GB/T 15909-1995 Silane (SiH4) gas for use in the electronics industry
Some standard content:
National Standard of the People's Republic of China
Gas for electronic industry
Silane (SiH)
Gas for electronic industry--Silane1 Subject content and scope of application
GB/T 15909-1995
This standard specifies the technical requirements, inspection methods, inspection rules, packaging, marking, transportation, storage and safety requirements of silane gas for electronic industry.
This standard is mainly used for epitaxial deposition of polycrystalline silicon and single crystal silicon, low-temperature chemical vapor deposition of silicon dioxide, and amorphous silicon thin film deposition in the electronic industry.
Molecular formula: SiH.
Relative molecular mass: 32.117 (according to the international relative atomic mass in 1991). Boiling point at 101.3kPa: -112℃.
Gas density at 20℃ and 101.3kPa: 1.342kg/m. - Liquid density at 185℃, 711kg/m. Reference standards
Dangerous goods packaging mark
General method for determination of chloride content in inorganic chemical products Mercury titration method GB/T3051
GB/T5274 Preparation of mixed gas for gas analysis calibration Weighing method GB/T5832.1 Determination of trace moisture in gas Electrolytic method GB7144 Color marking of gas cylinders
3 Technical requirements
3.1 Quality indicators
The quality of silane shall meet the requirements of the following table. The requirements for heavy metals and particles in silane shall be agreed upon by the supplier and the user. Item
Purity: 102
Carbon dioxide and carbon dioxide (CO+CO,) 10-6Total chloride (including ionizable chlorides such as chlorosilane and HCI) 106Hydrocarbon (C,C,), 10-6
Hydrogen (H2). 10 6
Nitrogen (N2), 10 6
Carbon dioxide (0.), 10
Water (H0), 10 6
Approved by the State Administration of Technical Supervision on December 20, 1995 600
Implemented on August 1, 1996
GB/T15909—1995
Note: ①The purity and impurity content in the table are expressed in molar fractions, mol/mol. ②The nitrogen content is not specified for polysilicon or silicon dioxide. 3.2 Electrical performance specifications
Resistivity should be greater than 100α2·cm (N type), and the resistivity determination method shall be agreed upon by the supplier and the user. 4 Inspection method
4.1 Purity
The purity of silane is expressed in mole fraction and calculated according to formula (1). For polysilicon or silicon dioxide applications, X is not included. (Nitrogen content) X = 100 -(X + X,+ X+ X,+ Xs+ X。+X,)× 10-4Where: X—silane purity (molar fraction), 10-2; Xr
Carbon monoxide and carbon dioxide (CO+CO2) content (molar fraction), 10-; X2——Total chloride content (molar fraction), 10-6; X,—Hydrogen (C,～C.) content (molar fraction), 10\, X,—Hydrogen (H,) content (molar fraction), 10-; X,—Nitrogen (N,) content (molar fraction), 10-6; X. Oxygen (O,) content (molar fraction), 10-°X, — Water (H,O) content (molar fraction), 10-6. 4.2 Determination of carbon monoxide and carbon dioxide content 4.2.1 Instruments and methods
· (1)
A gas chromatograph with a thermal conductivity detector or a nitrogen ionization detector, or a chromatograph-mass spectrometer can be used to determine carbon monoxide and carbon dioxide in silane.
Method detection limit (molar fraction): 1×10-. 4.2.2 Operating conditions
Chromatographic column: a stainless steel column with a length of about 2.4m and an inner diameter of about 4mm, or other equivalent chromatographic columns. Carrier gas: high-purity ammonia, flow rate of about 30mL/min. Injection volume: 3~5mL.
Detector temperature: 250℃.
Programmed temperature rise curve of chromatographic column:
Initial temperature: 110℃, holding time: 4.50min; Programmed temperature rise rate: 5℃/min,
Final temperature: 160℃, holding time: 6.00min. 4.2.3 Standard sample: Nitrogen as base gas, containing carbon monoxide and carbon dioxide (molar fraction) of 1×10-6~5×10-6 respectively, prepared according to GB/T5274.
4.2.4 Operation steps
4.2.4.1 Use the gas sampling valve to inject the silane sample into the chromatographic column, measure and record its retention time and peak area (or peak height). Repeat the injection twice, and the relative deviation of the two parallel determinations should not be greater than 5%, and take the average value. The elution order is carbon monoxide, carbon dioxide, and then backflush silane.
