CN114636714A - Transmission electron microscope in-situ gas phase temperature difference chip - Google Patents

Transmission electron microscope in-situ gas phase temperature difference chip Download PDF

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CN114636714A
CN114636714A CN202210151623.3A CN202210151623A CN114636714A CN 114636714 A CN114636714 A CN 114636714A CN 202210151623 A CN202210151623 A CN 202210151623A CN 114636714 A CN114636714 A CN 114636714A
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heating
chip
temperature difference
gas phase
situ
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韩晓东
田志永
毛圣成
栗晓辰
马东锋
张剑飞
李志鹏
张晴
杨晓萌
王梦龙
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Beijing University of Technology
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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
    • G01N23/20—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 using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
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    • 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
    • G01N23/20—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 using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
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    • G01N23/20033—Sample holders or supports therefor provided with temperature control or heating means

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Abstract

The invention provides a transmission electron microscope in-situ gas phase temperature difference chip, which comprises an upper chip and a lower chip, wherein the upper chip is provided with a plurality of gas phase temperature difference elements; the periphery between the upper chip and the lower chip is sealed to form a hollow cavity; in the hollow cavity, the upper surface of the lower chip is provided with a gas outlet, a first heating area, a second heating area, a third heating area and a gas inlet which are sequentially arranged in a straight line shape; an observation window is arranged in any heating zone, an electron beam window penetrating through the lower chip is arranged below the observation window, a lower thin film window is arranged in the electron beam window, and an upper thin film window corresponding to the lower thin film window is arranged in the upper chip. The transmission electron microscope in-situ gas phase temperature difference chip is accurate in heating temperature control, successfully coupled with a high-pressure gas field, capable of realizing loading of accurate temperature gradient by jointly heating a plurality of heating zones, capable of controlling quick response of temperature and capable of carrying out high-resolution measurement of in-situ reaction on a transmission electron microscope sample under gas-heat double loads.

Description

Transmission electron microscope in-situ gas phase temperature difference chip
Technical Field
The invention belongs to the technical field of material performance in-situ test, and particularly relates to a transmission electron microscope in-situ gas phase temperature difference chip.
Background
Conventional transmission electron microscopes can only obtain corresponding structural information within a fixed period of time. The real reaction conditions are the prerequisite for in situ studies. In-situ transmission electron microscopy provides possibility for simulating industrial conditions of materials under the condition of keeping high resolution, and researchers can obtain important information such as crystal size, form, crystal structure, chemical bond, heat energy change and the like through in-situ transmission electron microscopy introducing an air field and a temperature field for in-situ testing. In the research of catalysis, oxidation and nano-growth, the external environment influences the atomic structure on the micro-scale to cause macroscopic performance difference. In-situ Transmission Electron Microscopy (TEM) has been widely accepted in the fields of nanomaterial synthesis, catalysis, metal corrosion, and even energy materials as a powerful tool for direct observation of morphological and structural changes at atomic scale.
At present, methods for carrying out in-situ characterization in a gas-thermal environment mainly include an Environmental Transmission Electron Microscope (ETEM) and a gas chip based on an MEMS chip technology. The environmental transmission electron microscope is additionally provided with a set of differential pumping system by changing the structure of the original electron microscope, and the introduction of gas with proper flow is allowed. In the in-situ chip technology, the high-pressure gas is isolated from the cavity of the electron microscope through the assembly of the upper chip and the lower chip, so that the introduction of a thermal field or a gas field can be realized, and the in-situ chip technology has the advantages of small volume and high integratability.
However, existing ambient transmission electron microscopy allows gas pressures not exceeding 15.0 torr (0.02 atm), about two orders of magnitude lower than atmospheric pressures at which many practical gas phase reactions occur. This "pressure differential" does not facilitate bridging between in situ results and actual application; meanwhile, the differential pumping aperture blocks high-angle scattered electrons, and STEM imaging of the high-angle scattered electrons is influenced.
The existing gas chip can only realize single gas loading, and cannot provide a thermal field for an experiment to reduce the reaction barrier; the existing heating chip is difficult to realize the loading of the temperature gradient, the temperature response rate is slow, although the in-situ temperature difference chip developed by Liaohong and other people can realize the temperature gradient to a certain extent, the chip is not coupled with the air field, and the carried sample is single; the existing gas heating chip, such as a transmission electron microscope in-situ gas heating chip developed by J.Fredrk Creemer and the like, is limited to a uniform temperature field, cannot load a temperature gradient, realizes in-situ temperature difference observation and the like although coupling of gas and a thermal field is realized.
