CN116954020A - Micro-nano processing method and photoetching medium thereof - Google Patents
Micro-nano processing method and photoetching medium thereof Download PDFInfo
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- 238000013519 translation Methods 0.000 description 3
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- OVWPJGBVJCTEBJ-UHFFFAOYSA-K gold tribromide Chemical compound Br[Au](Br)Br OVWPJGBVJCTEBJ-UHFFFAOYSA-K 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
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- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/002—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor using materials containing microcapsules; Preparing or processing such materials, e.g. by pressure; Devices or apparatus specially designed therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention provides a micro-nano processing method and a photoetching medium thereof, which belong to the field of micro-nano processing, wherein inorganic small molecules are adopted as the photoetching medium to execute a photoetching process, a setting area of the photoetching medium is irradiated by utilizing high-energy beams of electrons, ions or/and photons, and the inorganic small molecules in the irradiated area are sublimated and etched to directly form a required photoetching pattern. In the process of removing the photoetching medium, physical dry adhesion stripping can be adopted, so that the use of solvents or liquids is avoided in the whole process, and micro-nano processing of sensitive materials is realized. Inorganic small molecules serving as a photoetching medium form a solid film through van der Waals acting force, and the thickness of the film is 5 nm-8000 nm. The photoetching medium comprises inorganic small molecular simple substance, binary or ternary inorganic small molecular compound or a mixture of at least two of the inorganic small molecular compound and the binary or ternary inorganic small molecular compound. The method can simplify the micro-nano processing step, avoid the use of developing solution, cleaning agent and the like, and realize micro-nano processing of sensitive materials and devices.
Description
Technical Field
The invention belongs to the field of micro-nano processing, and particularly relates to a micro-nano processing method and a photoetching medium thereof.
Background
Micro-nano lithography has been applied to integrated circuits, microelectromechanical systems, optoelectronic devices, biochips, flexible devices, microfluidic and magnetic storage. Photolithography techniques are largely classified into optical exposure techniques, electron beam exposure techniques, and ion beam exposure techniques, depending on the type of photolithography source. The common principle is that the photoetching medium is irradiated by high-energy beam, the physical and chemical properties of the photoetching medium in an irradiated area are changed, so that the photoetching medium in an irradiated area and the photoetching medium in an unirradiated area have obvious solubility difference, and after being soaked by developing solution, a part of the photoetching medium is dissolved to form a pre-designed pattern. Therefore, the photoetching medium is a core product of various photoetching technologies, and directly influences the processing technology and the photoetching patterning quality.
The traditional photoetching process is based on organic photoresist and mainly comprises the steps of photoresist homogenizing, photoresist baking, photoetching, developing, cleaning, coating, photoresist removing and the like. The developing, cleaning and photoresist removing steps involve various solutions or solvents, and comprise developing solution (for example, tetramethyl ammonium hydroxide alkaline aqueous solution), cleaning solution (for example, water, ethanol and other solvents) and photoresist remover (for example, acetone, chloroform and other polar solvents). The chemical corrosiveness of the liquid itself may cause dissolution of the active functional material of the micro-nano device during the soaking process, or residual solvent molecules on the surface of the active functional material, which may cause shrinkage, wrinkling and surface contamination of the active functional material during subsequent drying. Particularly, many sensitive active functional materials with nanometer thickness are very sensitive to solvents and chemical reagents, and the solutions or solvents directly influence the stability and performance exertion of the functional materials, such as star materials with great application potential including black phosphorus, perovskite, halides and the like, and are sensitive to the solvents or the solutions. In addition, some solutions or solvents may remain on the atomic scale surface of the liquid-sensitive material, creating oxygen defects or cracks, and even directly destroying the crystal structure of the active functional material, resulting in failure of the functional material during device construction.
Therefore, the development of a novel photoetching medium to avoid the use of corrosive liquid simplifies the photoetching process, realizes micro-nano patterning processing of sensitive materials, has important significance for effectively protecting sensitive active functional materials in the construction process of micro devices, and can simplify the steps of the photoetching process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a micro-nano processing method based on a novel inorganic micro-molecular lithography medium, which adopts a brand-new electrodeless micro-molecular lithography medium, and can sublimate after being irradiated by utilizing the high energy beam sensitivity of the micro-nano processing method to electrons, ions or/and photons, thereby omitting the use of a developing step and developing solution, simplifying the lithography step and meeting the construction of micro-nano devices.
In order to achieve the above-mentioned purpose, the present invention provides a micro-nano processing method, which uses a thin film composed of inorganic small molecules as a lithography medium layer to execute a lithography process, irradiates a set region of the lithography medium layer with a high energy beam of electrons, ions or/and photons, sublimates the inorganic small molecules in the irradiated region, etches the lithography medium layer in the irradiated region while the lithography medium layer in the non-irradiated region is reserved, and directly forms a desired lithography pattern, thereby omitting a developing step and the use of corrosive developing solution in the conventional micro-nano processing process.
Furthermore, inorganic small molecules serving as a photoetching medium form a solid film through van der Waals acting force, the thickness of the film is 5 nm-8000 nm, and the thickness can be accurately controlled according to requirements. Compared with the organic photoetching medium layer with the micron-sized thickness prepared by the traditional spin coating method, the inorganic micromolecules form a film by weak van der Waals acting force among molecules, and the nanometer-sized, uniform and flat photoetching medium layer can be formed.
