CN112763527B - Method for directly obtaining material interface oxygen potential and structure - Google Patents

Method for directly obtaining material interface oxygen potential and structure Download PDF

Info

Publication number
CN112763527B
CN112763527B CN202011453409.0A CN202011453409A CN112763527B CN 112763527 B CN112763527 B CN 112763527B CN 202011453409 A CN202011453409 A CN 202011453409A CN 112763527 B CN112763527 B CN 112763527B
Authority
CN
China
Prior art keywords
interface
sample
detected
oxygen
information
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011453409.0A
Other languages
Chinese (zh)
Other versions
CN112763527A (en
Inventor
王丽君
何晓波
薛未华
周国治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology Beijing USTB
Original Assignee
University of Science and Technology Beijing USTB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CN202011453409.0A priority Critical patent/CN112763527B/en
Publication of CN112763527A publication Critical patent/CN112763527A/en
Application granted granted Critical
Publication of CN112763527B publication Critical patent/CN112763527B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/227—Measuring photoelectric effect, e.g. photoelectron emission microscopy [PEEM]
    • G01N23/2273—Measuring photoelectron spectrum, e.g. electron spectroscopy for chemical analysis [ESCA] or X-ray photoelectron spectroscopy [XPS]
    • G—PHYSICS
    • G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
    • G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
    • G16C60/00—Computational materials science, i.e. ICT specially adapted for investigating the physical or chemical properties of materials or phenomena associated with their design, synthesis, processing, characterisation or utilisation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/07—Investigating materials by wave or particle radiation secondary emission
    • G01N2223/085—Investigating materials by wave or particle radiation secondary emission photo-electron spectrum [ESCA, XPS]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/10—Different kinds of radiation or particles
    • G01N2223/101—Different kinds of radiation or particles electromagnetic radiation
    • G01N2223/1016—X-ray
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/40—Imaging
    • G01N2223/401—Imaging image processing

Abstract

The invention discloses a method for directly obtaining the oxygen potential and structure of a material interface, belonging to the technical field of material interface research. The method comprises the following steps: etching the surface of a fresh solid sample to form a sample interface to be detected; carrying out XPS detection on a sample interface to be detected by using Al Kalpha or Mg Kalpha X rays to obtain an X-ray photoelectron spectrum full spectrum and a target element high-resolution spectrum; performing fitting treatment according to the full-spectrum quantification and the high-resolution spectrogram to obtain interface element quantification information and valence state distribution information of the sample to be detected; combining quantitative information of interface elements, and performing multivariate thermodynamic calculation to obtain the interface oxygen potential of the interface of the sample to be detected; combining valence state distribution information to obtain structural information of a sample interface to be detected; and combining the etching information to obtain the structural changes of different depths. The method solves the problem that the interface oxygen potential and the interface structure are difficult to directly obtain.

