EP3610248A1 - Dispositif d'échantillon liquide universel et procédé d'imagerie de microscope électronique en transmission à haute résolution et analyses multimodales de matériaux d'échantillon liquide - Google Patents

Dispositif d'échantillon liquide universel et procédé d'imagerie de microscope électronique en transmission à haute résolution et analyses multimodales de matériaux d'échantillon liquide

Info

Publication number
EP3610248A1
EP3610248A1 EP18735431.1A EP18735431A EP3610248A1 EP 3610248 A1 EP3610248 A1 EP 3610248A1 EP 18735431 A EP18735431 A EP 18735431A EP 3610248 A1 EP3610248 A1 EP 3610248A1
Authority
EP
European Patent Office
Prior art keywords
liquid sample
sample
membrane
tem
window
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.)
Withdrawn
Application number
EP18735431.1A
Other languages
German (de)
English (en)
Inventor
Xiao-ying YU
Libor KOVARIK
Bruce W. Arey
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.)
Battelle Memorial Institute Inc
Original Assignee
Battelle Memorial Institute Inc
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
Priority claimed from US15/483,939 external-priority patent/US10598609B2/en
Application filed by Battelle Memorial Institute Inc filed Critical Battelle Memorial Institute Inc
Publication of EP3610248A1 publication Critical patent/EP3610248A1/fr
Withdrawn legal-status Critical Current

Links

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
    • G01N23/2204—Specimen supports therefor; Sample conveying means therefore
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/02—Details
    • H01J37/20—Means for supporting or positioning the objects or the material; Means for adjusting diaphragms or lenses associated with the support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/20—Positioning, supporting, modifying or maintaining the physical state of objects being observed or treated
    • H01J2237/206—Modifying objects while observing
    • H01J2237/2065—Temperature variations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/26—Electron or ion microscopes