Further, the inorganic small molecules used as the photoetching medium comprise one or more of the following substances:
(1) Inorganic small molecule simple substance including phosphorus molecule P 4 Sulfur molecule S n1 Selenium molecule Se n2 Te molecule n3 And iodine molecule I 2 Wherein n1 is less than or equal to 2 and less than or equal to 8, n1 is an integer, n2 is more than or equal to 2, n2 is an integer, n3 is more than or equal to 2, and n3 is an integer;
(2) Binary or ternary inorganic small molecule compounds comprising P 4 Se 3 、Sb 2 O 3 、SbI 3 、SbI 3 ·3S 8 A combination of one or more of the following;
(3) And at the same time, the compound comprises a mixture of at least two of inorganic small molecular simple substances and binary or ternary inorganic small molecular compounds.
In the above inventive concept, the inorganic small molecular solid film as the lithography medium is mainly composed of short chain, ring or cage small molecules, and the molecules are connected with each other by weak van der waals force, and are easily changed when being impacted by external energy or medium. It is therefore relatively sensitive to high energy beams of electrons, ions or/and photons, which, after being irradiated by electrons, ions or/and photons, are capable of sublimating in molecular form.
Further, it comprises the following steps:
and (3) constructing a photoetching medium layer: covering a layer of solid film formed by inorganic small molecules on the surface to be processed,
etching step II: the high energy beam of electrons, ions or photons is utilized to irradiate a specific area of the photoetching medium layer, the inorganic micromolecular photoetching medium is directly sublimated, and the photoetching medium in the irradiated area is etched to form grooves, the non-irradiated part is reserved, so that the photoetching medium layer forms a required pattern,
deposition of target material step III: depositing a layer of target material with a specified thickness on the patterned inorganic small molecule photoetching medium layer, depositing one part of the target material layer in a groove formed after etching the inorganic small molecule, depositing the other part of the target material layer on the small molecule medium layer which is not etched,
removing the photoetching medium layer: and (3) removing the small molecular dielectric layer which is not irradiated in the step (II) by adopting a physical adhesion stripping method (IVa) or a nonpolar solvent soaking method (IVb), and reserving the target material layer filled in the groove of the photoetching dielectric layer in the step (III) to obtain the patterned target material layer.
Further, the deposition manner in the covering step and the target material deposition step is selected from one or a combination of more of molecular layer deposition, chemical vapor deposition, physical vapor deposition and magnetron sputtering.
Further, the covering step, etching step, target material deposition step and removal step can be cyclically combined in a sequential order or flexibly selected according to need.
Further, the surface to be processed is a planar or non-planar substrate surface in the micro-nano processing field, or a composite substrate surface covered with a functional active material.
Further, in the removing step, the physical adhesion stripping method is based on an adhesion stripping mode, and the adhesion substance comprises one or more of a Polydimethylsiloxane (PDMS) film, a polymethyl methacrylate (PMMA) film, a Polyethylene (PE) film, a Polypropylene (PE) film, a polyvinyl chloride (PVC) film, a polyvinyl alcohol (PVA) film and a tape film, or a photoetching medium film prepared by dissolving inorganic small molecules in a nonpolar solvent in the nonpolar solvent removing mode, wherein the nonpolar solvent comprises one or more of carbon disulfide, diethyl ether, carbon tetrachloride, hexane, isooctane, benzene, toluene and dichloromethane.
In the above inventive concept, the physical adhesion stripping method is to contact the adhesion with the surface of the target material, and the adhesion is tightly contacted with the target material due to the surface atomic level flatness and the adhesion force at the interface; meanwhile, the target material is closely contacted with the inorganic molecular medium, and the adhesion between the inorganic molecular medium and the substrate is the weakest; when the adhesive is acted by external force, the target material and the inorganic molecular medium fall off the substrate together with the adhesive.
According to a second aspect of the present invention there is also provided a lithographic medium for use in a micro-nano processing method as described above.
Furthermore, the inorganic micromolecular photoetching medium has stable physical and chemical properties, the photoetching medium can be applied in normal temperature, normal pressure and sunlight environment, the organic photoresist of the traditional process is sensitive to the surrounding environment and needs to be stored at low temperature, and the method is used in a special yellow light environment, so that the application range of the method is wider, the engineering property is stronger, and the cost is lower.
In the invention, the crystal configuration of the photoetching medium film formed by inorganic micromolecules mainly comprises
When the short chain, ring or cage small molecule form exists, when the solid film is formed as the photoetching medium, the molecules are connected with each other by weak van der Waals force, after being bombarded by high energy beam, the van der Waals force is destroyed, and the small molecules are etched and sublimated, so that the photoetching medium layer directly forms a pattern.
In general, the above technical solutions conceived by the present invention have the following compared with the prior art
The beneficial effects are that:
in terms of substance morphology, the traditional organic photoetching medium is a viscous liquid formed by dissolving high molecules in a specific solvent, and in the application of the invention, the inorganic small molecule photoetching medium layer is a dry solid, so that the damage of liquid components in the traditional organic photoresist to active functional materials on a processing surface can be directly avoided.
The process does not need developing step, inorganic molecules sublimate after laser irradiation, and exposure patterns are directly formed, so that the photoetching process flow is simplified, and the cost can be saved. The method can avoid contact between the surface of the substrate and the developing solution without developing, reduce solvent residues, and increase the cleanliness of the process.
In the step of removing the photoetching medium, compared with the existing processing technology based on the organic photoetching medium, the technology does not need a liquid photoresist remover, only needs to use an adhesive film, and adopts bonding stripping to remove the photoetching medium, so that the damage of the traditional polar solvent to the sensitive active functional material is avoided.
Compared with the existing commercial organic photoresist, the inorganic micromolecular photoresist has the advantages that the raw material of the inorganic micromolecular photoresist is commercial inorganic matter, the average price is 0.05-0.4 times of that of the organic photoresist, and the material price is greatly reduced. And the organic photoetching medium is usually stored at a low temperature, while the inorganic micromolecular photoetching medium is stored at normal temperature, so that the storage condition is more friendly. The organic photoetching medium is sensitive to natural light and needs to be used under the condition of yellow light, and the inorganic micromolecular photoetching medium can be stored and used under the condition of visible light, so that the application condition is wider.
