CN112630292A - Method for testing phosphorus content of silicon-based product with oxide film - Google Patents
Method for testing phosphorus content of silicon-based product with oxide film Download PDFInfo
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- CN112630292A CN112630292A CN202011471226.1A CN202011471226A CN112630292A CN 112630292 A CN112630292 A CN 112630292A CN 202011471226 A CN202011471226 A CN 202011471226A CN 112630292 A CN112630292 A CN 112630292A
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 129
- 239000011574 phosphorus Substances 0.000 title claims abstract description 129
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000012360 testing method Methods 0.000 title claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 23
- 239000010703 silicon Substances 0.000 title claims abstract description 23
- 238000004857 zone melting Methods 0.000 claims abstract description 31
- 150000002500 ions Chemical group 0.000 claims description 38
- -1 phosphorus ion Chemical class 0.000 claims description 37
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 25
- 239000010408 film Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 7
- 238000011109 contamination Methods 0.000 description 6
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Toxicology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention provides a method for testing the phosphorus content of an oxide film silicon-based product, which comprises the steps of detecting the ionic strength of a primary standard sample by using a secondary mass spectrometer, calculating an RSF value, calculating the phosphorus element concentration of a secondary standard sample by using the RSF value, comparing the phosphorus element concentration with the phosphorus element concentration of a known secondary standard sample, calculating the phosphorus element concentrations of a sample wafer to be tested and a zone-melting sample wafer by using the RSF value in a standard range, detecting the ionic strengths of the zone-melting sample wafer and the sample wafer to be tested, calculating the phosphorus element concentration, and subtracting the phosphorus element concentration of the zone-melting sample wafer from the temporary phosphorus element concentration of the sample wafer to be tested to obtain the phosphorus element concentration of the final sample wafer to be tested. The invention has the advantages that the problem that the whole product is invalid due to overhigh phosphorus content is effectively solved; the element concentration tested by the existing detection technology has uncertainty, and the problems that the influence of the background environment on the phosphorus element content cannot be removed and whether the RSF value is correct or not cannot be determined are solved.
Description
Technical Field
The invention belongs to the field of semiconductor materials, and particularly relates to a method for testing the phosphorus content of an oxide film silicon-based product.
Background
An integrated circuit is formed by integrating various circuit devices on the surface of a semiconductor, has the characteristics of lightness, thinness, shortness and smallness, and becomes the heart of modern electronic products. Nowadays, the integrated circuit manufacturing process is more and more refined, and impurity contamination becomes one of the main causes of abnormal failure of the integrated circuit product. Some impurity contamination, such as surface contamination of thin films, interface contamination, and contamination of semiconductor doping, cannot be observed and tested by conventional optical analysis means or electron microscopy, and must be understood by microscopic elemental testing. The content of phosphorus plays an important role in the silicon base of the oxide film, and the over-high content of phosphorus can cause the failure of the whole product.
As semiconductor devices and integrated circuits are scaled down, SIMS (secondary ion mass spectrometry) is used more and more frequently in the semiconductor industry, for example, for doping concentration of products and structural analysis thereof; impurity contamination analysis, failure analysis, and the like. For silicon-based products with different structures, the process and equipment are complex in the growth process, factors influencing doping are many, and quantitative analysis of phosphorus in silicon is a typical detection content in the field of semiconductors and a basic research subject in secondary ion mass spectrometry. In the 90 s, the international organization for standardization selected it as the first international standard to be established in the SIMS field. Referring to the SIMS quantitative research situation carried out by related laboratories at home and abroad in colleges and universities in recent ten years, the element deep research of silicon-based materials is concentrated in the field of semiconductors, the introduction of a phosphorus element detection method is lacked, and few documents are reported for the test of products containing non-conductive films.
In the prior art, when a secondary ion mass spectrometer is used for testing, a primary standard sample is generally tested, an RSF value is calculated according to the tested ion concentration, and the element concentration of a sample wafer to be tested is calculated by using the RSF value.