As the most extensive application of the combination of gas and temperature gradient, a material forming mechanism synthesized by CVD or CVT is not clear up till now, the synthesis process is still a black box, but the research on in-situ synthesis of two-dimensional materials under the current atmosphere is few, and although a macroscopic tube furnace can complete the synthesis of related materials, the yield is low, so that the method is not suitable for large-scale preparation; microscopically albeit Christian
Figure BDA0003510585360000021
The introduction of a low pressure of CVD precursor gas disilane into a conventional planar heated TEM substrate with deposited catalyst in ETEM completes the growth of Si nanowires under a temperature gradient, but is not applicable to other materials.
Meanwhile, the synthesis of the two-dimensional material is accompanied by the formation of byproducts, and because the temperature of the micro-area of the heat treatment furnace is difficult to control, great difficulty is caused for product collection, products and byproducts, products and reactants, and byproducts and reactants are generated and mixed in the same area, great trouble is caused for material preparation, and the problems especially become the technical development bottleneck of the two-dimensional material. For example, in the experiment of the mineralization method of black phosphorus, impurities such as metal phosphide or phosphorus allotrope are easy to generate, so that three temperature zones need to be arranged in the experiment of black phosphorus growth, wherein HT zone, MT zone and LT zone respectively represent a high temperature zone, a medium temperature zone and a low temperature zone, wherein the high temperature zone is a load zone of a precursor, and the temperature is generally set to be 600 ℃ in the experiment so as to promote the volatilization of the precursor; the substrate is placed in a medium-temperature area for growing black phosphorus; and a large amount of phosphorus vapor flows from the high-temperature area to the low-temperature area and is deposited in the low-temperature area due to the driving of the temperature gradient, and byproducts such as red phosphorus, white phosphorus and the like are further formed. Therefore, the existing gas heating chip is needed to be improved, a temperature gradient loading in the atmosphere can be realized in situ, the in-situ growth of the two-dimensional/nano material is carried out, and meanwhile, the high-efficiency separation and collection of the product and the by-product are realized through the regulation and control of the temperature zone gradient.
Disclosure of Invention
The invention provides a transmission electron microscope in-situ gas phase temperature difference chip which can carry out high-resolution measurement of in-situ reaction on a transmission electron microscope sample under gas-heat double loads.
Specifically, the invention provides the following technical scheme:
a transmission electron microscope in-situ gas phase temperature difference chip comprises an upper chip and a lower chip; the periphery between the upper chip and the lower chip is sealed to form a hollow cavity;
in the hollow cavity, the upper surface of the lower chip is provided with a gas outlet, a first heating area, a second heating area, a third heating area and a gas inlet which are sequentially arranged in a straight line shape;
an observation window is arranged in any heating area, an electron beam window penetrating through the lower chip is arranged below the observation window, a lower film window is arranged in the electron beam window, and an upper film window corresponding to the lower film window is arranged in the upper chip.
Preferably, in the transmission electron microscope in-situ gas phase temperature difference chip, the heating wire of the first heating zone is spiral ring-shaped or disc-shaped; the heating wires of the second heating area and the third heating area are in a snake shape. In a more preferred embodiment, the first heating zone can be a high-temperature zone for carrying the raw material, so that the heating wire is arranged in a spiral ring shape or a disc shape to be more beneficial to the concentration and control of the temperature, and the second heating zone (middle-temperature zone) and the third heating zone (low-temperature zone) are byproduct and/or product collecting zones, so that a larger temperature coverage area is ensured, and the heating wire is arranged in a serpentine shape which is repeatedly wired to ensure the product collecting efficiency of the middle-temperature zone and the low-temperature zone.
Preferably, in the in-situ gas phase temperature difference chip for the transmission electron microscope, the outer diameter of the spiral annular or disc-shaped heating wire of the first heating zone is 150-; the shape of the serpentine heating wire of the second heating zone has the size of (140-; the shape of the serpentine heating wire of the third heating zone has the size of (140-. The axial direction is parallel to the gas outlet, the first heating area, the second heating area, the third heating area and the gas inlet which are sequentially arranged in a straight line shape, and the transverse direction is vertical to the axial direction.
