CN112051713B - Electron beam exposure and positioning method with sub-ten nanometer precision - Google Patents
Electron beam exposure and positioning method with sub-ten nanometer precision Download PDFInfo
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- 238000010894 electron beam technology Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
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- 238000011161 development Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000000452 restraining effect Effects 0.000 claims abstract description 4
- 239000002086 nanomaterial Substances 0.000 claims abstract description 3
- 238000004528 spin coating Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 17
- 238000001771 vacuum deposition Methods 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 4
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- 238000000576 coating method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 238000011160 research Methods 0.000 description 4
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- 230000001133 acceleration Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70008—Production of exposure light, i.e. light sources
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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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- 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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/54—Absorbers, e.g. of opaque materials
- G03F1/56—Organic absorbers, e.g. of photo-resists
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- 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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/76—Patterning of masks by imaging
- G03F1/78—Patterning of masks by imaging by charged particle beam [CPB], e.g. electron beam patterning of masks
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Abstract
The invention relates to the technical field of nano processing, in particular to an electron beam exposure and positioning method with the precision of sub-ten nanometers, which comprises the following steps: s1: designing an exposure pattern for confining an electron beam; s2: spin-coating an electron beam resist on a substrate material, selecting a proper electron beam exposure step length and a proper dose, and performing electron beam exposure, development and fixation to obtain a pattern mask with a sub-ten nano structure; the exposure pattern for restraining the electron beams comprises trapezoidal electrodes on two sides and a central ellipse, the minor axis of the ellipse is parallel to the axes of the two electrodes, the short edge of the trapezoidal electrode is adjacent to the central ellipse, and the gaps between the two trapezoidal electrodes and the ellipse are respectively adjustable. The electron beam exposure and positioning method with the accuracy of the sub-ten nanometers, provided by the invention, can realize the controllable preparation of the sub-ten nanoparticles/gaps only by one-step exposure, is simple and feasible, and solves the problems of multiple process steps, complex flow and low alignment accuracy of the conventional technology for preparing the sub-ten nanoparticle/gap structure.
Description
Technical Field
The invention relates to the technical field of nano processing, in particular to an electron beam exposure and positioning method with the precision of sub-ten nanometers.
Background
In the information and intelligent era of high-speed development, the ultrahigh integration degree of devices is the trend of the development of the micro-nano electronic industry, and various structures/devices are inevitably required to be infinitely reduced in size and move to the processing and preparation limit. Among them, the accurate positioning and controllable fabrication of sub-ten nanoparticles, gaps, etc. structures currently remains a challenge for nanofabrication. The preparation quality of the composite material is very critical to the stable and efficient operation of a formed small electronic system, and the reliability and stability of the operation of a device/system are directly influenced. On the other hand, the method can also be used as a platform and a carrier for carrying out basic research in the fields of nano-optoelectronics, sensing, quantum information and the like.
At present, the conventional method for preparing nanoparticles in gaps is to fill chemically synthesized nanoparticles in the gaps through an alignment process, but the positioning accuracy of the nanoparticles is limited by the alignment accuracy of an instrument, which is usually more than ten nanometers, so that the requirement of structure/device research on sub-ten nanometer accuracy and controllability is difficult to meet. Especially for a system that the electrode and the particles are made of the same material, the alignment process is adopted, so that the complexity of the process is increased, and the requirement on the positioning precision of the sub-ten nanometers cannot be met. Even if the method for preparing the pattern mask with the sub-ten nano particles/double-gap structure by one-step electron beam exposure is realized by adjusting the overlapping length of two diagonal triangular electrodes and selecting a proper electron beam exposure step length, only the structure with two gaps with the same size can be obtained, and the adjustable range of the size of the central nano particles is very limited. In a word, no matter a conventional preparation method is adopted or a method for preparing a sub-ten nano-particle/gap structure by changing exposure dose through overlapping two diagonal triangles, the process flow is complex and is not easy to control accurately, or the adjustable range of the particle/gap size is very small and limited, so that the repeatability of prepared near-limit size devices such as nano-photoelectrons is poor, and even the manufacturing of target devices is difficult to complete. Therefore, it is difficult to provide device guarantee for basic research of nano-photoelectrons, sensors, quantum devices and the like, and the discovery and experimental verification of a new principle and a new phenomenon of a limit size device are not facilitated, so that the practical application and popularization of the device based on the new principle and the new phenomenon in the ultra-high integration micro-nano electronic industry are not facilitated. Therefore, an electron beam exposure and positioning method with sub-ten nm accuracy is urgently needed for the same material as the particles.
