CN114441561B - Test sample for electron microscope and manufacturing method thereof - Google Patents

Test sample for electron microscope and manufacturing method thereof Download PDF

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Publication number
CN114441561B
CN114441561B CN202011127123.3A CN202011127123A CN114441561B CN 114441561 B CN114441561 B CN 114441561B CN 202011127123 A CN202011127123 A CN 202011127123A CN 114441561 B CN114441561 B CN 114441561B
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protective layer
test sample
electron microscope
electron beam
electron
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CN114441561A (en
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陈健群
彭裕庭
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00Investigating 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
    • G01N23/02Investigating 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 transmitting the radiation through the material
    • G01N23/04Investigating 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 transmitting the radiation through the material and forming images of the material
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00Investigating 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
    • G01N23/22Investigating 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
    • G01N23/2202Preparing specimens therefor
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00Investigating 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
    • G01N23/22Investigating 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
    • G01N23/2204Specimen supports therefor; Sample conveying means therefore
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00Investigating 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
    • G01N23/22Investigating 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
    • G01N23/225Investigating 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 using electron or ion
    • G01N23/2251Investigating 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 using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00Investigating materials by wave or particle radiation
    • G01N2223/03Investigating materials by wave or particle radiation by transmission
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00Investigating materials by wave or particle radiation
    • G01N2223/07Investigating materials by wave or particle radiation secondary emission
    • G01N2223/09Investigating materials by wave or particle radiation secondary emission exo-electron emission
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00Investigating materials by wave or particle radiation
    • G01N2223/10Different kinds of radiation or particles
    • G01N2223/102Different kinds of radiation or particles beta or electrons

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)

Abstract

The application provides a test sample for an electron microscope and a manufacturing method thereof. The object to be measured is arranged on the bearing substrate, the protective layer is composed of amorphous alumina, and the thickness of the protective layer is not more than 5nm. The application uses the protective layer to cover the object to be detected, avoids the object to be detected from being damaged due to the irradiation of electron beams in the detection of an electron microscope, and also reduces the occurrence of carbon deposition effect. And the electrons of the electron beam do not generate lattice diffraction when traveling in the amorphous protective layer, so as not to influence the analysis and imaging of the object to be detected.