Further preferably, the first heating zone has a size of 180-.
Preferably, in the in-situ gas phase temperature difference chip for the transmission electron microscope, the distance between the first heating region and the second heating region is 140-. In a more preferred embodiment, the adjacent heating zones are each at a distance of 150 μm from one another, which in the temperature field simulation results in a temperature drop of 100 ℃ which meets the subsequent temperature requirements.
Preferably, in the above-mentioned tem in-situ gas phase temperature difference chip, the sum of the axial dimensions of the three heating zones is limited within 1mm (the limitation requirement of the field of view of the tem).
Preferably, in the transmission electron microscope in-situ gas phase temperature difference chip, any heating zone is composed of a heating wire with the outer diameter of 2-15 μm. In a more preferred embodiment, the first heating zone is a high temperature zone, the outer diameter of the heating wire is 6 μm of the inner heating wire (the inner ring is preferably 1-2 circles from the center outwards), the outer heating wire is 8 μm, the distance between adjacent heating wires is 8 μm, the second heating zone is a medium temperature zone, the outer diameter of the heating wire is 10 μm, the distance between adjacent heating wires is 12 μm, the third heating zone is a low temperature zone, which is also an important product collecting zone, the outer diameter of the heating wire is 12 μm, and the distance between adjacent heating wires is 14 μm. (the smaller the outer diameter of the heating wire, the smaller the distance, the higher the heating temperature, the main reason is that the heating wire is more densely distributed and the heat dissipation is smaller)
Preferably, in the transmission electron microscope in-situ gas phase temperature difference chip, the observation window is arranged in the center of the heating area or in the gap of the heating wire.
Preferably, in the in-situ gas-phase temperature difference chip for the transmission electron microscope, any one of the heating zones is respectively connected with one group of pressurizing electrodes and one group of temperature measuring electrodes.
Preferably, in the transmission electron microscope in-situ gas phase temperature difference chip, the height of the hollow cavity is 1-6 μm.
Preferably, in the above-mentioned transmission electron microscope normal position gas phase difference in temperature chip, the upper surface of lower chip still is equipped with spill gas circuit gasket, gas outlet and gas inlet set up respectively in the concave part of two spill gas circuit gaskets, just the open end of two spill gas circuit gaskets sets up relatively, can play the gas and assemble the effect, and the accessible is adjusted gas flow rate and flow control reaction rate.
Preferably, in the transmission electron microscope in-situ gas phase temperature difference chip, the height of the two concave gas path gaskets is 100-5000 nm.
According to the in-situ gas phase temperature difference chip for the transmission electron microscope, the loading of temperature gradients can be realized through the coupling of multiple heating areas, and meanwhile, the temperature value of each temperature field is more uniform and can be independently controlled and does not influence each other. The characterizable sample can be a nanoparticle, a nanowire or a bulk sample carried by a focused ion beam, and a controllable temperature gradient can be provided to realize in-situ growth of the nanowire or the nano-sheet material. Various deposition and synthesis reactions depending on temperature gradient control are carried out, such as preparation of various deposited films and synthesis of two-dimensional materials, the synthesis mechanism in the synthesis process of the two-dimensional materials is explored, and the action behaviors of various factors such as temperature, atmosphere, pressure and the like on the synthesis are explored.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the description below are some embodiments of the present invention, and those skilled in the art can obtain other drawings without creative efforts.
FIG. 1 is a schematic diagram of a TEM in-situ gas-phase thermoelectric chip according to an embodiment of the present invention.
FIG. 2 is a top view of a lower chip according to an embodiment of the present invention.
FIG. 3 is a top view of an upper chip according to an embodiment of the present invention.
Fig. 4 is a top view of three heating zones in accordance with an embodiment of the present invention.
Fig. 5 is a schematic diagram of a first heating region according to an embodiment of the present invention.
FIG. 6 is a schematic diagram of a second heating zone according to an embodiment of the present invention.
FIG. 7 is a cross-sectional view of a lower chip A-A according to an embodiment of the present invention.
FIG. 8 is a cross-sectional view of a bottom chip B-B in accordance with an embodiment of the present invention.
