CN113218983A - Method for calibrating XPS depth analysis etching rate of thin film material - Google Patents
Method for calibrating XPS depth analysis etching rate of thin film material Download PDFInfo
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- CN113218983A CN113218983A CN202110464287.3A CN202110464287A CN113218983A CN 113218983 A CN113218983 A CN 113218983A CN 202110464287 A CN202110464287 A CN 202110464287A CN 113218983 A CN113218983 A CN 113218983A
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- 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
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- 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]
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- 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
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Abstract
The invention relates to the technical field of surface analysis, in particular to a method for calibrating XPS depth profiling etching rate of a thin film material. The invention prepares a flat film sample by a vacuum evaporation method, and calibrates the depth of the arc pit by using a probe type surface profiler after ion etching, thereby obtaining the real ion etching rate and etching depth of the film sample. Because the property difference of different materials is large, if the etching rate is set according to the instrument reference value, the actual etching rate may have a large difference with the instrument reference value, which results in a large deviation when the etching analysis is performed on the material surface interface. The method is simple to implement, and the result is visual and accurate, so that the problem that the depth profiling etching rate cannot be accurately measured at present is solved. When the depth analysis and the etching analysis are carried out on the thin film material, the accuracy of the XPS analysis is improved.
Description
Technical Field
The invention relates to the technical field of surface analysis, in particular to a method for calibrating XPS depth profiling etching rate of a thin film material.
Background
The vacuum evaporation technology is that the target material is placed in a high vacuum environment to be heated, and the target material is gradually deposited on a substrate to form a film after being evaporated into a gas state. The method is simple to operate, and the prepared film has high purity, good compactness and smooth surface. Conventional X-ray photoelectron spectroscopy (XPS) analysis can only detect photoelectrons generated by X-ray excitation of species within 10nm of the sample surface, and if it is necessary to obtain elements and chemical state related information thereof at a depth of more than 10nm of the sample surface, it is necessary to physically peel off the sample surface by combining an ion etching means, and then XPS testing is performed. When the deep analysis of the thin film material is carried out, the instrument can only give a reference ion sputtering rate aiming at a certain standard substance. However, in actual tests, because physical properties of different samples and materials are greatly different, the actual sputtering rate is greatly different from the reference value of the standard substance, and the actual etching depth is difficult to obtain.
The patent CN110487833A discloses a method for rapidly etching and analyzing the chemical state of an interface element of a material by using an X-ray photoelectron spectrometer, which comprises the steps of firstly selecting a high-speed single-particle argon ion mode with the etching rate of 0.05-0.2 nm/s to remove the surface layer of a sample, and then selecting a low-speed cluster argon ion mode with the etching rate of 0.0005-0.001 nm/s to etch the sample, thereby analyzing the change rule of the chemical state of the element valence bond of the interface layer. The method reduces the sample etching time and improves the XPS test efficiency on the premise of ensuring that the XPS signal truly reflects the chemical valence bond information of the semiconductor material and the transition metal compound. However, when a depth profiling experiment is carried out, the instrument can only give a reference etching rate for a standard substance so as to estimate the etching depth. However, since the properties of different materials are different greatly, if the etching rate is set according to the instrument reference value, the actual etching rate may be different from the instrument reference value greatly, which causes a large deviation between the depth obtained by performing the etching analysis on the material surface interface and the actual situation. Therefore, a method for calibrating the actual sputtering rate of a thin film material is needed. After ion etching, the surface of the sample can be stripped layer by layer to form an arc pit structure, so that the etching depth can be determined by scanning an etching area through a probe type surface profiler, and the etching rate (nm/s) can be calculated.
Disclosure of Invention
The invention aims to solve the problems that the XPS depth analysis can only give the etching rate of a sample estimated according to the standard non-reference ion etching rate, and cannot know the real ion etching rate and the practical etching depth of the sample, and provides a method for calibrating the ion etching rate and the etching depth of a thin film material from the sample to the detection.
The technical scheme of the invention is as follows:
a method for calibrating XPS depth profiling etching rate of a thin film material comprises the following steps:
firstly, preparing a film material coating
Depositing the thin film material to be detected on a flat substrate by a vacuum evaporation method, wherein the deposition thickness is 100-300 nm, and obtaining a thin film material sample; the film material is required to evenly cover a part of the surface of the substrate, and an uncovered area is left.
