CN113184801B - Micro-nano structure and device direct writing method based on impulse difference particle desorption - Google Patents
Micro-nano structure and device direct writing method based on impulse difference particle desorption Download PDFInfo
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- 238000010894 electron beam technology Methods 0.000 claims abstract description 58
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- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims description 32
- 230000005684 electric field Effects 0.000 claims description 15
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 12
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- 238000006073 displacement reaction Methods 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/005—Bulk micromachining
- B81C1/00515—Bulk micromachining techniques not provided for in B81C1/00507
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00103—Structures having a predefined profile, e.g. sloped or rounded grooves
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66083—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by variation of the electric current supplied or the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched, e.g. two-terminal devices
- H01L29/6609—Diodes
- H01L29/66136—PN junction diodes
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Abstract
The invention relates to a micro-nano structure and device direct writing method based on impulse difference particle desorption, which comprises the following steps: fixing a material source on a substrate; placing the substrate and material source into an electron beam apparatus; vacuumizing the electron beam equipment; controlling the electron beam to obliquely enter the surface of the material source; and controlling the electron beam to perform space scanning by using a raster oscillation scanning field, and gradually moving according to a preset structural shape until a complete micro-nano structure is obtained. The invention can improve the micro-nano structure construction efficiency.
Description
Technical Field
The invention relates to the field of micro-nano structures and semiconductor devices, in particular to a direct writing method of a micro-nano structure and a device based on impulse difference particle desorption.
Background
The electron beam has strong functions in micro-nano structure and device construction, and forms micro-nano processing technologies such as electron beam induced in situ synthesis (EBIS), electron beam Etching (EBL), electron Beam Induced Deposition (EBID), electron beam carbonization direct writing and the like.
The EBIS technology prepares the micro-nano structure based on physical and chemical effects of electron beams, such as collision displacement and sputtering of sample atoms, charge effect and crystallization, desorption and oxidation-reduction reactions related to Knotek-Feibelman (K-F) mechanism, and the like, and is characterized in that the electron beam irradiation is controlled to realize modification and structure construction of local structures on a material source sample. The EBL technology utilizes electron beams to bombard resist molecules, so that resist molecular chains are broken, or cross-linking reaction occurs, or carbonization and the like are carried out to form a patterned template, and the micro-nano structure of the planar feature is prepared by combining corresponding processes. Some EBL improvement methods can also be used for 3D structure construction, such as gray EBL (Grayscale electron beam lithography), EBL (controlled-acceleration-voltage EBL) and ice-assisted EBL 3D nano structure construction technology, etc., the construction methods are all technological processes based on the EBL technology, and obviously, the steps are complicated and certain limitations exist for metal and semiconductor micro-nano structures and devices with large aspect ratio and 3D characteristics. The EBID technology overcomes the defects of the EBL related processing method in the aspects of high precision, large aspect ratio and 3D structure construction, and non-volatile materials such as metal, semiconductor materials and the like are deposited to form a micro-nano structure by controlling the reaction of electron beams and gaseous precursor sources, so that the template-free direct writing construction of the high-sensitivity and complex 3D nano structure is realized. The EBID has the defect that precursor fragments such as carbon, chlorine and the like are easy to generate in the structure construction process, and the performance of the micro-nano structure and the device is affected. In addition, the EBID method has low material source utilization, is dissipated in the structure construction process, increases construction cost, and brings possible environmental hazards.
The electron beam focus is utilized to directly drive the material source atoms to migrate and diffuse, and the construction of the high-precision and high-purity micro-nano structure can be realized. However, atoms, small clusters, and the like in the material source form quite firm blocks or films through the interaction of bonding such as ionic bonds, van der Waals forces, hydrogen bonds, and the like, so that the sub-nano particles forming the material source have strong desorption resistance, prevent the diffusion and migration of the particles, and have low structure construction efficiency. Therefore, by adopting an effective method, the dissociation, desorption and diffusion migration of particles are promoted, and the improvement of the direct writing construction efficiency of the micro-nano structure and the semiconductor device becomes a key problem which must be solved by commercial application.
Disclosure of Invention
The invention aims to provide a direct writing method of a micro-nano structure and a device based on impulse difference particle desorption, which can improve the micro-nano structure construction efficiency.
In order to achieve the above object, the present invention provides the following solutions:
a direct writing method of micro-nano structure and device based on impulse difference particle desorption comprises the following steps:
fixing a material source on a substrate;
placing the substrate and material source into an electron beam apparatus;
vacuumizing the electron beam equipment;
controlling the electron beam to obliquely enter the surface of the material source;
and controlling the electron beam to perform space scanning by using a raster oscillation scanning field, and gradually moving according to a preset structural shape until a complete micro-nano structure is obtained.