The photoetching medium has no special requirements on the ambient temperature and pressure in the micro-nano processing process when in use, can be stored and processed in the normal temperature and normal pressure environment, is convenient to operate, can be highly compatible with the existing micro-nano processing equipment, does not need expensive ultra-low temperature and ultra-low pressure special environment equipment, and can obviously reduce the processing cost.
Drawings
FIG. 1 is a flow chart of a micro-nano processing method based on an inorganic small molecule lithography medium provided by an embodiment of the invention;
fig. 2a is a conventional organic photoresist process, and fig. 2b is an inorganic molecular lithography process according to an embodiment of the present invention.
Fig. 3a is a schematic diagram of a layer to be processed of a silicon wafer according to an embodiment of the present invention, and fig. 3b is a schematic diagram of a thin film layer of selenium molecule covered over the layer to be processed of the silicon wafer;
FIGS. 4a to 4c are scanning electron microscope views of inorganic selenium molecule photoetching medium layers with different thicknesses in the embodiment of the invention, wherein the thickness of the inorganic small molecule photoetching medium in FIG. 4a is 190nm, the thickness of the inorganic small molecule photoetching medium in FIG. 4b is 450nm, and the thickness of the inorganic small molecule photoetching medium in FIG. 4c is 1.25 μm;
FIGS. 5a to 5c are photo-etching diagrams of inorganic small molecule photo-etching media with different thicknesses according to an embodiment of the present invention, wherein the thickness of the inorganic small molecule photo-etching media in FIG. 5a is 200nm, the thickness of the inorganic small molecule photo-etching media in FIG. 5b is 140nm, and the thickness of the inorganic small molecule photo-etching media in FIG. 5c is 80nm;
fig. 6a to 6b are physical diagrams of micro-nano processing based on inorganic molecular lithography medium in the embodiment of the invention, fig. 6a is a selenium molecular film evaporated on the surface of a silicon wafer, fig. 6b is a pattern after laser etching to expose a silicon substrate, fig. 6c is a deposited metal tin Sn film, and fig. 6d is a metal tin Sn pattern after stripping of the lithography medium;
FIG. 7 is a schematic diagram of removing inorganic molecular lithography media by physical adhesion stripping in an embodiment of the invention;
FIG. 8 shows a micro-copper metal structure based on an inorganic molecular lithography medium and micro-nano processing method in an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a micro-nano processing method based on a novel inorganic small molecule lithography medium, which adopts inorganic small molecules as the lithography medium to execute a lithography process, irradiates a lithography medium setting area by utilizing high-energy beams of electrons, ions or/and photons, sublimates the inorganic small molecules of the irradiated area, and etches the lithography medium setting area to directly form a needed lithography pattern. Compared with the traditional organic photoetching medium, the method can omit the development step and the use of the developing solution in the traditional micro-nano processing technology, and avoids the adverse effect of the corrosive developing solution and the soaking process thereof on the functional active materials in the micro-nano device. The inorganic small molecules used as the photoetching medium comprise inorganic small molecule simple substances, binary or ternary inorganic small molecule compounds or a mixture composed of at least two substances, the small molecules form a solid film through van der Waals force, and the thickness of the film is 5-8000 nm. The method of the invention can not only omit the development step and the use of the developing solution in the traditional micro-nano processing technology, but also omit the use of the glue solution and the cleaning solution in the later process link, thereby maximally avoiding the adverse effect of the use of the liquid solution or the solvent on the functional active material in the micro-nano processing process, realizing the micro-nano processing of the high-sensitivity material and meeting the efficient construction of micro-nano devices.
Fig. 1 is a flowchart of a micro-nano processing method based on an inorganic small molecule lithography medium according to an embodiment of the present invention, where the steps include: i, covering a layer of inorganic micromolecular photoetching medium film on a surface to be processed; II, irradiating a specific area of the photoetching medium by utilizing high-energy beams of electrons, ions or photons, and etching inorganic small molecules in the irradiated area to directly form a required pattern; III covering the upper surface of the configuration or pattern obtained in step II with a layer of target material; and IV, removing the lithography medium in the non-irradiated area, wherein the target material above the lithography medium is separated, and the target material in the irradiated area remains on the surface to be processed to form a target material pattern.
According to the requirement, the steps I-IV can be circulated, a plurality of layers of target materials are constructed on the surface to be processed, and the steps I, II, III and IV can be flexibly selected to be combined according to the requirement.
In more detail, in the step I of the present invention, the surface to be processed of the substrate may be planar or non-planar, and the surface to be processed material includes a semiconductor substrate, an insulating substrate, a conductive substrate, or a composite substrate covered with a functional active material. The main component of the planar substrate material is Au, ag, cu, al, pt, pd, mn, fe, co, ni, zn, cd, ge, sn, pb, sb, bi, si, ge, gaN, gaAs, gaP, ITO, inP, inAs, znS, znSe, cdS, cdSe, znO, tiO 2 、MgO、CdO、Al 2 O 3 、SiO 2 Or Si (or) 3 N 4 Any one or a combination of a plurality of the above. The semiconductor substrate may be Al 2 O 3 Substrate, si wafer substrate, surface SiO 2 Si substrate of layer, si of ITO-plated layer 3 N 4 Any one or more. The functional active material covered by the composite substrate can be graphene, black phosphorus, perovskite and HfO 2 、BN、MoS 2 、MoSe 2 、WS 2 、WSe 2 、In 2 Se 3 、PbI 2 、PbBr 2 Etc.
