions of certain elements for a long time than new bottles. Containers that have stored solutions with too high concentrations should not be used to store dilute solutions.
d. The validity period of standard solutions stored under the above conditions is one month. Storage at low temperatures can appropriately extend the validity period.
e. The best way is to use a concentrated solution and gradually dilute it before use to prepare a dilute solution. 8.5 Sampling technology
8.5.1 Liquid samples can be measured with a quartz or plastic measuring cylinder or pipette. First open the container, shake it well, rinse the bottle mouth with the sample, and then rinse the quartz measuring cylinder with the sample. After discarding these two parts of liquid, formal sampling can be carried out. 8.5.2 Powders or particles can be sampled with a quartz spoon. Grinding should be avoided as much as possible to avoid contamination. When grinding is necessary, the material of the mortar should be selected to be thicker than the sample and does not contain the impurity elements to be measured. 8.5.3 After mechanical cutting of large solid samples, first use a solvent to wash away surface contamination, then use an appropriate cleaning agent to clean, and finally rinse with high-purity water and dry. 8.6 Blank value control
The size and stability of the blank value directly affect the reliability of the analysis results. The main factors causing blank detection are dust in the air, impurities in the reagents, container contamination and the operator himself, which must be reduced or avoided as much as possible. Using a chemical room or a clean workbench can effectively reduce the blank value. The relationship between the blank value and the fluctuation of the blank value and the detection limit can be expressed by the following formula: DL- X +36..........
Wherein: DL detection limit,
mean value of blank value;
6-standard deviation of blank value.
. (2)
When analyzing semiconductor materials, blank tests must be performed simultaneously under the same conditions. For high-accuracy analysis, the blank value is required to be less than one-tenth of the content of the measured element. In general, the blank value should not exceed at least one-half of the content of the measured element.
8.7 Allowable error
The lower the concentration of the measured element, the worse the accuracy and precision. Therefore, the standard of constant analysis cannot be used to require micro-analysis. In the analysis of the ppb order of magnitude, a relative standard deviation within 50% is appropriate. Additional remarks:
This standard was proposed by the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. This standard was drafted at the expense of the 55th Institute and the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. The main drafters of this standard are Huang Wenyu and Zhao Changchun.1n1 internal standard solution, heat and rotate under infrared lamp to completely dissolve the residue on the wall, transfer the solution to a small quartz beaker containing 40mg high-purity phosphorus powder with a plastic dropper, wash the wall with a few drops of water and transfer it to the carbon powder. Dry the carbon powder under infrared lamp, mix it thoroughly, and then put it into the perforated graphite electrode for spectrum recording. The graphite electrode has a hole diameter of 3.5mm and a hole depth of 5mm. ① The carbon powder used in this method shall not contain the impurities to be measured. ② The carbon powder adsorption method generally uses DC arc excitation. 7.1.3 Solution direct atomization method
When using ICP as the excitation source, dilute the impurity concentrate with 1M hydrochloric acid solution to a certain volume, then atomize the sample solution with a pneumatic atomizer or ultrasonic atomizer and spray it into the desolventizing device. After heating and cooling, the solvent is removed, and the impurities enter the plasma torch in the form of extremely fine aerosols and are excited. Intercept a certain height of the plasma torch for irradiation.
7.1.4 While the sample is being processed, the standard series is made into a spectral electrode by the solution dry residue method or the powder adsorption method, or the standard series is sprayed into the plasma torch in the same way as the sample. Then, the standard and sample are spectrographically photographed under negotiated conditions.
7.2 Selection of spectral conditions
Depending on the different instrument conditions and analysis requirements, the following items should be selected to obtain the best analysis results. 7.2.1 Type of excitation source and its operating parameters. 7.2.2 Type of spectrograph, including the wavelength range of operation, illumination system, slit width, step dimmer, neutral optics, filters, etc.