Disclosure of Invention
Aiming at the conventional preparation technology of a device with the same material as the electrode and the particles, the invention provides an electron beam exposure and positioning method with the precision of sub-ten nanometers.
The method comprises the following steps:
s1, designing an exposure pattern for restraining an electron beam;
s2, spin-coating an electron beam resist on a substrate material, selecting a proper electron beam exposure step length and a proper dose, and performing electron beam exposure, development and fixation to obtain a pattern mask with a sub-ten nano structure;
the exposure pattern for restraining the electron beams comprises trapezoidal electrodes on two sides and a central ellipse, the minor axis of the ellipse is parallel to the axes of the two electrodes, the short edge of the trapezoidal electrode is adjacent to the central ellipse, and the gaps between the two trapezoidal electrodes and the ellipse are respectively adjustable.
The invention utilizes exquisite pattern design, cooperates with appropriate electron beam resist and exposure condition, the effective action range of the accelerated electrons is limited in a selected area, and the positioning precision reaches sub-ten nanometers. In addition, the technology can be completed only by one-time exposure technology, so that the preparation technology, the flow and the efficiency of structures such as the sub-ten nano particles/gaps and the like are greatly simplified, and the preparation quality, the preparation and the positioning precision of the structures can be improved.
Preferably, a layer of conductive film is covered on the substrate with the pattern mask by vacuum coating, and a particle/gap patterned structure with a characteristic size of sub-ten nanometers is obtained after a stripping process.
The preferable range of the short side size of the two trapezoidal electrodes is 5-15 nanometers; the size range of the long axis of the ellipse is 5-20 nanometers; the size range of the elliptical minor axis is 3-15 nanometers; the range of the two electrodes and the elliptical gap is 3-20 nanometers, and the two gaps can be equal or unequal.
The preferable electron beam exposure resist is polymethyl methacrylate, the thickness of the electron beam exposure resist is 80-150 nanometers, and the dosage of the electron beam exposure resist is 1000-1900 mu C/cm 2 ；
Or the electron beam exposure resist is ZEP520A, the thickness of the electron beam exposure resist is 80-150 nanometers, and the dosage is 130-200 mu C/cm 2 。
Preferably, the electron beam acceleration voltage used for the electron beam exposure is 50 to 100kV; the developing and fixing time is 10 to 60 seconds.
Preferably, the minimum line width dimension of the patterned nanoparticle/gap structure is in the range of 3 to 10 nm.
A preferred vacuum coating film is covered with a conductive film which is a multilayer or alloy film of one or more of Pt, pd, al, au, ti, cr, cu, V, W, ni, fe, co, znO, al, znO, tiN, ITO, gaAs, inAs, inP, ge, si.
According to the electron beam exposure and positioning method with the sub-ten nanometer precision, provided by the invention, the effective action range of accelerated electrons is restricted in a selected area by designing the size and the shape of a graph and matching with a proper electron beam resist and exposure conditions, and the method can be completed only by one-time exposure process, so that the preparation process and the flow of sub-ten nanometer particles/gaps are greatly simplified, and the double beneficial effects of simultaneously improving the preparation and positioning precision of the particles/gaps are obtained. FIG. 1 is a schematic top view of an exposure pattern and an electron confinement intensity distribution during exposure according to the present invention. Almost no electron action exists in a black area in an electron confinement action intensity distribution schematic diagram, and an electron beam resist is left after development; the white area is acted by the confined electrons, no electron beam resist is generated after development, and finally a patterned electron beam resist structure with a central hole and a peripheral electrode groove is formed. The invention utilizes one-step electron beam exposure technology to prepare the pattern mask with adjustable sub-ten nanometer particles/gaps, greatly simplifies the preparation technology and the flow, and is beneficial to promoting the basic research and the practical application of the devices.
Drawings
FIG. 1 is a schematic top view of an exposure design of the present invention;
FIG. 2 is a schematic top view of an electron confinement intensity distribution during exposure in accordance with the present invention;
FIG. 3 shows a 5 nm center particle and 4 nm and 5 nm gap structures formed after a coating stripping process according to example 1 of the present invention;
FIG. 4 shows a 5 nm center particle and 10 nm and 19 nm gap structures formed after a coating stripping process according to example 2 of the present invention;
fig. 5 shows 10 nm center particles and 10 nm and 16 nm gap structures formed after a coating film stripping process according to example 3 of the present invention.