In the step I of the present invention, the covering manner includes one or a combination of a plurality of molecular layer deposition, chemical vapor deposition, physical vapor deposition, and magnetron sputtering. The methods are effective methods for preparing large-area solid films, and have the advantages of simplicity, rapidness, uniform film thickness, accuracy, controllability and the like. Taking thermal evaporation sulfur molecules as an example, the basic principle is that a layer of uniform film is formed on the surface of a substrate by a series of physical processes such as heating melting, sublimation and deposition of elemental sulfur serving as a raw material. The main process sequentially comprises the following steps: heating and melting, heating raw materials, and then subjecting the raw materials to saturated vapor pressure action, enabling surface atoms or molecules to be gasified and escaped, and subjecting the raw materials to a solid phase or condensed phase-to-gas phase transformation process; sublimation diffusion, wherein the escaped atoms or molecules fly to a low concentration area of the chamber through concentration diffusion in a vacuum environment (the vacuum environment can reduce collision or reaction between the flying atoms or molecules and air molecules); the deposition of desublimation, the transition from gas phase to solid phase gradually occurs when high temperature atoms or molecules fly to encounter low temperature substrates or chambers, and the uniform and compact film is formed through nucleation, nuclear growth and nuclear connection.
In the step I of the invention, the thickness of the inorganic small molecular film is one time or more than that of the deposition target material, and more preferably, the thickness of the inorganic small molecular film is 5 nm-8000 nm.
In step II of the present invention, the performing lithography apparatus generally includes an energy beam control system, a microscope system, and a high-precision three-dimensional translation stage system, where a laser of the energy beam control system maintains a stable light pulse energy output, a microscope of the microscope system is used to detect a change signal of a material during laser processing, and a driver of the high-precision three-dimensional translation stage system controls a position of the translation stage through a pattern designed by a computer, so as to implement lithography pattern processing of the material.
In the step II, the high-energy beam of electrons, ions or photons is utilized to irradiate a specific area of the photoetching medium, inorganic small molecules of the irradiated area sublimate, and the photoetching medium film is etched to directly form a required pattern. The pattern forming process does not need the development step in the traditional micro-nano processing technology, eliminates the use of the developing solution, and can avoid the pollution of the developing solution to the solvent of the processing surface and the damage to sensitive materials.
In step II of the present invention, the lithography pattern is a single depth pattern or a pattern with multiple depth profiles. The single depth pattern photoetching process is that the inorganic micromolecular film is etched by energy beams under the same power parameter to form a groove pattern with the same depth; the photoetching process of patterns with various depth distributions is to etch the inorganic micromolecular film by energy beams under different power parameters to form groove patterns with different depths.
In the step III, in the target material deposition step, a target material is deposited on the surface of a required pattern, the target material is filled in a groove formed after the sublimation of the photoetching medium, and the deposition material is one or a combination of a plurality of metal, non-metal simple substance, oxide, sulfide, selenide, phosphide, telluride, halide and the like. The deposition material is essentially a uniform film formed on the surface of the photolithographic medium. The material covering mode is one or a combination of a plurality of molecular layer deposition, chemical vapor deposition and physical vapor deposition.
In the step IV, the inorganic molecular photoetching medium is removed by adopting a physical adhesion stripping method or a nonpolar solvent chemical method, a polar organic photoresist remover in the traditional micro-nano processing technology is not needed, and the damage to materials in the processing process can be further avoided. The physical adhesion stripping method has the basic principle that: the physical adhesion stripping method is adopted to separate the inorganic small molecular film from the substrate to be processed, and the material of the irradiation area is remained on the surface of the substrate to form the expected design pattern.
In the step IV of the invention, another strategy for removing the inorganic small molecule photoetching medium film is to use a nonpolar solvent method, and the basic principle is as follows: the nonpolar solvent dissolves the inorganic molecular film, the material film above the inorganic molecular film is separated from the substrate to be processed and dispersed in the nonpolar solvent, and the material of the irradiated area remains on the surface of the substrate to form the expected design pattern. The nonpolar solvent comprises one or more of carbon disulfide, diethyl ether, carbon tetrachloride, hexane, isooctane, benzene, toluene, and dichloromethane. The specific type of lithographic medium and the non-polar solvent are matched to each other.
Fig. 2a is a photolithography process flow chart of a conventional organic photoresist process, and fig. 2b is a photolithography process flow chart of an inorganic molecule in an embodiment of the present invention. As can be seen from the two figures, the conventional wet process based on organic photoresist not only involves a large amount of solution and solvent in the process, but also has complicated process flow, which severely limits the application of the liquid sensitive material in the microelectronic device. The inorganic molecular lithography process provided by the invention eliminates the use of traditional developing solution, photoresist remover and cleaning solution, simplifies the process flow in the micro-nano processing process and saves the manufacturing and processing cost.
The process according to the invention is described in further detail below in connection with specific examples. In embodiments of the present invention, examples 1 to 9 disclose the preparation and etching of the photolithographic medium, i.e., the capping or deposition step and the etching step. Examples 10 to 19 disclose a target material deposition step and a removal step, and a target material pattern was prepared.
Example 1: preparation and etching of single-layer selenium molecular lithography medium
First, a selenium molecular film is deposited on a silicon substrate by a thermal evaporation method. Fig. 3a is a schematic diagram of a layer to be processed of a silicon wafer in an embodiment of the present invention, and fig. 3b is a schematic diagram of a thin film layer of selenium molecules covered on the layer to be processed of the silicon wafer, wherein under vacuum condition, selenium powder sublimates under heating and gradually deposits on a clean substrate to form a thin film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.1 Pa to 50Pa, and the heating temperature is controlled at 100 ℃ to 200 ℃. The deposition thickness of the selenium molecular film is controlled by different deposition time or different quality selenium powder. Fig. 4a to 4c are sem images of inorganic selenium molecule photoetching medium layers with different thicknesses in the embodiment of the invention, wherein the thickness of the inorganic small molecule photoetching medium in fig. 4a is 190nm, the thickness of the inorganic small molecule photoetching medium in fig. 4b is 450nm, and the thickness of the inorganic small molecule photoetching medium in fig. 4c is 1.25 μm, and the inorganic small molecule photoetching medium layers are uniformly covered. Then, the laser beam is directly irradiated on the selenium molecule film to realize etching patterning. The etching effect of the partial area of the selenium molecular film can be accurately controlled by accurately adjusting the intensity, the scanning speed and the exposure position of the energy beam.