In the figure: 1. mounting a chip; 2. chip unloading; 3. a gas pipeline 3-1 and a gas outlet; 3-2, an air inlet; 4. a concave gas circuit gasket; 5. a heating zone; 5-1, a first heating zone; 5-2, a second heating zone; 5-3, a third heating zone; 6. a lead wire; 7. a conductive sheet; 8. an isolation layer 9, a heating layer 10 and a support layer; 11. a silicon substrate; 12. a lower silicon nitride film window; 13. a heating wire; 14. an upper silicon nitride film window; 15. sample particles; 16. an observation window; 17. an electron beam window.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The transmission electron microscope in-situ gas phase temperature difference chip provided by the embodiment of the invention needs to be combined with a transmission electron microscope to finish in-situ growth and microscopic structure evolution of in-situ observation samples.
In order to realize the field control of the sample from room temperature to 1300 ℃ in a stable atmosphere and controllable pressure so as to obtain an in-situ atomic resolution image and an image, as shown in fig. 1 to 8, the in-situ gas thermal difference chip provided by the embodiment of the invention is formed by combining a lower chip 2 and an upper chip 1.
In the embodiment of the invention, the transmission electron microscope in-situ gas phase temperature difference chip is arranged in the transmission electron microscope in cooperation with the sample rod, the alignment of the upper chip and the lower chip and the matching with the sample rod are completed in an alignment tool in the early stage, the temperature and the gas flow parameters are adjusted in the electron microscope to be stable, and the optimal observation state is ensured. The transmission electron microscope in-situ gas phase temperature difference chip can realize high temperature response rate, high thermal uniformity, adjustable temperature gradient and gas flow rate, can realize atom scale resolution gas-solid reaction experiment under 2atm, and reveals the gas-solid reaction principle.
The in-situ gas phase temperature difference chip for the transmission electron microscope, as shown in fig. 1, comprises an upper chip 1 and a lower chip 2 which are sequentially connected from top to bottom; the upper chip and the lower chip are divided into a front surface and a back surface, wherein the combination of the upper chip and the lower chip is fixed and sealed through a sealing O ring or filled with a proper amount of sealant, and a small amount of vacuum sealant is coated at the connecting seams of the upper chip 1 and the cover plate and the lower chip 2 and the sample rod substrate for fixing and sealing according to the situation.
According to the in-situ gas phase temperature difference chip for the transmission electron microscope, as shown in fig. 2, an air outlet 3-1, a first heating region 5-1, a second heating region 5-2, a third heating region 5-3 and an air inlet 3-2 are sequentially arranged in a straight line on the surface of a lower chip 2, wherein the first heating region 5-1, the second heating region 5-2 and the third heating region 5-3 jointly form the heating region 5. Any heating zone adopts a four-electrode method for temperature measurement, and is respectively connected with a pair of pressurizing electrodes and a pair of measuring electrodes through leads 6, the pressurizing electrodes are responsible for providing voltage required by heating, and the measuring electrodes detect the actual temperature generated by the heating zone by measuring the real-time voltage in the heating process. The power of the resistance wire 13 in the heating zone 5 is precisely controlled by the application of an external potential to the conducting strip 7 to achieve precise control of the sample temperature. The lead 6 adopts the symmetrical design, has further got rid of the temperature measurement error that lead resistance change brought, improves the temperature measurement precision. The three heating zones are distributed on the same axis and respectively correspond to four electrodes for control, so that not only can a uniform temperature field be realized, but also different voltages can be applied through three sets of systems, different temperatures can be provided at the heating zones, and a macroscopic temperature field required by life of the two-dimensional material/nano material is generated.
As shown in fig. 2, the upper surface of the lower chip 2 is further provided with two concave gas circuit gaskets 4, the gas outlet 3-1 and the gas inlet 3-2 are respectively arranged in the concave portions of the two concave gas circuit gaskets 4, the open ends of the two concave gas circuit gaskets 4 are oppositely arranged, and gas sequentially passes through a flow channel formed by the gas outlet 3-1 and the concave gas circuit gaskets 4, the gas inlet 3-2 and a communicating gas circuit inside the sample rod.
In the in-situ gas phase temperature difference chip for the transmission electron microscope, as shown in fig. 4, the first heating zone 5-1 is a high temperature zone which is disc-shaped and is more beneficial to the concentration and control of temperature, and the second heating zone 5-2 and the third heating zone 5-3 are byproduct and product collecting zones respectively, which need to ensure larger temperature coverage area, so that the chip is set in a serpentine shape with reciprocating wiring to ensure the product collecting efficiency of the medium temperature zone and the low temperature zone. The adjacent heating zones are all 150 μm apart from each other along the edge.