Description

Method for directly obtaining material interface oxygen potential and structure
Technical Field
The invention belongs to the technical field of material interface research, and relates to a method for directly obtaining an oxygen potential and a structure of a material interface, in particular to a surface interface aiming at a metal material, a catalytic material and a coating.
Background
The surface, interface and internal body of the material have obvious difference in structure and chemical composition, because the internal atoms are distributed with atoms, the force field applied to the internal atoms is balanced, and for the interface atoms, the force field applied to the internal atoms is unbalanced, and the surface energy is generated on the surface of the material. The material surface interface has great influence on the overall performance of the material, and some even directly determine the performance of the material. The physical and chemical interaction at the surface/interface of the material layer is a key problem for solving the service life of the material. The current material production processes, for example, processes of metal smelting, smelting of single crystal silicon for IC substrates, soldering, glass manufacturing, and the like, are mostly composed of heterogeneous systems containing two or more phases, such as metals, slag, glass, salts, and refractory materials as containers, in a molten state.
In metallurgical processes, physicochemical reactions typically occur at interfaces that include: a gas-slag interface where the slag foams, a liquid-liquid (solid) interface between molten steel and inclusions, and a solid-liquid interface between the refractory material and molten steel and slag. Therefore, the correlation between the smelting process and the interface phenomenon is very important. The structure and properties of the interface between the two phases, especially the dynamic change of the interfacial oxygen potential, significantly affect the metallurgical reaction process. For example, in the desulfurization process, the lower interfacial tension between slag and metal is beneficial to forming a metastable reaction interface, forming dispersed steel drops and slag drops, and effectively increasing the reaction area, thereby promoting the rapid completion of the desulfurization process; meanwhile, the larger slag-metal interfacial tension is beneficial to preventing slag from being rolled up in the continuous casting process and is beneficial to the production of clean steel. However, the interfacial investigation of metallurgical melts is extremely challenging due to the difficulties of high temperature testing and observation. Moreover, in the measurement of the interfacial properties, the control thereof is more difficult due to the presence of the interfacial active ingredient and the interfacial contamination caused thereby, thus further increasing the difficulty of the measurement.
Researchers have long been dedicated to obtaining dynamic changes of two-phase interfaces, for example, dynamic changes of interface morphology are observed in situ by adopting an X-ray imaging technology, or the interface oxygen potential is indirectly obtained by assuming carbon-oxygen balance and conversion coefficient through the CO generation amount of decarburization reaction, and the rule that the interface oxygen potential changes along with external conditions is given to a certain extent. For structural studies, raman spectroscopy, infrared spectroscopy, and nuclear magnetic resonance spectroscopy are commonly used. All the structural characterization methods aim at the characterization of the body structure, and the information of the distribution and the structure of surface/interface elements cannot be comprehensively given. Therefore, the element distribution and the structural change at the interface cannot be well characterized by the methods. In conclusion, no method for directly obtaining the surface/interface oxygen potential of the melt is reported in the literature at present.
Disclosure of Invention
In order to solve the problems, the invention provides a method for directly obtaining the oxygen potential and the structure of a material interface by combining multivariate thermodynamic calculation on the basis of combining an X-ray photoelectron spectrum with an etching technology. The method provides a method for directly measuring the element distribution and the element valence state of the surface interface and obtaining the interface oxygen potential and the interface structure based on multivariate thermodynamic calculation, and solves the problem that the interface oxygen potential and the interface structure are difficult to directly obtain.