Disclosure of Invention
The invention aims to provide a method for testing the phosphorus content of an oxide film silicon-based product, which effectively solves the problem that the whole product is invalid due to overhigh phosphorus content; the element concentration tested by the existing detection technology has uncertainty, and the problems that the influence of the background environment on the phosphorus element content cannot be removed and whether the RSF value is correct or not cannot be determined cannot be solved.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for testing the phosphorus content of an oxide film silicon-based product comprises the following steps: preparing a first-stage standard sample, a second-stage standard sample, a zone-melting sample wafer and a sample wafer to be detected, wherein the DOSE value and the RP value of the first-stage standard sample are known, the concentration of phosphorus element of the second-stage standard sample is known, the first-stage standard sample, the second-stage standard sample, the zone-melting sample wafer and the sample wafer to be detected are placed on a sample rack, and the sample rack is placed into a sample chamber; adjusting a secondary ion mass spectrometer to an electron gun mode, and measuring the phosphorus ion intensity of the primary standard sample; the secondary ion mass spectrometer calculates an RSF value according to the phosphorus ion intensity, the DOSE value and the RP value of the primary standard sample; measuring the phosphorus ion intensity of the secondary standard sample by using the secondary ion mass spectrometer, and calculating the phosphorus element concentration in the secondary standard sample according to the RSF value and the phosphorus ion intensity of the secondary standard sample; comparing the concentration of the phosphorus element in the secondary standard sample with the known concentration of the phosphorus element in the secondary standard sample, judging whether the concentration of the phosphorus element in the secondary standard sample is in a standard range, and if so, calculating the concentrations of the phosphorus element in the sample wafer to be detected and the zone melting sample wafer by using the RSF value; if not, recalculating the RSF value; measuring the phosphorus ion intensity of the zone melting sample by using the secondary ion mass spectrometer, and calculating the phosphorus element concentration of the zone melting sample according to the RSF value and the phosphorus ion intensity of the zone melting sample; measuring the phosphorus ion intensity of the sample to be measured by using the secondary ion mass spectrometer, and calculating the temporary phosphorus element concentration of the sample to be measured according to the RSF value and the phosphorus ion intensity of the sample to be measured; and subtracting the phosphorus element concentration of the zone melting sample wafer from the temporary phosphorus element concentration of the sample wafer to be detected to obtain the phosphorus element concentration of the sample wafer to be detected.
Preferably, the method for testing the phosphorus ion strength of the primary standard sample comprises the following steps: adjusting parameters of the secondary ion mass spectrometer, bombarding the surface of the primary standard sample by using a primary ion source to excite secondary ions of the primary standard sample, screening the nuclear-to-mass ratio of the secondary ions of the primary standard sample, and selecting a phosphorus ion mass peak of the primary standard sample to obtain the phosphorus ion intensity of the primary standard sample.
Preferably, the mass peak of the phosphorus ion of the primary standard is selected as a small peak which deviates from the left of the large peak by 0.0075.
Preferably, the parameters are primary current 200nA, primary voltage 15KV, secondary voltage 5KV, incident angle 23.3, maximum area 150, mass resolution 4500, entrance slit 16, exit slit 4500, CA/FA 400.
Preferably, the primary ion source is a cesium source.
Preferably, after the secondary ion mass spectrometer is adjusted to the electron gun mode, the optical path of the secondary ion mass spectrometer is adjusted.
Preferably, the formula for calculating the concentration of phosphorus element in the secondary standard sample according to the RSF value calculated from the primary standard sample is:
wherein I is the ionic strength and C is the concentration.
Preferably, the calculated standard range of the phosphorus element concentration of the secondary standard sample is 95% -105% of the known phosphorus element concentration of the secondary standard sample.
Preferably, the first-level standard sample, the second-level standard sample, the zone-melting sample sheet and the sample sheet to be measured are cut into small pieces and placed on the sample rack.