Optionally, the raster oscillating scan field refers to line-by-line scanning or column-by-column scanning of the electron beam focus according to a certain contour with any vertex as a starting point.
Optionally, the raster oscillating scan field includes a plurality of scan paths within a certain contour, the plurality of scan paths are parallel to each other, and the scan directions of two adjacent scan paths are opposite and connected end to end.
Optionally, the outline size or diameter of the raster oscillation scan field is less than or equal to 200nm, and the scan frequency is in the electron beam scan frequency range of electron microscope imaging.
Optionally, the material source is a semiconductor or a metallic material.
Optionally, the material source is SnO 2 。
Alternatively, the stepwise movement according to the predetermined structural shape is achieved by a high precision displacement stage.
Alternatively, the stepwise movement according to the predetermined structural shape is achieved by varying the degree of deflection of the electron beam.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
the invention uses the electric field attractive force of oscillation change generated when the electron beam is used for raster oscillation scanning, couples and overlaps the oscillation coulomb repulsive force among the sub-nano particles, and generates a flushing difference among charged particles, thereby opening the bonding among the particles, improving the migration and diffusion of the sub-nano particles and improving the construction efficiency of the nano structure.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, it will be obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a first raster scan field profile and scan path according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a profile and a scan path of a second raster scan field according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a third raster scan field profile and scan path according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of micro-nano structure direct writing according to an embodiment of the present invention;
FIG. 5 is a schematic direct-write diagram of a micro-nano structured pn junction prototype device according to an embodiment of the present invention;
wherein: 1-contours of the scan field; 2-horizontal scan path; 3-horizontal regression line feed path; 4-vertical regression path; 5-a vertical scan path; 6-a vertical retrace path; 7-horizontal regression path; 8-horizontal column (row) change path; 9-a horizontal retrace path; 10-scan path illustration; 11-the direction of the scan field movement; 12-with SiO 2 A silicon substrate of the layer; 13-material source one; 14-a first nanostructure; 15-incident electron beam; 16-metal electrodes; 17-metal electrodes; 18-material source two; 19-material source three; 20-a second nanowire; 21-a third nanowire; 22-nanowire contact junction.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention aims to provide a direct writing method of a micro-nano structure and a device based on impulse difference particle desorption, which aims to solve the technical problems of large particle diffusion energy barrier and low efficiency in the prior art.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description.
The invention utilizes the oscillation change electric field attractive force generated when the electron beam is used for raster scanning, couples and overlaps the oscillation coulomb repulsive force among the sub-nano particles, and generates a flushing difference among charged particles, thereby opening the bonding among the particles, improving the migration and diffusion of the sub-nano particles and improving the construction efficiency of the nano structure.
The main technical concept of the invention is as follows:
(1) Preparing a material source on a substrate, putting the material source into electron beam equipment, and vacuumizing to reach normal working conditions of the equipment;
(2) The electron beam is controlled to obliquely enter the surface of the material source, and the space scanning is carried out by using a grating type oscillating scanning field, wherein the grating type oscillating scanning field can cause oscillation change of stress of sub-nano particles on the surface layer of the composition material source, and the impulse between the sub-nano particles at different positions is different, so that the bonding between the sub-nano particles on the surface layer is broken, dissociated and desorbed, and the sub-nano particles are diffused in the stress direction.
(3) And controlling the raster oscillation scanning field of the electron beam to gradually move according to the designed micro-nano structure shape, and enabling the dissociated and desorbed sub-nano particles to migrate and accumulate to a stress balance position in the scanning field and forming a corresponding micro-nano structure according to the displacement track of the scanning field.
Specifically, the material source in the step (1) may be a semiconductor or a metal material. The raster oscillating scan field in the step (2) refers to that the electron beam focus is scanned line by line or column by column with a certain contour under the control of a program, the contour size or diameter of the scan field is required to be below 200nm, and the scan frequency is within the electron beam scan frequency range of electron microscope imaging. The stress of the sub-nano particles in the step (2) refers to the coupling superposition force of the strong electric field attraction force received by the surface sub-nano particles and the coulomb repulsion force among the particles under the action of electrostatic induction. The impulse difference in the step (2) refers to the difference of the coupling superposition forces between the surface layer sub-nano particles at different positions and the accumulation amounts with time. The stress balance position in the scan field in the step (3) refers to a spatial position where the electric field coupling superposition force applied to the sub-nano particles and the capillary action between the particles are balanced with each other. The step (3) of controlling the raster scan field of the electron beam to gradually move according to the designed micro-nano structure shape refers to the relative position change of the raster scan field and the initial point of the growth of the nano structure, and can be realized by the change of the deflection degree of the electron beam under the control of a program or by the space displacement of a high-precision displacement table.
