CN116380582B - Preparation method of ultrathin suspended film transmission electron microscope sample - Google Patents
Preparation method of ultrathin suspended film transmission electron microscope sample Download PDFInfo
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- CN116380582B CN116380582B CN202310336556.7A CN202310336556A CN116380582B CN 116380582 B CN116380582 B CN 116380582B CN 202310336556 A CN202310336556 A CN 202310336556A CN 116380582 B CN116380582 B CN 116380582B
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- 230000005540 biological transmission Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000010410 layer Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 45
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 41
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 35
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000005498 polishing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 7
- -1 tetrakis (dimethylammonium) hafnium Chemical compound 0.000 claims description 4
- 238000012512 characterization method Methods 0.000 abstract description 8
- 239000011241 protective layer Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 75
- 239000012528 membrane Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 17
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 11
- 238000003917 TEM image Methods 0.000 description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/221—Ion beam deposition
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- 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
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Abstract
The invention provides a preparation method of an ultrathin suspended film transmission electron microscope sample, which comprises the following steps: (1) Alternately carrying out multi-layer atomic layer deposition on the surface of the suspended film by using a hafnium source and an oxygen source to obtain a hafnium oxide layer; (2) And (3) adopting a focused ion beam to sequentially deposit carbon and metal films on the surface of the hafnium oxide layer in the step (1) to prepare a suspended film transmission electron microscope sample. According to the preparation method, the hard HfO 2 protective layer is sequentially and alternately deposited and grown at low temperature, so that a film layer without deformation can be rapidly obtained; simultaneously, the HfO 2 which grows alternately can release the stress of the film layer in the ALD growth process, can keep the stability of the suspended film structure in the subsequent FIB preparation process, does not damage the suspended film, obtains real suspended structure information, and ensures that the subsequent TEM characterization data are real and reliable.
Description
Technical Field
The invention belongs to the technical field of electron microscope sample preparation, and particularly relates to a preparation method of an ultrathin suspended membrane transmission electron microscope sample.
Background
Transmission electron microscopy is one of the important instruments for researching the microstructure of a material, but the premise that the electron beam of the transmission electron microscopy can penetrate through a sample is that the quality of an image observed by the transmission electron microscopy is strongly dependent on the thickness of the sample, so that the observed part of the sample must be very thin. The ability of an electron beam to penetrate a solid sample is largely dependent on the acceleration voltage and atomic number of the sample composition. Generally, the higher the accelerating voltage is, the smaller the atomic number of the sample is, the larger the thickness of the sample can be penetrated by the electron beam, and the thickness of the sample is generally controlled to be 5-200 nm, which brings great difficulty to the sample preparation work of the transmission electron microscope.
At present, the basic preparation method of a sample for transmission electron microscope observation is a thinning technology, CN101216386 discloses a preparation method of a transmission electron microscope sample of a film material, a magnetron sputtering coating method is adopted to prepare a film, and a substrate of the film is thermosetting polyimide; putting the film after film coating into a dual-network; immersing the double-networking and thin film into 80% hydrazine hydrate, taking out and putting into alcohol for cleaning after the thermosetting polyimide is completely dissolved; and (3) placing the washed duplex net into an ion thinning instrument, and thinning by using an angle of 6-9 degrees until leakage is reduced.
CN114088751a discloses a method for preparing a transmission electron microscope sample of a multilayer film, which comprises the following steps: 1) Cutting pretreatment: cutting the film into long strips, soaking in a solvent, wiping the film clean, and removing the solvent on the surface of the film; 2) And (3) sticking: mixing a hardener with resin to obtain G1 glue, smearing the G1 glue on the surfaces of the cut and treated films, attaching the surfaces of the two films together, and baking and curing; 3) Cutting again: cutting the cured sample into a plurality of thin slices along the normal direction; 4) Mechanically polishing; 5) Ion thinning: and simultaneously thinning the two sides, controlling voltage to thin each side, and obtaining the transmission electron microscope sample of the multilayer film, wherein the thin thickness of the sample is below 0.1 micrometer.
