CN104897700B - To the transmission scattering imaging device and method of liquid nano sample in ESEM - Google Patents
To the transmission scattering imaging device and method of liquid nano sample in ESEM Download PDFInfo
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Abstract
Electronic Micro-Analysis engineering device technique field is belonged to the transmission scattering imaging device and method of liquid nano sample in ESEM, more particularly to the reflection in scanning electron microscope sem to liquid nano sample and transmission scattering technical field of imaging, it is characterized in that, in SEM sample rooms, immediately below the thin window of liquid nano sample at 5mm~10mm, one transmission scattered electron detector TSD is installed, under conditions of incident electron energy is 15keV~30keV, nano particle formation resolution ratio to a few nm~500nm in sealing liquid is several nm, enlargement ratio is × 50~× 100000 and the good transmission scattered electron picture of image contrast, TSD detectors are adapted to mount in all kinds of SEM, with secondary electron detector ETD, energy disperse spectroscopy EDS and cathode-luminescence spectrometer CL collaborations are used, observe metal, semiconductor, it is inorganic, it is organic, compound, the class nano material such as biology.
Description
Technical field
The present invention is using a kind of transmission scattered electron detector TSD devices, the liquid nano sample observed in scanning electron microscope sem
Product, obtain the transmission scattered electron picture of high-resolution (a few nm) and high magnification (× 100000), Momentum profiles instrument EDS and the moon
Pole spectral fluorometer CL, original position obtains pattern, composition, crystal structure, band structure and luminous spectrum of liquid nano chip sample etc.
Information.Liquid nano sample is the nano particle for the nm of several nm~hundreds of being sealed in liquid chip.The structure of TSD detector assemblies
Make simple, suitable in tungsten filament ESEM, field emission scanning electron microscope is used in environmental scanning electronic microscope.Transmission scattering imaging side
Method can be in nanometer technology, energy environment, IT industry, and the field such as biomedicine is applied.Nanotube sample includes metal, partly led
Body, inorganic, organic, compound and Bio-Nano-Materials.
Background technology
Scientific and technological progress of the electron microscopy to material subject and life science plays an important role.Scanning electron microscope sem
With nanometer and atomic resolution, there is provided the letter such as material microscopic pattern, chemical composition and crystal structure respectively with transmission electron microscope TEM
Breath.Traditional SEM and TEM can only observe solid sample and can not observe fluid sample.Directly observe nano material in the solution
Synthesis, structural evolution, the interfacial reaction, electrochemistry and light-catalyzed reaction of solid-liquid-gas phase, research nano material and environment
Interaction be that numerous scientific and technical personnel are highly desirable, nanometer technology, energy environment, IT industry, biological doctor can be greatly facilitated
The deep development of etc. subject and technical field.In recent years, the TEM and SEM of wet environment and liquid environment have obtained considerable hair
Exhibition.It is using the Si-Si prepared by MEMS micro-processing technology in wet environment transmission electron microscope (Wet-TEM)3N4Chip, suspension
The solution sealing for having nano particle/line in the chips, allows electron beam to penetrate the imaging of liquid nano chip sample.At present, Wet-TEM
It has been observed that in liquid nano particle atomic response.
The technology being imaged in SEM using liquid chip is also developed.Because SEM and TEM is in incident electron energy, letter
Number receive and imaging mode, sample type in terms of all there is larger difference so that SEM resolution ratio (being less than 1nm) is substantially low
In TEM (being less than 0.1nm).Therefore, observation macromolecular and biological species sample, times magnification are used for using liquid chip in SEM
Rate is not bery high, is thousands of times~30000 times.Usual SEM uses the secondary electron SE image formations of high resolution.And for liquid
Chip sample, the imaging effect that can not be got well using SE signals, because SE is the valence electron that sample top layer is reflected, energy
Low, signal comes from top layer, and SE substantially decays through signal intensity after liquid and chip window.Therefore, to liquid core in SEM
Piece is needed using the high backscattered electron BS imagings of energy.BS is more from electronics and the 1/2~1/3 of solid sample interaction area
Deeper scope, acted on by electronics multiple scattering in the sample, the resolution ratio of BS pictures is significantly lower than common SE pictures.