Definitions

  • This invention relates generally to transmission electron microscopy (TEM) and more particularly to TEM liquid sample imaging systems and processes.
  • TEM transmission electron microscopy
  • a recent innovation by the same research group has produced a System for Analysis of Surfaces of Liquids at the Liquid Vacuum Interface (SALVI) (described in issued U.S. Patent 8,555,710 and progeny thereof cited above) that allow for imaging of liquid surfaces with advantages not seen in the prior art. These include vacuum compatibility and low cost fabrication which also allows multimodal analyses of the same sample by multiple analysis platforms. In addition to these advantages various additional modifications have enhanced the capability of the original design.
  • the present description provides a sample holder device that enables TEM imaging to be transmitted through the sample. These TEM liquid sample holders are compatible with standard TEM chips and TEM sample holders and can eliminate the need for specialized liquid sample holders and chips. These sample holders enable multimodal analyses of the same liquid samples utilizing multiple instrument platforms, and have a lower fabrication cost. This improved system and device provide for better results with lower costs and are another advancement in the development of improved sample processing technologies.
  • the present invention is a TEM liquid sample device for static and dynamic TEM imaging and multimodal analyses of liquid samples in situ.
  • the device i ncludes a sample chamber formed by a pai r of membranes.
  • Membranes can be made of various materials includi ng silicon contai ning materials, ceramics, glass, graphene, including combi nations of these materials.
  • Each membrane includes a non- opaque window.
  • At least one membrane includes a vent apertu re.
  • These devices allow the liquid sample to be held in the sample chamber without an O-ring type seal.
  • the sample chamber holds a selected quantity of a liquid sample while a probe beam passes throug h the wi ndow and internal gases are vented throug h the vent apertu re.
  • Vent apertu res may include various sizes and dimensions in order to retai n the liquid sample within the sample chamber when the TEM vacuu m is applied .
  • I n some embodi ments and applications the liqu id sample has a generally u niform thickness.
  • I n some embodi ments these devices include a sample injection port or valve to allow delivery of the liquid sample to the sample chamber.
  • a frame is sandwiched between the two membranes to i mpart a preselected height to the sample chamber.
  • I n some embodi ments a spacer is positioned on one or both of the membranes between the membrane and the sample chamber to enhance optical characteristics of images created by the probe beam such as an en hanced i mage resolution or an enhanced field of view. Spacers of varying thicknesses may be utilized to enable formation of various liquid sample layer thicknesses in the sample chamber between the membranes for i maging and multi modal analyses.
  • I n some embodi ments windows on one membrane are not identical to wi ndows on the second membrane.
  • the first membrane i n cludes a different nu mber of windows than the second membrane.
  • At least one window in each membrane is alig ned with the other to form a probe beam transmission zone th roug h which the probe beam passes.
  • windows are orthogonally alig ned .
  • vent apertu res are positioned outside the probe beam transmission zone.
  • I n some embodi ments the vent apertu re is not a probe beam apertu re.
  • the method includes interrogating the liquid sample in the sample chamber formed by a pair of membranes. Each membrane includes a non-opaque window and at least one membrane forms a vent aperture.
  • the sample chamber holds a preselected quantity of the liquid sample therein while a probe beam passes through the window and internal gases are vented through the vent aperture. Venting of the internal gases includes delivering the gases to the TEM vacuum when the TEM vacuum is applied.
  • interrogating the liquid sample includes holding the liquid sample in a generally uniform thickness in the sample chamber while passing the probe beam through the windows and through the liquid sample of the sample chamber while venting the internal gases through the vent aperture. This arrangement allows imaging of the liquid sample to be performed at spatial resolutions as low as one nanometer or less.
  • Figures 2A-2B show different window configurations utilized in accordance with the present invention.
  • Figures 3A-3D show various TEM images and different multimodal images of liquid sample particles acquired in accordance with one embodiment of the present invention.
  • Figures 4A-4F show TEM images of liquid sample particles dynamically acquired as a function of time and temperature in accordance with one embodiment of the present invention.
  • FIG. 1A one embodiment of a TEM liquid sample device 100 is shown.
  • Device 100 includes a pair of membranes 2 that form a sample chamber 3 into which the liquid sample is introduced between the membranes.
  • Membranes are made of a TEM vacuum compatible material such as ceramics including silicon nitride (SiN), silicon containing materials such as SiO2, other materials such as glass, graphene, and combinations of these various materials.
  • Membranes 2 may include various shapes such as round and square and various thicknesses.
  • device 100 includes a support frame 4 sandwiched between the membranes made of an inert and vacuum compatible material such as silicon (Si). Support frame 4 may include various thicknesses.
  • Membranes 2 may include an optional spacer 6 made of an inert material that attaches to and circumvolves the outer edge of a surface of the membranes. Spacers 6 may be attached using methods known in the chip fabrication arts such as spin coating. Spacer 6 thicknesses (Z-direction) determine the thickness or depth of the liquid sample layer 8 in the sample chamber 3 between the membranes 2 in the assembled device 100. Liquid layer thickness also depends in part on such factors as type of liquid; liquid physical properties such as viscosity; materials in the liquid being imaged or analyzed such as biological materials, crystalline materials, and particulate materials; material concentrations and volumes; and other like factors.
  • Membranes include an electron transparent (non-opaque) window 10 made of a TEM vacuum compatible material such as a silicon nitride (SiN) ceramic, other silicon containing materials such as silicon dioxide (Si02), and other suitable materials disclosed above.