Along with the smaller and smaller integrated point size of the semiconductor chip and more complex and diversified functions of the chip, the method brings greater challenges to detection and failure analysis of the semiconductor integrated circuit chip, particularly preparation of an ultrathin suspended film transmission electron microscope sample, on one hand, the method hopes to analyze the thinner and thinner preparation of the sample, but can not damage the sample or deform the original structure of the sample. The method adopts a liquid/ion thinning mode to cause deformation, cracking and the like of a film sample, and the real structural information of the suspended film cannot be obtained.
Therefore, in order to solve the above-mentioned problems, a new sample preparation technology for ultra-thin suspended membrane transmission electron microscope samples is needed to be solved by those skilled in the art.
Disclosure of Invention
Compared with the prior art, the preparation method provided by the invention can keep the stability of the suspended film structure, obtain the real suspended structure information of the sample, does not damage the sample, and can be widely applied.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a preparation method of an ultrathin suspended film transmission electron microscope sample, which comprises the following steps:
(1) Alternately carrying out at least two atomic layer depositions on the surface of the suspended film by using a hafnium source and an oxygen source to obtain a hafnium oxide layer;
(2) And (3) adopting a focused ion beam to sequentially deposit carbon and metal films on the surface of the hafnium oxide layer in the step (1) to prepare a suspended film transmission electron microscope sample.
In the invention, at least two atomic layer depositions are carried out on the upper surface and the lower surface of the suspended film.
According to the preparation method, the atomic layer deposition technology is adopted to alternately grow very thin and non-deformable hard hafnium oxide protective film layers on the upper surface and the lower surface of the suspended film, and the alternately grown HfO 2 can release the stress of the film layer in the ALD growth process, so that the stability of the suspended film structure can be conveniently maintained in the follow-up Focused Ion Beam (FIB) sample preparation process, the suspended film is not damaged, and the original and real suspended structure information of a sample is ensured to be obtained.
In a preferred embodiment of the present invention, the thickness of the suspended film is 5 to 15nm, and may be, for example, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm or 14nm, etc., but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
As a preferred embodiment of the present invention, the atomic layer deposition temperature in the step (1) may be 45℃or less, 47℃or 50℃or 52℃or 54℃or 56℃or 58℃or 60℃or 63℃or the like, but the atomic layer deposition temperature is not limited to the values listed, and other values not listed in the numerical range are applicable, and preferably 50 to 60 ℃.
Preferably, the atomic layer deposition rate in step (1) is 0.1-0.2nm/cycle, which may be, for example, 0.12nm/cycle, 0.14nm/cycle, 0.16nm/cycle, 0.18nm/cycle or 0.19nm/cycle, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 0.15nm/cycle.
In the invention, the atomic layer deposition equipment in the step (1) is a powder atomic layer deposition system.
It is worth noting that by using Atomic Layer Deposition (ALD) technology, a deformation-free, hard, suspended film protection layer can be rapidly obtained by sequentially and alternately growing hafnium oxide layers at low temperatures.
As a preferred embodiment of the present invention, the hafnium source in step (1) includes tetra (dimethylammonium) hafnium.
Preferably, the oxygen source of step (1) comprises water vapour.
Preferably, in the atomic layer deposition process of step (1): the heating temperature of the hafnium source bottle is 80-90 ℃, the introducing time of the hafnium source is 55-65mS/cycle, and the introducing flow rate of the hafnium source is 3.5-4.5mg/cycle.
In the present invention, the heating temperature of the hafnium source bottle may be 80 to 90℃such as 82℃and 84℃and 85℃and 86℃and 88℃or 89℃and the passage time of the hafnium source may be 55 to 65mS/cycle such as 57mS/cycle, 59mS/cycle, 60mS/cycle, 61mS/cycle or 63mS/cycle, and the passage rate of the hafnium source may be 3.5 to 4.5mg/cycle, for example, 3.7mg/cycle, 3.9mg/cycle, 4.0mg/cycle, 4.1mg/cycle or 4.3mg/cycle, but the present invention is not limited to the values listed and other values not listed in the numerical range are applicable.
Preferably, in the atomic layer deposition process of step (1): the oxygen source is introduced for 55-65mS/cycle, and the oxygen source is introduced at a flow rate of 3.5-4.5mg/cycle.
