CN104867868B - Method without catalyst cross growth nanowire mesh circuit - Google Patents
Method without catalyst cross growth nanowire mesh circuit Download PDFInfo
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- CN104867868B CN104867868B CN201510291933.5A CN201510291933A CN104867868B CN 104867868 B CN104867868 B CN 104867868B CN 201510291933 A CN201510291933 A CN 201510291933A CN 104867868 B CN104867868 B CN 104867868B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
Abstract
The present invention provides a kind of method of no catalyst cross growth nanowire mesh circuit, applied to semiconductor applications, the method includes：1）One surface is provided and prepares the silicon substrate for having periodic nanometer silicon column and the boat for holding chemical reactant；2）The silicon substrate is prepared to have periodic nanometer silicon column one to place facing towards the boat for filling chemical reactant；3）The zinc-oxide nano gauze of cross growth is prepared in each nanometer silicon column side edges and corners using high temperature chemical vapor deposition method.The silicon electrode substrate growth that surface preparation has period nano-pillar is placed on the boat for fill chemical reactant and places by the present invention downwards, and then cross growth nanowire mesh can be controlled to form nano net bridgt circuit, gold-plated film is not needed to as catalyst, saving process reduces cost.
Description
Technical field
The present invention relates to one kind, more particularly to a kind of method of no catalyst cross growth nanowire mesh circuit.
Background technology
Scientific investigations showed that nanowire mesh can improve the specific surface area and electric property of semi-conducting material, therefore for such as
The research what prepares nanowire mesh is also studied constantly.It is existing about there are mainly two types of the technologies for preparing nanowire mesh：
First, (being specifically shown in the end of writing) in the document 1 having disclosed, disclose a kind of method using post processing and prepare horizontal stroke
To the method for single armed carbon nano-tube network (Carbon nanotube nanonets) circuit, Fig. 1 is may refer to, this method is will to receive
Mitron is distributed in the surface of silicon of silica, then by the use of the method metal-coated membrane of uv-exposure photoetching as grid, leakage
Pole, the technical method of gate electrode prepare the triode electronic device based on carbon nano-tube network.
Although nanowire mesh can be made in the above method, its there are it is certain the defects of.The shortcomings that above-mentioned prior art one, exists
In：It is needed in preparation process in the photoetching processes such as nanowire surface whirl coating, uv-exposure, complex process, the multistep work of processing
Skill, the density of the nano wire included between two grids and drain electrode is difficult control, can not ensure the nano net prepared every time
The homogeneity of nanometer cable that electronic device is included.
Second, in the relevant technical literature (2) having disclosed, a kind of utilization electrostatic spinning (electro- is disclosed
Netting method) is prepared for the polyacrylic acid nano net (polyacrylic acid nano-nets) of class soap blister,
With huge specific surface area.
Although obtained nanowire mesh is needed with larger specific surface area in preparation process in the above method two
Various various additives are added, and also need to various soda acid chemical environments, so as to be unfavorable for answering for silicon substrate nanometer electronic device
With.
In conclusion via the nanowire mesh prepared by the prior art, not only complex in preparation process, step is numerous
It is more, need various additives, and the density for nanometer cable and all bad control of last homogeneity in the production process
System.Therefore, it is necessary that this is improved.
It is attached：Existing open source literature：
Document 1, [Ninad Pimparkar and Muhammad Ashraful Alam, IEEE ELECTRON
DEVICE LETTERS, VOL.29, NO.9,1036-1039,2008]；
Document 2, [Shangbin Yang et al, Nanoscale, 2011,3,564-568].
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of no catalyst cross growths to receive
The method of rice noodles net circuit, not only complex in preparation process for solving the nanowire mesh prepared by the prior art, step
It is rapid various, need various additives, and the density for nanometer cable and last homogeneity be not in the production process
The problem of controlling well.