The phosphorus element in the oxide film is detected, so that whether the concentration of the phosphorus element in the silicon-based product of the oxide film exceeds the standard can be judged, and the problem that the product is invalid due to high content of the phosphorus element is solved; due to the design of the secondary standard sample, the problem that the concentration of the detected phosphorus element is uncertain and whether the RSF value is accurate or not can not be confirmed is solved; due to the design of the zone-melting sample wafer, the problem that the background environment influences the content of the phosphorus element of the silicon-based product of the oxide film is solved; due to the adoption of the method for testing the phosphorus content of the silicon-based product of the oxide film, the productivity is improved on the basis of ensuring the accuracy of data, and the application of the secondary ion mass spectrometer in production is fully exerted.
Detailed Description
The invention is further illustrated by the following examples:
in the description of the embodiments of the present invention, it is to be understood that the terms "surface" and the like are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be taken as limiting the present invention.
In one embodiment of the invention, a method for testing the oxygen and carbon content of heavily doped silicon wafers comprises the following steps:
s1: sample preparation: preparing a first-stage standard sample, a second-stage standard sample, a zone-melting sample piece and a sample piece to be detected, putting an operator on gloves and a mask to prevent dust pollution, cutting the first-stage standard sample, the second-stage standard sample, the zone-melting sample piece and the sample piece to be detected into small pieces, putting the small pieces on a sample frame, and putting the sample frame into a sample chamber again. Wherein the DOSE value (area concentration) of phosphorus in the first-order standard sample is 1.13e13atom/cm2The RP value (the highest depth of the ion implantation standard) is 230 nm; the concentration of phosphorus element in the second grade standard sample is 1.0e15atom/cm3。
S2: preparing an instrument: preparing a secondary ion mass spectrometer, adjusting to an electron gun mode, adjusting a light path of the secondary ion mass spectrometer in the electron gun mode to the optimal test light, and starting to test. The required parameters, primary current 200nA, primary voltage 15KV, secondary voltage 5KV, incidence angle 23.3, maximum area 150, mass resolution 4500, entrance slit 16, exit slit 4500, CA/FA400 are input, and part of the parameters have no unit because no unit is selected on the instrument, and the unit is automatically generated. The method comprises the steps of bombarding the surface of a primary standard sample by using a primary ion source to excite secondary ions on the surface of the primary standard sample, wherein the primary ion source adopts a cesium source, different secondary ions are divided into different ion beams through the turning of a magnetic field, the ion beams to be tested are aligned to a slit according to the strength and the direction of the magnetic field and pass through a magnetic field area, other particles are screened out, a mass peak curve is obtained, and because the mass number of phosphorus elements is 31 and is influenced by 30si + H in a silicon substrate, the mass peak of phosphorus ions of the primary standard sample is selected to be a small peak which deviates from the left side of a large peak by 0.0075, and the phosphorus ion intensity of the primary standard sample is obtained.
S3: RSF value (relative sensitivity factor) was calculated: and the secondary ion mass spectrometer measures the phosphorus ion strength of the primary standard sample, inputs the DOSE value and the RP value of the primary standard sample, and automatically calculates the RSF value.
S4: and (3) calculating the phosphorus element concentration of the secondary standard sample: detecting the phosphorus ion intensity of the secondary standard sample by using a secondary ion mass spectrometer by using the method same as the method for testing the phosphorus ion intensity of the primary standard sample, and calculating the phosphorus element concentration in the secondary standard sample according to the RSF value and the phosphorus ion intensity of the secondary standard sample; the calculation formula is as follows: #
And when the concentration of the phosphorus element is calculated, substituting the I into the phosphorus ion strength to obtain the concentration of the phosphorus element.
S5: and (3) concentration comparison: calculating the concentration of the phosphorus element in the secondary standard sample, comparing the concentration with the known concentration of the phosphorus element in the secondary standard sample, and judging whether the concentration of the phosphorus element in the secondary standard sample is in a standard range, wherein the standard range is 95% -105% of the concentration of the phosphorus element in the known secondary standard sample, and the standard range of the concentration of the phosphorus element is 0.95e15 atom/cm3~10.5e15 atom/cm3。
If the phosphorus concentration of the sample wafer to be detected and the zone melting sample wafer is in the standard range, calculating the phosphorus concentration of the sample wafer to be detected and the zone melting sample wafer by using the RSF value; if not, the RSF value is recalculated.
