阅读说明：本技术 一种利用射频辉光放电光谱仪检测钨中氘含量分布的方法 (A method of it is distributed using deuterium content in radio frequency glow discharge spectrometer detection tungsten ) 是由 王鹏 乔丽 柴利强 于 2019-09-12 设计创作，主要内容包括：本发明涉及一种利用射频辉光放电光谱仪检测钨中氘含量分布的方法,是先通过物理气相沉积方法制备含氘金属薄膜材料作为标准样品,再采用卢瑟福背散射光谱与热脱附质谱法分别检测标准样品中金属与氘的含量,然后在射频辉光放电光谱仪上使用标准样品将检测氘的电信号曲线转换为氘含量信息,同时采用白光干涉三维轮廓测试仪对标准样品进行射频辉光放电光谱溅射深度与测试时长关系的标定用以确定射频辉光放电光谱仪检测氘在样品中的深度信息；最后使用射频辉光放电光谱法检测经过氘等离子体辐照的钨块进行该方法的验证。该方法特别适用于为托卡马克装置用面对等离子体部件提供低含量氢同位素测试。(The present invention relates to a kind of methods using deuterium content distribution in radio frequency glow discharge spectrometer detection tungsten, it is to first pass through physical gas-phase deposite method preparation metallic film material containing deuterium as standard sample, the content with deuterium is belonged to using Rutherford backscattering spectrum and thermal desorption mass spectrography difference examination criteria Gold Samples again, it then the use of the electric signal Curve transform that standard sample will test deuterium is deuterium content information on radio frequency glow discharge spectrometer, the calibration of radio frequency glow discharge spectrum sputter depth and length of testing speech relationship is carried out to determine the depth information of radio frequency glow discharge spectrometer detection deuterium in the sample to standard sample using white light interference three-D profile tester simultaneously；Finally the tungsten block using radio frequency glow discharge spectroscopic methodology detection by deuterium plasma irradiation carries out the verifying of this method.This method is especially suitable for providing the test of low content hydrogen isotope in face of plasma source components for tokamak device.)

1. utilizing the method for deuterium content distribution in radio frequency glow discharge spectrometer detection tungsten, it is characterised in that: first pass through physics gas Phase sedimentation one layer of W film containing deuterium of Direct precipitation in single crystal silicon substrate；Rutherford backscattering spectral detection film is used again Middle metal atom content, using the total content of deuterium in thermal desorption mass spectrography examination criteria sample；Film sample based on said determination Metal and deuterium content data in product carry out the calibration of deuterium electric signal and deuterium content relationship, so on radio frequency glow discharge spectrometer It analyzes to obtain sputter depth and length of testing speech relationship using white light interference three-D profile tester afterwards, thus to radio frequency glow discharge The depth of spectrometer test standard sample is demarcated, and finally obtains the deuterium concentration of radio frequency glow discharge spectrum test out in sample Distribution curve on depth direction.

2. as described in claim 1 using the method for deuterium content distribution in radio frequency glow discharge spectrometer detection tungsten, feature exists In: the physical gas-phase deposition are as follows: using argon gas and the mixed atmosphere of deuterium as working gas, use business magnetron sputtering etc. Gas ions equipment sputters tungsten target: tungsten target purity is 99.995%, and diameter is 75mm；In deposition process, argon gas flow For 19 ~ 21sccm, deuterium gas flow is 2 ~ 40sccm, and operating air pressure is 6.5 ~ 8.5 × 10^-1Pa, depositing temperature are 120 ~ 160 DEG C, sedimentation time is 10 ~ 65min, and DC power supply sputtering power is 270 ~ 350W；Film thickness is 0.5 ~ 2 μm.

3. as described in claim 1 using the method for deuterium content distribution in radio frequency glow discharge spectrometer detection tungsten, feature exists In: Rutherford backscattering spectral detection carries out on accelerator, uses in test process⁴He²⁺Ion, ion energy be 2 ~ 4MeV；Incidence angle in test process is 0 °, and the angle of emergence is 20 °, and angle of scattering is 160 °, in conjunction with SIMNRA6.05 software to experiment The simulation of data progress elemental constituent and depth.

4. as described in claim 1 using the method for deuterium content distribution in radio frequency glow discharge spectrometer detection tungsten, feature exists In: vacuum tube furnace of the thermal desorption using subsidiary quartz ampoule, model OTF-1200X-S, heating rate are 10 DEG C/min, highest Temperature is 880 ~ 900 DEG C, and the time of thermal desorption deuterium is 90min.

5. as described in claim 1 using the method for deuterium content distribution in radio frequency glow discharge spectrometer detection tungsten, feature exists In: mass spectrography detects the deuterium total content being desorbed out using quadrupole mass spectrometer.