In order to achieve the above objects and other related objects, the present invention provides solution below：
A kind of method of no catalyst cross growth nanowire mesh circuit, the method includes：1) surface is provided to prepare
The silicon substrate and the boat for holding chemical reactant for having periodic nanometer silicon column；2) silicon substrate preparation there is into periodic nanometer
The one of silicon column is placed facing towards the boat for filling chemical reactant；3) using high temperature chemical vapor deposition method in each nano-silicon
Prepare the zinc-oxide nano gauze of cross growth in column side edges and corners.
The preferred embodiment of method as above-mentioned no catalyst cross growth nanowire mesh circuit, the step in the method
3) it specifically includes：3-1) that the boat for filling chemical reactant and silicon substrate placed thereon are put into a high-temperature tubular together is true
In empty stove；The high-temperature tubular vacuum drying oven 3-2) is maintained as vacuum and vacuum tube therein is heated to 900-1000 DEG C；3-3)
100-150sccm inertia current-carrying gas and 1-2sccm oxygen are passed through, and controls pressure to 300mbar；3-4) keep growth time
It is 30-35 minutes, then allows the high-temperature tubular vacuum drying oven Temperature fall, is prepared in the nano-pillar side edges and corners of silicon substrate
Go out the zinc-oxide nano gauze of cross growth.
Advanced optimizing preferably, the inertia current-carrying gas are nitrogen or argon gas.
Advanced optimizing preferably, the volume flow ratio of the inertia current-carrying gas and oxygen is 100：1.5.
As the method for above-mentioned no catalyst cross growth nanowire mesh circuit and its advanced optimizing for preferred embodiment, institute
Chemical reactant is stated as oxide powder and zinc and graphite powder.
The preferred embodiment of method as above-mentioned no catalyst cross growth nanowire mesh circuit, the periodic nanometer silicon
Column is etching forming in multiple polygon silicon columns on the silicon substrate.
Advanced optimizing preferably, the height of each polygon silicon column is 500-800 μm, and described more
The mutual spacing range of a polygon silicon column is 50-200 μm.
As described above, the present invention's has the advantages that：Surface is prepared the silicon electricity for having period nano-pillar by the present invention
Pole substrate growth is placed on the boat for fill chemical reactant and places downwards, and then cross growth nanowire mesh can be controlled to be formed
Nano net bridgt circuit does not need to gold-plated film as catalyst, and saving process reduces cost.
Description of the drawings
The method that Fig. 1 is shown as this utilization post processing prepares the design sketch of lateral single armed carbon nano-tube network circuit.
Fig. 2 is shown as a kind of realization flow of the method for no catalyst cross growth nanowire mesh circuit provided by the invention
Figure.
Fig. 3 is shown as the specific embodiment flow chart in above-mentioned Fig. 1 steps S50.
Drawing reference numeral explanation
S10-S50 method and steps
S501-S507 method and steps
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.It should be noted that in the absence of conflict, following embodiment and implementation
Feature in example can be combined with each other.
It should be noted that the diagram provided in following embodiment only illustrates the basic structure of the present invention in a schematic way
Think, component count, shape and size when only display is with related component in the present invention rather than according to actual implementation in schema then
It draws, kenel, quantity and the ratio of each component can be a kind of random change during actual implementation, and its assembly layout kenel
It is likely more complexity.
First before specific method of the offer in relation to no catalyst cross growth nanowire mesh circuit provided by the present invention, hair
A person of good sense additionally provides a kind of method (referring to CN103966662A) that cross growth zinc oxide nanowire is positioned on silicon electrode,
The method discloses a kind of methods for the zinc oxide nanowire that cross growth can individually be made on silicon electrode, and inventor is at it
On the basis of, and by experiment and research, a kind of method of no catalyst cross growth nanowire mesh circuit is proposed again, in detail
Scheme please refers to following embodiment.