Example 2: preparation and etching of monolayer sulfur molecular lithography medium
First, a sulfur molecular film is deposited on Si by thermal vapor deposition 3 N 4 A substrate. Under vacuum condition, sulfur powder is heated to sublimate and gradually deposited on a clean substrate to form a film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.1 Pa to 50Pa, and the heating temperature is controlled at 60 ℃ to 150 ℃. The electron beam directly irradiates on the sulfur molecular film to realize etching patterning. The etching effect of the local area of the sulfur molecular film can be accurately controlled by accurately adjusting the intensity, the scanning speed and the exposure position of the energy beam.
Example 3: single layer of Sb 2 O 3 Preparation and etching of molecular lithography media
First, sb 2 O 3 Molecular film is deposited on Al by thermal evaporation method 2 O 3 A substrate. Sb under vacuum condition 2 O 3 The powder sublimates when heated and gradually deposits on a clean substrate to form a thin film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.01 Pa to 50Pa, and the heating temperature is controlled at 200 ℃ to 300 ℃. Oxygen ion beam at Sb 2 O 3 And directly irradiating the molecular film to realize etching patterning. By precisely adjusting the intensity, scanning speed and exposure position of the energy beam, the Sb can be precisely controlled 2 O 3 Etching effect of local area of the molecular film.
Example 4: preparation and etching of double-layer sulfur-selenium molecular photoetching medium
First, a sulfur-selenium molecular film is deposited on a silicon substrate by a thermal evaporation method in sequence. Under vacuum conditions, selenium powder sublimates under heating and gradually deposits on a clean substrate to form a film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.1 Pa to 50Pa, and the heating temperature is controlled at 100 ℃ to 200 ℃. And replacing the evaporated raw material with sulfur powder, and heating and sublimating the sulfur powder to gradually deposit on the surface of the selenium film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.1 Pa to 50Pa, and the heating temperature is controlled at 60 ℃ to 150 ℃. Then, the laser beam is directly irradiated on the double-layer sulfur-selenium molecular film to realize etching patterning. The etching effect of the local area of the double-layer sulfur-selenium molecular film can be accurately controlled by accurately adjusting the intensity, the scanning speed and the exposure position of the energy beam.
Example 5: double layer sulfur-P 4 Se 3 Preparation and etching of molecular lithography media
First, sulfur-P 4 Se 3 The molecular film is deposited on the silicon substrate by a thermal evaporation method in sequence. Under vacuum condition, P 4 Se 3 The powder sublimates when heated and gradually deposits on a clean substrate to form a thin film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.1 Pa to 50Pa, and the heating temperature is controlled at 150 ℃ to 250 ℃. Changing the evaporating raw material into sulfur powder, heating and sublimating the sulfur powder, and gradually depositing the sulfur powder on P 4 Se 3 The surface of the film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.1 Pa to 50Pa, and the heating temperature is controlled at 60 ℃ to 150 ℃. Splicing jointThe laser beam is used for double-layer sulfur-P 4 Se 3 And directly irradiating the molecular film to realize etching patterning. The etching effect of the local area of the double-layer sulfur-selenium molecular film can be accurately controlled by accurately adjusting the intensity, the scanning speed and the exposure position of the energy beam.
Example 6: preparation and etching of mixed sulfur-selenium-tellurium molecular lithography medium
First, sulfur-selenium-tellurium molecules are simultaneously deposited on a silicon substrate by a thermal evaporation method. Under vacuum condition, the sulfur-selenium-tellurium mixed powder is heated to sublimate and deposited on a clean substrate to form a film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.1 Pa to 50Pa, the heating temperature is gradually increased at 60 ℃ to 300 ℃, and sulfur molecules, selenium molecules and tellurium molecules are mixed and deposited on the substrate. Then, the ion beam directly irradiates on the mixed sulfur-selenium-tellurium molecular film to realize etching patterning. The etching effect of the local area of the mixed sulfur-selenium-tellurium molecular film can be accurately controlled by accurately adjusting the intensity, the scanning speed and the exposure position of the laser energy beam.
Example 7: multilayer selenium-tellurium-SbI 3 ·3S 8 Preparation and etching of molecular lithography media
First, selenium-tellurium-SbI 3 ·3S 8 The molecular film is deposited on the silicon substrate by a thermal evaporation method in sequence. Under vacuum condition, tellurium powder is heated to sublimate and gradually deposited on a clean substrate to form a film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.1 Pa to 50Pa, and the heating temperature is controlled at 180 ℃ to 300 ℃. Replacement of vaporized raw material to SbI 3 ·3S 8 Powder, sbI 3 ·3S 8 The powder sublimates when heated and gradually deposits on the surface of the tellurium film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.1 Pa to 50Pa, and the heating temperature is controlled at 100 ℃ to 200 ℃. Replacing the evaporating raw material with selenium powder, heating to sublimate the selenium powder, and gradually depositing the selenium powder on SbI 3 ·3S 8 The surface of the film. Wherein, the vacuum degree of the vacuum coating machine is maintained at about 0.1 Pa to 50Pa, and the heating temperature is controlled at 100 ℃ to 200 ℃. Next, the laser beam is irradiated onto the multilayer selenium-tellurium-SbI 3 ·3S 8 And directly irradiating the molecular film to realize etching patterning. By precisely adjusting the laser intensity, scanning speed and exposure positionCan precisely control the selenium-tellurium-SbI of multiple layers 3 ·3S 8 Etching effect of local area of the molecular film.