Receiving side signal formula in SEM is reflective, receives secondary electron SE, the back scattering for reflecting solid sample surface
The signals such as electronics BS, X-ray and cathode-luminescence CL.The spy for being imaged and being analyzed to solid sample using plain scan Electronic Speculum
The mounting means for surveying device and spectrometer is shown in Fig. 2.14 in scanning electron microscope example room, solid sample 17 is placed on solid sample support 18
On.Secondary electron detector ETD5 and X-ray energy disperse spectroscopy EDS4 is arranged on the top in the left side of solid sample 17；Back scattering electricity
Sub- detector BSD16 or cathode-luminescence spectrometer CL13 sphere collection mirror is all arranged on lower section and the solid-like of the pole shoe of object lens 3
The surface of product 17.Therefore, in common SEM configuration, BSD detectors 16 and CL spectrometers 13 can not be used simultaneously.
Because TEM reflection receivable mode of the transmission reception mode than SEM has a higher resolution, SEM scanning transmission into
Image space formula (SEM-STEM) is also developed in recent years, and SEM imaging resolution is brought up to~0.8nm.However, current STEM
Imaging mode is not yet popularized in SEM, and main cause has：I) SEM incident electron energies (30keV) are incident far below TEM
Electron energy (200keV), makes STEM still be significantly lower than TEM as resolution ratio as resolution ratio, and can not carry out choosing electricity in SEM
Sub- diffraction analysis；Ii) STEM detectors can only be configured in Flied emission SEM, and price is costly；Iii) STEM high-resolution imagings are needed
Want several mm short operating distance, it is difficult to realize in situ to film sample progress CL spectrum and EDS energy spectrum analysis；Iv) STEM is imaged
Film sample is needed, the difficulty of sample preparation is added.
The content of the invention
The present invention be directed to a kind of transmission scatter sounding device that liquid nano sample is proposed is observed in scanning electron microscope sem
And imaging method.Using transmission scattered electron detector TSD, the scattered electron TS imagings for penetrating liquid nano sample are received.With
Secondary electron SE pictures and backscattered electron BS pictures compare, and TS pictures have higher resolution ratio (a few nm) and amplification to liquid nano sample
Multiplying power (~× 100000), and preferably image contrast and signal to noise ratio snr.Liquid nano sample is sealed in liquid chip
Nanoparticle suspension particle and nano wire (nm of several nm~hundreds of,<500nm).TSD detectors and secondary electron detector, energy disperse spectroscopy EDS
Used cooperatively with cathode-luminescence spectrometer CL, obtain pattern, composition, crystal structure, band structure and the hair of nano particle in liquid
The integrated informations such as spectrum.The simple structure of TSD detector assemblies, is adapted for mount on tungsten filament SEM, Flied emission SEM and environment and sweeps
Retouch and used in Electronic Speculum ESEM.Liquid suspension includes metal and alloy, semiconductor, ceramics, polymer, compound, biological and micro-
The nano particle such as biology/nano wire.
The launching electronics of electron gun 1 of ESEM, after condenser 2 and object lens 3 are focused on, in liquid nano sample 12
Surface scan.The signal that electron-beam excitation sample is produced, by the electron detector and spectrum in scanning electron microscope example room 14
Instrument is received.Wherein, transmission scattered electron detector TSD 10 receives the scattered electron formation TS pictures for penetrating liquid nano sample 12；
Secondary electron detector ETD5 receives the secondary electron formation SE pictures for reflecting sample surfaces；Energy disperse spectroscopy EDS4 is received and is reflected sample
The characteristic X-ray on product surface, forms energy spectrum diagram；Cathode-luminescence spectrometer CL13 receives the photon formation CL for reflecting sample surfaces
Spectrogram.