The method for directly obtaining the material interface oxygen potential and the structure provided by the technical scheme of the invention specifically comprises the following steps:
step 1: etching the surface of a fresh solid sample to form a sample interface to be detected;
step 2: performing X-ray Photoelectron Spectroscopy (XPS) detection on an interface of a sample to be detected by using Al K alpha or Mg K alpha X rays to obtain an X-ray Photoelectron spectrum full spectrum and a target element high-resolution spectrum;
and step 3: performing fitting treatment according to the full-spectrum quantification and the high-resolution spectrogram to obtain interface element quantification information and valence state distribution information of the sample to be detected;
and 4, step 4: combining quantitative information of interface elements, and performing multivariate thermodynamic calculation to obtain the interface oxygen potential of the interface of the sample to be detected; combining valence state distribution information to obtain structural information of a sample interface to be detected; and combining the etching information to obtain the structural changes of different depths.
Further, the step 1 specifically includes: on the basis of a fresh solid sample of the material obtained by the experiment, ion beam (Ar) is carried out on the surface of the fresh solid sample in an X-ray photoelectron spectrometer under the condition of ensuring that the interface is not polluted+) And (4) performing bombardment etching to remove some surface atoms and expose an internal area to form a sample interface to be detected.
Further, in the step 1, the size of the etching light spot is 500 micrometers, and the etching speed is 0.2 nm/s.
Further, the fresh solid sample has a length, width and thickness not exceeding 5 x 3 mm.
Further, the step 2 specifically includes: and detecting all elements except hydrogen and helium in the periodic table at an interface of a sample to be detected formed by etching by using Al Kalpha or Mg Kalpha X-rays as an excitation source to obtain an X-ray photoelectron spectrum full spectrum and a target element high-resolution spectrogram.
Further, in the step 2, the full spectrum of the X-ray photoelectron spectrum and the high resolution spectrogram of the target element obtained by the elements on the interface of the sample to be detected are obtained by the following formula:
Ek＝hν-EB
in the formula, EkIs the emitted photoelectron kinetic energy; h v is the energy of X-ray source photons; eBIs the binding energy on a particular atom orbital, i.e., different atom orbitals have different binding energies.
Further, the step 3 specifically includes:
step 31: based on the full spectrum of the X-ray photoelectron spectrum, quantitatively analyzing elements of a sample interface to be detected;
step 32: and (4) carrying out valence state distribution analysis on the elements of the sample interface to be detected based on the target element high-resolution spectrum.
Further, in step 31, an element sensitivity factor method is adopted to perform quantitative analysis on the elements of the sample interface to be detected, and the following formula is adopted:
I＝n*S
i is the peak area of the characteristic peak after X-ray irradiation, n is the concentration of the element atom in the sample, and S is the sensitivity factor of the element.
Further, in step 32, analyzing the valence distribution of the element on the interface of the sample to be detected specifically includes:
and (3) spectrogram correction: calibrating the characteristic peak position by taking C1s as a reference and 284.8eV as a reference;
and (3) spectral peak fitting: performing addition fitting on the characteristic peak according to the binding energy positions of different elements;
quantitative treatment: and on the basis of the fitting result, quantifying according to the atomic ratio or the mass ratio to obtain the proportions of different valence states and determining the distribution relation of the proportions.
Further, the step 4 specifically includes:
step 41: converting interface elements of a sample to be detected into an oxide form, assuming that elements etched on each layer are uniformly distributed and each layer is in an equilibrium state under experimental conditions, and calculating to obtain interface oxygen potentials under different composition conditions by utilizing a Factsage software Equilib module based on multivariate melt thermodynamic equilibrium calculation;
step 42: performing similar valence state fitting treatment on the interface oxygen, performing spectrogram correction, spectral peak fitting and quantitative treatment to obtain quantitative results of oxygen in different forms according to three kinds of oxygen O2-Free oxygen, O0Bridging oxygen and O-Obtaining the proportion of different oxygen by the relation of non-bridging oxygen, and determining the structural distribution of the oxygen;