Fig. 6 shows 20 nm center particles and 18 nm and 5 nm gap structures formed after the coating stripping process of example 4.
Detailed Description
For the purpose of promoting a clear understanding of the features and technical advantages of the present invention, reference is made to the accompanying drawings, which are included to provide a further understanding of the invention, and the description is not intended to limit the invention.
Example 1
The embodiment provides an electron beam exposure and positioning method with the precision of 3 nanometers, which comprises the following steps:
an exposure layout is set, the short side size of the two trapezoid electrodes is 5 nanometers, the long axis size of the ellipse is 6 nanometers, the short axis size of the ellipse is 3 nanometers, the left side electrode and the ellipse gap are 4 nanometers, and the right side electrode and the ellipse gap are 6 nanometers.
Sequentially soaking the silicon wafer in acetone, isopropanol and deionized water for 5 minutes and carrying out ultrasonic treatment for 1 minute, cleaning the silicon wafer serving as the substrate material in the embodiment, and drying the silicon wafer by using nitrogen; spin-coat a layer of electron beam resist, in this example PMMA with a thickness of 80 nm, and bake in an oven for 30 minutes at a temperature of 180 ℃.
The electron beam acceleration voltage used for carrying out electron beam exposure on the substrate is 100kV, the beam current size is 100pA, the acceleration voltage is matched with the exposure step length of 1 nanometer, and the exposure dose is 1000 mu C/cm 2 After electron beam exposure, development for 40s and fixing for 60s, a pattern mask was obtained.
And preparing a conductive film on the surface of the substrate with the pattern mask by using a vacuum coating method, wherein the metal in the embodiment is platinum with the thickness of 10 nanometers. After the stripping process, 5 nm central particles and 3 nm and 5 nm gap structures were obtained, as shown in fig. 3.
Example 2
The embodiment provides an electron beam exposure and positioning method with the precision of 5 nanometers, which comprises the following steps:
an exposure layout is set, the short sides of the two trapezoid electrodes are 10 nanometers in size, the long axis of the ellipse is 5 nanometers in size, the short axis of the ellipse is 4 nanometers in size, the left side electrode is 10 nanometers in clearance with the ellipse, and the right side electrode is 20 nanometers in clearance with the ellipse.
The same cleaning procedure of the substrate material as in example 1, in which PMMA electron beam resist having a thickness of 150 nm was selected, was baked on a hot plate for 5 minutes,the baking temperature was 180 ℃. The electron beam exposure dose was 1900. Mu.C/cm 2 Other exposure conditions were the same as in example 1, and a device pattern mask was obtained after development for 10s and fixing for 40 s.
And preparing a conductive film on the surface of the substrate with the pattern mask by using a vacuum coating method, wherein the metal in the embodiment is palladium with the thickness of 10 nanometers. After the lift-off process, 5 nm central particles and 10 nm and 19 nm gap structures were obtained, as shown in fig. 4.
Example 3
The embodiment provides an electron beam exposure and positioning method with the precision of 10 nanometers, which comprises the following steps:
an exposure layout is set, the short sides of the two trapezoid electrodes are 12 nanometers in size, the long axis of the ellipse is 10 nanometers in size, the short axis of the ellipse is 8 nanometers in size, the left side electrode and the ellipse gap are 11 nanometers in size, and the right side electrode and the ellipse gap are 18 nanometers in size.
The same cleaning procedure for the base material as in example 1 was used. In this example, a ZEP520A electron beam resist having a thickness of 80 nm was selected and baked on a hot plate for 2 minutes at a baking temperature of 180 ℃. The electron beam exposure dose was 130. Mu.C/cm 2 The other exposure conditions were the same as in example 1, and a device pattern mask was obtained after development for 20s and fixing for 30 s.
And preparing a conductive film on the surface of the substrate with the pattern mask by using a vacuum coating method, wherein the metal in the embodiment is palladium with the thickness of 10 nanometers. After the lift-off process, 10 nm central particles and 10 nm and 16 nm gap structures were obtained, as shown in fig. 5.