As shown in fig. 5, the disc-shaped heater wires of the first heating zone 5-1 have an outer diameter of 200 μm, an inner circumference of 6 μm (inner circumference of 2 circles from the center), an outer circumference of 8 μm, and a pitch of adjacent wires of 8 μm. The method meets the requirement of temperature uniformity in the region while ensuring higher temperature, the temperature uniformity in the annular range reaches more than 99.5%, and after the Si back bottom matched with the temperature uniformity is etched, the thermal mass of a heating region is reduced, so that the heating power is reduced, the thermal drift is reduced, and the image stability under atomic scale resolution is ensured. The first heating zone 5-1 is provided with a viewing window 16 in the center.
As shown in fig. 6, the second heating zone is an intermediate temperature zone, the size of the shape of the serpentine heating wire is 150 μm by 200 μm (axial by lateral), the outer diameter of the heating wire is 10 μm, and the distance between adjacent heating wires is 12 μm. An observation window 16 is arranged in the gap of the heating wire of the second heating area 5-2.
The third heating zone is a low temperature zone and also an important product collecting zone, the shape of the serpentine heating wire has the size of 180 mu m by 200 mu m (axial direction by transverse direction), the outer diameter of the heating wire is 12 mu m, and the distance between adjacent heating wires is 14 mu m. An observation window 16 is arranged in the gap of the heating wire of the third heating zone 5-3.
According to the in-situ gas phase temperature difference chip for the transmission electron microscope, as shown in fig. 7 and 8, a lower chip 1 sequentially comprises a silicon substrate 11, a supporting layer 10, a heating layer 9 and an isolating layer 8 from bottom to top, wherein the heating layer 9 comprises a heating region 5 and a lead 6 and is connected with an external circuit through a conducting strip 7, and the isolating layer 8 is used for separating the heating layer 9 from sample particles and external atmosphere and preventing a heating wire from being oxidized or short-circuited. An electron beam window 17 penetrating through the lower chip 2 is arranged below the heating area 5 in the heating layer 9, and a lower silicon nitride film window 12 is arranged in the electron beam window 17. And a gas pipeline 3 penetrating through the lower chip 2 is arranged below the gas outlet 3-1 and the gas inlet 3-2.
As shown in fig. 3, an upper silicon nitride film window 14 corresponding to the lower silicon nitride film window 12 is formed in the upper chip 1.
According to the in-situ gas phase temperature difference chip for the transmission electron microscope, the upper and lower layers of silicon nitride film windows are adopted, the upper silicon nitride film window 14 of the upper chip 1 is aligned with the heating area 5 of the lower chip 2, and the upper surface of the aligned upper chip is aligned and tightly pressed into a gas sample rod of the transmission electron microscope through an O-shaped sealing ring, so that the gas content in the direction of an electron beam is greatly reduced, the electron beam is ensured not to be excessively scattered by gas, and a higher-quality electron map is presented when the electron beam penetrates through a sample.