Description

Test sample for electron microscope and manufacturing method thereof
Technical Field
The present application relates to a test sample and a method for manufacturing the same, and more particularly, to a test sample suitable for an electron microscope and a method for manufacturing the same.
Background
In the academic field or industry, detection of samples on a nano-scale or a micro-scale, analysis of materials, or acquisition of three-dimensional images are often performed by using an electron microscope (e.g., SEM, TEM, STEM, or the like). The method generally includes applying an electron beam to a sample to be measured, utilizing electron scattering generated after electrons strike the surface of the sample to be measured, measuring crystal structures and surface morphologies of the sample to be measured at different angles based on electron tunneling effects, and integrating analysis data measured at different angles to obtain a three-dimensional image of the sample to be measured.
However, when a three-dimensional image of the sample to be measured is obtained by electron microscopy, such as Transmission Electron Microscopy (TEM), it is necessary to photograph the sample for a long time, but the longer the time of detection/photographing, the more easily the sample to be measured is damaged due to long-time exposure to the irradiation of electron beams, or carbon deposition is generated on the surface or periphery of the sample to be measured, resulting in poor quality of the detected image.
Disclosure of Invention
The application aims to provide a test sample for an electron microscope, which can be prevented from being damaged by electron beam irradiation.
The present application provides a test sample for an electron microscope, comprising: an object to be measured, and a protective layer.
The protective layer is made of amorphous alumina and is coated on the object to be detected, and the thickness of the protective layer is not more than 5nm.
Preferably, the test sample for an electron microscope of the present application further comprises a carrier substrate, the object to be tested is disposed on a surface of the carrier substrate, and the protective layer further extends to cover the surface of the carrier substrate.
Preferably, the test sample for an electron microscope according to the present application, wherein the electron microscope generates an electron beam and applies the electron beam to the test sample at a specific incident angle, and the thickness of the protective layer is controlled such that the traveling distance of the electron beam in the protective layer is not more than 10nm.
Still another object of the present application is to provide a method for producing a test sample for an electron microscope.
The method for manufacturing the test sample for the electron microscope comprises the following steps: forming a protective layer made of amorphous aluminum oxide on the surface of an object to be measured on a bearing substrate, wherein the thickness of the protective layer is not more than 5nm.
Preferably, the method for manufacturing a test sample for an electron microscope according to the present application, wherein the protective layer is formed by atomic layer deposition.
Preferably, in the method for manufacturing a test sample for an electron microscope according to the present application, the sample to be tested is prepared by cleaning the surface of the object to be tested with argon plasma, and then forming the protective layer.
Preferably, in the method for manufacturing a test sample for an electron microscope according to the present application, the electron microscope may generate an electron beam and apply the electron beam to the test sample at a specific incident angle, and the thickness of the protective layer is controlled such that the traveling distance of the electron beam in the protective layer is not more than 10nm.
The beneficial effects of the application are that: the protective layer is used for coating the object to be detected so as to prevent the object to be detected from being damaged due to irradiation of electron beams in the process of detection or three-dimensional image imaging by an electron microscope, and meanwhile, the situation that carbon deposition is generated around an electron beam irradiation area of the test sample can be reduced. In addition, the protective layer is made of amorphous alumina, and the thickness of the protective layer is not more than 5nm, so that the detection analysis of the object to be detected is not interfered.
Drawings
FIG. 1 is a schematic side view illustrating an embodiment of a test sample for an electron microscope of the present application;
FIG. 2 is a schematic diagram showing the case where the test sample of this embodiment is set on a stage dedicated to TEM and an electron beam is applied;
FIG. 3 is a schematic cross-sectional view taken along line III-III of FIG. 2, illustrating the application of an electron beam to the test sample of the embodiment after rotation of the stage;
FIG. 4 is an image diagram illustrating the scanned transmission image of the test sample of comparative example 1 measured in STEM mode of TEM;
FIG. 5 is an image diagram illustrating the scanned penetration image of the test sample of Experimental example 1 measured in STEM mode;
FIG. 6 is an image diagram illustrating a scanned transmission image obtained by detecting the test sample of Experimental example 2 in STEM mode and a transmission image obtained by TEM detection; a kind of electronic device with high-pressure air-conditioning system
Fig. 7 is an image diagram illustrating a transmission image obtained by TEM examination of the test sample of experimental example 2, and a lattice diffraction pattern.
Detailed Description
The present application will now be described in detail with reference to the drawings and examples, wherein like reference numerals refer to like or functionally similar elements throughout the separate views. Before the present application is described in detail, it should be noted that the drawings are for illustrative purposes only and are not drawn to scale and are not intended to represent actual dimensions or actual relative dimensions of the components described below.
Referring to fig. 1 and 3, an embodiment of a test sample 100 for an electron microscope according to the present application is suitable for an electron microscope, and includes a carrier substrate 1, an object 2 to be tested, and a protective layer 3.
The object 2 is disposed on the carrier substrate 1. In the present embodiment, the object 2 to be detected generally refers to any object that can be detected by the electron microscope, and the constituent materials and the shape and state thereof are not particularly limited as long as they conform to the usage specification of the electron microscope.
The protective layer 3 is made of amorphous alumina and covers the object 2, and the thickness of the protective layer 3 is not more than 5nm. Preferably, when an electron microscope generates an electron beam and applies the electron beam to the test sample 100 at a specific incident angle, the thickness of the protective layer 3 is also controlled such that the traveling distance D of the electron beam in the protective layer 3 is not more than 10nm. In the present embodiment, the protection layer 3 also extends to cover the surface of the carrier substrate 1.
The method for manufacturing the test sample 100 includes the steps (1) and (2) in sequence.
The step (1) is to clean the surface of the object 2 to be tested disposed on the carrier substrate 1. In this embodiment, the step (1) is to treat the surface of the object to be measured 2 by plasma cleaning. Specifically, the step (1) is to apply an electric field to argon gas to dissociate the argon gas into argon plasma (Ar) in a plasma state + ) And utilizes argon plasma (Ar) in a plasma state + ) The charged charges adsorb pollutants on the surface of the object 2 to be detected, so as to achieve the cleaning effect. The plasma cleaning method does not use chemical agents or heat treatment processes in the process, so that the plasma cleaning method is suitable for cleaning the object 2 made of various materials (such as semiconductors, polymers or metals), and is beneficial to cleaning the object 2 with a complex structure.
In the step (2), the protective layer 3 made of amorphous alumina is formed on the object 2 disposed on the carrier substrate 1, and the thickness of the protective layer 3 is not greater than 5nm. In this embodiment, the step (2) is to form the protective layer 3 closely attached to the surface of the object 2 by atomic layer deposition. Preferably, the thickness of the protective layer 3 is also controlled such that the electron beam travels a distance D of not more than 10nm in the protective layer 3 when the electron beam is applied to the test specimen 100 at a specific incident angle.
It is noted that the test sample 100 prepared in the present application is applicable to various types of electron microscopes, such as a Transmission Electron Microscope (TEM), a Scanning Electron Microscope (SEM), or a Scanning Transmission Electron Microscope (STEM). In the present embodiment, the test sample 100 is used in a transmission electron microscope (hereinafter, referred to as a TEM) for illustration, but the present application is not limited thereto.