Transmission scattering imaging device of the present invention in ESEM to liquid nano sample, it is characterised in that
Collectively formed by the lens barrel of the sample room of scanning electron microscope sem and scanning electron microscope sem, wherein：
The lens barrel of scanning electron microscope sem, radio is entered by the axis launched along electron beam is in symmetric configuration from top to bottom
The accelerating potential of son is 14 in 10keV~30keV electron gun 1, condenser 2, and the insertion scanning electron microscope example room
Diaphragm collectively forms for 40 μm~100 μm of object lens 3；
14 are configured with scanning electron microscope sem sample room：Transmit scattered electron detector TSD10, transmission scattered electron detection
Device TSD support arms 15, transmission scattered electron detector TSD fixed supports 9, liquid nano sample 12, liquid nano sample support
Arm 11, liquid nano sample fixed support 6, support fixed disk 7, scanning electron microscope sem sample stage 8, secondary electron detector ETD5,
Energy disperse spectroscopy EDS4 and cathode-luminescence spectrometer CL13, wherein：
Scattered electron detector TSD10 is transmitted, is an annular monocrystalline silicon detector, installed in the transmission scattering electricity
On the upper surface of sub- detector TSD support arms 15, positioned at the underface of the liquid nano sample 12, described receive is penetrated to receive
The scattered electron TS imagings of the rice thin window of fluid sample 12, the transmission scattered electron detector TSD10 to the liquid nano
The distance of the lower surface of sample 12 is 5mm~10mm, and solid acceptance angle is 20 °~47 °, and the nano fluid is penetrated in reception to take into account
The detection efficient and image resolution ratio of scattered electron during the scattered electron of the thin window of body sample 12,
Scattered electron detector TSD fixed supports 9 are transmitted, the right side of the support fixed disk 7 is vertically fixed on, in height
On it is lower than the liquid nano sample fixed support 6, in the left side of the transmission scattered electron detector TSD fixed supports 9
Face upper level is connected to the transmission scattered electron detector TSD support arms 15,
Support fixed disk 7 is fixedly mounted on the upper surface of the scanning electron microscope sem sample stage 8, the scanning electron microscope sem
Sample stage 8, is fixed on the bottom surface in the scanning electron microscope sem sample room 14,
Liquid nano sample 12, is sealed in the through hole of the upper surface diameter 2.8mm of liquid nano sample support arm 11
Liquid chip that is upper and being clung with conductive silver glue or carbon paste band, internal liquid nano is a kind of nanometer material suspended in the solution
Material, or the solution medium chemically reacted, the nano material at least include following any particle/line and generation
The solution medium of chemical reaction：Metal, semiconductor, ceramics, polymer, compound, biology and microorganism, medicine, catalyst, magnetic
Property particle, aerosol, hydrogel, latex, battery material, the diameter of nano particle is between a few nm~500nm, the nano fluid
The upper surface of body sample 12 to the pole shoe lower surface of object lens 3 operating distance be 5mm~13mm,
Liquid nano sample fixed support 6, is vertically fixed on the left side of the support fixed disk 7, in the liquid nano
The liquid nano sample support arm 11 is connected to the right flank upper horizontal of sample fixed support 6,
Secondary electron detector ETD5, on the left wall medial surface of the scanning electron microscope sem sample room 14, is faced
The upper left side of the liquid nano sample 12, with receive reflect the secondary electron SE on the surface of liquid nano sample 12 into
Picture,
On energy disperse spectroscopy EDS4, the left wall medial surface for being similarly installed at the scanning electron microscope sem sample room 14, but positioned at described
Secondary electron detector ETD5 top, to receive the X-ray for reflecting the surface of liquid nano sample 12, carries out chemistry
Constituent analysis,
Cathode-luminescence spectrometer CL13, positioned at the upper right side of the liquid nano sample 12, installed in the scanning electron microscope sem
On the right wall medial surface of sample room 14, the hemisphere face receive mirror detector of the cathode-luminescence spectrometer CL13 faces the nanometer
The surface of fluid sample 12, the lower section of the pole shoe of the object lens 3, the surface of liquid nano sample 12 is reflected to receive
Photon, carries out spectrum analysis,
In transmission scattering imaging device, the transmission scattered electron detector TSD10, secondary electron detector ETD5,
The control signal of energy disperse spectroscopy EDS4 and cathode-luminescence spectrometer CL13 inputs is to receive successively in time, and for Cooperative Analysis
's.