step 43: and (4) obtaining depth information based on the etching rate and the etching time in the step (1), and obtaining oxygen potential distribution and structure change of different depths by utilizing interface oxygen potentials and structure information of different depths based on the step (41) and the step (42), so as to show gradient evolution from the surface to the body.
Further, the step 42 specifically includes:
and (3) spectrogram correction: calibrating peak positions with reference to C1s (standard peak of C element in 1s orbit) and 284.8 eV;
and (3) spectral peak fitting: fitting peaks according to different binding energy positions of different oxygens, wherein O2-(free oxygen), O0(bridging oxygen) and O-The binding energy of the (non-bridging oxygen) is 528.4eV, 532.12eV (532.6-532.5 eV, 532eV) and 531eV (531.5-531.4 eV), respectively;
quantitative treatment: and (3) on the basis of the fitting result, quantifying by using an atomic ratio or a mass ratio, wherein the relationship of three kinds of oxygen is as follows:
O2-+O0＝2O-
Figure BDA0002832376740000041
the ratio of different oxygen is obtained, the structural distribution is determined, and K is an equilibrium constant and is related to the temperature.
The invention has the beneficial effects that: the method is suitable for researching the structure of the material interface and the interface oxygen potential and is used for judging the binding capacity of the material. Moreover, the method is easy to implement, strong in transportability and good in application prospect.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
In the drawings:
FIG. 1 illustrates an X-ray photoelectron spectroscopy and etching schematic according to an embodiment of the present invention;
FIG. 2 shows a schematic flow diagram according to an embodiment of the invention;
FIG. 3 shows a quantitative full spectrum schematic according to an embodiment of the invention;
FIG. 4 shows an elemental high resolution spectrum according to an embodiment of the invention;
FIG. 5 shows a variable valence element fit graph according to an embodiment of the invention;
FIG. 6 is a graph illustrating an example of interfacial oxygen potential calculation according to an embodiment of the present invention;
FIG. 7 shows a graph of the variation of interfacial oxygen potential according to an embodiment of the present invention;
fig. 8 shows the fitting results of oxygen according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the invention, as detailed in the appended claims.
The terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are, for example, capable of operation in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
A plurality, including two or more.
And/or, it should be understood that, as used herein, the term "and/or" is merely one type of association that describes an associated object, meaning that three types of relationships may exist. For example, a and/or B, may represent: a exists alone, A and B exist simultaneously, and B exists alone.
The method for directly obtaining the interface oxygen potential and the interface structure representation provided by the technical scheme of the invention specifically comprises the following steps:
step 1: and etching the fresh solid surface interface of the material.
Based on fresh solid samples of the materials obtained in the experiment, the length, width and thickness of the samples do not exceed 5 x 3 mm. Ion beam (Ar) is applied to the surface of a solid sample in an X-ray photoelectron spectrometer under conditions that ensure that the interface is free of contamination+) And (3) performing bombardment etching, wherein the size of an etching light spot is 500 micrometers, the etching speed is 0.2nm/s, some surface atoms are removed, an internal area is exposed, and a sample interface to be detected is formed.
Step 2: and carrying out XPS detection on the interface of the sample to be processed by utilizing Al K alpha or Mg K alpha X rays to obtain an X-ray photoelectron spectrum full spectrum and a target element high-resolution spectrum.
And detecting all elements except hydrogen and helium in the periodic table at the exposed interface by using Al Kalpha or Mg Kalpha X-ray as an excitation source to obtain an X-ray photoelectron spectrum full spectrum and a target element high-resolution spectrogram.
The principle of acquiring a full spectrum and a high-resolution common spectrum of elements on an interface of a sample to be processed is as follows:
Ek＝hν-EB