6. as described in claim 1 using the method for deuterium content distribution in radio frequency glow discharge spectrometer detection tungsten, feature exists In: radio frequency glow discharge spectrometer is the instrument of the model GD PROFILER 2 of French Horiba Jobin Yvon company production Device；When test mode of excitation be radio frequency, anode dimension 4mm, vacuum chamber pressure be 400 ~ 800Pa, frequency 3000Hz, Power is 7.5 ~ 15W, and module value is 6.8V, and mutually value is 6.0V.

Technical field

The present invention relates to a kind of detection of Hydrogen in Metals isotope more particularly to a kind of utilization radio frequency glow discharge light The method that spectrometer detects deuterium content distribution in tungsten is mainly used for facing the detection of plasma source components in nuclear fusion stack, belong to In the application field of hydrogen isotope detection field and radio frequency glow discharge spectrometer.

Background technique

In Tokamak nuclear fusion experimental provision, the plasma facing material in face of plasma will be by including hydrogen isotope The bombardment of high throughput and particles at low energies including fuel.Steady-state plasma operation is the key request of next-generation fusion facility One of.The delay of hydrogen isotope may will affect density, the plasma density of plasma boundary particle in plasma facing material And discharging efficiency, so that the safe operation and stable state use to the following fusion facility have significant impact.Therefore, in the first wall In the ANALYSIS ON DEPTH PROFILES of material and existing equipment component, it is necessary to fuel retention characteristics be described in detail, to predict fusion facility Service state.In addition, to plasma facing material carry out reliable ANALYSIS ON DEPTH PROFILES for understand fusion facility plasma with The interaction of plasma facing material is also vital.

Summary of the invention

The method that deuterium content is distributed in tungsten is detected using radio frequency glow discharge spectrometer the object of the present invention is to provide a kind of, Aim to solve the problem that commercial radio frequency glow discharge spectrometry concentration and depth distribution of deuterium element of volume in detection tungsten metal material Quantification and sensitivity problem.

The present invention is to first pass through object using deuterium content location mode in radio frequency glow discharge spectrometer detection tungsten metal material Physical vapor deposition method prepares metallic film material containing deuterium as standard sample, then uses Rutherford backscattering spectrum and thermal desorption Mass spectrography distinguishes the content of examination criteria Gold Samples category and deuterium, and standard sample is then used on radio frequency glow discharge spectrometer The electric signal Curve transform that will test deuterium is deuterium content information, while using white light interference three-D profile tester to standard sample The calibration of radio frequency glow discharge spectrum sputter depth and length of testing speech relationship is carried out to determine the inspection of radio frequency glow discharge spectrometer Survey the depth information of deuterium in the sample；Finally pass through the tungsten block of deuterium plasma irradiation using radio frequency glow discharge spectroscopic methodology detection Carry out the verifying of this method.Specifically includes the following steps:

(1) metallic film material containing deuterium is prepared as standard sample by physical gas-phase deposite method.Film deposition process technique: Using argon gas and the mixed atmosphere of deuterium as working gas, sputter tungsten target using business magnetron sputtering plasma apparatus: tungsten target is pure Degree is 99.995%, diameter 75mm；Argon gas flow is 19 ~ 21sccm, and deuterium gas flow is 2 ~ 40sccm, work Air pressure is 6.5 ~ 8.5 × 10^-1Pa, depositing temperature are 120 ~ 160 DEG C, and sedimentation time is 10 ~ 65min, DC power supply sputtering power It is 270 ~ 350W.

Regulate and control film thickness by changing deposition duration, film thickness is 0.5 ~ 2 μm.

Before Physical Vapor Deposition Films, first with the argon plasma etch single crystal silicon substrate 10min with -500V bias, Remove substrate surface dust and natural oxidizing layer.

(2) using metal atom content in the above-mentioned film of Rutherford backscattering spectral detection.The inspection of Rutherford backscattering spectrum Survey carries out on accelerator, uses in test process⁴He²⁺Ion, ion energy are 2 ~ 4MeV；Incidence angle in test process is 0 °, the angle of emergence is 20 °, and angle of scattering is 160 °, carries out elemental constituent and depth to experimental data in conjunction with SIMNRA6.05 software Simulation.

(3) using the content of deuterium in thermal desorption mass spectrography examination criteria sample.Thermal desorption is using the vacuum for being attached to quartz ampoule Tube furnace, model OTF-1200X-S.Heating rate be 10 DEG C/min, maximum temperature be 880 ~ 900 DEG C, thermal desorption deuterium when Between be 90min.Due to deuterium from desorption temperature in W film about within the scope of 300 DEG C to 800 DEG C, under this parameter deuterium all from contain deuterium It is desorbed out in film sample.