Example 8: etching pattern with single depth distribution
The etching pattern of the single-depth inorganic selenium molecular lithography medium is shown in fig. 5a to 5b, wherein the thickness of the inorganic small molecular lithography medium in fig. 5a is 200nm, the thickness of the inorganic small molecular lithography medium in fig. 5b is 140nm, and the thickness of the inorganic small molecular lithography medium in fig. 5c is 80nm. FIG. 5 is a graph of lithographically bar graph of inorganic molecular lithography medium of different thickness, thermally vapor depositing selenium film of different thickness on a silicon substrate, etching line pattern on the selenium film surface using a laser of 0.1mW power, channel width of about 1 μm in FIG. 5a, depth of 200nm each, channel width of about 1 μm in FIG. 5b, depth of 140nm each, channel width of about 1 μm in FIG. 5c, depth of 80nm.
Example 9: etching pattern with multiple depth distribution
Thermal vapor deposition of 200nm thick sulfur molecular films on a substrate, etching patterns of different depths on the sulfur film surface using lasers of 400nm wavelength and different powers of 0.1mW, 0.5mW, 1mW and 2mW, or using 1000 μc cm -2 、5000μc cm -2 、10000μc cm -2 、20000μc cm -2 Patterns of different depths are etched on the sulfur film surface.
In actual engineering practice, different fine patterns, such as arrayed patterns, curvilinear patterns, alphanumeric patterns, can be prepared by precisely adjusting the energy beam intensity, scanning speed, and exposure position.
Example 10: method for preparing metal tin micropattern (polymethyl methacrylate PMMA film) by physical adhesion stripping method
Fig. 6 is a micro-nano processing process physical diagram based on an inorganic molecular lithography medium in the embodiment of the invention, fig. 6a is a selenium molecular film deposited on the surface of a silicon wafer, fig. 6b is a pattern after laser etching, a silicon substrate is exposed, fig. 6c is a deposited metal tin Sn film, fig. 6d is a pattern after photoresist removal, specifically, the embodiment of the invention is to deposit a 250nm inorganic selenium molecular film on the silicon substrate by thermal evaporation, a ten-shaped pattern is etched on the surface of the selenium film by using a laser with the wavelength of 532nm and the power of 1mW, selenium molecules in a laser irradiation area volatilize along with laser irradiation, a silicon dioxide basal layer at the bottom layer is exposed, a layer of tin film is deposited on the surface of the selenium molecular film by using a magnetron sputtering mode, a layer of adhesive PMMA film is covered above the selenium molecular film, the adhesive film is closely contacted with a metal film layer, the adhesive film is peeled off again under the action of external force, the selenium molecular film and the metal film on the surface of the silicon wafer is followed by the PMMA film, finally, a metal tin micro pattern on the surface of the substrate is obtained, and the target material deposition step and the removal step is completed.
Example 11: preparation of Metal chromium-gold micropattern (polydimethylsiloxane PDMS film) by physical adhesion stripping method
Firstly, depositing a 250nm inorganic selenium molecular film on a silicon substrate by thermal evaporation; then, etching patterns on the surface of the selenium film by using laser with the wavelength of 532nm and the power of 1mW, volatilizing selenium molecules in a laser irradiation area along with laser irradiation, and exposing a silicon dioxide basal layer of the bottom layer; then, sequentially depositing a chromium film with the thickness of 10nm and a gold film with the thickness of 90nm on the surface of the selenium molecular film by using a vacuum thermal evaporation technology; finally, a layer of Polydimethylsiloxane (PDMS) film is covered on the surface of the substrate, the PDMS film is closely contacted with the metal film layer, the bonded PDMS film is peeled off again under the action of external force, the selenium molecular film and the metal film on the surface of the silicon wafer are peeled off together with the PDMS, and finally, the metal chromium/gold micro pattern on the surface of the substrate is obtained, as shown in FIG. 7, and FIG. 7 is a schematic diagram of the adhesion peeling inorganic molecular lithography medium in the embodiment of the invention.
Example 12: preparation of metal chromium-gold micro pattern (adhesive tape) by physical adhesion stripping method
Firstly, depositing a 250nm inorganic selenium molecular film on a silicon substrate by thermal evaporation; then, etching patterns on the surface of the selenium film by using laser with the wavelength of 532nm and the power of 1mW, volatilizing selenium molecules in a laser irradiation area along with laser irradiation, and exposing a silicon dioxide basal layer of the bottom layer; then, sequentially depositing a chromium film (10 nm) and a gold film (90 nm) on the surface of the selenium molecular film by using a vacuum thermal evaporation technology; and finally, covering a layer of adhesive tape film on the surface of the silicon wafer, closely contacting the adhesive tape film with the metal film layer, peeling off the adhered adhesive tape film again under the action of external force, and peeling off the selenium molecular film and the metal film on the surface of the silicon wafer along with the adhesive tape film, thereby finally obtaining the metal chromium-gold micro pattern on the surface of the substrate.
Example 13: method for preparing aluminum oxide micro pattern (polyvinyl chloride PVC film) by physical adhesion stripping method
Firstly, depositing a 250nm inorganic sulfur molecular film on a silicon substrate by thermal evaporation; then, etching a pattern on the surface of the sulfur film by using an electron beam, volatilizing selenium molecules in an irradiation area along with laser irradiation, and exposing a silicon dioxide basal layer of the bottom layer; then, depositing an alumina film with the thickness of 50nm on the surface of the sulfur molecule film by using a vacuum thermal evaporation technology; and finally, covering a layer of polyvinyl chloride (PVC) film on the surface of the silicon wafer, wherein the PVC film is tightly contacted with the metal film layer, the bonded PVC film is peeled off again under the action of external force, and the sulfur molecular film and the metal film on the surface of the silicon wafer fall off along with the PVC film, so that the aluminum oxide micro pattern on the surface of the substrate is finally obtained.