The preparation method of the lower chip 1 of the transmission electron microscope in-situ gas phase temperature difference chip provided in this embodiment is explained in detail:
s1, preparing a wafer A which is polished on two sides and is grown with a silicon nitride or silicon oxide insulating layer and is provided with single crystal Si (100), wherein the thickness of the insulating layer is 10nm-1 mu m, and the thickness of a silicon wafer is 100 mu m-1 mm;
and S2, transferring the SiNx observation window film pattern to the front surface of the wafer A through low-pressure chemical vapor deposition, photoetching and dry etching processes. Obtaining a wafer A-1;
s3, growing a metal layer on the front surface of the wafer A-1 by utilizing a magnetron sputtering growth technology, transferring a heating resistor pattern from a photoetching mask plate to the front surface of the wafer through photoetching and etching, developing in a positive photoresist developing solution, and cleaning the surface by using deionized water to form a heating resistor and a lead. Obtaining a wafer A-2;
and S4, growing a layer of silicon nitride on the front surface of the wafer A-2 as a protective layer through an LPCVD (low pressure chemical vapor deposition) process. Obtaining a wafer A-3; (SIN protective layer)
S5, depositing a layer of silicon oxide or polysilicon on the front surface of the wafer A-3 by a PECVD (plasma enhanced chemical vapor deposition) process, transferring a gas circuit pattern from a photoetching mask plate to the front surface of the wafer by adopting a photoetching process, developing in a positive photoresist developing solution, cleaning the surface by using deionized water, and etching to form a gas channel to obtain the wafer A-4; (deposition of gas channel)
S8, transferring the pattern of the area to be etched from the photoetching mask plate to the front surface of the wafer A-5 through a photoetching process, developing in a positive photoresist developing solution, sequentially cleaning with organic cleaning and deionized water, and removing the residual photoresist on the surface by adopting plasma to obtain a wafer A-6; (exposure of detail bonding area)
S9, evaporating a layer of metal film on the front surface of the wafer A-6 by using an electron beam evaporation coating process to form a heating electrode. Placing the wafer with the right side facing upwards into acetone for soaking and stripping, washing with deionized water, removing the photoresist, and leaving a metal electrode to obtain a wafer A-7; (deposition of electrode)
S10, etching silicon nitride or silicon oxide on a region to be etched on the back of the wafer A-7 by using a reactive ion etching process, sequentially soaking the back of the wafer in acetone with the back facing upwards, and finally washing the wafer with acetone to remove photoresist to obtain a wafer A-8; (removal of the protective layer on the back)
S11, placing the wafer A-8 with the back face upward into a water bath for wet etching until the etching of the substrate silicon of the corresponding window part is completed, taking out the wafer and cleaning the photoresist to obtain a wafer A-9; (bottom silicon etching)
S12, etching away a silicon nitride or silicon oxide or aluminum oxide protective layer exposed on the front side of the wafer A-9 through a reactive ion etching process, then placing the wafer with the front side facing upwards into acetone for soaking, finally washing with acetone, and removing photoresist to obtain a wafer A-10; (air inlet and outlet port window)
S13, carrying out laser or mechanical scribing on the wafer A-10 to divide the wafer into independent chips.
The transmission electron microscope in-situ gas phase temperature difference chip provided by the embodiment of the invention is combined with a specific experiment of 'mineralization method in-situ preparation of black phosphorus', and the assembling and testing process of the chip can comprise the following steps:
wherein, the synthetic raw material for preparing the black phosphorus in situ by the mineralization method is high-purity tin and high-purity red phosphorus I2. The involved reaction equations include:
Sn(s)→Sn(g)+Sn(l)
Sn+I2→SnI4or Sn + I2→SnI2
SnI4→SnI2+I2
RP→P4(g)
s is solid, l is liquid, g is gaseous, wherein the by-products involved comprise SnI2，SnI4Purple phosphorus, red phosphorus. The experimental principle is that high-purity tin and high-purity red phosphorus are mixed and dispersed at the 5-1 position of a high-temperature area of a chip, reaction raw materials are sublimated by heating, and I is introduced2The gas, carrying sublimed substance with reaction gas, enters the medium temperature zone 5-2 at medium temperatureBy-product SnI by regulating temperature2，SnI4And collecting purple phosphorus and red phosphorus, and observing while synthesizing black phosphorus in the low-temperature region 5-3.