Embodiment 1
Fig. 2 is referred to, a kind of method of no catalyst cross growth nanowire mesh circuit provided by the invention, this method is extremely
Include the following steps less：
Step S10 provides a surface and prepares the silicon substrate for having periodic nanometer silicon column and the boat for holding chemical reactant；
Silicon substrate preparation is had the one of periodic nanometer silicon column facing towards the boat for filling chemical reactant by step S30
It is placed；
Step S50 prepares cross growth using high temperature chemical vapor deposition method in each nanometer silicon column side edges and corners
Zinc-oxide nano gauze.
Specifically, in above-mentioned steps S10, providing to prepare on a surface of silicon substrate has periodic nanometer silicon column, should
Multiple polygon silicon columns that periodic nanometer silicon column specially etches on the silicon substrate, the polygon silicon column both may be used
To be the square column of rule or rectangle cylinder or irregular polygon cylinder, such as trapezoid cylinder, triangle
Shape cylinder etc..Moreover, a variety of different polygon silicon columns can also be included on the end face of same silicon substrate or only included multiple
A kind of polygon silicon column.It that is to say, as long as the periodic nanometer column has corner angle, and pay no attention to its concrete shape.
For in further detail, although having various selections for the shape of periodic nanometer column, the periodicity is received
Spacing range between each polygon silicon column of meter Zhu Zhong is to have certain limitations, generally by spacing anti-counterfeiting design at 50-200 μm
It is all good.If the narrow so preparation-obtained nano wire effect by line space design is unsatisfactory, and also needs to more
The stringent or better reaction condition of specification, then be unfavorable for the condition simply prepared；And if spacing is excessive, then it is possible that
By unavailable nanometer cable, and the time prepared can also accordingly increase.
In addition, the height of each polygon silicon column be generally 500-800 μm it is all good, if excessive height is so reacted
Gas effectively can not contact reflection with periodic nanometer column, and then lead to not nanometer cable is made；And if height
It is too low, then to be also unfavorable for reaction gas and pass through smoothly, so as to which longer lateral nano wire can not also be made.
Further, in above-mentioned steps S30, surface will be prepared the silicon electrode substrate growth of period nano-pillar towards
Under be placed on the boat for filling chemical reactant, can control cross growth nanowire mesh formed nano net bridgt circuit, do not need to
For gold-plated film as catalyst, saving process reduces cost.
Further, Fig. 3 are referred to, in the step S50, are prepared using high temperature chemical vapor intermediate processing
The specific method of zinc-oxide nano gauze is：
The boat for filling chemical reactant and silicon substrate placed thereon are put into a high-temperature tubular by step S501 together
In vacuum drying oven；
Step S503 maintains the high-temperature tubular vacuum drying oven as vacuum and vacuum tube therein is heated to 900-1000
DEG C, usually, it is all good to be heated to 950 DEG C or so；
Step S505 is passed through 100-150sccm inertia current-carrying gas and 1-2sccm oxygen, and controls pressure extremely
Usually, the inert gases such as nitrogen or argon gas may be used as the current-carrying gas in 300mbar；
Step S507, it is 30-35 minutes to keep growth time, then allows the high-temperature tubular vacuum drying oven Temperature fall, with
The zinc-oxide nano gauze of cross growth is prepared in the nano-pillar side edges and corners of silicon substrate.
Method in above-described embodiment 1 provided by the invention, by no plating metallic catalyst, be carved with period silicon and receive
The silicon substrate of meter Zhu realizes cross growth nanometer towards on the boat of chemical reactant in the side edges and corners of silicon substrate nano-pillar
The purpose of gauze, the nanometric circuit that such method can be using the multiple silicon electrodes preparations of nanowire mesh bridge joint truly, and
The preparation of nano net circuit is carried out on the silicon microelectrode of etching, to realize nano net circuit and nanometer electronic device truly
Provide a succinct method.
From the above embodiment it is recognised that the key point of the present invention is that not metal-coated membrane, surface etch has week
The silicon electrode aufwuchsplate of phase distribution nano-pillar is directly placed at towards chemical reactant on the boat for filling reactant, and it is anti-to carry out chemistry
It should.