In this embodiment, the calculated RSF value is used to calculate the phosphorus concentration of the secondary standard sample to be 0.98e15 atom/cm3Within the standard range of phosphorus element, the RSF value can be used to calculateAnd measuring the phosphorus element concentration of the sample wafer and the zone melting sample wafer.
S6: calculating the phosphorus element concentration of the zone melting sample wafer: and detecting the phosphorus ion intensity of the zone melting sample by using a secondary ion mass spectrometer by using the method same as the method for detecting the phosphorus ion intensity of the primary standard sample, and calculating the phosphorus element concentration of the zone melting sample according to the RSF value and the phosphorus ion intensity of the zone melting sample.
S7: calculating the concentration of the temporary phosphorus element of the sample wafer to be detected: and detecting the phosphorus ion intensity of the sample to be detected by using a secondary ion mass spectrometer by using the method same as the method for detecting the phosphorus ion intensity of the primary standard sample, and calculating the temporary phosphorus element concentration of the sample to be detected according to the RSF value and the phosphorus ion intensity of the sample to be detected.
S8: and finally, the phosphorus element concentration of the sample wafer to be detected: and subtracting the phosphorus element concentration of the zone melting sample wafer from the temporary phosphorus element concentration of the sample wafer to be detected to obtain the final phosphorus element concentration of the sample wafer to be detected.
After the concentration of the phosphorus element of the sample wafer to be detected is obtained, judging whether the concentration exceeds the standard, if so, determining that the product is not qualified; if the standard does not exceed the standard, the product is qualified. The detected phosphorus concentration is used for judging the product, so that unqualified products can be greatly reduced and the use quality of a user is ensured.
The accuracy of the final value can be ensured again by judging whether the RSF value is correct by using the secondary standard sample, the influence of the background environment on the sample to be detected can be removed by detecting the concentration of the zone melting sample, the productivity is improved on the basis of ensuring the newness and the success of data, and the application of the secondary ion mass spectrometer in production is fully exerted.
While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (9)
1. A method for testing the phosphorus content of an oxide film silicon-based product comprises the following steps:
preparing a first-stage standard sample, a second-stage standard sample, a zone-melting sample wafer and a sample wafer to be detected, wherein the DOSE value and the RP value of the first-stage standard sample are known, the concentration of phosphorus element of the second-stage standard sample is known, the first-stage standard sample, the second-stage standard sample, the zone-melting sample wafer and the sample wafer to be detected are placed on a sample frame, and the sample frame is placed into a sample chamber;
adjusting a secondary ion mass spectrometer to an electron gun mode, and measuring the phosphorus ion intensity of the primary standard sample;
the secondary ion mass spectrometer calculates an RSF value according to the phosphorus ion strength, the DOSE value and the RP value of the primary standard sample;
measuring the phosphorus ion intensity of the secondary standard sample by using the secondary ion mass spectrometer, and calculating the phosphorus element concentration in the secondary standard sample according to the RSF value and the phosphorus ion intensity of the secondary standard sample;
comparing the concentration of the phosphorus element in the secondary standard sample with the known concentration of the phosphorus element in the secondary standard sample, judging whether the concentration of the phosphorus element in the secondary standard sample is in a standard range, and if so, calculating the concentrations of the phosphorus element in the sample wafer to be detected and the zone-melting sample wafer by using the RSF value; if not, recalculating the RSF value;
measuring the phosphorus ion intensity of the zone melting sample by using the secondary ion mass spectrometer, and calculating the phosphorus element concentration of the zone melting sample according to the RSF value and the phosphorus ion intensity of the zone melting sample;
measuring the phosphorus ion intensity of the sample wafer to be measured by using the secondary ion mass spectrometer, and calculating the temporary phosphorus element concentration of the sample wafer to be measured according to the RSF value and the phosphorus ion intensity of the sample wafer to be measured;
and subtracting the phosphorus element concentration of the zone melting sample wafer from the temporary phosphorus element concentration of the sample wafer to be detected to obtain the phosphorus element concentration of the sample wafer to be detected.