Transmission of the present invention in ESEM to liquid nano sample scatters imaging method, it is characterised in that
Realized successively according to following steps：
Step (1), liquid nano sample 12 is sealed in a liquid chip, then the liquid chip is placed on described
On the through hole of the liquid nano sample support arm 11 of liquid nano sample fixed support 6, with conductive silver glue or carbon paste band handle
The liquid chip is clung, and the liquid nano sample fixed support 6 and the support fixed disk 7 are fixed with nut；
Step (2), the support fixed disk 7 that step (1) is obtained is inserted on the scanning electron microscope sem sample stage 8,
The thin window of the upper surface of liquid nano sample 12 is faced the electron beam of vertical incidence, and positioned at the pole shoe of object lens 3 just under
At square 5mm~13mm, incident beam is set to penetrate the thin window scanning of the liquid nano sample 12；
One transmission scattered electron detector TSD10, is arranged on the transmission scattered electron detector TSD by step (3)
On support arm 15, then the transmission scattered electron detection for being connected to the transmission scattered electron detector TSD support arms 15
Device TSD fixed supports 9 are inserted into the support fixed disk 7, make the upper surface of the transmission scattered electron detector TSD10 just right
The electron beam of vertical incidence, and at the underface 5mm of the liquid nano sample 12~10mm, transmits the figure of scattered electron
As resolution ratio be several nm, enlargement ratio be × 50~× 100000；
Step (4), is evacuated down to the scanning electron microscope sem sample room 14 vacuum of setting, is applied to the electron gun 1
Plus 15kV~30kV accelerating potential, 10-8A~10-11A incident current, after focusing, in the thin window of liquid nano sample 12
The surface point by point scanning of mouth, shows transmission scattered electron TS pictures and secondary electron SE pictures and is recorded as successively over the display
Picture.
Transmit scattered electron detector TSD10 be arranged at least include tungsten filament ESEM, field emission scanning electron microscope or
Used in all kinds of ESEMs including environmental scanning electronic microscope.
The effect of the present invention：The transmission scattered electron detection device and imaging mode of the present invention has following characteristics：
1st, using transmission-type receiving side signal formula, imaging resolution of the ESEM to liquid nano sample is significantly improved
And enlargement ratio, the transmission for obtaining contrast and the good high-resolution of signal to noise ratio snr (a few nm) and high magnification (× 100000) is scattered
Penetrate charge pattern.
2nd, transmission scattered electron detector TSD10 is arranged on the lower section of liquid chip, can be with secondary electron detector
ETD, X-ray energy spectrometer EDS and cathode-luminescence spectrometer CL are used cooperatively, and original position obtains pattern, composition, the crystalline substance of liquid nano sample
The integrated informations such as body structure, band structure and luminous spectrum.
3rd, the liquid nano sample that the present invention is observed is the nano particle/line being sealed in liquid chip and occurs chemistry instead
The solution medium answered, including：Metal, semiconductor, ceramics, polymer, compound, biology and microorganism, medicine, catalyst, magnetic
Property particle, aerosol, hydrogel, latex, battery material.
4th, scattering detector TSD device simple structures are transmitted, suitable for be used in different types of ESEM,
Including tungsten filament ESEM, field emission scanning electron microscope or environmental scanning electronic microscope.
Brief description of the drawings：
Fig. 1, the present invention scanning electron microscope sem schematic diagram.
Fig. 2, plain scan Electronic Speculum SEM schematic diagrames.
Fig. 3, liquid chip profile secondary electron SE pictures：
Fig. 3 (a) is to have Si in the middle of liquid chip outline drawing, chip3N4Thin window, enlargement ratio is × 60；
Fig. 3 (b) is the rectangle Si of 50 μm of 400 μ m in the middle of liquid chip3N4Thin window, enlargement ratio is × 250.
Fig. 4, using TSD detectors and ETD detectors, to TiO2Liquid chip sample is imaged, and accelerating potential is 30kV, is put
Big multiplying power is × 60000：
Fig. 4 (a) is nano-TiO2The TS pictures of particle in a liquid；
Fig. 4 (b) is nano-TiO2The SE pictures of particle in a liquid.
Fig. 5, using transmission scattered electron detector TSD10 and secondary electron detector ETD5, to liquid chip sample into
TiO is suspended with picture, liquid2With Au nano particles, accelerating potential is 30kV, and enlargement ratio is × 100000：
Fig. 5 (a) is TiO2With the FS pictures of Au mixing nano particles；
Fig. 5 (b) is TiO2With the SE pictures of Au mixing nano particles.