  • windows 10 are composed of a same material as the membranes 2 to minimize fabrication costs but window materials are not intended to be limited. Windows 10 may include various shapes, dimensions, and orientations in selected arrangements or chip patterns. And, various numbers of windows may also be utilized as described further in reference to Figure 2 hereafter. Windows 10 are introduced into the membranes 2 using methods known in the chip fabrication arts such as wet etching, dry etching, and laser lithography.
  • vent aperture 12 is shown positioned in one membrane 2 that provides dynamic release of internal gases formed in the liquid sample 8 in the sample chamber 3 that maintains uniformity of the liquid sample layer 8 in the sample chamber 3 while liquid sample imaging is performed in the TEM under high vacuum, which enhances effective liquid sample viewing area in the TEM as well as resolution in images created while imaging these liquid samples.
  • Vent aperture 12 is introduced into the chip membrane by methods such as laser drilling or combined Scanning Electron Microscope (SEM)/Focused Ion Beam (SEM-FIB) drilling.
  • SEM Scanning Electron Microscope
  • SEM-FIB Fluor-FIB
  • vent apertures 12 are positioned in each membrane 2 above and below the liquid sample layer 8.
  • Vent apertures 12 may also be utilized to accommodate TEM liquid sample devices with different and smaller dimensions; different spatial depths; different liquid types and liquid sample materials; different liquid sample properties such as viscosity; different sample liquid thicknesses, spatial resolutions, and spatial depths as well as process conditions such as sample heating or cooling during TEM and multimodal imaging.
  • This capability to release internal gases from the liquid sample provides a unique and non-obvious innovation that addresses the well-known problem of sample bulging not provided by conventional TEM liquid sample devices and approaches that retain these gases in the sealed sample devices during TEM imaging known to generally reduce both the effective sample viewing area as well as the image resolution in these prior art devices.
  • Figure 1B shows another embodiment of the TEM liquid sample device 100.
  • this embodiment also includes an injection port 16 or other introduction device 16 that delivers the liquid sample 8 into the sample chamber 3 between the membranes 2 of the assembled device.
  • the injection port 16 is shown positioned so as to introduce liquid sample 8 into the sample chamber 3 through one end of the support frame 4 but positions are not intended to be limited.
  • FIG. 1C shows yet another embodiment of the TEM liquid sample device 100.
  • device 100 includes a sample chamber 3 sandwiched between a pair of membranes 2 that encloses the liquid sample 8 with transmission windows 10 in each of the membranes 2.
  • This embodiment utilizes no frame or spacer as in embodiments described previously. Vent apertures 12 are shown positioned in one of the membranes 2 outside probe beam transmission zone 14, but number of vent apertures and their position in one or more membranes 2 are not intended to be limited.
  • FIG. 2A is a top surface view showing one exemplary arrangement and alignment of single windows 10 in one embodiment of an assembled TEM liquid sample device 100 of the present invention in respective membranes 2.
  • chip membranes 2 are round.
  • Each window 10 also has a rectangular shape with an orientation that is orthogonal to the window 10 in the respective membrane 2.
  • FIG. 2B shows another exemplary arrangement and alignment of windows 10 in another assembled TEM liquid sample device 100.
  • chip membranes 2 are square.
  • a top membrane 2 includes three windows 10 positioned adjacent to each other with a single window positioned in a bottom membrane 2 oriented orthogonal to windows in the top membrane 2 forming three transmission zones 14 in this particular alignment and arrangement.
  • Gas release vents 12 are shown positioned at various locations in respective membrane 2 windows 10 but again are not intended to be limited thereto. In preferred embodiments gas release vents 12 are positioned in windows 10 outside the transmission zone 14 so as not to interfere with transmission of the electron probe beam through the membrane windows 10. Other window orientations and arrangements may also be utilized such as a parallel orientation or orientations between the orthogonal and parallel positions.
  • the TEM electron probe beam passes through the transmission zone 14 of the first membrane window 10 then proceeds through the liquid sample and exits the device through the transmission zone 14 of a second window 10 in the opposing membrane 2.
  • Images of the liquid sample and materials therein formed by interaction of the electron probe beam with the liquid sample and materials therein in situ are collected by a TEM image collection plate or other detectors (not shown) from which images of the liquid samples and materials can be generated.
  • Multimodal imaging and analyses of the same liquid sample materials in other analytical platforms can also be performed such as in electron diffraction (ED) and crystal diffraction instruments and platforms, Helium Ion Microscopes (HelM), Scanning Electron Microscopes (SEM), Scanning Transmission X-Ray Microscopes (STXM), and Scanning Transmission Electron Microscopes (STEM) as well as other instruments and analytical platforms.
  • ED electron diffraction
  • HelM Helium Ion Microscopes
  • SEM Scanning Electron Microscopes
  • STXM Scanning Transmission X-Ray Microscopes
  • STEM Scanning Transmission Electron Microscopes
  • Chip membranes included a thickness selected from about 10 nm to about 50 nm and a spacer thickness selected from about 100 nm to about 800 nm attached to the Si support frames with a typical thickness of about 100 Mm resulting in a typical liquid sample layer thickness in the assembled device of from about 200 nm to about 1600 nm.
  • chip membranes each included a single SiN window with rectangular shapes of various dimensions such as, for example, 50 Mm by 200 Mm and 30 Mm by 200 Mm oriented orthogonally to the opposing membrane window with a chip membrane thickness of 25 nm and a spacer thickness of 400 nm providing a liquid sample layer thickness in the assembled device of about 800 nm (2 x 400 nm) and a total device thickness of -200 Mm.
  • vent apertures were introduced using SEM/FIB into one or more membrane windows on respective sides of the TEM liquid sample device 100 outside the transmission zone 14 to prevent sample bulging and to maintain chip membrane uniformity during TEM and multimodal imaging.
  • vent apertures included sizes from about 700 nm to about 1000 nm but sizes are not intended to be limited. For example, in some applications vent apertures included sizes selected from about 500 nm to about 2 ⁇ . In some applications vent apertures included a size less than or equal to about 1 ⁇ to accommodate lower spatial resolution depths in the TEM as low as ⁇ 1 nm without needing to alter the liquid samples in the device such as by freezing or drying as performed in the prior art.