7.2.3 Type and size of electrodes.
7.2.4 Pre-burning time and noise time.
7.2.5 Type of photosensitive plate and conditions of development and fixing. 7.2.6 Wavelength of analytical line pairs.
7.3 Photometry and data processing
Use the S scale (or W scale, P scale) of the microphotometer to measure the black value of each element in the standard sample and the analytical sample, take the average value of three parallel measurements, draw the △S (or W, △P) and logC working curve or logR and logC working curve, find out the absolute content of each impurity element in the analytical sample and the blank from the curve, and take the average value of three parallel samples. Calculate the percentage of each impurity element in the sample according to the following formula: X% -- C*-Co 1.....
Where: Cx, Co are the impurity contents in the sample and blank found from the working curve, g, G--sample mass, g.
The wavelengths of the spectral lines of each impurity element selected for photometry are shown in Table 4. In order to avoid the interference of the spectral lines of matrix elements or high-content impurity elements, spectral lines of other wavelengths can sometimes be selected. -5-
8 General provisions
Wavelength nm
8.1 Purification of water and chemical reagents
SJ/Z3206.13—89
Table 4 Spectral line wavelength table for semiconductor material analysis Elements
Ia (internal standard)
In (internal standard)
In (internal standard)
Wavelength nm
Wavelength nm
Since the impurity content required to be measured in semiconductor materials is generally within the ppb range, the purity of water and chemical reagents used in the analysis process should be higher than that of the analysis sample. In order to meet this requirement, water and reagents must be purified in advance. Water and acids are generally purified by distillation, including sub-boiling distillation, isothermal distillation, rectification, etc., and organic solvents are also purified by distillation. Solid high-purity reagents can be purified by recrystallization, extraction, complexation, electrolysis, sublimation and other methods. The purified reagents must be qualified in the blank test before they can be used. 8.2 Selection of container materials
Pudao's glass instruments are not suitable for the analysis of semiconductor materials due to their high impurity content and poor corrosion resistance. The only container materials suitable for semiconductor analysis are polytetrafluoroethylene, polyethylene, transparent quartz and platinum. 8.3 Cleaning of containers
The importance of container cleaning is no less than the correct analysis operation. Unclean containers will cause the entire analysis operation to fail. The following is a general cleaning method. Soak the plastic or quartz container in aqua regia for one day, and then soak it in 6N high-purity hydrochloric acid for several days. After taking it out, rinse it with a large amount of high-purity water with a resistivity greater than 10MQ. ctn, and then dry it in a clean laminar flow hood. After taking out the quartz instrument from the hydrochloric acid, it can also be cleaned in 5-10% dilute hydrofluoric acid for 10 minutes, and then rinsed with a large plate of water and dried.
Platinum instruments can be cleaned with hot concentrated hydrochloric acid.
8.4 Storage of standard solutions
The following factors that may cause the concentration of standard solutions to change with storage time must be considered: 8.4.1 Evaporation of solvents.
8.4.2 Adsorption of trace elements on the wall of the storage container and dissolution of impurities in the container. SJ/Z3206.13—89
8.4.3 Chemical changes such as precipitation and colloid formation occur under storage conditions. The following storage conditions are generally adopted:
a. Use polytetrafluoroethylene or polyethylene bottles to store standard solutions and sample solutions. b. The solution is an acidic medium with a pH of less than 2 to make the impurities contained relatively stable. C. It is more appropriate to use old bottles that have been used to store dilute solutions of certain elements for a long time than new bottles. Containers that have stored solutions with too high concentrations should not be used to store dilute solutions.
d. The validity period of standard solutions stored under the above conditions is one month. Storage at low temperatures can appropriately extend the validity period.