4.2.4.2 Inject the standard sample in the same way as the sample, and record the retention time and peak area (or peak height). Repeat the injection twice, and the relative deviation of the two parallel determinations should not be greater than 5%, and the average value is taken. 4.2.5 Calculation of results
The content of carbon oxide and carbon dioxide in silane is calculated according to formula 2): X = X.
GB/T15909—1995
Wherein: X:——the content of the measured component in the sample (molar fraction), 10-6; X—-the content of the measured component in the standard sample (molar fraction), 10-6; H (A)--the peak height (peak area) of the measured component in the sample gas, mm (mm2); H (A.)--the peak height (peak area) of the measured component in the standard sample, mm (mm2). 4.3 Determination of total chloride
4.3.1 Method
The total chloride in the sample is determined by titrating the silane hydrolyzate. The detection limit of this method (mole fraction): 0.5×10-6. 4.3.2 Sampling device
The sampling device is shown in Figure 1. Silane is prone to spontaneous combustion, so the sampling device must be sealed and thoroughly purged with nitrogen before injecting silane. Figure 1 Total chloride determination device
1-magnetic stirrer; 2-water bath; 3-gas outlet; 4-conical flask (2000mL) 5-washing bottle (125mL): 6-flow meter; 7-pressure regulator: 8-silane gas bottle; 9-high-purity nitrogen bottle 4.3.3 Instruments and materials
Micro titration, the graduation value is 0.01mL or 0.02mL. Other conventional laboratory instruments and materials, such as triangular flask (250mL), burette rack, various clamps, brackets, rubber tubes, rubber stoppers, etc. 4.3.4 Reagents and solutions
Potassium hydroxide (GB/T2306): 15×10~2 solution (15g KOH dissolved in 100mL deionized water). Mercuric nitrate, 0.001~0.005mol/L standard solution, prepared and calibrated according to GB/T3051. Sodium chloride (GB/T1253), 0.001~0.005mol/L standard solution, prepared according to GB/T3051. Indicator solution, dissolve 5g diphenylmethane and 0.5g bromophenol blue in 750mL ethanol, then add 250mL deionized water to prepare the indicator solution.
Nitric acid (GB/T 337), 0.2mol/L solution. 4.3.5 Operating steps
4.3.5.1 Inject 1700mL 15×10~2KOH solution into the conical flask (4). 4.3.5.2 Inject 75 mL of deionized water into the gas washing bottle (5). 4.3.5.3 Connect the various parts according to the sampling device diagram. 4.3.5.4 Purge the entire system with high-purity nitrogen at a gentle flow rate for about 30 minutes to completely blow away the air in the device. 4.3.5.5 While maintaining medium-speed stirring, pass the calculated amount of silane (SiH) gas (according to Formula 3) at a flow rate not higher than 250 mL/min. Stop passing silane. Purge the system with nitrogen again for about 30 minutes to completely blow away and absorb the silane in the device. 4.3.5.6 Take out the gas washing bottle, transfer the solution in the bottle quantitatively to a 250 mL conical flask, and wash it three times with 25 mL of deionized water. 4.3.5.7 Add a few drops of indicator solution and add 0.2 mol/L HNO: solution in a linear drop shape until the color of the solution just changes from purple to yellow.
4.3.5.8 Titrate with standard solution of mercuric nitrate. GB/T 15909—1995
4.3.5.9 Titrate 150 mL of deionized water with standard solution of mercuric nitrate as blank test. 4.3.6 Result processing
The total amount of chloride is calculated according to formula (3):
X = V; = 0XX(273: 16 + 2 × 22. 4 × 101 000 × V3 × 273.16
Wherein: X-
Total chloride content in silane (molar fraction), 10-6; V-bzxZ.net
-Amount of mercuric nitrate standard solution consumed in blank titration, mL; V2--Amount of mercuric nitrate standard solution consumed in sample solution titration, mL; V:-Silane sample volume, L;
-Concentration of mercuric nitrate standard solution, mol/L; c
Room temperature, ℃.
Take the average value of two parallel determinations as the determination result, and its relative deviation should not be greater than 5%. 4.4 Determination of hydrocarbons (C~C.)
4.4.1 Instrument and method
The hydrocarbons (methane, ethane and propane) in silane are determined by gas chromatograph with thermal conductivity detector. The detection limit of this method (mole fraction): 10×10-6. 4.4.2 Determination conditions
4.4.2.1 Determination of ethane and propane
Chromatographic column: stainless steel column with PorapakS, about 3m long and about 4mm inner diameter, or other equivalent chromatographic columns. Carrier gas: high-purity hydrogen, flow rate of about 30mL/min. Injection volume: 10mL.