Step S1: red phosphorus (RP, the purity is more than 99.999%) and tin particles (Sn, the purity is more than 99.999%) in the raw materials used for the experiment are uniformly mixed by absolute ethyl alcohol, are dripped into a heating area 5-1 of a lower chip 2, and are dried by a hot table to be stably attached to the surface of the chip;
step S2: placing the lower chip 2 in the groove of the sample rod to enable the length direction of the electron beam window to be parallel to the axial direction of the sample rod;
step S3: assembling an O-shaped sealing ring on the lower chip 2, and symmetrically assembling the O-shaped sealing ring on the outer edge of the heating area;
step S4: the surface of a lower chip 2 carrying a sample is placed horizontally under a light mirror, and an upper chip 1 and the lower chip 2 are centered, so that a sample carrying area of the lower chip 2 is aligned with an upper silicon nitride film window 14 of the upper chip;
step S5: checking whether an upper silicon nitride film window 14, a sample and a lower silicon nitride film window 12 of the upper chip 1 are aligned under a light mirror, and carrying out fine adjustment;
step S6: covering the pressing plate and fixing the pressing plate by fastening screws;
step S7: carrying out electrical connection test;
step S8: introducing Ar gas through a gas channel and a gas valve of the sample rod, and performing vacuum leakage detection in a light mirror and an He mass spectrometer leak detector;
step S9: after vacuum leakage detection is carried out, the gas seal is confirmed to be good, and then the sample rod is inserted into the transmission electron microscope;
step S10: introducing a circulating gas I2Opening the electron beam after confirming that the vacuum of the transmission electron microscope is good, finding a sample on an electron beam window, and adjusting to a proper multiple;
step S11: after the electrical control system is connected, the heating wire 13 on the lower chip 2 is electrified and heated, the first heating zone 5-1 is gradually heated and kept above the sublimation temperature of red phosphorus (650 ℃), the temperature of the second heating zone 5-2 is controlled at 620-;
step S12: the solid red phosphorus particles are sublimated into gas particles in the first heating zone 5-1 by the loading of the temperature gradient, and the reaction gas I2Under the load, the collection of red phosphorus and purple phosphorus byproducts is completed in the second heating area 5-2, the in-situ deposition and growth of black phosphorus are completed in the third heating area 5-3, and real-time observation is carried out to reveal the growth mechanism in the growth process of the black phosphorus.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A transmission electron microscope in-situ gas phase temperature difference chip is characterized by comprising an upper chip and a lower chip; the periphery between the upper chip and the lower chip is sealed to form a hollow cavity;
in the hollow cavity, the upper surface of the lower chip is provided with a gas outlet, a first heating area, a second heating area, a third heating area and a gas inlet which are sequentially arranged in a straight line shape;
an observation window is arranged in any heating area, an electron beam window penetrating through the lower chip is arranged below the observation window, a lower film window is arranged in the electron beam window, and an upper film window corresponding to the lower film window is arranged in the upper chip.
2. The TEM in-situ gas phase temperature difference chip as claimed in claim 1, wherein the heating wire of the first heating zone is in the shape of a spiral ring or a disc; the heating wires of the second heating area and the third heating area are in a snake shape.
3. The TEM in-situ gas phase temperature difference chip as claimed in claim 1 or 2, wherein the outer diameter of the spiral ring-shaped or disc-shaped heating wire of the first heating zone is 150-220 μm; the shape of the serpentine heating wire of the second heating zone has the size of (140-; the shape of the serpentine heating wire of the third heating zone has the size of (140-.
4. The TEM in-situ gas phase temperature difference chip as claimed in any one of claims 1-3, wherein the distance between the first heating region and the second heating region is 140-160 μm, and the distance between the second heating region and the third heating region is 140-160 μm.
5. The in-situ gas phase temperature difference chip for the transmission electron microscope as claimed in any one of claims 1 to 4, wherein any one of the heating zones is composed of heating wires with an outer diameter of 2 to 15 μm, and the distance between adjacent heating wires is 5 to 15 μm.
6. The TEM in-situ gas phase temperature difference chip as claimed in any one of claims 1-5, wherein the observation window is arranged in the center of the heating zone or in the gap of the heating wire.
7. The TEM in-situ gas phase temperature difference chip as claimed in any one of claims 1-6, wherein any one of the heating zones is connected to a set of pressure electrodes and a set of temperature measurement electrodes respectively.
8. The TEM in-situ gas phase temperature difference chip as claimed in any one of claims 1-7, wherein the height of the hollow cavity is 1-6 μm.
9. The TEM in-situ gas phase temperature difference chip as claimed in any one of claims 1-8, wherein the upper surface of the lower chip is further provided with concave gas path gaskets, the gas outlet and the gas inlet are respectively arranged in the concave portions of the two concave gas path gaskets, and the open ends of the two concave gas path gaskets are oppositely arranged.
10. The TEM in-situ gas phase temperature difference chip as claimed in claim 9, wherein the two concave gas path pads have a height of 100-5000 nm.
CN202210151623.3A 2022-02-18 2022-02-18 Transmission electron microscope in-situ gas phase temperature difference chip Pending CN114636714A (en)

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Application Number Priority Date Filing Date Title
CN202210151623.3A CN114636714A (en) 2022-02-18 2022-02-18 Transmission electron microscope in-situ gas phase temperature difference chip

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210151623.3A CN114636714A (en) 2022-02-18 2022-02-18 Transmission electron microscope in-situ gas phase temperature difference chip

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Publication Number Publication Date
CN114636714A true CN114636714A (en) 2022-06-17

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