In the present invention, the oxygen source may be introduced at a time of 55 to 65mS/cycle, for example, 57mS/cycle, 59mS/cycle, 60mS/cycle, 61mS/cycle or 63mS/cycle, etc., and the oxygen source may be introduced at a flow rate of 3.5 to 4.5mg/cycle, for example, 3.7mg/cycle, 3.9mg/cycle, 4.0mg/cycle, 4.1mg/cycle or 4.3mg/cycle, etc., but the present invention is not limited to the values listed, and other values not listed in the numerical range are applicable.
It is worth to say that the invention can control the uniformity of the deposition of the film layer on the surface of the sample by controlling the inlet time and the inlet flow of the hafnium source and the oxygen source and controlling the inlet flow of the air source based on the small sample chamber.
As a preferable technical scheme of the invention, nitrogen is also introduced in the atomic layer deposition process in the step (1).
The flow rate of the nitrogen gas is preferably 8 to 12sccm, and may be, for example, 8.5sccm, 9sccm, 9.5sccm, 10sccm, 10.5sccm, 11sccm, or 11.5sccm, etc., but the flow rate is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
As a preferred embodiment of the present invention, the thickness of the monolayer hafnium oxide layer deposited in the step (1) is not more than 15nm, and may be, for example, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm or 14nm, etc., but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the total thickness of the single-sided hafnium oxide layer of the suspended film in the step (1) is not less than 30nm, for example, 32nm, 35nm, 37nm, 40nm, 42nm, 45nm, 50nm, 55nm or 60nm, etc., but not limited to the values listed, other non-listed values within the range of values are equally applicable, and preferably 40-50nm.
In a preferred embodiment of the present invention, the deposited carbon in the step (2) has a thickness of 200 to 300nm, for example, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm or 300nm, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the voltage of the deposited carbon in the step (2) is 2-10kV, for example, 3kV, 4kV, 5kV, 6kV, 7kV, 8kV or 9kV, etc., but the voltage is not limited to the listed values, and other non-listed values in the numerical range are equally applicable.
Preferably, the beam current of the carbon deposition in the step (2) is 20-35pA, for example, 22pA, 24pA, 25pA, 26pA, 28pA, 30pA or 33pA, but not limited to the listed values, and other non-listed values in the range of values are equally applicable.
It is worth noting that carbon deposition on the surface of the hafnium oxide layer is favorable for filling the structure of the support material, samples cannot be broken in the subsequent sheet extraction process, and meanwhile, the lining degree of the support material cannot shade the lining degree of the ALD HfO 2 film layer in a TEM mode, so that the support material is convenient for subsequent TEM analysis.
As a preferable technical scheme of the invention, the metal in the metal film in the step (2) comprises Pt.
Preferably, the thickness of the deposited metal film in the step (2) is 0.8-1.2. Mu.m, for example, 0.85. Mu.m, 0.9. Mu.m, 0.95. Mu.m, 1. Mu.m, 1.05. Mu.m, 1.1. Mu.m, or 1.15. Mu.m, etc., but not limited to the values listed, and other non-listed values within the numerical range are equally applicable.
Preferably, the voltage of the deposited metal film in the step (2) is 25-30kV, for example, 26kV, 27kV, 28kV, 29kV or 30kV, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the beam current of the deposited metal film in the step (2) is 80-100pA, for example, 82pA, 84pA, 86pA, 88pA, 90pA, 92pA, 94pA, 96pA or 98pA, etc., but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
It is worth to say that the invention deposits metal Pt film on the outer layer, which is favorable for etching of Ga ion resistance, and increases the conductivity of the sheet, so that TEM imaging is clearer in the subsequent preparation process, and thickness control is facilitated.
As a preferable technical scheme of the invention, the step (2) further comprises polishing and finishing by adopting a focused ion beam after the metal film is deposited.
In the invention, the polishing finishing comprises rough digging, fine finishing, first polishing and second polishing which are sequentially carried out.