Fig. 6, using TSD detectors, to nano-TiO2Liquid chip sample is imaged, and accelerating potential is 30kV, enlargement ratio
For × 5000 times.
Fig. 7, using energy disperse spectroscopy EDS and cathode-luminescence spectrometer CL, liquid chip sample is analyzed, the aqueous solution of chip
In include TiO2With FeO nano particles, accelerating potential is 30kV, and enlargement ratio is × 5000：
Fig. 7 (a) is TiO in liquid2The EDS spectrums of nano particle and corresponding SE pictures；
Fig. 7 (b) is the EDS spectrums and corresponding SE pictures of FeO nano particles in liquid；
Fig. 7 (c) is TiO in liquid2The CL spectrums of nano particle.
Fig. 8, using transmission scattered electron detector TSD10 and secondary electron detector ETD5, to resin liquid chip sample
Product are imaged, and resin glue is included in the aqueous solution in liquid chip, and accelerating potential is 30kV, and enlargement ratio is × 30000：
Fig. 8 (a) is the TS pictures of resin glue；
Fig. 8 (b) is the SE pictures of resin glue.
Accompanying drawing is marked：
In fig. 1 and 2：1st, electron gun, 2, condenser, 3, object lens, 4, energy disperse spectroscopy EDS, 5, secondary electron detector
ETD, 6, liquid nano sample fixed support, 7, support fixed disk, 8, scanning electron microscope sem sample stage, 9, transmission scattered electron visits
Survey device TSD fixed supports, 10, transmission scattered electron detector TSD, 11, liquid nano sample support arm, 12, liquid nano sample
Product, 13, cathode-luminescence spectrometer CL, 14, scanning electron microscope sem sample room, 15, transmission scattered electron detector TSD support arms, 16,
Back scattering electronic detector BSD, 17, solid sample, 18, solid sample support.
Embodiment：
Using FEI Quanta 600F environmental scanning electronic microscopes, dress transmission scattered electron detector TSD10, secondary electron are visited
Device ETD5, energy disperse spectroscopy EDS4 and CL spectrometer are surveyed, liquid nano sample is imaged and analyzed.Observation condition, accelerating potential：
10kV~30kV, lens isis：40 μm~100 μm, incident current：10-8A~10-11A；Operating distance：8mm~13mm, amplification
Multiplying power：× 50~× 100000；CL spectrometer detector voltages：800V~1060V, wavelength：300nm~900nm, diffraction grating：
1200mm/l, slit width：5mm.
Embodiment 1：Be the present invention scanning electron microscope sem schematic diagram (see Fig. 1), including scanning electron microscope sem sample room and
The lens barrel of ESEM.In scanning electron microscope sem sample room 14, transmission scattered electron detector 10, liquid nano sample are installed
12 and corresponding fixing device.Secondary electron detector ETD5, energy disperse spectroscopy are configured with scanning electron microscope sem sample room 14
EDS4, cathode-luminescence spectrometer CL13, cooperate with transmission scattered electron detector TSD10 and use, original position obtains liquid nano sample
12 microscopic appearance, composition, crystal structure, band structure and luminous spectrum information.As a comparison, Fig. 2 is provided to solid sample 17
The plain scan Electronic Speculum SEM schematic diagrames being observed.Transmission scattered electron is fitted without in scanning electron microscope sem sample room 14 to visit
Device TSD10 is surveyed, solid sample support 18, secondary electron detector ETD5, energy disperse spectroscopy EDS4, back scattering electronic detector is configured with
BSD16 or cathode-luminescence spectrometer CL13.Cathode-luminescence spectrometer CL13 is not marked in Fig. 2, it and back scattering electronic detector 16 are all
On the same position of the lower section of the pole shoe of object lens 3, therefore in plain scan Electronic Speculum SEM, the two can not be used simultaneously.