Referring to fig. 2, the test sample 100 of the present embodiment is detected and analyzed by using the TEM, wherein the test sample 100 is fixed on a stage 4 dedicated to the TEM and is sent into a cavity dedicated to the TEM (not shown); then, applying a vertical electron beam onto the test sample 100 from above the test sample 100 (as shown in fig. 2), part of electrons of the electron beam penetrating the test sample 100; part of the electrons penetrate through the protective layer 3 and then collide with the object 2 to be detected, and collide with the atomic structure on the surface layer of the object 2 to generate electron scattering, and the internal structure of the object 2 to be detected can be known by collecting the scattered electrons and analyzing the advancing direction of the electrons, so that a penetration image is obtained. In addition, in the present embodiment, the TEM can also be switched to a scan-through mode (hereinafter referred to as STEM mode), and the electron beam is used to scan the test sample 100 to obtain a scan-through image. In some embodiments, the scattered electrons interfere with each other to generate electron diffraction, and the diffraction pattern of the object 2 is obtained by collecting the diffracted electrons and analyzing the electrons (e.g. fourier transform).
When the test sample 100 is detected and analyzed by using STEM mode of TEM, a three-dimensional image of the test sample 100 can be obtained by photographing with a three-dimensional image technique. During detection, the TEM rotates the stage 4 (see fig. 3) carrying the test sample 100, so that the electron beam can be applied to the test sample 100 from different incident angles in an oblique incident manner, so as to measure several scanning transmission images of the test sample 100 from different angles, and integrate the analysis data measured from different angles, thereby obtaining a three-dimensional image of the test sample 100. The operation procedures of the TEM and STEM modes thereof and the setting of the relevant parameter conditions are well known in the related art and will not be described in detail herein.
Since the protective layer 3 is selected from amorphous aluminum oxide, the electrons of the incident electron beam do not generate lattice diffraction when passing through the amorphous protective layer 3, thereby interfering with the detection result of the object 2. In addition, since the thickness of the protective layer 3 is not greater than 5nm, and when the electron beam is applied to the test sample 100 from a specific incident angle, the thickness of the protective layer 3 can be further controlled such that the travel distance D of the electron beam in the protective layer 3 is not greater than 10nm, so that the electron beam is ensured to irradiate the test sample 100 from a vertical direction or to obliquely enter at a specific incident angle, and the energy of the electron beam is sufficient to penetrate the protective layer 3 to contact the object 2 to be tested and avoid that the travel distance D of the electron beam is too large to influence the detection result by the protective layer 3.
In addition, the protection layer 3 can prevent the object 2 to be measured from being directly irradiated by the electron beam, so as to slow down the damage or deformation of the object 2 to be measured due to receiving too much energy from the electron beam, and meanwhile, the protection layer 3 can also inhibit the migration of pollutants on the surface of the object 2 to be measured, so that the problems that in the three-dimensional imaging process, the surface of the sample to be measured or the pollutants around the electron beam are attracted by the electron beam to form carbon deposition on the periphery of the electron beam, and the image quality is reduced along with the increase of shooting time can be avoided.
The foregoing examples will be further described using TEM and STEM imaging experiments, but it should be understood that the experiments are illustrative only and should not be construed as limiting the practice of the application.
Comparative example 1
Referring to fig. 4, in the comparative example 1, platinum-rhodium-gold nanoparticles are placed on the stage 4 of the TEM as an object to be measured, and the TEM is switched to STEM mode to perform three-dimensional image capturing on the platinum-rhodium-gold nanoparticles, wherein the capturing time of each three-dimensional image capturing is 5 hours, and detection recording is performed during the capturing process, so as to obtain a scanning transmission image as shown in fig. 4.
Fig. 4 is a scanning transmission image of the test sample of comparative example 1 measured before three-dimensional image capturing; then, after the first three-dimensional image shooting is carried out on the test sample, the test sample is detected again at the same angle and position to obtain a scanning penetration image in the middle of the figure 4; finally, the test sample of comparative example 1 is photographed for the second time, and after photographing, the test sample of comparative example 1 is photographed again at the same angle and position, so as to obtain the right-most scanning transmission image as shown in fig. 4.
Comparing the left-to-right scanning transmission images in fig. 4, as the number of times of three-dimensional image photographing increases, the halation formed at the periphery of the platinum-rhodium-gold nanoparticles becomes more pronounced, and it can be known that as the test sample of comparative example 1 is photographed in the TEM for a longer time, that is, the longer the test sample is subjected to electron beam irradiation, the more carbon deposition is generated at the periphery and surface of the platinum-rhodium-gold nanoparticles, resulting in gradual degradation of the image quality.
Experimental example 1
Referring to fig. 1 and 5, in the experimental example 1, the test sample 100 is a platinum-rhodium gold nanoparticle 2 having the protective layer 3 on the surface. In TEM detection in STEM mode, electron beams are applied to the test sample 100 from different angles and scanned to obtain several scanned transmission images at different angles. The left side of fig. 5 is a scan-through image measured at the earlier stage of photographing, and the right side of fig. 5 is another scan-through image measured after photographing the test sample 100 of the experimental example 1 in the STEM mode for 10 hours. As can be seen from comparing the two images in fig. 5, the platinum-rhodium-gold nanoparticle 2 (i.e., the object 2 to be tested in the experimental example 1) with the protective layer 3 (not shown) formed on the surface thereof is not damaged or deformed after being irradiated by the electron beam for a long time (10 hours of irradiation in the experimental example 1), and carbon deposition is not generated around the platinum-rhodium-gold nanoparticle 2, so that the imaging quality of the scanning-penetrating image can be maintained.
Experimental example 2
Referring to fig. 1 and 6, in the experimental example 2, the test sample 100 is a tungsten needle 2 having the protective layer 3 on a surface thereof, and a transmission image is obtained by detecting the test sample 100 of the experimental example 2 by a TEM (right image of fig. 6), and then the TEM is switched to STEM mode to measure a scanning transmission image (left image of fig. 6).
The left image of fig. 6 is the scanning through image of the test example 2, and the magnification thereof is 120kx, the right image is the through image, and the magnification thereof is 730kx, and it can be seen from fig. 6 that the surface of the tungsten needle 2 (i.e., the object 2 to be tested of the test example 2) is covered with a protective layer 3 having a thickness of about 5nm. Referring to fig. 7 again, the left image in fig. 7 is a transmission image of the test sample 100 of experimental example 2 measured in TEM from another angle (i.e., facing the tip of the tungsten needle 2), and the right image is a lattice diffraction image obtained by performing Fast Fourier Transform (FFT) on the transmission image. As is clear from the results of fig. 7, the definition of the lattice points in the lattice diffraction pattern is good, so that it is known that the formation of the protective layer 3 on the tungsten needle 2 does not interfere with the detection of the object 2.
In summary, the test sample 100 of the present application utilizes the protective layer 3 to cover the object 2 to be tested to provide a protection effect, so as to prevent the object 2 to be tested from being damaged or deformed due to the irradiation of the electron beam during the detection of the electron microscope, and reduce the occurrence of carbon deposition around the test sample 100, and in addition, the protective layer 3 is composed of amorphous alumina with a thickness not greater than 5nm, so that the detection and analysis of the object 2 are not interfered, and the purpose of the present application can be achieved.
The above description is only of the preferred embodiments of the present application, but not limited thereto, and any person skilled in the art can make further modifications and variations without departing from the spirit and scope of the present application, and the scope of the present application is defined by the appended claims.