e. The best way is to use a concentrated solution and gradually dilute it before use to prepare a dilute solution. 8.5 Sampling technology
8.5.1 Liquid samples can be measured with a quartz or plastic measuring cylinder or pipette. First open the container, shake it well, rinse the bottle mouth with the sample, and then rinse the quartz measuring cylinder with the sample. After discarding these two parts of liquid, formal sampling can be carried out. 8.5.2 Powders or particles can be sampled with a quartz spoon. Grinding should be avoided as much as possible to avoid contamination. When grinding is necessary, the material of the mortar should be selected to be thicker than the sample and does not contain the impurity elements to be measured. 8.5.3 After mechanical cutting of large solid samples, first use a solvent to wash away surface contamination, then use an appropriate cleaning agent to clean, and finally rinse with high-purity water and dry. 8.6 Blank value control
The size and stability of the blank value directly affect the reliability of the analysis results. The main factors causing blank detection are dust in the air, impurities in the reagents, container contamination and the operator himself, which must be reduced or avoided as much as possible. Using a chemical room or a clean workbench can effectively reduce the blank value. The relationship between the blank value and the fluctuation of the blank value and the detection limit can be expressed by the following formula: DL- X +36..........
Wherein: DL detection limit,
mean value of blank value;
6-standard deviation of blank value.
. (2)
When analyzing semiconductor materials, blank tests must be performed simultaneously under the same conditions. For high-accuracy analysis, the blank value is required to be less than one-tenth of the content of the measured element. In general, the blank value should not exceed at least one-half of the content of the measured element.
8.7 Allowable error
The lower the concentration of the measured element, the worse the accuracy and precision. Therefore, the standard of constant analysis cannot be used to require micro-analysis. In the analysis of the ppb order of magnitude, a relative standard deviation within 50% is appropriate. Additional remarks:
This standard was proposed by the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. This standard was drafted at the expense of the 55th Institute and the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. The main drafters of this standard are Huang Wenyu and Zhao Changchun.2 Spectrograph type, including working wavelength range, illumination system, slit width, step dimmer, neutral optics, filters, etc.
7.2.3 Electrode type and size.
7.2.4 Pre-burning time and noise time.
7.2.5 Photosensitive plate type and developing and fixing conditions. 7.2.6 Wavelength of analytical line pair.
7.3 Photometry and data processing bzxz.net
Use the S scale (or W scale, P scale) of the microphotometer to measure the black value of each element cumulative spectral line in the standard sample and the analytical sample, take the average value of three parallel measurements, draw the △S (or W, △P) and logC working curve or logR and logC working curve, find out the absolute content of each impurity element in the analytical sample and the blank from the curve, and take the average value of three parallel samples. The percentage of each impurity element in the sample is calculated by the following formula: X% -- C*-Co 1.....
Wherein: Cx and Co are the impurity contents in the sample and blank respectively obtained from the working curve, g, and G is the sample mass, g.
The wavelengths of the spectral lines of each impurity element selected for photometry are shown in Table 4. In order to avoid interference from the spectral lines of matrix elements or high-content impurity elements, spectral lines of other wavelengths can sometimes be selected. -5-
8 General provisions
Wavelength nm
8.1 Purification of water and chemical reagents
SJ/Z3206.13—89
Table 4 Spectral line wavelength table for semiconductor material analysis Elements
Ia (internal standard)
In (internal standard)
In (internal standard)
Wavelength nm
Wavelength nm
Since the impurity content required to be measured in semiconductor materials is generally within the ppb range, the purity of water and chemical reagents used in the analysis process should be higher than that of the analysis sample. In order to meet this requirement, water and reagents must be purified in advance. Water and acids are generally purified by distillation, including sub-boiling distillation, isothermal distillation, rectification, etc., and organic solvents are also purified by distillation. Solid high-purity reagents can be purified by recrystallization, extraction, complexation, electrolysis, sublimation and other methods. The purified reagents must be qualified in the blank test before they can be used. 8.2 Selection of container materials
Pudao's glass instruments are not suitable for the analysis of semiconductor materials due to their high impurity content and poor corrosion resistance. The only container materials suitable for semiconductor analysis are polytetrafluoroethylene, polyethylene, transparent quartz and platinum. 8.3 Cleaning of containers
The importance of container cleaning is no less than the correct analysis operation. Unclean containers will cause the entire analysis operation to fail. The following is a general cleaning method. Soak the plastic or quartz container in aqua regia for one day, and then soak it in 6N high-purity hydrochloric acid for several days. After taking it out, rinse it with a large amount of high-purity water with a resistivity greater than 10MQ. ctn, and then dry it in a clean laminar flow hood. After taking out the quartz instrument from the hydrochloric acid, it can also be cleaned in 5-10% dilute hydrofluoric acid for 10 minutes, and then rinsed with a large plate of water and dried.