Embodiment 2：It is the secondary electron SE pictures of liquid chip outward appearance, enlargement ratio is respectively × 60 and × 250 (see figure
3).Chip is 2.2mm × 2.2mm square, upper and lower each 200 μm of chip thickness.Upper and lower chip intermediate etch goes out 400 μ ms
50 μm of rectangle Si3N4Thin window, forms liquid tank.Thin window thickness is that the liquid between 20nm~50nm, upper and lower groove is thick
Spend for 50nm~100nm.Thin window gross thickness (upper and lower chip liquid feeding body) reaches 200nm.Liquid is instilled in lower chip, by core
Locating slot (Fig. 3 (a)) on the right side of piece aligns upper and lower chip, with epoxide-resin glue chip good seal.
Embodiment 3：It is using transmission scattered electron detector TSD10 and secondary electron detector ETD5, to TiO2Liquid
Chip sample is imaged, to TiO2Liquid chip sample is imaged, and accelerating potential is 30kV, and enlargement ratio is × 60000 (Fig. 4).
Nano-TiO2Active height, good, harmless stability, light induced electron and hole-recombination rate are low, are that the light received much attention is urged
Change material, be used widely in fields such as environmental protection, atmospheric cleaning, medical antibacterials.Under illumination, TiO2The photoproduction that particulate is produced is empty
Cave and OH free radicals have very strong oxidability, decompose oxidation operation.Nano-TiO2Enhance O2Adsorption capacity, improve
Liquid phase photocatalytic activity.In addition, nano-TiO2Catalytic activity and crystal structure and defect, particle diameter, light radiation intensity, solvent
The factors such as species and concentration are closely related.Therefore, nano-TiO is directly observed2Liquid phase reactor, the pattern of particle, knot in liquid
Structure, composition and the characteristics of luminescence, to research TiO2Photocatalytic activity and photocatalytic mechanism are significant.
Nano-TiO in comparative liquid2The TS pictures and SE pictures (Fig. 4 (a) and (b)) of particle are understood：I) resolution ratio of TS pictures, as
Contrast and SNR are above SE pictures.TS pictures clearly show tens nm TiO2Particle；And in corresponding SE pictures, due to anti-
The wall and corner effect that formula imaging belt comes is penetrated, the edge of nano particle is thickened.Ii) TS is opposite as foring contrast with SE pictures
Complementary picture.
Embodiment 4：It is, using transmission scattered electron detector TSD10 and secondary electron detector ETD5, to obtain liquid core
It is suspended with the TS pictures and SE pictures of piece sample, the TS pictures and SE pictures (Fig. 5 (a) and (b)) of the liquid chip sample of acquisition, liquid
TiO2With Au nano particles, accelerating potential is 30kV, and enlargement ratio is × 100000.In × 100000 high power picture, transmission
Scattered electron detector TSD10 shows more obvious advantage.I) TS pictures have in higher resolution ratio, TS pictures clearly than SE picture
Show the Au particles less than 10nm, and more than ten nm~300nm TiO2Particle.Ii) TS pictures have preferably as lining than SE picture
Au particles and TiO are clearly showed that in degree and signal to noise ratio snr, TS pictures2The contrast difference of particle.Au particles show darker
Contrast comes from incident electron and weakens caused to high-quality quantity of material penetration capacity.Iii) imaging of liquid nano sample high power can not be adopted
The Au particles for being difficult to tell several nm in SE signals, SE pictures are used, to hundreds of nm TiO2Particle is also difficult to obtain that contrast is good and side
Boundary's clearly image.This is due to that SE electron energies are low, through liquid and Si3N4After chip thin window, to SE detection efficient and
Image resolution ratio is substantially reduced.
Embodiment 5：It is using transmission scattered electron detector TSD10, to nano-TiO2Liquid chip sample is imaged, and is accelerated
Voltage is 30kV, and enlargement ratio is × 5000 times (see Fig. 6).As can be seen from Figure 6, under electron beam irradiation, TiO2Particle is water-soluble
Bubble, i.e. TiO are generated in liquid2Gas in solution is changed under electron beam irradiation, shows nano-TiO2Particle may
Hydrolysis is generated in the solution.