Secondly, ion etching of the coating of the thin film material
Placing the sample prepared in the step one in an X-ray photoelectron spectrometer, and performing a film material depth analysis experiment, wherein the etching range is selected to be 4-9 mm2Setting the profiling depth to be 50-150 nm; the analysis depth is an estimated value of an instrument, a reference sputtering rate calibrated according to certain standard reference substances can be given by an X-ray photoelectron spectrometer when the X-ray photoelectron spectrometer performs a depth analysis experiment, and the analysis depth can be roughly calculated by adjusting the energy of an ion gun, the ion sputtering time and the etching range.
Thirdly, measuring the thickness and the etching depth of the coating of the thin film material
Taking out the etched sample obtained in the second step, firstly scanning the height difference between the region of the un-etched film material coating and the substrate by using a probe type surface profiler, and determining the thickness of the film material coating; then scanning the height difference between the etching area and the coating, and determining the real etching depth of the ion gun in the XPS depth profiling experiment;
fourthly, calculating the etching rate of the film
When the real etching depth obtained in the third step is less than the thickness of the film coating measured in the third step, the etching speed of the ion gun on the film material under the condition can be directly calculated by using the etching thickness and the etching time, and the unit is nm/s. And when the real etching depth is greater than or equal to the thickness of the thin film material coating, keeping other conditions unchanged, reducing the original etching time by 10% each time, repeating the second step and the third step until the measured real etching depth is less than the thickness of the thin film coating, and further calculating the etching rate.
The invention has the beneficial effects that: the invention provides a method for preparing a flat film sample by a vacuum evaporation method, and calibrating the depth of an arc pit by using a probe type surface profiler after ion etching so as to obtain the real ion etching rate and the etching depth of the film sample. Because the property difference of different materials is large, if the etching rate is set according to the instrument reference value, the actual etching rate may have a large difference with the instrument reference value, which results in a large deviation when the etching analysis is performed on the material surface interface. The method is simple to implement, and the result is visual and accurate, so that the problem that the depth profiling etching rate cannot be accurately measured at present is solved. When the depth analysis and the etching analysis are carried out on the thin film material, the accuracy of the XPS analysis is improved.
Drawings
FIG. 1 is a schematic view of a prepared film material, wherein 1 is a substrate, 2 is a film coating layer which does not completely cover the substrate, and 3 is the depth d of an arc-shaped groove generated by ion etching 24 is an arc groove, and 5 is the thickness d of the film material coating1；
FIG. 2 is a flow chart of a method for calibrating XPS depth profiling etch rate of thin film materials;
FIG. 3 is a step chart of the thickness of the coating of the antimony selenide thin film calibrated by a surface profiler in example 1;
FIG. 4 is a scan of the surface etch pit depth of an antimony selenide film calibrated by a surface profiler as in example 1;
FIG. 5 is a step chart of the thickness of the gold thin film plating layer calibrated by the surface profiler in example 2;
FIG. 6 is a scanned graph of the etch pit depth on the surface of the gold thin film calibrated by the surface profiler in example 2;
Detailed Description
In order to make the technical purpose and the implementation method of the present invention clearer, the following description is further provided with reference to the accompanying drawings in the embodiments of the present invention.
The invention provides a method for calibrating the ion etching rate of a thin film material from sample preparation to detection, which comprises the following specific steps as shown in figure 1.
Example 1:
(1) sb2Se3The thin film is deposited on the FTO glass substrate by a vacuum evaporation method, the deposition thickness is 100nm, and in the preparation process, a specific mask plate is covered on the FTO substrate to control a film forming area (as shown in figure 1). After the evaporation is finished, placing the sample in a tube furnace, and annealing for 40min at 330 ℃ in Ar atmosphere;
(2) placing the prepared sample in an X-ray photoelectron spectrometer, and performing a thin film material depth analysis etching experiment, wherein the etching range is selected to be 2.5 multiplied by 2.5mm2Selecting a single-atom mode for the ion gun, selecting 2000eV energy, and selecting 400s etching time, wherein the reference etching rate of the instrument is 0.25nm/s, and the estimated analysis depth is 100 nm;
(3) taking out the sample after ion etching, placing in a probe-type surface profiler, scanning the step between the film material and the substrate (as shown in FIG. 3), and determining the thickness d of the film material 1150 +/-10 nm; the step between the sputter area and the coating is then scanned (as shown in FIG. 4) to determine the true etch depth of the gun as d285 +/-10 nm;
(4) due to d1＞d2And the ion etching is proved not to penetrate through the film coating, so that the real etching rate of the antimony selenide film under the condition can be calculated to be 0.2125 +/-0.025 nm/s through the etching time and the etching depth.