Platinum instruments can be cleaned with hot concentrated hydrochloric acid.
8.4 Storage of standard solutions
The following factors that may cause the concentration of standard solutions to change with storage time must be considered: 8.4.1 Evaporation of solvents.
8.4.2 Adsorption of trace elements on the wall of the storage container and dissolution of impurities in the container. SJ/Z3206.13—89
8.4.3 Chemical changes such as precipitation and colloid formation occur under storage conditions. The following storage conditions are generally adopted:
a. Use polytetrafluoroethylene or polyethylene bottles to store standard solutions and sample solutions. b. The solution is an acidic medium with a pH of less than 2 to make the impurities contained relatively stable. C. It is more appropriate to use old bottles that have been used to store dilute solutions of certain elements for a long time than new bottles. Containers that have stored solutions with too high concentrations should not be used to store dilute solutions.
d. The validity period of standard solutions stored under the above conditions is one month. Storage at low temperatures can appropriately extend the validity period.
e. The best way is to use a concentrated solution and gradually dilute it before use to prepare a dilute solution. 8.5 Sampling technology
8.5.1 Liquid samples can be measured with a quartz or plastic measuring cylinder or pipette. First open the container, shake it well, rinse the bottle mouth with the sample, and then rinse the quartz measuring cylinder with the sample. After discarding these two parts of liquid, formal sampling can be carried out. 8.5.2 Powders or particles can be sampled with a quartz spoon. Grinding should be avoided as much as possible to avoid contamination. When grinding is necessary, the material of the mortar should be selected to be thicker than the sample and does not contain the impurity elements to be measured. 8.5.3 After mechanical cutting of large solid samples, first use a solvent to wash away surface contamination, then use an appropriate cleaning agent to clean, and finally rinse with high-purity water and dry. 8.6 Blank value control
The size and stability of the blank value directly affect the reliability of the analysis results. The main factors causing blank detection are dust in the air, impurities in the reagents, container contamination and the operator himself, which must be reduced or avoided as much as possible. Using a chemical room or a clean workbench can effectively reduce the blank value. The relationship between the blank value and the fluctuation of the blank value and the detection limit can be expressed by the following formula: DL- X +36..........
Wherein: DL detection limit,
mean value of blank value;
6-standard deviation of blank value.
. (2)
When analyzing semiconductor materials, blank tests must be performed simultaneously under the same conditions. For high-accuracy analysis, the blank value is required to be less than one-tenth of the content of the measured element. In general, the blank value should not exceed at least one-half of the content of the measured element.
8.7 Allowable error
The lower the concentration of the measured element, the worse the accuracy and precision. Therefore, the standard of constant analysis cannot be used to require micro-analysis. In the analysis of the ppb order of magnitude, a relative standard deviation within 50% is appropriate. Additional remarks:
This standard was proposed by the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. This standard was drafted at the expense of the 55th Institute and the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. The main drafters of this standard are Huang Wenyu and Zhao Changchun.2 Spectrograph type, including working wavelength range, illumination system, slit width, step dimmer, neutral optics, filters, etc.
7.2.3 Electrode type and size.
7.2.4 Pre-burning time and noise time.
7.2.5 Photosensitive plate type and developing and fixing conditions. 7.2.6 Wavelength of analytical line pair.
7.3 Photometry and data processing
Use the S scale (or W scale, P scale) of the microphotometer to measure the black value of each element cumulative spectral line in the standard sample and the analytical sample, take the average value of three parallel measurements, draw the △S (or W, △P) and logC working curve or logR and logC working curve, find out the absolute content of each impurity element in the analytical sample and the blank from the curve, and take the average value of three parallel samples. The percentage of each impurity element in the sample is calculated by the following formula: X% -- C*-Co 1.....