The detection of desorption gas is carried out in entire heating process using mass spectrography, mass spectrography uses quadrupole mass spectrometer, model For Pfeiffer QME220, multiple types desorption gas of the mass number less than 100 can detect.

(4) metal and deuterium content data in the film sample based on said determination, it is enterprising in radio frequency glow discharge spectrometer The calibration of row deuterium electric signal and deuterium content relationship.The commercial radio frequency glow discharge spectrometry is French Horiba Jobin Yvon The instrument of the model GD PROFILER 2 of company's production.Mode of excitation is radio frequency, anode dimension 4mm, vacuum when test Chamber pressure is 400 ~ 800Pa, and frequency 3000Hz, power is 7.5 ~ 15W, and module value is 6.8V, and mutually value is 6.0V.In the survey It tries instrument to carry in the calibration procedure of software, element species and constituent content contained by standard sample is inputted, by standard sample The relationship that element electrical signal detection obtains being converted to deuterium content by deuterium electric signal is (using the radio frequency glow discharge light under above-mentioned parameter Spectrometer tests metallic film containing deuterium, and the sputtering hole corresponding to different durations is left on sample).

(5) it analyzes to obtain sputter depth and length of testing speech relationship using white light interference three-D profile tester, thus to penetrating The depth of frequency glow discharge spectrometry test standard sample is demarcated, and the deuterium that radio frequency glow discharge spectrum test goes out is finally obtained Distribution curve of the concentration on sample depth direction.I.e. using the radio frequency glow discharge spectrometer under above-mentioned parameter to metal containing deuterium Film is tested, and the sputtering hole corresponding to different durations is left on sample, carries out white light interference by cheating to above-mentioned sputtering Three-D profile test, obtains the step scanning curve in sputtering hole, to be sputtered from the three-dimensional contour shape appearance figure of sample Caused different sputtering holes depth after certain time length, i.e., sputtering speed of the radio frequency glow discharge spectrometer to standard sample under the parameter Rate.The radio frequency glow discharge spectrometer that above-mentioned test analysis obtains is input to test software to the sputter rate of standard sample In, the sputtering time of radio frequency glow discharge spectrometer test sample containing deuterium and the relationship of sputter depth are obtained, to obtain radio frequency Distribution curve of the deuterium content that glow discharge optical emission spectrometry tests out on the block sample depth of tungsten containing deuterium direction.

Tungsten block of the method for the present invention using radio frequency glow discharge spectroscopic methodology detection by deuterium plasma irradiation carries out the party The verifying of method, it was demonstrated that the reliability of this method.

The method of the present invention is used especially suitable for tokamak device and provides low content hydrogen isotope in face of plasma source components The practicable techniques and experience of test, and can be extended in the test of elemental gas contained by other materials, it is commercial radio frequency aura Discharging light spectrometer tests distribution of the elemental gas in metal material and provides practicable techniques and experience.

Detailed description of the invention

Fig. 1 is the wolfram element content of different-thickness W film containing deuterium of the present invention.

Fig. 2 is that radio frequency glow discharge spectrometer is tested to obtain tungsten block after deuterium plasma described in the embodiment of the present invention 1 irradiates Curve of the electric signal of middle deuterium about the testing time.

Fig. 3 be radio frequency glow discharge spectrometer test to obtain the atom content of deuterium in tungsten block after deuterium plasma irradiation about The curve of testing time.

Fig. 4 is to obtain the sectioned, three dimensional wheel in the sputtering of W film containing deuterium hole after radio frequency glow discharge spectrometer tests different time Wide scanning curve.

Fig. 5 be radio frequency glow discharge spectrometer test to obtain the atom content of deuterium in tungsten block after deuterium plasma irradiation about The curve of test depth.

Specific embodiment

The radio frequency glow discharge spectroscopic methodology demarcated the present invention is based on metallic film containing deuterium is examined below by specific embodiment Deuterium content location mode in tungsten metal material is surveyed to be described further.

(1) physical gas-phase deposite method prepares the tungsten metallic film containing deuterium.It is set in experiment using Tianwan businessman's industry magnetron sputtering It is standby, have 1 individually controllable magnetic control multitarget sputter source, using DC power supply in single crystal silicon substrate one layer of Direct precipitation containing deuterium Titanium or W film.Multitarget sputter source is the tungsten target that purity is 99.995%, target diameter 75mm.Before depositing coating, bias-is first used The impurity that the argon plasma etch single crystal silicon substrate 10 minutes removal substrate surfaces of 500V adhere to naturally.