2. The method for testing the phosphorus content of an oxide film silicon-based product according to claim 1, wherein the method comprises the following steps: the method for testing the phosphorus ion strength of the primary standard sample comprises the following steps: adjusting parameters of the secondary ion mass spectrometer, bombarding the surface of the primary standard sample by using a primary ion source to excite secondary ions of the primary standard sample, screening the nuclear-to-mass ratio of the secondary ions of the primary standard sample, and selecting a phosphorus ion mass peak of the primary standard sample to obtain the phosphorus ion intensity of the primary standard sample.
3. The method for testing the phosphorus content of the oxide film silicon-based product according to claim 2, wherein the method comprises the following steps: and selecting the phosphorus ion mass peak of the primary standard sample as a small peak which deviates from the left side of the large peak by 0.0075.
4. The method for testing the phosphorus content of the oxide film silicon-based product according to claim 2, wherein the method comprises the following steps: the parameters are primary current 200nA, primary voltage 15KV, secondary voltage 5KV, incidence angle 23.3, maximum area 150, mass resolution 4500, entrance slit 16, exit slit 4500, and CA/FA 400.
5. The method for testing the phosphorus content of the oxide film silicon-based product according to claim 2, wherein the method comprises the following steps: the primary ion source is a cesium source.
6. The method for testing the phosphorus content of an oxide film silicon-based product according to claim 1, wherein the method comprises the following steps: and adjusting the secondary ion mass spectrometer to an electron gun mode, and then adjusting the light path of the secondary ion mass spectrometer.
7. The method for testing the phosphorus content of an oxide film silicon-based product according to claim 1, wherein the method comprises the following steps: and calculating the phosphorus concentration in the secondary standard sample according to the RSF value calculated by the primary standard sample by the following formula:
wherein I is the ionic strength and C is the concentration.
8. The method for testing the phosphorus content of an oxide film silicon-based product according to any one of claims 1 to 7, wherein: in the step S5, the calculated standard range of the phosphorus element concentration of the secondary standard sample is 95% to 105% of the known phosphorus element concentration of the secondary standard sample.
9. The method for testing the phosphorus content of an oxide film silicon-based product according to claim 1, wherein the method comprises the following steps: and cutting the first-stage standard sample, the second-stage standard sample, the zone-melting sample wafer and the sample wafer to be detected into small pieces and placing the small pieces on the sample rack.
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CA2211135A1 (en) * | 1996-07-25 | 1998-01-25 | He Holdings, Inc. | Volatile organic compound sensors |
JP2002181746A (en) * | 2000-12-18 | 2002-06-26 | Matsushita Electric Ind Co Ltd | Quantitative analysis method and auxiliary sample and standard sample thereof |
GB0329554D0 (en) * | 2003-12-22 | 2004-01-28 | Micromass Ltd | Mass spectrometer |
JP2004157089A (en) * | 2002-11-08 | 2004-06-03 | Foundation For Promotion Of Material Science & Technology Of Japan | Concentration profile calibration method and concentration profile analysis processing apparatus |
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- 2020-12-15 CN CN202011471226.1A patent/CN112630292A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2211135A1 (en) * | 1996-07-25 | 1998-01-25 | He Holdings, Inc. | Volatile organic compound sensors |
JP2002181746A (en) * | 2000-12-18 | 2002-06-26 | Matsushita Electric Ind Co Ltd | Quantitative analysis method and auxiliary sample and standard sample thereof |
JP2004157089A (en) * | 2002-11-08 | 2004-06-03 | Foundation For Promotion Of Material Science & Technology Of Japan | Concentration profile calibration method and concentration profile analysis processing apparatus |
GB0329554D0 (en) * | 2003-12-22 | 2004-01-28 | Micromass Ltd | Mass spectrometer |
Non-Patent Citations (2)
Title |
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国金属学会主编: "《金属手册 第9版 第10卷 材料特征性能及测定》", 31 August 1993 * |
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Application publication date: 20210409 |