Based on the above, the invention provides a direct writing method of a micro-nano structure and a device based on impulse difference particle desorption, wherein the preparation of the micro-nano structure is shown in fig. 4, and the method comprises the following steps:
(1) Preparation of SnO on silicon substrate 12 2 Placing the solid material source I13 into electron beam equipment to be vacuumized to reach the working condition of electron beams;
(2) Controlling oblique incidence of electron beam 15 to SnO 2 A solid material source 13 surface for focusing electron beam on SnO 2 The scanning field moving direction 11 of the solid material source surface is from bottom to top, the scanning field moving direction can be from left to right, the scanning path 10 can also perform raster oscillation scanning according to the scanning field outline and the scanning path shown in fig. 2, a strong electric field with nanometer scale oscillation alternating is formed, and the strong electric field can lead SnO to be formed 2 Positive and negative charges on the surface of the film are separated, and SnO with positive charges on the surface layer 2 The sub-nano particles are subjected to the attraction of a strong electric field and the repulsive force between positively charged particles. Under the coupling superposition of the attraction force and the repulsive force between particles, the surface layer is positively provided withCharged SnO 2 The sub-nano particles obtain instantaneous impulse and different SnO 2 The instant impulse between particles is different, and the instant impulse difference can open the bonding action between particles to lead the SnO with positive electricity 2 The sub-nano particles become particles capable of directionally migrating and migrate to a stress balance position in a scanning field;
in fig. 2, the electron beam focus performs a path scan in a form of "one line" in the outline 1 of the scan field, the vertical scan path 5 and the vertical retrace path 6 are parallel to each other, and the horizontal column (row) changing path 8 connects the end of the vertical scan path 5 and the beginning of the vertical retrace path 6; the horizontal regression path 7 connects the end of the vertical retrace path 6 and the beginning of the next vertical scan path 5.
(3) The profile 1 of the electron beam scan field is controlled to move stepwise according to the designed micro-nanostructure morphology, thereby forming corresponding first nanostructures 14 on the scan field movement spatial trajectory.
Based on the scanning mode, the electron beam scanning field can be replaced by a raster scanning field shown in fig. 1 or 3, wherein the electron beam focus in fig. 1 scans line by line or column by column in a form of a horizontal scanning path 2, a horizontal regression line feed path 3 and a vertical regression path 4 by taking any vertex as a starting point in the outline 1 of the scanning field; the movement pattern of the electron beam focus in fig. 3 is similar to that of fig. 2, the horizontal scan path 2 and the horizontal retrace path 9 are parallel to each other, but the horizontal column (row) path 8 of the electron beam focus in fig. 3 is scanned along the edge of the outline of the predetermined scan field.
Based on the scanning mode of fig. 1, fig. 2 and fig. 3, the material source can be replaced by other metal oxide and metal nonmetal compound semiconductor material sources, so that new embodiments can be formed, and corresponding nano structures are finally prepared.
Specifically, the micro-nano structure and device direct writing method based on impulse difference particle desorption provided by the invention can also adopt SnO 2 The structure of the NiO PN junction direct writing structure is shown in fig. 5, and the method comprises the following steps:
(1) According to the shape of the prepared PN junction, a gold electrode 16 is deposited on a specific adjacent region on the silicon substrate 12And 17; on the gold electrode, localized selective area is adopted by laser direct writing method, and SnO is deposited by magnetron sputtering method 2 The film is a material source II 18, the NiO film is a material source III 19, and the materials are placed into electron beam equipment and vacuumized;
(2) First, the electron beam 15 is controlled to obliquely enter SnO 2 The surface of the second film material source 18 makes the electron beam focus on the surface of the second film material source 18 to perform raster oscillating scanning as shown in figure 1 to form a strong electric field with nano-scale oscillating alternation on the surface, and the strong electric field can make SnO 2 Positive and negative charges on the surface of the film are separated, and SnO with positive charges on the surface layer 2 The sub-nano particles are subjected to the action of the attractive force of an electric field of an electron beam focus and the repulsive force among positively charged particles. Oscillating alternating strong electric field attraction and SnO 2 SnO with positively charged surface layer under superposition of inter-particle coulomb repulsion 2 The sub-nano particles obtain instantaneous impulse and different SnO 2 The instantaneous impulse between particles may be different, and this instantaneous impulse difference opens the bonding between particles, making the charged SnO 2 The sub-nanoparticles become free particles that can migrate directionally.
(3) The electron beam raster scan field 1 is controlled to gradually move to the area close to NiO, so that SnO is formed on the scan field moving space track 2 The suspended nanowire is a second nanowire 20;
(4) And (3) controlling the electron beam to obliquely enter the surface of the NiO film 19, repeating the steps (2) and (3), growing the NiO suspended nanowire into a third nanowire 21, and enabling the second nanowire and the third nanowire to form a nanowire contact junction 22 to complete the construction of a PN junction prototype device.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, by controlling the electron beam to obliquely enter the surface of the material source and performing space scanning on the surface of the material source by using a grating oscillating scanning field, the grating oscillating scanning field can cause the oscillation change of the electric field attraction force and the coulomb repulsive force among particles, which are born by the surface layer sub-nano particles of the composition material source, and the impulse among the sub-nano particles at different positions is different, so that the bonding among the surface layer sub-nano particles is broken and dissociated.