It is noted that the focused ion beam may be a gallium ion beam, an ammonia ion beam, a neon ion beam, or the like.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Alternately carrying out at least two layers of atomic layer deposition on the surface of a suspended film with the thickness of 5-15nm by using a hafnium source and an oxygen source to obtain a single-sided hafnium oxide layer of the suspended film, wherein the total thickness of the single-sided hafnium oxide layer is more than or equal to 30nm;
The thickness of the atomic layer deposited monolayer hafnium oxide layer is less than or equal to 15nm;
The atomic layer deposition temperature is less than or equal to 65 ℃ and the deposition speed is 0.1-0.2nm/cycle;
in the atomic layer deposition process: the heating temperature of the hafnium source bottle is 80-90 ℃, the introducing time of the hafnium source is 55-65mS/cycle, and the introducing flow rate of the hafnium source is 3.5-4.5mg/cycle; the oxygen source is introduced for 55-65mS/cycle, and the oxygen source is introduced at a flow rate of 3.5-4.5mg/cycle; the flow rate of the nitrogen is 8-12sccm;
(2) Depositing carbon with the thickness of 200-300nm on the surface of the hafnium oxide layer in the step (1) by using a focused ion beam with the voltage of 2-10kV and the beam current of 20-35pA, then depositing a metal film with the thickness of 0.8-1.2 mu m by using a focused ion beam with the voltage of 25-35kV and the beam current of 80-100pA, and then polishing and finishing by using the focused ion beam to obtain a suspended film transmission electron microscope sample.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method provided by the invention, the hard HfO 2 protective layer is sequentially and alternately deposited and grown at low temperature, so that a deformation-free film layer can be rapidly obtained; simultaneously, the alternately grown HfO 2 can release the stress of the film layer in the ALD growth process, can keep the stability of the suspended film structure and does not damage the suspended film in the subsequent FIB preparation process, obtain real suspended structure information, and ensure that the subsequent TEM characterization data is real and reliable;
(2) The preparation method provided by the invention has high process adaptation degree, is simple to operate, and can be industrially applied.
Drawings
FIG. 1 is a TEM image (1 μm) of a suspended membrane transmission electron microscope sample prepared in example 1;
FIG. 2 is a cross-sectional TEM image (3 μm) of a suspended membrane transmission electron microscope sample prepared in example 1;
FIG. 3 is a cross-sectional TEM image (50 nm) of a suspended membrane transmission electron microscope sample prepared in example 1;
FIG. 4 is a TEM image (1 μm) of a suspended membrane transmission electron microscope sample prepared in comparative example 1;
FIG. 5 is a TEM image (100 nm) of a suspended membrane transmission electron microscope sample prepared in comparative example 1;
FIG. 6 is a TEM image (10 μm) of a suspended membrane transmission electron microscope sample prepared in comparative example 2;
FIG. 7 is a TEM image (10 μm) of a suspended membrane transmission electron microscope sample prepared in comparative example 2;
FIG. 8 is a TEM image (1 μm) of a suspended membrane transmission electron microscope sample prepared in comparative example 3;
FIG. 9 is a TEM image (500 nm) of a suspended membrane transmission electron microscope sample prepared in comparative example 3;
FIG. 10 is a TEM image (500 nm) of a suspended membrane transmission electron microscope sample prepared in comparative example 3;
Wherein, 1-the hollow membrane, 2-the support body formed by combining a hafnium oxide layer, a carbon layer and a Pt layer; the black contrast film layer in the arrow span region in fig. 3 is a hafnium oxide layer.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of an ultrathin suspended film transmission electron microscope sample, which comprises the following steps:
(1) Alternately performing 4-layer atomic layer deposition on the upper surface and the lower surface of a suspended film with the thickness of 10nm by using tetra (dimethylammonium group) hafnium and water vapor to obtain a single-sided hafnium oxide layer of the suspended film, wherein the total thickness of the single-sided hafnium oxide layer of the suspended film is 40nm;
the thickness of the atomic layer deposited monolayer hafnium oxide layer is 10nm;
The atomic layer deposition temperature is 50 ℃ and the deposition speed is 0.15nm/cycle;
In the atomic layer deposition process: the heating temperature of the hafnium source bottle is 85 ℃, the introducing time of the hafnium source is 60mS/cycle, and the introducing flow rate of the hafnium source is 4mg/cycle; the water vapor is introduced for 60mS/cycle, and the water vapor is introduced for 4mg/cycle; the flow rate of the nitrogen is 10sccm;
(2) Depositing carbon with the thickness of 240nm on the surface of the hafnium oxide layer in the step (1) by using a gallium ion beam with the voltage of 5kV and the beam current of 26pA, then depositing metal Pt with the thickness of 1 mu m by using a gallium ion beam with the voltage of 30kV and the beam current of 90pA, then roughly digging by using the gallium ion beam with the voltage of 30kV and the beam current of 9.1nA, finely repairing by using the gallium ion beam with the voltage of 30kV and the beam current of 0.75nA, performing first polishing by using the voltage of-5 kV and the beam current of 26pA, and performing second polishing by using the voltage of 2kV and the beam current of 20pA to obtain a suspended film transmission electron microscope sample.