Embodiment 6：It is to use energy disperse spectroscopy EDS4 and cathode-luminescence spectrometer CL, liquid chip sample is analyzed, chip
In the aqueous solution include TiO2With FeO nano particles, accelerating potential is 30kV, and enlargement ratio is × 5000 (see Fig. 7).Fig. 7 (a)
EDS spectrum and corresponding SE pictures show that the nanoparticles composition in liquid chip is Si, O, Ti, this is TiO2Nanometer
Grain and Si3N4The composition of window material.Fig. 7 (b) EDS is composed and corresponding SE pictures show, the chain nano particle in liquid chip
Composition is Si, O, Fe, mainly N, K, FeO nano particles and Si3N4The composition of window material.Fig. 7 (c) CL, which is composed, to be shown, calcium titanium
Ore deposit type TiO2Launching wavelength isIt is E with energy gapg=3.0eV stronger visible ray.
Embodiment 7：It is using transmission scattered electron detector TSD10 and secondary electron detector ETD5, to resin liquid
Chip sample is imaged, and accelerating potential is 30kV, and enlargement ratio is × 30000 (see Fig. 8).As shown in Figure 8, transmission scattered electron is visited
The good image of contrast can be obtained to organic type nano granular of low atomic number by surveying device TSD10, and this comes from the small material pair of quality
The less scattering process of incident electron, more penetration of electrons resin liquid samples, forms bright contrast.
Above example shows, is visited with the traditional secondary electron detector ETD and backscattered electron in scanning electron microscope sem
The reflective receiving side signal formula for surveying device BSD is compared, and transmission scattered electron detector TSD has following to the imaging of liquid chip sample
Main feature：
1st, high power TS pictures (× 100000) have higher resolution ratio, more preferably image contrast and SNR.
2nd, transmission scattered electron detector TSD10 matches somebody with somebody with secondary electron detector ETD5, CL spectrometer and energy disperse spectroscopy EDS4
Conjunction is used, can the integrated information such as in situ pattern, composition, crystal structure, band structure and the luminous spectrum for obtaining liquid nano sample.
3rd, liquid nano sample includes polytype nano materials such as metal, metal oxide, semiconductor, organic matter.
Claims (3)
1. to the transmission scattering imaging device of liquid nano sample in ESEM, it is characterised in that by scanning electron microscope sem
The lens barrel of sample room and scanning electron microscope sem is collectively formed, wherein：
The lens barrel of scanning electron microscope sem, by the axis launched along electron beam incident electron energy in symmetric configuration from top to bottom
The diaphragm measured in electron gun (1), condenser (2) and interleave scan Electronic Speculum SEM sample rooms (14) for 15keV~30keV is
40 μm~100 μm of object lens (3) are collectively formed；
Scanning electron microscope sem sample room (14), is configured with：Transmit scattered electron detector TSD (10), transmission scattered electron detector
TSD support arms (15), transmission scattered electron detector TSD fixed supports (9), liquid nano sample (12), liquid nano sample
Support arm (11), liquid nano sample fixed support (6), support fixed disk (7), scanning electron microscope sem sample stage (8), secondary electricity
Sub- detector ETD (5), energy disperse spectroscopy EDS (4) and cathode-luminescence spectrometer CL (13), wherein：
Scattered electron detector TSD (10) is transmitted, is an annular monocrystalline silicon detector, installed in the transmission scattered electron
On the upper surface of detector TSD support arms (15), positioned at the underface of the liquid nano sample (12), penetrated with reception described
The scattered electron TS imagings of liquid nano sample (12) thin window, the transmission scattered electron detector TSD (10) is received described in
The distance of rice fluid sample (12) lower surface is 5mm~10mm, and solid acceptance angle is 20 °~47 °, and institute is penetrated in reception to take into account
The detection efficient and image resolution ratio of scattered electron when stating the scattered electron of liquid nano sample (12) thin window,
Scattered electron detector TSD fixed supports (9) are transmitted, the right side of the support fixed disk (7) is vertically fixed on, in height
On it is than the liquid nano sample fixed support (6) lower, in the transmission scattered electron detector TSD fixed supports (9)
Left surface upper level is connected to the transmission scattered electron detector TSD support arms (15),
Support fixed disk (7) is fixedly mounted on the upper surface of the scanning electron microscope sem sample stage (8), the scanning electron microscope sem
Sample stage (8), is fixed on the bottom surface in the scanning electron microscope sem sample room (14),
Liquid nano sample (12), is sealed in the through hole of liquid nano sample support arm (11) the upper surface diameter 2.8mm