2. And controlling the space reciprocating scanning field of the electron beam to gradually move according to the designed micro-nano structure shape, and enabling the dissociated and desorbed sub-nano particles to migrate and accumulate to the stress balance position in the scanning field and forming a corresponding micro-nano structure according to the displacement track of the electron beam space scanning field.
Compared with the prior art, the invention also has the following technical effects:
the invention utilizes the oscillation change electric field attractive force generated when the electron beam is used for raster scanning, couples and overlaps the oscillation coulomb repulsive force among the sub-nano particles, and generates a flushing difference among charged particles, thereby opening the bonding among the particles, improving the migration and diffusion of the sub-nano particles and improving the construction efficiency of the nano structure. The nano structure is induced to grow by controlling the movement of the raster scanning field, and the semiconductor prototype device is constructed by combining other technologies through direct writing, so that the method has important significance for improving the growth rate of the nano structure and the construction efficiency of the prototype device.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to assist in understanding the methods of the present invention and the core ideas thereof; also, it is within the scope of the present invention to be modified by those of ordinary skill in the art in light of the present teachings. In view of the foregoing, this description should not be construed as limiting the invention.
Claims (8)
1. A direct writing method of a micro-nano structure and a device based on impulse difference particle desorption is characterized by comprising the following steps:
fixing a material source on a substrate;
placing the substrate and material source into an electron beam apparatus;
vacuumizing the electron beam equipment;
controlling the electron beam to obliquely enter the surface of the material source;
the electron beam is controlled to make space scanning by a raster oscillating scanning field, and gradually moves according to a preset structural shape until a complete micro-nano structure is obtained;
when the electron beam is controlled to perform space scanning by using a grating type oscillation scanning field, the oscillating change electric field attraction generated on the surface layer of the material source is coupled and overlapped with the oscillating coulomb repulsive force among the sub-nano particles to generate a pulse difference among the sub-nano particles; the impulse difference enables the bonding between the sub-nano particles to be broken, dissociated and desorbed; the dissociated and desorbed sub-nano particles migrate and accumulate to a stress balance position in the grating type oscillating scanning field, and form a corresponding micro-nano structure according to a displacement track of the grating type oscillating scanning field;
the impulse difference is used for representing the difference of the accumulation of coupling superposition forces among the surface layer sub-nano particles at different positions along with time; the stress balance position refers to a space position where the electric field coupling superposition force applied to the sub-nano particles and the capillary action among the particles are balanced.
2. The direct writing method of micro-nano structure and device based on impulse difference particle desorption as claimed in claim 1, wherein the raster oscillating scan field refers to the electron beam focus scanning line by line or column by column according to a certain contour with any vertex as the starting point.
3. The direct writing method of micro-nano structure and device based on impulse difference particle desorption as claimed in claim 1, wherein the raster oscillating scanning field comprises a plurality of scanning paths in a certain outline, the plurality of scanning paths are parallel to each other, and the scanning directions of two adjacent scanning paths are opposite and connected end to end.
4. A method of direct writing micro-nano structures and devices based on impulse difference particle desorption as claimed in any one of claims 1-3, wherein the profile size or diameter of the raster oscillating scan field is less than or equal to 200nm, the scanning frequency is in the electron beam scanning frequency range of electron microscope imaging.
5. The direct writing method of micro-nano structure and device based on impulse difference particle desorption as claimed in claim 1, wherein the material source is semiconductor or metal material.
6. The direct writing method of micro-nano structure and device based on impulse difference particle desorption as claimed in claim 1 or 5, wherein the material source is SnO 2 。
7. The direct writing method of micro-nano structure and device based on impulse difference particle desorption according to claim 1, wherein the raster oscillating scanning field is realized by the space displacement of a high-precision displacement table, and the gradual movement according to the preset structural shape is realized.
8. The direct writing method of micro-nano structure and device based on impulse difference particle desorption according to claim 1, wherein the raster oscillating scan field is realized by changing the deflection degree of electron beam, and the stepwise movement is realized according to the preset structural shape.
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| CN202110466336.7A CN113184801B (en) | 2021-04-28 | 2021-04-28 | Micro-nano structure and device direct writing method based on impulse difference particle desorption |
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| CN202110466336.7A CN113184801B (en) | 2021-04-28 | 2021-04-28 | Micro-nano structure and device direct writing method based on impulse difference particle desorption |
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