in the formula, EkIs the emitted photoelectron kinetic energy; h v is the energy of X-ray source photons; eBA binding energy on a particular atom orbital (different atom orbitals have different binding energies). As can be seen from the formula, the energy of the photoelectrons is characteristic for a particular monochromatic excitation source and a particular atomic orbital. When the excitation source energy is fixed, the energy of its photoelectrons is only related to the species of the element and the atomic orbitals of the ionized excitation. Therefore, the element species of the substance can be qualitatively analyzed based on the binding energy of the photoelectrons.
And step 3: and fitting the full-spectrum quantification and the high-resolution spectrogram to obtain interface element quantification information and valence state distribution information.
The element sensitivity factor method is adopted for quantitative analysis of the elements of the sample interface to be processed, and the following formula is adopted:
I＝n*S
i is the peak area of the characteristic peak after X-ray irradiation, n is the concentration of the element atom in the sample, and S is the sensitivity factor of the element.
The valence analysis of the element on the interface of the sample to be processed specifically comprises the following steps: correcting a spectrogram, fitting a spectral peak and carrying out quantitative treatment. The spectral correction was based on C1s and the peak position was calibrated based on 284.8 eV. The spectral peak fitting is to perform additive fitting on peaks according to the binding energy positions of different elements. The quantitative processing is to perform quantitative determination in terms of atomic ratio or mass ratio based on the fitting result. As a result, the proportion of different valence states can be obtained, and the distribution relation of the valence states can be determined.
And 4, step 4: and combining quantitative information, and performing multivariate thermodynamic calculation to obtain the interfacial oxygen potential of the sample to be treated. And combining the valence state information to obtain the interface structure information of the sample to be treated. And combining the etching information to obtain the structural changes of different depths.
And (3) converting into an oxide form on the basis of the step 3, calculating to obtain the interface oxygen potential under different composition conditions by utilizing a Factsage software Equilib module based on the multivariate melt thermodynamic equilibrium calculation, and giving the change trend of the interface oxygen along with the depth and the gradient evolution from the surface to the body. Because of the existence of interface active elements, the composition of interface and bulk elements has a certain difference, so the assumed condition of the calculation is that the element distribution of each layer is uniform, and each layer is balanced and in a balanced state under the experimental condition.
On the basis of the step 3, performing similar valence state fitting treatment on the interface oxygen, and performing spectrogram correction, spectral peak fitting and quantitative treatment to obtain quantitative results of different forms of oxygen; the spectral correction was based on C1s and the peak position was calibrated based on 284.8 eV. The fitting of the spectral peak is to fit the peak according to different binding energy positions of different oxygen. Wherein O is2-(free oxygen), O0(bridging oxygen) and O-The binding energies of the (non-bridging oxygens) are 528.4eV, 532.12eV (532.6-532.5 eV, 532eV) and 531eV (531.5-531.4 eV), respectively. The quantitative processing is to perform quantitative determination in terms of atomic ratio or mass ratio based on the fitting result. The relationship of the three oxygens is:
O2-+O0＝2O-
Figure BDA0002832376740000061
as a result, the ratio of different oxygen can be obtained, and the structural distribution of the oxygen can be determined.
Based on step 1, the depth information can be obtained by the etching rate and the etching time. By utilizing the interfacial oxygen potentials and the structural information of different depths, the oxygen potential distribution and the structural change of different depths can be obtained, and the gradient evolution from the surface to the body is indicated.
Examples
For Cr2O3Adding P-CaO-MgO-SiO2-Al2O3The influence of a slag system is shown in a table 1, a gas-slag balance method is adopted, quenching is carried out at a temperature of 1873K, the surface is etched and quantified by using an X-ray photoelectron spectrum and an etching technology, the distribution state of elements such as Cr, O and the like on the interface is determined by a quantitative and fitting analysis method, and the interface oxygen potential and the interface structure change are obtained by combining multivariate thermodynamic equilibrium calculation. In order to more clearly embody the steps, the specific flow is shown in fig. 2.