Example 14: non-polar solvent method for preparing metal copper micropattern (carbon disulfide solvent)
In the embodiment, a 250nm inorganic selenium molecular film is deposited on a silicon substrate by thermal evaporation, and a laser with wavelength of 633nm and power of 5mW is used for etching a pattern on the surface of the selenium film. Then, selenium molecules in the laser irradiation area volatilize along with the laser irradiation, and the silicon dioxide basal layer of the bottom layer is exposed. And then, depositing a layer of 20nm copper film on the surface of the selenium molecular film by using a magnetron sputtering technology. And finally, immersing the silicon substrate into a carbon disulfide solvent, dissolving selenium molecules in the carbon disulfide solvent, removing the copper film above the selenium molecule film from the substrate, and retaining the copper film in direct contact with the substrate on the substrate to finally obtain the metal copper micropattern on the surface of the substrate. FIG. 8 shows a micro-metal structure prepared by a nonpolar solvent method according to an embodiment of the present invention.
Example 15: preparation of tungsten dioxide micropattern by nonpolar solvent method
Firstly, covering a 250nm inorganic sulfur molecular film on a silicon substrate by a vapor deposition method; next, an oxygen plasma is used to etch a pattern on the sulfur film surface. Then, selenium molecules in the laser irradiation area volatilize along with the laser irradiation, and the silicon dioxide basal layer of the bottom layer is exposed. Then, a layer of 20nm tungsten dioxide film is deposited on the surface of the sulfur molecule film by using a thermal evaporation method. And finally, immersing the silicon substrate into a carbon disulfide solvent, dissolving sulfur molecules in the carbon disulfide solvent, enabling the tungsten dioxide film above the sulfur molecule film to fall off the substrate, and keeping the tungsten dioxide film in direct contact with the substrate on the substrate to finally obtain the tungsten dioxide micro pattern on the surface of the substrate.
Example 16: non-polar solvent method for preparing lead bromide micro pattern (carbon tetrachloride solvent)
Firstly, covering a 250nm inorganic iodine molecular film on a silicon substrate by a vapor deposition method; next, a pattern was etched on the surface of the iodine thin film using a laser having a wavelength of 633nm and a power of 5 mW. Then, iodine molecules in the laser irradiation area volatilize with the laser irradiation, and the silicon dioxide basal layer of the bottom layer is exposed. Then, a layer of 20nm lead bromide film is deposited on the surface of the sulfur molecule film by using a thermal evaporation method. And finally, immersing the silicon substrate in a carbon tetrachloride solvent, dissolving iodine molecules in the carbon tetrachloride solvent, removing the lead bromide film above the iodine molecule film from the substrate, and retaining the lead bromide film in direct contact with the substrate on the substrate to finally obtain the lead bromide micro pattern on the surface of the substrate.
Example 17: preparation of lead bromide-gold micropattern (carbon tetrachloride solvent) by nonpolar solvent method
Firstly, covering a 250nm inorganic iodine molecular film on a silicon substrate by a vapor deposition method; next, a pattern was etched on the surface of the iodine thin film using a laser having a wavelength of 633nm and a power of 5 mW. Then, iodine molecules in the laser irradiation area volatilize with the laser irradiation, and the silicon dioxide basal layer of the bottom layer is exposed. Then, a 20nm lead bromide film and a 50nm gold film were sequentially deposited on the surface of the sulfur molecule film using a thermal evaporation method. And finally, immersing the silicon substrate into a carbon tetrachloride solvent, dissolving iodine molecules in the carbon tetrachloride solvent, separating the lead bromide film and the gold film above the iodine molecule film from the substrate, and retaining the lead bromide film in direct contact with the substrate on the substrate to finally obtain the lead bromide-gold micropattern on the surface of the substrate.
Example 18: preparation of black phosphorus semiconductor device (black phosphorus-silicon composite substrate) by physical adhesion stripping method
Firstly, covering a 250nm inorganic selenium molecular film on a molybdenum disulfide-silicon composite surface to be processed; then, etching a pattern on the surface of the selenium film by using oxygen plasma, volatilizing selenium molecules in an irradiation area, and exposing the black phosphorus nano-sheet and the silicon substrate layer of the bottom layer; then, sequentially depositing a chromium film with the thickness of 5nm and a gold film with the thickness of 50nm on the surface of the selenium molecular film by using an electron beam deposition technology; and finally, covering a layer of Polydimethylsiloxane (PDMS) film on the surface of the silicon substrate, closely contacting the PDMS film with the metal film layer, peeling off the bonded PDMS film again under the action of external force, and peeling off the selenium molecular film and the metal film on the surface of the silicon substrate along with the PDMS, wherein the metal chromium/gold microelectrode on the surface of the silicon substrate is connected with the black phosphorus nanosheet, so that the black phosphorus semiconductor device is finally obtained.
Example 19: non-polar solvent method for preparing molybdenum disulfide semiconductor device (molybdenum disulfide-silicon composite substrate)
Firstly, covering a 250nm inorganic selenium molecular film on a molybdenum disulfide-silicon composite surface to be processed; then, etching a pattern on the surface of the selenium film by using oxygen plasma, volatilizing selenium molecules in an irradiation area, and exposing the molybdenum disulfide nanosheets and the silicon substrate layer of the bottom layer; then, sequentially depositing a chromium film with the thickness of 5nm and a gold film with the thickness of 50nm on the surface of the selenium molecular film by using an electron beam deposition technology; and finally, immersing the silicon substrate into a carbon disulfide solvent, dissolving selenium molecules in the carbon disulfide solvent, separating the chromium-gold film above the selenium molecule film from the substrate, retaining the chromium-gold film which is in direct contact with the substrate on the substrate, and connecting a metal chromium/gold microelectrode on the surface of the silicon substrate with the molybdenum disulfide nanosheets to finally obtain the molybdenum disulfide semiconductor device.