Example 2:
(1) depositing an Au thin film on an FTO glass substrate by a vacuum evaporation method, wherein the deposition thickness is 300nm, and covering a specific mask plate on the FTO substrate in the preparation process to control a film forming area;
(2) will make intoPlacing the prepared sample in an X-ray photoelectron spectrometer for performing a depth analysis etching experiment on the thin film material, wherein the etching range is 2X 2mm2Selecting a single-atom mode for the ion gun, 3000eV for energy, 300s for etching time, 0.48nm/s for instrument reference etching rate and 144nm for estimated analysis depth;
(3) taking out the sample after ion etching, placing in a probe-type surface profiler, scanning the step between the film material and the substrate (as shown in FIG. 5), and determining the thickness d of the film material1Is 110 +/-10 nm; the step between the sputter area and the coating is then scanned (as shown in FIG. 6) to determine the true etch depth of the gun as d2Is 72 +/-10 nm;
(4) due to d1＞d2And the ion etching is proved not to penetrate through the film coating, so that the real etching rate of the antimony selenide film under the condition can be calculated to be 0.24 +/-0.033 nm/s through the etching time and the etching depth.
Claims (1)
1. A method for calibrating XPS depth profiling etching rate of a thin film material is characterized by comprising the following steps:
firstly, preparing a film material coating
Depositing the thin film material to be detected on a flat substrate by a vacuum evaporation method, wherein the deposition thickness is 100-300 nm, and obtaining a thin film material sample; the film material needs to be flatly and uniformly covered on a part of the surface of the substrate, and an uncovered area is reserved;
secondly, ion etching of the coating of the thin film material
Placing the sample prepared in the step one in an X-ray photoelectron spectrometer, and performing a film material depth analysis experiment, wherein the etching range is selected to be 4-9 mm2Setting the profiling depth to be 50-150 nm;
thirdly, measuring the thickness and the etching depth of the coating of the thin film material
Taking out the etched sample obtained in the second step, firstly scanning the height difference between the region of the un-etched film material coating and the substrate by using a probe type surface profiler, and determining the thickness of the film material coating; then scanning the height difference between the etching area and the coating, and determining the real etching depth of the ion gun in the XPS depth profiling experiment;
fourthly, calculating the etching rate of the film
When the real etching depth obtained in the third step is less than the thickness of the film coating measured in the third step, the etching speed of the ion gun on the film material under the condition can be directly calculated by using the etching thickness and the etching time, and the unit is nm/s; and when the real etching depth is greater than or equal to the thickness of the thin film material coating, keeping other conditions unchanged, reducing the original etching time by 10% each time, repeating the second step and the third step until the measured real etching depth is less than the thickness of the thin film coating, and further calculating the etching rate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115060755A (en) * | 2022-08-18 | 2022-09-16 | 季华实验室 | Depth analysis method for unknown sample layer structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5872629A (en) * | 1997-06-23 | 1999-02-16 | Charles Evans & Associates | Analytical depth monitor utilizing differential interferometric analysis |
| US20040238735A1 (en) * | 2001-10-26 | 2004-12-02 | Larson Paul E. | System and method for depth profiling and characterization of thin films |
| CN1614416A (en) * | 2004-12-03 | 2005-05-11 | 北京科技大学 | Method for measuring speed rate of thin-membrane deposition |
| JP2015004604A (en) * | 2013-06-21 | 2015-01-08 | 住友金属鉱山株式会社 | Depth direction analysis method for organic sample |
-
2021
- 2021-04-28 CN CN202110464287.3A patent/CN113218983A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5872629A (en) * | 1997-06-23 | 1999-02-16 | Charles Evans & Associates | Analytical depth monitor utilizing differential interferometric analysis |
| US20040238735A1 (en) * | 2001-10-26 | 2004-12-02 | Larson Paul E. | System and method for depth profiling and characterization of thin films |
| CN1614416A (en) * | 2004-12-03 | 2005-05-11 | 北京科技大学 | Method for measuring speed rate of thin-membrane deposition |
| JP2015004604A (en) * | 2013-06-21 | 2015-01-08 | 住友金属鉱山株式会社 | Depth direction analysis method for organic sample |
Non-Patent Citations (2)
| Title |
|---|
| 陈静允等: "X射线光电子能谱法和深度剖析法检测CdS薄膜的成分", 《理化检验(化学分册)》 * |
| 魏雄邦等: "氧化钒薄膜成分及价态的深度刻蚀分析", 《材料导报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115060755A (en) * | 2022-08-18 | 2022-09-16 | 季华实验室 | Depth analysis method for unknown sample layer structure |
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