TABLE 1 slag System composition Table
Figure BDA0002832376740000071
Step 1: to quenched CaO-MgO-SiO2-Al2O3And containing Cr2O3-CaO-MgO-SiO2-Al2O3The slag system is processed, and the length, width and thickness of the slag system do not exceed 5 x 3 mm. Ar is carried out on the surface of a solid sample in a Thermo ESCALAB 250XI model X-ray photoelectron spectrometer under the condition of ensuring no pollution of an interface+Bombard and etch, the size of etching light spot is 500 micrometers, the energy of etching ion is 500eV, and etchThe etching speed is 0.2nm/s, some surface atoms are removed, the internal area is exposed, and the interface of the sample to be detected is formed, as shown in fig. 1.
Step 2: for Cr2O3-CaO-MgO-SiO2-Al2O3XPS detection of the interface of the sample to be treated with Al K alpha (hv) 1486.6eV radiation, with the degree of vacuum of the analysis cell being 8xl0-10Pa, working voltage 12.5kV, filament current 16mA, and signal accumulation for 10 cycles. The full spectrum of the test Energy (Passing-Energy) is 100eV, the narrow spectrum is 30eV, the step length is 0.05eV, the retention time is 40-50ms, and the full spectrum of the X-ray photoelectron spectrum and the high-resolution spectrum of the target element are obtained, as shown in FIG. 3 and FIG. 4.
And step 3: based on the full spectrum in the step 2, automatic element peak searching is firstly carried out on the full spectrum, elements which exist but are not identified are manually added, and a method of combining the full spectrum and a high-resolution spectrum can be adopted for quantitative target elements. And quantifying by using an Avantage software by adopting a sensitivity factor method, and quantitatively analyzing the element distribution of different depths of the interface by quantifying at different etching times. The quantitative results are shown in Table 2:
TABLE 2 XPS relative content results
Figure BDA0002832376740000072
Figure BDA0002832376740000081
Based on the high resolution spectrum in the step 2, for the valence analysis containing Cr, the high resolution spectrogram is subjected to charge correction by taking C1s 284.8.8 eV as a reference, the Cr2p3/2 binding energy of Cr2+ is 576.0eV (575.9-576.2 eV), and the Cr2p1/2 binding energy of Cr2+ is 585.1-585.7 eV. The Cr2p3/2 binding energy of Cr3+ is about 577eV, and the Cr2p1/2 binding energy of Cr3+ is 586.5-587.6 eV. For the transition metal element Cr, due to different orbitals, a pair of peaks is required to be added, and the area ratio of the two pairs of peaks is 2: 1. and then carrying out spectral peak fitting and quantitative analysis in sequence, wherein fitting results are shown in figure 5, which shows that Cr mainly exists in the slag in a valence state of +2 and a valence state of +3, and quantitative results are shown in a table 3, which shows that the valence state of Cr is different along with depth distribution.
TABLE 3 fitting results of Cr valence states
Figure BDA0002832376740000082
And 4, step 4: based on the quantitative information in step 3, the elements were converted to the oxide form, as shown in Table 4 below
TABLE 4 results of oxide conversion
Figure BDA0002832376740000083
And (3) performing multivariate thermodynamic equilibrium calculation by using multivariate thermodynamic equilibrium calculation and utilizing a Factsage software Equilib module, such as a graph 6, inputting data in a table 2, and performing multivariate thermodynamic calculation to obtain interface oxygen potential values with different depths, such as a graph 7, wherein the oxygen potential is gradually reduced along with the increase of the etching depth.
And (3) performing similar valence state fitting treatment on the interface oxygen to obtain quantitative results of different forms of oxygen, and combining valence state information to obtain interface structure information of the sample to be treated, such as a graph. For CaO-MgO-SiO containing Cr2-Al2O3Slag interface structure, fitting analysis of oxygen peaks, O0(bridging oxygen) and O-The binding energy of the (non-bridging oxygen) is 532.12eV (532.6-532.5 eV, 532eV) and 531eV (531.5-531.4 eV), and the obtained product is subjected to spectrogram correction, spectral peak fitting and quantitative analysis. As shown in fig. 4, at 60s of etching, the oxygen at the interface consisted primarily of a distribution of bridging and non-bridging oxygen, with no free oxygen.
The depth information can be obtained by calculating the etching rate and the time. For example, taking 60s as an example, the standard etching rate is 0.2 nm/s. Therefore, the etching depth is about d 0.2 × 60s 12 nm.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (8)