Example 4
The embodiment provides an electron beam exposure and positioning method with the precision of 5 nanometers, which comprises the following steps:
an exposure layout is set, the short side dimension of the two trapezoid electrodes is 15 nanometers, the long axis dimension of the ellipse is 20 nanometers, the short axis dimension of the ellipse is 15 nanometers, the left side electrode and the ellipse gap are 19 nanometers, and the right side electrode and the ellipse gap are 4 nanometers.
The same cleaning procedure for the base material as in example 1 was used. In this example, a ZEP520A electron beam resist having a thickness of 150 nm was selected, baked on a hot plate for 5 minutes, and bakedThe baking temperature was 180 ℃. The electron beam exposure dose was 200. Mu.C/cm 2 Other exposure conditions were the same as in example 1, and a device pattern mask was obtained after development for 30s and fixing for 40 s.
And preparing a conductive film on the surface of the substrate with the graphic mask by using a vacuum coating method, wherein the metal in the embodiment is 10 nm palladium. After the lift-off process, 20 nm central particles and 18 nm and 5 nm gap structures were obtained, as shown in fig. 6.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (3)
1. An electron beam exposure and positioning method with the precision of sub-ten nanometers is characterized by comprising the following steps:
s1: designing an exposure pattern for confining an electron beam;
s2: spin-coating an electron beam resist on a substrate material, selecting an electron beam exposure step length and a dosage, and obtaining a pattern mask with a sub-ten nano structure through electron beam exposure, development and fixation;
the exposure pattern for restraining the electron beams comprises trapezoidal electrodes on two sides and a central ellipse, the minor axis of the ellipse is parallel to the axes of the two electrodes, the short edge of the trapezoidal electrode is adjacent to the central ellipse, and the gaps between the two trapezoidal electrodes and the ellipse are respectively adjustable;
the size range of the short sides of the two trapezoidal electrodes is 5-15 nanometers; the size range of the long axis of the ellipse is 5-20 nanometers; the size range of the elliptical minor axis is 3-15 nanometers; the range of the two electrodes and the oval gap is 3-20 nanometers, and the two gaps can be equal or unequal;
the electron beam exposure resist is polymethyl methacrylate with the thickness of 80-150 nanometersRice with dosage of 1000-1900 μ C/cm 2 ；
Or the electron beam exposure resist is ZEP520A, the thickness of the electron beam exposure resist is 80-150 nanometers, and the dosage is 130-200 mu C/cm 2 ；
The electron beam accelerating voltage used by the electron beam exposure is 50-100 kV; the developing and fixing time is 10-60 s;
s3: and covering a layer of conductive film on the substrate with the pattern mask by using a vacuum coating film, and obtaining the particle/gap patterned structure with the characteristic dimension of sub-ten nanometers through a stripping process.
2. The method of claim 1, wherein the patterned nanoparticle/gap structures have a minimum line width dimension in the range of 3 nm to 10 nm.
3. The method of claim 1, wherein the vacuum coating is applied with a conductive film of one or more of Pt, pd, al, au, ti, cr, cu, V, W, ni, fe, co, znO, al, znO, tiN, ITO, gaAs, inAs, inP, ge, and Si.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101067719A (en) * | 2007-06-04 | 2007-11-07 | 中国科学院上海技术物理研究所 | Method for constituting sub-10 nano gap and array thereof |
| CN110854020A (en) * | 2019-11-22 | 2020-02-28 | 国家纳米科学中心 | Preparation method of sub-10 nanometer coulomb blocking device |
| CN110993487A (en) * | 2019-11-22 | 2020-04-10 | 国家纳米科学中心 | Preparation method and application of sub-10 nanometer gap structure |
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| TWI227516B (en) * | 2003-12-26 | 2005-02-01 | Ind Tech Res Inst | Nano-electronic devices using discrete exposure method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101067719A (en) * | 2007-06-04 | 2007-11-07 | 中国科学院上海技术物理研究所 | Method for constituting sub-10 nano gap and array thereof |
| CN110854020A (en) * | 2019-11-22 | 2020-02-28 | 国家纳米科学中心 | Preparation method of sub-10 nanometer coulomb blocking device |
| CN110993487A (en) * | 2019-11-22 | 2020-04-10 | 国家纳米科学中心 | Preparation method and application of sub-10 nanometer gap structure |
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