  • Assembled TEM liquid sample devices of the present invention were then loaded into a standard type TEM solid sample holder or a standard type TEM sample heating holder such as Gatan® holders (Pleasanton, CA, USA) and inserted into the TEM high vacuum for static and dynamic TEM sample imaging.
  • one embodiment of the TEM liquid sample device was loaded with liquid samples containing AIOOH (e.g., APYRAL AOH-60 Boehmite, Nabaltec, Germany) particles in Dl water at concentrations from about 10 micrograms per cubic meter (10 Mg/m 3 ) to about 10 milligrams per cubic meter (10 mg/m 3 ) that were then loaded into a standard type TEM sample holder for TEM imaging of the particles in the liquid sample in situ in an Environmental TEM (ETEM) while under vacuum. Vacuum in the ETEM was sustained throughout the experiments from about 2 x 10 7 mbar to about 1 x 10 3 mbar. Vacuum inside the objective pole piece was maintained by differential pumping.
  • AIOOH e.g., APYRAL AOH-60 Boehmite, Nabaltec, Germany
  • Figure 3A shows a TEM image of a collection of AIOOH particles in the liquid sample obtained in high vacuum mode utilizing the present invention including a cluster of AIOOH particles and a few additional individual AIOOH particles.
  • Figure 3B shows a TEM image of a single AIOOH particle from the cluster of AIOOH particles in Figure 3A.
  • FIG. 3C shows a multimodal electron diffraction pattern image of the same AIOOH particle viewed in Figure 3B showing the crystal symmetry and lattice spacing of this particle.
  • Figure 3D shows another multimodal image of the same single AIOOH particle in Figure 3B acquired with HelM. Standard imaging conditions for each of these instrument platforms whether for TEM solid samples, ED solid samples, or HelM solid samples were utilized demonstrating universality, utility, and advantages provided by the present invention for multimodal imaging of liquid sample materials in situ compared to prior art systems and approaches.
  • liquid samples containing Bayerite [ -aluminum hydroxide or AI(OH)3] particles e.g., APYRAL AOH-180, Bayerite, Nabaltec, Germany
  • concentration of 100 micrograms per cubic meter 100 Mg/m 3
  • pipette total volume of ⁇ 20 ⁇ _
  • Vacuum ( ⁇ 10 7 Torr) was maintained throughout these experiments allowing TEM images to be acquired dynamically under constantly changing conditions.
  • Liquid samples were then heated under vacuum by ramping holder temperature from room temperature of about 21 degrees (°C) to 400 °C in order to observe particle phase transformation in situ. Heating rates were selected from about 1 °C per min to about 20 °C per minute with a 4 hour run time on average.
  • Liquid samples were first heated to 100 °C to remove water from inside the device cell and then held at 200 °C for 30 minutes to ensure water was removed as evidenced by pressure stabilization inside the cell. Cell was then heated, for example, to 400 °C at 50 degree increments and held at temperature for 30 min.
  • FIGS. 4A-4F show a series of high resolution TEM images of a same set of bayerite particles acquired dynamically in time-elapsed manner while dynamically heating these particles in a TEM solid sample heating holder under high vacuum conditions as a function of temperature and time from room temperature (4A) to 400 °C (4F) showing phase changes as the particles change from bayerite to AI2O3.
  • Figure 4A is an image of a cluster of bayerite particles in the liquid sample acquired at room temperature showing initial sharp particle shapes and edges.
  • Figure 4B is an image of the same bayerite particles after heating from room temperature to 100 degrees to remove water and then to 250 degrees which was held for 10 minutes at temperature. After water loss particle shapes and edges are not as sharp reflecting changes in particle structure.
  • Figure 4C is an image of the same bayerite particles after heating to 300 degrees and held 10 minutes at temperature. This image shows progressive changes to particle shape, morphology, and porosity at the particle surface with increasing pore size as a function of increasing temperature.
  • Figures 4D-4E show subsequent images collected for these same sample particles at yet higher temperatures or longer times. Further progression in changes to particle shape, morphology, and porosity at the particle surface are evident.
  • Figure 4F is an image after heating the same sample particles to 400 degrees held 10 minutes at temperature. Large differences in particle shape, morphology, and porosity at the particle surface are evident compared to the same particles at room temperature (4A).
  • embodiments of the present invention allow imaging of same liquid sample materials in situ in either static or dynamic conditions.
  • TEM imaging data combined with other multimodal data collected in other instrument platforms from the same liquid sample materials utilizing embodi ments of the present invention can be expected to find many varied applications in such areas as microanalysis usi ng electron microscopy and focused spectroscopy ; characterization of heterogeneous catalysts and catalytic processes ; particle evolution and growth ; particle morphology and structu re ; particle porosity; and predictive materials and processes.
  • the present invention provides novel and non-obvious advances in TEM liquid sample i magi ng as compared to prior art TEM liquid sample systems and approaches taught i n the prior art.
  • the invention utilizes standard type TEM chips compatible with standard type TEM sample holders thus eli mi nating need for specialized TEM chips and TEM liquid sample holders or specialized and i nvolved sealing approaches utilized in the prior art.
  • vent apertu res of the present i nvention add ress liquid sample bulgi ng not resolved by systems and approaches taug ht i n the prior art thereby providing a novel and non-obvious approach for enhanced TEM and multi modal image resolution , a sig nificant advancement i n the art.
  • Thi rd, i nvention devices have a significantly lower material and fabrication cost compared to prior art devices and are easily assembled.
  • Fou rth, device parameters are easily tailored or modified providi ng a high modular flexibility and versatility enabling mu ltimodal imaging and analyses of the same liqu id sample materials i n other analytical platforms such as a Hel M .
  • the i nvention enables dynamic TE M imagi ng of liquid sample materials in situ not previously achieved with prior art systems and approaches.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (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