1. A method for directly obtaining the interfacial oxygen potential and the structure of a material is characterized by comprising the following steps:
step 1: etching the surface of the solid sample to form a sample interface to be detected;
step 2: carrying out XPS detection on a sample interface to be detected by using Al Ka or Mg Ka X rays to obtain an X-ray photoelectron spectroscopy full spectrum and a target element high-resolution spectrogram;
and step 3: performing fitting treatment according to the full-spectrum quantification of the X-ray photoelectron spectrum and the high-resolution spectrogram of the target element to obtain quantitative information and valence state distribution information of the interface element of the sample to be detected;
and 4, step 4: combining quantitative information of interface elements of the sample to be detected, and performing multivariate melt thermodynamic equilibrium calculation to obtain the interface oxygen potential of the interface of the sample to be detected; combining valence state distribution information to obtain structural information of a sample interface to be detected; combining the etching information to obtain the structure changes of different depths,
wherein, the step 4 specifically comprises:
step 41: converting interface elements of a sample to be detected into an oxide form, assuming that elements etched on each layer are uniformly distributed and each layer is in an equilibrium state under experimental conditions, combining quantitative information of the interface elements of the sample to be detected, calculating by utilizing a Factsage software Equilib module based on multivariate melt thermodynamic equilibrium calculation to obtain interface oxygen potentials under different composition conditions;
step 42: performing similar valence state fitting treatment on the interface oxygen, combining valence state distribution information, performing spectrogram correction, spectral peak fitting and quantitative treatment to obtain quantitative results of different forms of oxygen according to three types of oxygen O2-Free oxygen, O0Bridging oxygen and O-Obtaining the proportion of different oxygen by the relation of non-bridging oxygen, determining the structural distribution of the different oxygen, and obtaining the structural information of the interface of the sample to be detected;
step 43: obtaining depth information based on the etching rate and the etching time in the step 1, obtaining oxygen potential distribution and structure change of different depths by using the interface oxygen potentials and the structure information of different depths in combination with the step 41 and the step 42, showing the gradient evolution from the surface to the body,
wherein the step 42 specifically includes:
and (3) spectrogram correction: calibrating the characteristic peak position by taking C1s as a reference and 284.8eV as a reference;
and (3) spectral peak fitting: fitting characteristic peaks according to different oxygen different binding energy positions, wherein O2-Free oxygen, O0Bridging oxygen and O-The binding energies of the non-bridging oxygens are 528.4eV, 532.12eV and 531eV respectively;
quantitative treatment: and (3) on the basis of the fitting result, quantifying by using an atomic ratio or a mass ratio, wherein the relationship of three kinds of oxygen is as follows:
O2-+O0＝2O-
Figure FDA0003369607290000011
the ratio of different oxygen is obtained, the structural distribution is determined, and K is an equilibrium constant and is related to the temperature.
2. The method of claim 1, wherein the step of removing the metal oxide layer comprises removing the metal oxide layer from the metal oxide layerThe step 1 specifically includes: on the basis of a solid sample of the material obtained by the experiment, Ar is carried out on the surface of the solid sample in an X-ray photoelectron spectrometer under the condition of ensuring that an interface is not polluted+And (4) carrying out ion beam bombardment etching to remove some surface atoms and expose an internal area to form a sample interface to be detected.
3. The method of claim 2, wherein in step 1, the etching spot size is 500 microns and the etching speed is 0.2 nm/s.
4. The method according to claim 1, wherein the step 2 specifically comprises: and (3) detecting all elements except hydrogen and helium in the periodic table at an interface of a sample to be detected formed by etching by using AlK alpha or Mg K alpha X-rays as an excitation source to obtain an X-ray photoelectron spectrum full spectrum and a target element high-resolution spectrogram.
5. The method according to claim 4, wherein in the step 2, the full spectrum of the X-ray photoelectron spectrum and the high resolution spectrum of the target element obtained from the elements of the sample interface to be detected are obtained by the following formula:
Ek＝hν-EB
in the formula, EkIs the emitted photoelectron kinetic energy; h v is the energy of X-ray source photons; eBIs the binding energy on a particular atom orbital, i.e., different atom orbitals have different binding energies.
6. The method according to claim 1, wherein step 3 specifically comprises:
step 31: based on the full spectrum of the X-ray photoelectron spectrum, quantitatively analyzing elements of a sample interface to be detected to obtain quantitative information of the elements of the sample interface to be detected;
step 32: and performing spectrogram correction, spectral peak fitting and quantitative treatment based on the high-resolution spectrogram of the target element so as to analyze the valence state distribution of the elements on the interface of the sample to be detected and obtain the valence state distribution information of the elements on the interface of the sample to be detected.
7. The method according to claim 6, wherein in step 31, the element sensitivity factor method is adopted for quantitative analysis of the elements of the sample interface to be detected, according to the following formula:
I＝n*S
i is the peak area of the characteristic peak after X-ray irradiation, n is the concentration of a certain element atom in the sample, and S is the sensitivity factor of the element.
8. The method according to claim 6, wherein the step 32 comprises in particular:
and (3) spectrogram correction: calibrating the characteristic peak position by taking C1s as a reference and 284.8eV as a reference;
and (3) spectral peak fitting: performing addition fitting on the characteristic peak according to the binding energy positions of different elements;
quantitative treatment: and on the basis of the fitting result, quantifying according to the atomic ratio or the mass ratio to obtain the proportions of different valence states and determining the distribution relation of the proportions.
CN202011453409.0A 2020-12-11 2020-12-11 Method for directly obtaining material interface oxygen potential and structure Active CN112763527B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011453409.0A CN112763527B (en) 2020-12-11 2020-12-11 Method for directly obtaining material interface oxygen potential and structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011453409.0A CN112763527B (en) 2020-12-11 2020-12-11 Method for directly obtaining material interface oxygen potential and structure