For the composite surface to be processed with the functional active material, a physical adhesion stripping method or a nonpolar solvent method can be respectively selected according to the type of the functional active material when the photoetching medium layer is removed. Examples of different micro-nano processing conditions are shown in table 1.
Table 1 micro-nano processing examples based on inorganic small molecule lithography media
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A micro-nano processing method is characterized in that a thin film consisting of inorganic small molecules is adopted as a photoetching medium layer to execute a photoetching process, a set area of the photoetching medium layer is irradiated by utilizing high-energy beams of electrons, ions or/and photons, inorganic small molecules in the irradiated area sublimate, the photoetching medium layer in the irradiated area is etched, the photoetching medium layer in the non-irradiated area is reserved, and a needed photoetching pattern is directly formed, so that a developing step and the use of corrosive developing solution in the traditional micro-nano processing process are omitted.
2. The micro-nano processing method according to claim 1, wherein the photoetching medium layer is a solid film formed by inorganic small molecules through van der waals force, and the thickness of the solid film is 5 nm-8000 nm.
3. The micro-nano processing method according to claim 1, wherein the inorganic small molecule solid film used as the photoetching medium layer is composed of one or more of the following substances:
(1) Inorganic small molecular simple substance including phosphorus molecule P 4 Sulfur molecule S n1 Selenium molecule Se n2 Te molecule n3 And iodine molecule I 2 Wherein n1 is more than or equal to 2 and less than or equal to 8, and n1 is an integer; n2 is more than or equal to 2, and n2 is an integer; n3 is more than or equal to 2, and n3 is an integer;
(2) Binary or ternary inorganic small molecule compoundsAn object comprising P 4 Se 3 、Sb 2 O 3 、SbI 3 、SbI 3 ·3S 8 A combination of one or more of the following;
(3) And at the same time, the inorganic micromolecular simple substance and the binary or ternary inorganic micromolecular compound are mixed.
When the structural units of the substances are in short chain, ring or cage-shaped small molecular forms, when the structural units are used as a photoetching medium to form a solid film, molecules are connected with each other by weak van der Waals force, after being bombarded by high-energy beams, the van der Waals force is destroyed, and the small molecules are etched and sublimated, so that the photoetching medium layer directly forms a pattern.
4. A micro-nano machining method according to any one of claims 1-3, comprising the steps of:
the construction step of the photoetching medium layer comprises the following steps: covering a layer of solid film formed by inorganic small molecules on the surface to be processed,
etching: the high energy beam of electrons, ions or photons is utilized to irradiate the set area of the photoetching medium layer, the inorganic micromolecular photoetching medium obtains energy to be sublimated directly, the photoetching medium in the irradiated area is etched to form grooves, the non-irradiated part is reserved, thus the photoetching medium layer forms a required pattern,
a deposition step of a target material: depositing a layer of target material with a specified thickness on the patterned inorganic small molecule photoetching medium layer, depositing one part of the target material layer in a groove formed after etching the inorganic small molecule, depositing the other part of the target material layer on the photoetching medium layer which is not etched,
removing the photoetching medium layer: removing the non-irradiated photoetching medium layer by adopting a physical adhesion stripping method or a nonpolar solvent soaking method, and reserving the target material layer filled in the photoetching medium layer groove in the target material deposition step to obtain the patterned target material layer.
5. The micro-nano processing method according to claim 4, wherein in the construction step of the photo-etching medium layer, the photo-etching medium layer is a single kind of small molecular film or a plurality of kinds of small molecular films; the covering sequence of the various small molecule films is that various small molecules are simultaneously mixed and covered, or the small molecule film layers are sequentially covered in a plurality of layers according to different small molecule types; the photoetching medium layer can be flexibly selected and set according to the type of energy beam and etching parameters in the etching step; the photoetching medium layer covering mode is one or a combination of a plurality of molecular layer deposition, chemical vapor deposition, physical vapor deposition and magnetron sputtering.
6. The micro-nano processing method according to claim 4, wherein the steps of constructing the photo-etching dielectric layer, etching the photo-etching dielectric layer, depositing the target material and removing the photo-etching dielectric layer can be combined in a cyclic manner in a tandem order or flexibly according to processing requirements.
7. The micro-nano processing method according to claim 4, wherein the surface to be processed is a planar or non-planar substrate surface in the micro-nano processing field or a composite substrate surface on which a functional active material has been placed.
8. The micro-nano processing method according to claim 4, wherein in the step of removing the photoetching medium layer, the physical adhesion stripping method is based on an adhesion stripping mode, and the adhesion comprises one or a combination of a plurality of polydimethyl siloxane film, polymethyl methacrylate film, polyethylene film, polypropylene film, polyvinyl chloride film, polyvinyl alcohol film and adhesive tape film,
or, in the mode of removing the photoetching medium layer by adopting a nonpolar solvent soaking method, the nonpolar solvent comprises one or a combination of more of carbon disulfide, diethyl ether, carbon tetrachloride, hexane, isooctane, benzene, toluene and methylene dichloride.
9. The micro-nano processing method according to any one of claims 1-8, wherein the used lithography medium layer can be stored and used in normal temperature, normal pressure, sunlight environment.
10. A lithographic medium for use in a micro-nano processing method according to any one of claims 1-9.
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