Tungsten metallic film physical gas-phase deposition containing deuterium: one layer of W film containing deuterium is deposited in single crystal silicon substrate and is made For standard sample.The working gas of film deposition process is the mixed atmosphere of argon gas and deuterium, and wherein argon flow is 20sccm, Deuterium flow is 10sccm, and depositing temperature is 150 DEG C, and operating air pressure is 7.5 × 10^-1Pa sputters tungsten using 300W DC power supply Target, sedimentation time are respectively 30min, 60min and 120min, and corresponding film thickness is 0.5 μm, 1 μm and 2 μm.

(2) pass through wolfram element content and depth in Rutherford backscattering testing film.Rutherford backscattering spectral detection exists It carries out on accelerator, is used in test process⁴He²⁺Ion, ion energy 4MeV；Incidence angle in test process is 0 °, out Firing angle is 20 °, and angle of scattering is 160 °, carries out the simulation of elemental constituent and depth to experimental data in conjunction with SIMNRA6.05 software. As a result as shown in Figure 1.

(3) pass through deuterium constituent content in thermal desorption Quadrupole mass spectrometry testing film.Specific experiment process are as follows: by sample to be tested It is placed in vacuum tube furnace pipe center, tube furnace back end vacuum is evacuated to 1 × 10 later^-5Pa is hereinafter, be 10 in heating rate DEG C/min and maximum temperature be 900 DEG C parameter under carry out heating in vacuum, use quadrupole mass spectrometer (type in entire heating process Number be Pfeiffer QME220) carry out desorption gas detection, detection mass number be 3 and 4(correspond respectively to D-atom and deuterium Gas molecule) desorption gas, time of thermal desorption deuterium is 90min.It is thin by the available tungsten containing deuterium as shown in table 1 of the above method The content data of tungsten and deuterium in film:

(4) based on tungsten and deuterium content data in above-mentioned W film containing deuterium, in radio frequency glow discharge spectrometer (model GD PROFILER 2) on carry out deuterium electric signal and deuterium content relationship calibration.Mode of excitation is radio frequency when test, and anode dimension is 4mm, vacuum chamber pressure are 650Pa, frequency 3000Hz, power 7.5W, and module value is 6.8V, and mutually value is 6.0V.At this Tester carries in the calibration procedure of software, element species and constituent content contained by standard sample is inputted, by standard sample Element electrical signal detection obtain the relationship that deuterium content is converted to by deuterium electric signal, obtain deuterium plasma as shown in Figure 2 irradiation Deuterium plasma as shown in Figure 3 after curve of the electric signal of deuterium about the testing time in tungsten block afterwards, and calibration deuterium content Curve of the atom content of deuterium about the testing time in tungsten block after irradiation.

(5) radio frequency glow discharge spectrum sputter depth is carried out to W film containing deuterium using white light interference three-D profile tester With the calibration of duration relationship.White light interference three-D profile tester is the contactless white light of KLA-Tencor company production Interferometric optical surface profiler, model MicroXAM-800.Detailed process are as follows: join using described in the present embodiment (4) step Radio frequency glow discharge spectrometer under several tests metallic film containing deuterium, tests 101s, 201s and 363s respectively, exists in this way The sputtering hole corresponding to different durations is left on sample.The test of white light interference three-D profile is carried out by sputtering hole to these, from The step scanning curve in sputtering hole is obtained in the three-dimensional contour shape appearance figure of sample, as shown in Figure 4.Finally obtain one timing of sputtering Caused different sputtering holes depth after length, i.e., radio frequency glow discharge spectrometer is right to the sputter rate of standard sample under the parameter For tungsten material, sputter rate is about 18.3nm/s under this parameter.

(6) using tungsten block sample of the radio frequency glow discharge spectrometer detection by deuterium plasma irradiation under above-mentioned parameter The content of middle deuterium carries out the verifying of the above method.Detailed process are as follows: the high density that can generate a straightway using one constrains The device of deuterium plasma beam vertically gets to deuterium plasma on tungsten metal sample, obtains by deuterium plasma irradiation Tungsten block sample.Tungsten block sample is having a size of 15mm(length) × 12mm(width) × 1mm(thickness).Use radio frequency glow discharge spectrum Instrument tests the tungsten block sample by deuterium plasma irradiation, obtains deuterium content as shown in Figure 5 in tungsten block sample Depth distribution curve.By Fig. 5, it can be seen that, deuterium is mainly distributed on inside tungsten block in 6 μm, and concentration is between 0.005%-1%.To figure It is about 3.75 × 10 that curve, which integrate deuterium total content in available tungsten block sample, in 5²⁰ atoms/m², the sample as a comparison Product carry out thermal desorption and test deuterium total content in available sample to be 4.03 × 10²⁰ atoms/m², it is seen that by radio frequency glow discharge Deuterium content data error is within 10% in the tungsten block that spectrometer tests out.