The TEM characterization result of the suspended membrane transmission electron microscope sample prepared in this embodiment is shown in fig. 1-3, and as can be seen from fig. 1-3, the structure of the suspended membrane can be clearly observed, and the suspended membrane structure is not deformed.
Example 2
The embodiment provides a preparation method of an ultrathin suspended film transmission electron microscope sample, which comprises the following steps:
(1) Alternately performing 5 atomic layer deposition on the upper surface and the lower surface of a suspended film with the thickness of 8nm by using tetra (dimethylammonium group) hafnium and water vapor to obtain a single-sided hafnium oxide layer of the suspended film, wherein the total thickness of the single-sided hafnium oxide layer of the suspended film is 45nm;
The thickness of the atomic layer deposited monolayer hafnium oxide layer is 9nm;
the atomic layer deposition temperature is 60 ℃ and the deposition speed is 0.2nm/cycle;
In the atomic layer deposition process: the heating temperature of the hafnium source bottle is 85 ℃, the introducing time of the hafnium source is 65mS/cycle, and the introducing flow rate of the hafnium source is 3.5mg/cycle; the water vapor is introduced for 65mS/cycle, and the water vapor is introduced for 3.5mg/cycle; the flow rate of the nitrogen is 10sccm;
(2) Depositing carbon with the thickness of 300nm on the surface of the hafnium oxide layer in the step (1) by using a gallium ion beam with the voltage of 10kV and the beam current of 35pA, then depositing metal Pt with the thickness of 0.8 mu m by using the voltage of 35kV and the beam current of 80pA, then roughly digging by using the gallium ion beam with the voltage of 30kV and the beam current of 9.1nA, finely repairing by using the voltage of 30kV and the beam current of 0.75nA, performing first polishing by using the voltage of-5 kV and the beam current of 26pA, and performing second polishing by using the voltage of 2kV and the beam current of 20pA in sequence to obtain the suspended film transmission electron microscope sample.
Example 3
The embodiment provides a preparation method of an ultrathin suspended film transmission electron microscope sample, which comprises the following steps:
(1) Alternately performing 5 atomic layer deposition on the upper surface and the lower surface of a suspended film with the thickness of 15nm by using tetra (dimethylammonium group) hafnium and water vapor to obtain a single-sided hafnium oxide layer of the suspended film, wherein the total thickness of the single-sided hafnium oxide layer of the suspended film is 50nm;
the thickness of the atomic layer deposited monolayer hafnium oxide layer is 10nm;
The atomic layer deposition temperature is 65 ℃ and the deposition speed is 0.1nm/cycle;
in the atomic layer deposition process: the heating temperature of the hafnium source bottle is 85 ℃, the introducing time of the hafnium source is 55mS/cycle, and the introducing flow rate of the hafnium source is 4.5mg/cycle; the water vapor is introduced for 55mS/cycle, and the water vapor is introduced for 4.5mg/cycle; the flow rate of the nitrogen is 10sccm;
(2) Depositing carbon with the thickness of 200nm on the surface of the hafnium oxide layer in the step (1) by using a gallium ion beam with the voltage of 2kV and the beam current of 20pA, then depositing metal Pt with the thickness of 1.2 mu m by using a gallium ion beam with the voltage of 25kV and the beam current of 100pA, then roughly digging by using the gallium ion beam with the voltage of 30kV and the beam current of 9.1nA, finely repairing by using the gallium ion beam with the voltage of 30kV and the beam current of 0.75nA, performing first polishing by using the voltage of-5 kV and the beam current of 26pA, and performing second polishing by using the voltage of 2kV and the beam current of 20pA to obtain the suspended film transmission electron microscope sample.