L'invention concerne des dispositifs et des procédés d'imagerie d'échantillon liquide pour imagerie de microscope électronique en transmission (MET) à haute résolution et analyses multimodales de matériaux d'échantillon liquide in situ sous vide poussé qui sont compatibles avec des membranes de puce de MET de type standard et des supports d'échantillon de MET permettant d'effectuer une imagerie d'échantillon liquide de MET dès lors qu'un instrument de MET est accessible et à un coût sensiblement réduit par comparaison avec les systèmes et les approches de l'état de la technique.
EP18735431.1A 2017-04-10 2018-04-09 Dispositif d'échantillon liquide universel et procédé d'imagerie de microscope électronique en transmission à haute résolution et analyses multimodales de matériaux d'échantillon liquide Withdrawn EP3610248A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15/483,939 US10598609B2 (en) 2011-03-14 2017-04-10 Universal liquid sample device and process for high resolution transmission electron microscope imaging and multimodal analyses of liquid sample materials
PCT/US2018/026708 WO2018191167A1 (fr) 2017-04-10 2018-04-09 Dispositif d'échantillon liquide universel et procédé d'imagerie de microscope électronique en transmission à haute résolution et analyses multimodales de matériaux d'échantillon liquide

Publications (1)

Publication Number Publication Date
EP3610248A1 true EP3610248A1 (fr) 2020-02-19

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WO (1) WO2018191167A1 (fr)

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CN114324417B (zh) * 2021-12-29 2024-02-13 华东师范大学 一种减小原位液体腔窗口在负压环境中形变的装置

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US8555710B2 (en) 2011-03-14 2013-10-15 Battelle Memorial Institute Systems and methods for analyzing liquids under vacuum
US9373480B2 (en) * 2013-04-12 2016-06-21 Hitachi High-Technologies Corporation Charged particle beam device and filter member
NL2013706B1 (en) * 2014-10-29 2016-10-04 Univ Delft Tech Improved microreactor for use in microscopy.
US9594034B1 (en) * 2015-09-30 2017-03-14 Premier Lab Supply Inc. Oxford style sample cup

Also Published As

Publication number Publication date
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