Embodiment 2
Further, the present embodiment is prepared according to by 1 method of above-described embodiment in each nanometer silicon column side edges and corners
The zinc-oxide nano gauze of cross growth.Zinc-oxide nano gauze is made, then the chemical reactant held in boat is
Oxide powder and zinc and graphite powder, and with nitrogen as inertia current-carrying gas, then walked according to the preparation provided in above-described embodiment 1
Suddenly, you can zinc-oxide nano gauze is made.
Preferably, in the present embodiment, the volume flow ratio of the inertia current-carrying gas and oxygen is set as 100：
1.5, and keep managing interior nitrogen and oxygen atmosphere pressure in 300mbar, so as to obtain zinc-oxide nano gauze quickly.
In conclusion the principle of the present invention is, according to crystal growth principle, since electrode rim edges and corners combine energy
It is low, it is placed, and pass through control atmosphere towards chemical reaction raw material using the silicon electrode aufwuchsplate for surface being carved with period nano-pillar
Flow distribution so as to fulfill only in nano-pillar electrode rim cross growth nano net bridged electrodes, not surface growth as a result,
The unnecessary zinc oxide nanowire grown when reducing on processing electrode surface using conventional growth method.The innovation of the present invention
It puts and is：The silicon electrode substrate growth that prepared by surface have period nano-pillar, which is placed on downwards on the boat for fill chemical reactant, to be put
It puts, and then cross growth nanowire mesh can be controlled to form nano net bridgt circuit, do not need to gold-plated film as catalyst, save work
Sequence reduces cost.So the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (6)
- A kind of 1. method of no catalyst cross growth nanowire mesh circuit, which is characterized in that the method includes：1) surface is provided and prepares the silicon substrate for having periodic nanometer silicon column and the boat for holding chemical reactant, the nano-silicon Column is the polygon silicon column with corner angle；2) silicon substrate is prepared to have periodic nanometer silicon column one to place facing towards the boat for filling chemical reactant；3) zinc oxide nano of cross growth is prepared in each nanometer silicon column side edges and corners using high temperature chemical vapor deposition method Rice noodles net.
- 2. the method for no catalyst cross growth nanowire mesh circuit according to claim 1, it is characterised in that：The side Step 3) in method specifically includes：3-1) boat for filling chemical reactant and silicon substrate placed thereon are put into together in a high-temperature tubular vacuum drying oven；The high-temperature tubular vacuum drying oven 3-2) is maintained as vacuum and vacuum tube therein is heated to 900-1000 DEG C；100-150sccm inertia current-carrying gas and 1-2sccm oxygen 3-3) are passed through, and controls pressure to 300mbar；It is 30-35 minutes 3-4) to keep growth time, the high-temperature tubular vacuum drying oven Temperature fall is then allowed, in silicon substrate Prepare the zinc-oxide nano gauze of cross growth in nano-pillar side edges and corners.
- 3. the method for no catalyst cross growth nanowire mesh circuit according to claim 2, it is characterised in that：It is described lazy Property current-carrying gas be nitrogen or argon gas.
- 4. the method for no catalyst cross growth nanowire mesh circuit according to claim 2, it is characterised in that：It is described lazy Property current-carrying gas and oxygen volume flow ratio be 100：1.5.
- 5. according to method of the claim 1-4 any one of them without catalyst cross growth nanowire mesh circuit, feature exists In：The chemical reactant is oxide powder and zinc and graphite powder.
- 6. the method for no catalyst cross growth nanowire mesh circuit according to claim 5, it is characterised in that：Each institute It is 500-800 μm to state the height of polygon silicon column, and the mutual spacing range of the multiple polygon silicon column is 50-200 μm.
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| CN105845714B (en) * | 2016-02-27 | 2019-12-03 | 黄辉 | A kind of nano-wire devices and preparation method thereof based on bridge joint growth |
| CN109490262B (en) * | 2018-10-23 | 2021-11-02 | 中国科学院重庆绿色智能技术研究院 | Zinc oxide nanowire-based microcystin sensor, and preparation method and application thereof |
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