Example 4
The present embodiment provides a method for preparing an ultrathin suspended film transmission electron microscope sample, which is the same as that of embodiment 1 except that 2 atomic layer deposition is performed in step (1) to obtain a suspended film with a total thickness of 20nm of a single-sided hafnium oxide layer.
Example 5
The present embodiment provides a method for preparing an ultrathin suspended film transmission electron microscope sample, wherein the conditions are the same as those in embodiment 1 except that the atomic layer deposition temperature in step (1) is 40 ℃.
Example 6
The present embodiment provides a method for preparing an ultrathin suspended film transmission electron microscope sample, wherein the conditions are the same as those in embodiment 1 except that the atomic layer deposition temperature in step (1) is 80 ℃.
Example 7
The present example provides a method for preparing an ultrathin suspended film transmission electron microscope sample, and the conditions are the same as those of example 1 except that the time for introducing tetra (dimethylammonium) hafnium and water vapor is 45 mS/cycle.
Example 8
The present example provides a method for preparing an ultrathin suspended film transmission electron microscope sample, and the conditions are the same as those of example 1 except that the time of introducing tetra (dimethylammonium) hafnium and water vapor is 80 mS/cycle.
Example 9
The present embodiment provides a method for preparing an ultrathin suspended film transmission electron microscope sample, wherein the conditions are the same as those in embodiment 1 except that the thickness of the deposited carbon in the step (2) is 100 nm.
Example 10
The present embodiment provides a method for preparing an ultrathin suspended film transmission electron microscope sample, which is the same as that of embodiment 1 except that the thickness of the deposited carbon in step (2) is 400 nm.
Example 11
The present embodiment provides a method for preparing an ultrathin suspended film transmission electron microscope sample, which is the same as that of embodiment 1 except that the thickness of the deposited metal Pt in step (2) is 0.6 μm.
Example 12
The present embodiment provides a method for preparing an ultrathin suspended film transmission electron microscope sample, which is the same as that of embodiment 1 except that the thickness of the deposited metal Pt in step (2) is 1.4 μm.
Comparative example 1
The comparative example provides a method for preparing an ultrathin suspended film transmission electron microscope sample, which is the same as that of example 1 except that the hafnium oxide layer in step (1) is not deposited alternately, and the total thickness of the single-sided hafnium oxide layer of the suspended film obtained only by one-step atomic layer deposition is 40 nm.
TEM characterization results of the suspended membrane transmission electron microscope sample prepared in the comparative example are shown in figures 4-5, and as can be seen from figures 4-5, the suspended membrane layer is observed to bend.
Comparative example 2
The comparative example provides a method for preparing an ultra-thin suspended film transmission electron microscope sample, which is the same as example 1 except that carbon is not deposited on the surface of the hafnium oxide layer in the step (2).
TEM characterization results of the suspended membrane transmission electron microscope samples prepared in this comparative example are shown in FIGS. 6-7, and it can be seen from FIGS. 6-7 that only the Pt layer is deposited, resulting in breakage of the suspended membrane layer.
Comparative example 3
The comparative example provides a method for preparing an ultra-thin suspended film transmission electron microscope sample, which is the same as example 1 except that carbon is deposited only on the surface of the hafnium oxide layer in step (2), and metal Pt is not deposited.
TEM characterization results of the suspended membrane transmission electron microscope samples prepared in the comparative example are shown in figures 8-10, and as can be seen from figures 8-10, deformation of the suspended membrane layer can be observed.
TEM characterization analysis is carried out on the suspended membrane transmission electron microscope samples prepared in the examples and the comparative examples, and the characterization results are shown in Table 1.