Claims (5)

1. A test sample for an electron microscope, comprising:
an object to be measured; a kind of electronic device with high-pressure air-conditioning system
A protective layer composed of amorphous alumina and coated on the object to be tested, wherein the thickness of the protective layer is not more than 5nm,
wherein the electron microscope is capable of generating an electron beam and applying the electron beam to the test sample at a specific angle of incidence, and the thickness of the protective layer is controlled such that the electron beam travels a distance of not more than 10nm in the protective layer.
2. The test specimen for an electron microscope according to claim 1, further comprising a carrier substrate, the object to be tested being disposed on a surface of the carrier substrate, and the protective layer further extending over the surface of the carrier substrate.
3. A method of making a test sample for an electron microscope, comprising:
forming a protective layer composed of amorphous aluminum oxide on the surface of the object to be tested arranged on the bearing substrate, wherein the thickness of the protective layer is not more than 5nm,
wherein the electron microscope is capable of generating an electron beam and applying the electron beam to the test sample at a specific angle of incidence, and the thickness of the protective layer is controlled such that the electron beam travels a distance of not more than 10nm in the protective layer.
4. A method of fabricating a test sample for an electron microscope according to claim 3 wherein the protective layer is formed by atomic layer deposition.
5. The method according to claim 3, wherein the test sample is prepared by cleaning the surface of the object with argon plasma and forming the protective layer.
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