Liquid chip that is upper and being clung with conductive silver glue or carbon paste band, internal liquid nano is a kind of nanometer material suspended in the solution
Material, or the solution medium chemically reacted, the nano material at least include following any particle/line and generation
The solution medium of chemical reaction：Metal, semiconductor, ceramics, polymer, compound, biology and microorganism, medicine, catalyst, magnetic
Property particle, aerosol, hydrogel, latex, battery material, the diameter of nano particle is between a few nm~500nm, the nano fluid
Body sample (12) upper surface to the object lens (3) pole shoe lower surface operating distance be 5mm~13mm,
Liquid nano sample fixed support (6), is vertically fixed on the left side of the support fixed disk (7), in the liquid nano
The liquid nano sample support arm (11) is connected to the right flank upper horizontal of sample fixed support (6),
Secondary electron detector ETD (5), on the left wall medial surface of the scanning electron microscope sem sample room (14), is faced
The upper left side of the liquid nano sample (12), to receive the secondary electron SE for reflecting liquid nano sample (12) surface
Imaging,
On energy disperse spectroscopy EDS (4), the left wall medial surface for being similarly installed at the scanning electron microscope sem sample room (14), but positioned at described
Secondary electron detector ETD (5) top, to receive the X-ray for reflecting liquid nano sample (12) surface, is carried out
Chemical composition analysis,
Cathode-luminescence spectrometer CL (13), positioned at the upper right side of the liquid nano sample (12), installed in the scanning electron microscope sem
On the right wall medial surface of sample room (14), the hemisphere face receive mirror detector of the cathode-luminescence spectrometer CL (13) faces described
Surface, the lower section of the pole shoe of the object lens (3) of liquid nano sample (12), the liquid nano sample is reflected to receive
(12) photon on surface, carries out spectrum analysis,
Transmission scattering imaging device in, the transmission scattered electron detector TSD (10), secondary electron detector ETD (5),
The control signal of energy disperse spectroscopy EDS (4) and cathode-luminescence spectrometer CL (13) inputs is to receive successively in time, and supplies Cooperative Analysis
.
2. according to claim 1 transmit the saturating of scattering imaging device proposition in ESEM to liquid nano sample
Penetrate scattering imaging method, it is characterised in that realized successively according to following steps：
Step (1), liquid nano sample (12) is sealed in a liquid chip, then the liquid chip is placed on described receive
On the through hole of the liquid nano sample support arm (11) of rice fluid sample fixed support (6), with conductive silver glue or carbon paste band
The liquid chip is clung, it is with nut that the liquid nano sample fixed support (6) and the support fixed disk (7) is solid
It is fixed；
Step (2), the support fixed disk (7) that step (1) is obtained is inserted on the scanning electron microscope sem sample stage (8),
The thin window of liquid nano sample (12) upper surface is set to face the electron beam of vertical incidence, and positioned at object lens (3) pole shoe
At underface 5mm~13mm, incident beam is set to penetrate the thin window scanning of the liquid nano sample (12)；
One transmission scattered electron detector TSD (10), is arranged on the transmission scattered electron detector TSD branch by step (3)
In brace (15), then the transmission scattered electron spy for being connected to the transmission scattered electron detector TSD support arms (15)
Survey device TSD fixed supports (9) and be inserted into the support fixed disk (7), make the upper of the transmission scattered electron detector TSD (10)
Surface faces the electron beam of vertical incidence, and at 5mm~10mm immediately below the liquid nano sample (12), transmission dissipates
Radio image resolution ratio be several nm, enlargement ratio be × 50~× 100000；
Step (4), is evacuated down to the scanning electron microscope sem sample room (14) vacuum of setting, is applied to the electron gun (1)
Plus 15kV~30kV accelerating potential, 10-8A~10-11A incident current is thin in the liquid nano sample (12) after focusing
The surface point by point scanning of window, shows transmission scattered electron TS pictures and secondary electron SE pictures and is recorded as successively over the display
Picture.
3. the transmission according to claim 2 in ESEM to liquid nano sample scatters imaging method, its feature
It is, the transmission scattered electron detector TSD (10), which is arranged on, at least includes tungsten filament ESEM, field emission scanning electron microscope
Or used in all kinds of ESEMs including environmental scanning electronic microscope.
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