Detector temperature: 40℃.
Chromatographic column temperature: 40℃.
4.4.2.2 Determination of methane
Chromatographic column: stainless steel column with PorapakS, about 3m long and about 4mm inner diameter and stainless steel column with 5A molecular sieve, about 3m long and about 4mm inner diameter. Or other equivalent chromatographic columns. Carrier gas: high-purity hydrogen, flow rate of about 30mL/min. Injection volume: 10mL.
Detector temperature: 70℃.
Column temperature: 40℃.
4.4.3 Standard sample: Prepared according to GB/T5274, with high-purity hydrogen as the base gas, in which the content (molar fraction) of methane, ethane and propane is 1×10-6~5×10-6 respectively.
4.4.4 Operation steps
4.4.4.1 Use the gas sampling valve to inject the standard sample into the chromatographic column. Repeat the injection twice, measure the peak height (or peak area) of its components, and record its retention time. The relative deviation of two parallel determinations should not be greater than 5%, and the average value is taken. 4.4.4.2 Inject the silane sample to be tested in the same way as 4.4.4.1. The relative deviation of two parallel determinations should not be greater than 5%, and the average value is taken.
4.4.5 Result calculation
The hydrocarbon (C1,～C1,) impurity content in silane is calculated according to formula (2). 4.5 Determination of hydrogen content
4.5.1 Instrument and method
GB/T15909-1995
The hydrogen content in silane was determined by gas chromatograph with thermal conductivity detector. The detection limit of this method (molar fraction): 15×10-6.4.5.2 Operating conditions
Chromatographic column: stainless steel column with 5A molecular sieve, about 2.4m long and about 4mm inner diameter, or other equivalent chromatographic columns. Carrier gas: high-purity fluorine, flow rate of about 30mL/mol. Injection volume is about 1mL.
Detector temperature: 40°C.
Chromatographic column temperature: 40℃.
4.5.3 Standard sample: Prepared according to GB/T5274, with high-purity fluorine as the base gas, the hydrogen content in the prepared standard mixed gas is similar to the hydrogen content in the sample.
4.5.4 Operation steps
4.5.4.1 Use a gas sample to inject the hydrogen standard into the chromatographic column. Record the retention time of the component and determine the peak height (or peak area) of the component. The relative deviation of two parallel determinations should not be greater than 5%, and the average value is taken. 4.5.4.2 Inject the silane sample to be tested in the same way as 4.5.4.1. The relative deviation of two parallel determinations should not be greater than 5%, and the average value is taken.
4.5.5 Result calculation
The hydrogen impurity content in silane is calculated according to formula (2). 4.6 Determination of nitrogen and oxygen content
4.6.1 Instrument and method
Use a chromatograph with a thermal conductivity detector or an ammonia ionization detector, or a chromatograph-mass spectrometer to determine oxygen and nitrogen in silane. Oxygen analysis is carried out at -78°C to effectively separate oxygen and argon. Method detection limit (molar fraction): 1×10-°. 4.6.2 Operating conditions
Chromatographic column: a stainless steel column with PorapakS, about 3m long and about 4mm inner diameter, followed by a stainless steel column with 5A molecular sieve, about 3m long and about 4mm inner diameter, or other equivalent chromatographic columns, carrier gas: high-purity hydrogen (or high-purity nitrogen), flow rate of about 30mL/min. Injection volume: 10mL.
Detector temperature: 125℃.