Wherein: Cx and Co are the impurity contents in the sample and blank respectively obtained from the working curve, g, and G is the sample mass, g.
The wavelengths of the spectral lines of each impurity element selected for photometry are shown in Table 4. In order to avoid interference from the spectral lines of matrix elements or high-content impurity elements, spectral lines of other wavelengths can sometimes be selected. -5-
8 General provisions
Wavelength nm
8.1 Purification of water and chemical reagents
SJ/Z3206.13—89
Table 4 Spectral line wavelength table for semiconductor material analysis Elements
Ia (internal standard)
In (internal standard)
In (internal standard)
Wavelength nm
Wavelength nm
Since the impurity content required to be measured in semiconductor materials is generally within the ppb range, the purity of water and chemical reagents used in the analysis process should be higher than that of the analysis sample. In order to meet this requirement, water and reagents must be purified in advance. Water and acids are generally purified by distillation, including sub-boiling distillation, isothermal distillation, rectification, etc., and organic solvents are also purified by distillation. Solid high-purity reagents can be purified by recrystallization, extraction, complexation, electrolysis, sublimation and other methods. The purified reagents must be qualified in the blank test before they can be used. 8.2 Selection of container materials
Pudao's glass instruments are not suitable for the analysis of semiconductor materials due to their high impurity content and poor corrosion resistance. The only container materials suitable for semiconductor analysis are polytetrafluoroethylene, polyethylene, transparent quartz and platinum. 8.3 Cleaning of containers
The importance of container cleaning is no less than the correct analysis operation. Unclean containers will cause the entire analysis operation to fail. The following is a general cleaning method. Soak the plastic or quartz container in aqua regia for one day, and then soak it in 6N high-purity hydrochloric acid for several days. After taking it out, rinse it with a large amount of high-purity water with a resistivity greater than 10MQ. ctn, and then dry it in a clean laminar flow hood. After taking out the quartz instrument from the hydrochloric acid, it can also be cleaned in 5-10% dilute hydrofluoric acid for 10 minutes, and then rinsed with a large plate of water and dried.
Platinum instruments can be cleaned with hot concentrated hydrochloric acid.
8.4 Storage of standard solutions
The following factors that may cause the concentration of standard solutions to change with storage time must be considered: 8.4.1 Evaporation of solvents.
8.4.2 Adsorption of trace elements on the wall of the storage container and dissolution of impurities in the container. SJ/Z3206.13—89
8.4.3 Chemical changes such as precipitation and colloid formation occur under storage conditions. The following storage conditions are generally adopted:
a. Use polytetrafluoroethylene or polyethylene bottles to store standard solutions and sample solutions. b. The solution is an acidic medium with a pH of less than 2 to make the impurities contained relatively stable. C. It is more appropriate to use old bottles that have been used to store dilute solutions of certain elements for a long time than new bottles. Containers that have stored solutions with too high concentrations should not be used to store dilute solutions.
d. The validity period of standard solutions stored under the above conditions is one month. Storage at low temperatures can appropriately extend the validity period.
e. The best way is to use a concentrated solution and gradually dilute it before use to prepare a dilute solution. 8.5 Sampling technology
8.5.1 Liquid samples can be measured with a quartz or plastic measuring cylinder or pipette. First open the container, shake it well, rinse the bottle mouth with the sample, and then rinse the quartz measuring cylinder with the sample. After discarding these two parts of liquid, formal sampling can be carried out. 8.5.2 Powders or particles can be sampled with a quartz spoon. Grinding should be avoided as much as possible to avoid contamination. When grinding is necessary, the material of the mortar should be selected to be thicker than the sample and does not contain the impurity elements to be measured. 8.5.3 After mechanical cutting of large solid samples, first use a solvent to wash away surface contamination, then use an appropriate cleaning agent to clean, and finally rinse with high-purity water and dry. 8.6 Blank value control
The size and stability of the blank value directly affect the reliability of the analysis results. The main factors causing blank detection are dust in the air, impurities in the reagents, container contamination and the operator himself, which must be reduced or avoided as much as possible. Using a chemical room or a clean workbench can effectively reduce the blank value. The relationship between the blank value and the fluctuation of the blank value and the detection limit can be expressed by the following formula: DL- X +36..........
Wherein: DL detection limit,
mean value of blank value;
6-standard deviation of blank value.
. (2)
When analyzing semiconductor materials, blank tests must be performed simultaneously under the same conditions. For high-accuracy analysis, the blank value is required to be less than one-tenth of the content of the measured element. In general, the blank value should not exceed at least one-half of the content of the measured element.
8.7 Allowable error
The lower the concentration of the measured element, the worse the accuracy and precision. Therefore, the standard of constant analysis cannot be used to require micro-analysis. In the analysis of the ppb order of magnitude, a relative standard deviation within 50% is appropriate. Additional remarks:
This standard was proposed by the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. This standard was drafted at the expense of the 55th Institute and the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. The main drafters of this standard are Huang Wenyu and Zhao Changchun.3. Container cleaning
Container cleaning is as important as correctly performing the analysis. Unclean containers will cause the entire analysis to fail. The following is a general cleaning method. Soak the plastic or quartz container in aqua regia for one day, then soak it in 6N high-purity hydrochloric acid for several days. After taking it out, rinse it with a large amount of high-purity water with a resistivity greater than 10MQ. ctn, and then dry it in a clean laminar flow hood. After taking out the quartz instrument from the hydrochloric acid, it can also be cleaned in 5-10% dilute hydrofluoric acid for 10 minutes, then rinsed with a large pan of water and dried.
Platinum instruments can be cleaned with hot concentrated hydrochloric acid.
8.4 Storage of standard solutions
The following factors that may cause the concentration of the standard solution to change with storage time must be considered: 8.4.1 Evaporation of solvents.
8.4.2 Adsorption of trace elements on the wall of the storage container and dissolution of impurities in the container. SJ/Z3206.13—89
8.4.3 Chemical changes such as precipitation and colloid formation occur under storage conditions. The following storage conditions are generally adopted:
a. Use polytetrafluoroethylene or polyethylene bottles to store standard solutions and sample solutions. b. The solution is an acidic medium with a pH of less than 2, so that the impurities contained are relatively stable. C. It is more appropriate to use old bottles that have been used to store dilute solutions of certain elements for a long time than new bottles. Containers that store solutions with too high concentrations should not be used to store dilute solutions.
d. The standard solution stored under the above conditions is valid for one month. Storage at low temperatures can appropriately extend the validity period.
e. The best way is to gradually dilute the concentrated solution to prepare a dilute solution before use. 8.5 Sampling technology
8.5.1 Liquid samples can be measured with a quartz or plastic measuring cylinder or pipette. First open the container, shake it well, rinse the bottle mouth with the sample, and then rinse the quartz measuring cylinder with the sample. After discarding these two parts of liquid, formal sampling can be carried out. 8.5.2 Powders or particles can be sampled with a quartz spoon. Grinding should be avoided as much as possible to avoid contamination. When grinding is necessary, the material of the mortar should be selected to be finer than the sample and not contain the impurity elements to be measured. 8.5.3 After mechanical cutting of large solid samples, first use a solvent to wash away surface contamination, then use an appropriate cleaning agent to clean, and finally rinse with high-purity water and dry. 8.6 Control of blank value
The size and stability of the blank value directly affect the reliability of the analysis results. The main factors causing blank detection are dust in the air, impurities in the reagents, container contamination and the operator himself, which must be reduced or avoided as much as possible. Using a chemical room or a clean workbench can effectively reduce the blank value. The relationship between the blank value and the fluctuation of the blank value and the detection limit can be expressed by the following formula: DL- X +36..........
Wherein: DL detection limit,
mean value of blank value;
6-standard deviation of blank value.
. (2)
When analyzing semiconductor materials, blank tests must be performed simultaneously under the same conditions. For high-accuracy analysis, the blank value is required to be less than one-tenth of the content of the measured element. In general, the blank value should not exceed at least one-half of the content of the measured element.
8.7 Allowable error
The lower the concentration of the measured element, the worse the accuracy and precision. Therefore, the standard of constant analysis cannot be used to require micro-analysis. In the analysis of the ppb order of magnitude, a relative standard deviation within 50% is appropriate. Additional remarks:
This standard was proposed by the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. This standard was drafted at the expense of the 55th Institute and the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. The main drafters of this standard are Huang Wenyu and Zhao Changchun.3. Container cleaning
Container cleaning is as important as correctly performing the analysis. Unclean containers will cause the entire analysis to fail. The following is a general cleaning method. Soak the plastic or quartz container in aqua regia for one day, then soak it in 6N high-purity hydrochloric acid for several days. After taking it out, rinse it with a large amount of high-purity water with a resistivity greater than 10MQ. ctn, and then dry it in a clean laminar flow hood. After taking out the quartz instrument from the hydrochloric acid, it can also be cleaned in 5-10% dilute hydrofluoric acid for 10 minutes, then rinsed with a large pan of water and dried.
Platinum instruments can be cleaned with hot concentrated hydrochloric acid.
8.4 Storage of standard solutions
The following factors that may cause the concentration of the standard solution to change with storage time must be considered: 8.4.1 Evaporation of solvents.
8.4.2 Adsorption of trace elements on the wall of the storage container and dissolution of impurities in the container. SJ/Z3206.13—89
8.4.3 Chemical changes such as precipitation and colloid formation occur under storage conditions. The following storage conditions are generally adopted:
a. Use polytetrafluoroethylene or polyethylene bottles to store standard solutions and sample solutions. b. The solution is an acidic medium with a pH of less than 2, so that the impurities contained are relatively stable. C. It is more appropriate to use old bottles that have been used to store dilute solutions of certain elements for a long time than new bottles. Containers that store solutions with too high concentrations should not be used to store dilute solutions.
d. The standard solution stored under the above conditions is valid for one month. Storage at low temperatures can appropriately extend the validity period.
e. The best way is to gradually dilute the concentrated solution to prepare a dilute solution before use. 8.5 Sampling technology
8.5.1 Liquid samples can be measured with a quartz or plastic measuring cylinder or pipette. First open the container, shake it well, rinse the bottle mouth with the sample, and then rinse the quartz measuring cylinder with the sample. After discarding these two parts of liquid, formal sampling can be carried out. 8.5.2 Powders or particles can be sampled with a quartz spoon. Grinding should be avoided as much as possible to avoid contamination. When grinding is necessary, the material of the mortar should be selected to be finer than the sample and not contain the impurity elements to be measured. 8.5.3 After mechanical cutting of large solid samples, first use a solvent to wash away surface contamination, then use an appropriate cleaning agent to clean, and finally rinse with high-purity water and dry. 8.6 Control of blank value
The size and stability of the blank value directly affect the reliability of the analysis results. The main factors causing blank detection are dust in the air, impurities in the reagents, container contamination and the operator himself, which must be reduced or avoided as much as possible. Using a chemical room or a clean workbench can effectively reduce the blank value. The relationship between the blank value and the fluctuation of the blank value and the detection limit can be expressed by the following formula: DL- X +36..........
Wherein: DL detection limit,
mean value of blank value;
6-standard deviation of blank value.
. (2)
When analyzing semiconductor materials, blank tests must be performed simultaneously under the same conditions. For high-accuracy analysis, the blank value is required to be less than one-tenth of the content of the measured element. In general, the blank value should not exceed at least one-half of the content of the measured element.
8.7 Allowable error
The lower the concentration of the measured element, the worse the accuracy and precision. Therefore, the standard of constant analysis cannot be used to require micro-analysis. In the analysis of the ppb order of magnitude, a relative standard deviation within 50% is appropriate. Additional remarks:
This standard was proposed by the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. This standard was drafted at the expense of the 55th Institute and the Electronic Standardization Institute of the Ministry of Machinery and Electronics Industry. The main drafters of this standard are Huang Wenyu and Zhao Changchun.
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