TABLE 1
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (21)
1. The preparation method of the ultrathin suspended film transmission electron microscope sample is characterized by comprising the following steps of:
(1) Alternately carrying out at least two atomic layer depositions on the surface of the suspended film by using a hafnium source and an oxygen source to obtain a hafnium oxide layer;
the atomic layer deposition temperature is 50-60 ℃; in the atomic layer deposition process: the inlet time of the hafnium source is 55-65mS/cycle, and the inlet time of the oxygen source is 55-65mS/cycle;
the total thickness of the single-sided hafnium oxide layer of the suspended film is more than or equal to 30nm;
(2) And (3) adopting a focused ion beam to sequentially deposit carbon and metal films on the surface of the hafnium oxide layer in the step (1) to prepare a suspended film transmission electron microscope sample.
2. The method of claim 1, wherein the thickness of the suspended film is 5-15nm.
3. The method of claim 1, wherein the atomic layer deposition rate in step (1) is 0.1-0.2nm/cycle.
4. A method according to claim 3, wherein the atomic layer deposition rate in step (1) is 0.15nm/cycle.
5. The method of claim 1, wherein the source of hafnium in step (1) comprises tetrakis (dimethylammonium) hafnium.
6. The method of claim 1, wherein the oxygen source of step (1) comprises water vapor.
7. The method of claim 1, wherein during the atomic layer deposition of step (1): the heating temperature of the hafnium source bottle is 80-90 ℃, and the inlet flow rate of the hafnium source is 3.5-4.5mg/cycle.
8. The method of claim 1, wherein during the atomic layer deposition of step (1): the oxygen source flow rate is 3.5-4.5mg/cycle.
9. The method of claim 1, wherein nitrogen is further introduced during the atomic layer deposition in step (1).
10. The method of claim 9, wherein the nitrogen is at a flow rate of 8-12sccm.
11. The method of claim 1, wherein the atomic layer deposited monolayer hafnium oxide layer of step (1) has a thickness of 15nm or less.
12. The method of claim 1, wherein the suspended film of step (1) has a total thickness of 40-50nm on one side of the hafnium oxide layer.
13. The method of claim 1, wherein the deposited carbon of step (2) has a thickness of 200-300nm.
14. The method of claim 1, wherein the voltage of the deposited carbon in step (2) is 2-10kV.
15. The method according to claim 1, wherein the carbon-deposited beam in step (2) is 20 to 35pA.
16. The method of claim 1, wherein the metal in the metal film of step (2) comprises Pt.
17. The method according to claim 1, wherein the deposited metal film of step (2) has a thickness of 0.8 to 1.2. Mu.m.
18. The method according to claim 1, wherein the voltage of the deposited metal film in the step (2) is 25-30kV.
19. The method according to claim 1, wherein the beam current of the deposited metal film in the step (2) is 80-100pA.
20. The method of claim 1, wherein the depositing of the metal film in step (2) further comprises polishing with a focused ion beam.
21. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Alternately carrying out at least two layers of atomic layer deposition on the surface of a suspended film with the thickness of 5-15nm by using a hafnium source and an oxygen source to obtain a single-sided hafnium oxide layer of the suspended film, wherein the total thickness of the single-sided hafnium oxide layer is more than or equal to 30nm;
The thickness of the atomic layer deposited monolayer hafnium oxide layer is less than or equal to 15nm;
the atomic layer deposition temperature is 50-60 ℃ and the deposition speed is 0.1-0.2nm/cycle;
in the atomic layer deposition process: the heating temperature of the hafnium source bottle is 80-90 ℃, the introducing time of the hafnium source is 55-65mS/cycle, and the introducing flow rate of the hafnium source is 3.5-4.5mg/cycle; the oxygen source is introduced for 55-65mS/cycle, and the oxygen source is introduced at a flow rate of 3.5-4.5mg/cycle; the flow rate of the nitrogen is 8-12sccm;
(2) Depositing carbon with the thickness of 200-300nm on the surface of the hafnium oxide layer in the step (1) by using a focused ion beam with the voltage of 2-10kV and the beam current of 20-35pA, then depositing a metal film with the thickness of 0.8-1.2 mu m by using a focused ion beam with the voltage of 25-35kV and the beam current of 80-100pA, and then polishing and finishing by using the focused ion beam to obtain a suspended film transmission electron microscope sample.
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