Column temperature: 65℃ for nitrogen content determination, -78℃ for oxygen content determination. 4.6.3 Standard sample: prepared according to GB/T5274, with hydrogen as the base gas, in which the contents (molar fraction) of oxygen and nitrogen are 1×10-6～5×10~6 respectively. 4.6.4 Operating steps
4.6.4.1 Use a six-way valve to inject the standard sample into the chromatographic column. Repeat the injection twice and record the retention time and peak height (or peak area) of each component. The relative deviation of two parallel determinations shall not exceed 5%, and the average value shall be taken. 4.6.4.2 Inject the silane sample in the same way as in 4.6.4.1. The relative deviation of two parallel determinations shall not exceed 5%, and the average value shall be taken. 4.6.5 Result calculation
The oxygen and nitrogen contents in silane shall be calculated according to formula (2). 4.7 Determination of water content
Perform according to GB/T5832.1. Before introducing the silane sample gas, the air in the instrument system shall be completely blown out with dry nitrogen. 5 Inspection rules
5.1 Silane shall be inspected by the quality supervision and inspection department of the manufacturer, and its product quality shall be guaranteed to meet the requirements of this standard. 5.2 The quality of silane products shall be inspected bottle by bottle and item by item. 5.3 When one of the indicators in the inspection result does not meet the requirements of this standard, the bottle of product shall be unqualified. 601
GB/T 15909—1995
5.4 Users have the right to conduct acceptance in accordance with the provisions of this standard. 5.5 When the user and the manufacturer have a disagreement on the product quality, both parties shall jointly inspect or apply for arbitration. 6 Packaging, marking, transportation, storage and safety requirements Silane can spontaneously combust in the air, is toxic, colorless, and has a slightly disgusting odor. The maximum allowable concentration in the air is 5×10-6. During filling, storage, transportation, sampling and use, the following regulations shall be strictly observed: 6.1 The packaging, marking, transportation and storage of silane shall comply with the relevant provisions of the "Regulations on Safety Supervision of Gas Cylinders" and the "Regulations on the Transportation of Dangerous Goods". 6.2 The gas cylinders filled with silane can be carbon steel, stainless steel or aluminum alloy cylinders, which meet the requirements of the corresponding gas cylinder standards. The gas cylinders should be strictly cleaned before filling.
6.3 The gas cylinder valve is made of stainless steel and is a reverse screw diaphragm gas cylinder valve. It is prohibited to use QF-2, PX-32 and QF-30A valves as silane gas cylinder valves.
6.4 The maximum filling pressure of silane should be less than or equal to 8.5MPa. 6.5 The filling amount of silane is measured by direct weighing method. 6.6 The color of silane cylinders shall comply with GB7144. 6.7 The warehouse where silane cylinders are stored should be away from heat sources and fire sources and transported away from residential areas. The floor, roof and surrounding walls of the warehouse have good flame retardant effect and are equipped with good ventilation facilities. The ambient temperature for storing silane should not be higher than 40℃. 6.8 Silane has strong reducing properties. It is strictly forbidden to store strong oxidizing gases such as oxygen and chlorine in the warehouse. When storing, silane should be isolated from other dangerous gases and corrosive substances.
6.9 The warehouse should be equipped with good fire extinguishing equipment. Halogen fire extinguishing agents shall not be used. 6.10 During transportation, gas cylinders should have sunshade and rain protection facilities to avoid exposure to the sun and heavy rain. 6.11 Gas cylinders must be capped during transportation, and the valve mouths of the bottles should also be equipped with sealing caps. 6.12 It is strictly forbidden to touch or hit the valve of the gas cylinder during transportation and handling. It is strictly forbidden to collide with each other or be impacted by other rigid materials. 6.13 Before filling silane, make sure that the valve of the gas cylinder is intact and leak-free. 6.14 Before use or sampling, make sure that the markings of silane and carrier gas containers (gas name, pressure, concentration, etc.) are correct. Do not use unmarked or unclearly marked gases.
6.15 Silane containers are prohibited from being used for non-silane gas operations and must not be mixed with other gases, especially oxidizing gases. 6.16 The working system and sampling container should be carefully checked for airtightness before work, and they should be cleaned repeatedly using a combination of high-purity nitrogen, or high-purity hydrogen, nitrogen, argon replacement and vacuum hydraulic pump (or extrusion exhaust). 6.17 Silane products leaving the factory should have a quality certificate, the contents of which include: a. Product name;
Manufacturer name;
Analysis results of major impurities in silane; Cylinder number;
Filling quantity (kg), pressure, concentration, diluent gas, production date;
Standard code and number, etc.
Additional instructions:
GB/T15909—1995
This standard is proposed by the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Southwest Research Institute of Chemical Industry of the Ministry of Chemical Industry. This standard was drafted by the Southwest Research Institute of Chemical Industry of the Ministry of Chemical Industry, the Department of Materials of Zhejiang University, and the Institute of Semiconductors of the Chinese Academy of Sciences. The main drafters of this standard are Yu Jingsong and Yu Zhongyu. This standard is equivalent to SEMI-93 "Epitaxial, polysilicon and/or silicon dioxide grade silane in cylinders". 606
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