Publications (2)

Publication Number Publication Date
CN112763527A CN112763527A (en) 2021-05-07
CN112763527B true CN112763527B (en) 2022-04-05

Family

ID=75693585

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011453409.0A Active CN112763527B (en) 2020-12-11 2020-12-11 Method for directly obtaining material interface oxygen potential and structure

Country Status (1)

Country Link
CN (1) CN112763527B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114460114B (en) * 2022-04-13 2022-06-21 季华实验室 Sample analysis method, device, apparatus and storage medium
CN115060755B (en) * 2022-08-18 2022-11-01 季华实验室 Depth analysis method for unknown sample layer structure
CN115165945A (en) * 2022-09-08 2022-10-11 季华实验室 Sample analysis method, device, equipment and storage medium based on test optimization
CN116735643B (en) * 2023-08-14 2023-11-24 季华实验室 Method for measuring interface cut-off point of sample structure

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110309595B (en) * 2019-07-02 2021-05-04 中国原子能科学研究院 MOX pellet oxygen potential calculation method
CN110487833B (en) * 2019-08-28 2022-04-12 哈尔滨工业大学 Method for rapidly etching and analyzing chemical state of material interface element by utilizing X-ray photoelectron spectrometer
CN111678927A (en) * 2020-06-08 2020-09-18 首钢集团有限公司 Method for analyzing oxide on surface of steel

Also Published As

Publication number Publication date
CN112763527A (en) 2021-05-07

Similar Documents

Publication Publication Date Title
CN112763527B (en) Method for directly obtaining material interface oxygen potential and structure
Tarzimoghadam et al. Multi-scale and spatially resolved hydrogen mapping in a Ni–Nb model alloy reveals the role of the δ phase in hydrogen embrittlement of alloy 718
Vickerman et al. Surface analysis: the principal techniques
Greczynski et al. X-ray photoelectron spectroscopy of thin films
Robson Analytical electron microscopy of grain boundary segregation: application to Al-Zn-Mg-Cu (7xxx) alloys
Kronz et al. Analysis of low element concentrations in quartz by electron microprobe
Shard et al. Intensity calibration for monochromated Al Kα XPS instruments using polyethylene
JP2008020386A (en) Method and apparatus for analyzing chemical state by auger electron spectroscopy
CN112198184B (en) Analysis method for detecting indium element content and distribution of high-purity aluminum target material after acid washing by EPMA
Ilyin Auger electron spectroscopy
JP2008298770A (en) Method for laser ionization mass spectrometry and sample-supporting substrate for use in laser ionization mass spectrometry
EP3226278B1 (en) Quantitative analysis device for trace carbon and quantitative analysis method for trace carbon
Ferrero et al. Improving the detection limits for vapor phase decomposition-inductively coupled plasma mass spectrometry (VPD-ICP-MS) analysis
Engel et al. Electron energy-loss spectroscopy and the crystal chemistry of rhodizite. Part 1.—Instrumentation and chemical analysis
JPH11316220A (en) Method and apparatus for high-accuracy analysis of trace element in metal
Takahara et al. Vapor phase treatment–total reflection X-ray fluorescence for trace elemental analysis of silicon wafer surface
Tsuji et al. Surface studies by grazing‐exit electron probe microanalysis (GE‐EPMA)
Goldstein et al. Quantitative Analysis: The SEM/EDS Elemental Microanalysis k-ratio Procedure for Bulk Specimens, Step-by-Step
Rostam-Khani et al. Quantitative analysis of surface contaminants on silicon wafers by means of TOF-SIMS
Rigby et al. Electron probe micro-analysis of oxygen in cordierite: potential implications for the analysis of volatiles in minerals
Powell et al. Comparisons of SIMS, SNMS, ISS, RBS, AES, and XPS methods for surface compositional analysis
Gimenes Rodrigues Albuquerque et al. Assessing the Impurities in Neptunium Metal
Gerhard et al. LIBS Analysis of Optical Surfaces and Thin Films
JP6332639B2 (en) Hot metal removal Se treatment method
Grasserbauer Quantitative Secondary Ion Mass Spectrometry

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant