CN109637975A - The preparation method of CNT and Cu compound wire based on single solutions - Google Patents
The preparation method of CNT and Cu compound wire based on single solutions Download PDFInfo
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- CN109637975A CN109637975A CN201811332249.7A CN201811332249A CN109637975A CN 109637975 A CN109637975 A CN 109637975A CN 201811332249 A CN201811332249 A CN 201811332249A CN 109637975 A CN109637975 A CN 109637975A
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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
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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
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53276—Conductive materials containing carbon, e.g. fullerenes
Abstract
The invention discloses the preparation methods of CNT and Cu compound wire based on single solutions to obtain the composite conductor with high current current-carrying capability by preparing CNT array, preparing electrode, etching, plating, hydrogen annealing, current annealing.During the present invention forms CNT/Cu compound wire, seed layer and conventional be electroplated are completed in same solution, are avoided and are needed in acetonitrile/copper acetate mixed solution in traditional handicraft after plating seed layer again in CuSO4The problem of being electroplated in solution not only simplifies plating step, and avoids the oxidation of the internal Cu particle in replacement solution processes, and the surface C u grain graininess of preparation is compared to using CuSO4The sample of preparation is more uniformly fine and close.CNT/Cu compound wire prepared by the present invention, can effectively improve the current-carrying capability of conducting wire, so that circuit is not easy to fuse in high current work lower wire.
Description
Technical field
The invention belongs to microelectric techniques, microsystems technology field, and in particular to CNT and Cu based on single solutions
The preparation method of compound wire.
Background technique
Atom Chip be it is a kind of may be implemented to cold atom manipulate on piece micro-system, common method first is that specific
Lead to high current on the conducting wire of pattern and generate magnetic well to realize above-mentioned function, can greatly reduce the volume of cold atom experimental provision
And complexity, have great importance for the functionization of cold atom system.Tight beam is carried out to cold atom cloud to generate deep potential well
It ties up, needs several amperes of long time loading on the micron order conducting wire of Atom Chip of electric current, this requires the current densities of conducting wire
Reach 106A/cm2It is more than magnitude.Meanwhile in order to reduce ohm heat when conducting wire is powered, conducting wire needs to have big conductivity.This
Outside, as the integrated level of electronic device is continuously improved, under the premise of limiting conductor size, the current carrying density of carrying needed for conducting wire
It need to also be continuously increased.
Currently, metal material Cu, Ag with relatively high conductivity and current-carrying capability, conductivity and current-carrying capability
Theoretical value is respectively 105S/cm and 106A/cm2Magnitude.In contrast, graphene and carbon nanotube (CNT) although conductivity compared with
It is low, only 103S/cm magnitude, but there is 109A/cm2The current-carrying capability of magnitude.Foreign study mechanism is proposed CNT and Cu system
It is standby the stream ability of conducting wire to be made from the 10 of Cu at uniform composite material6A/cm2It is promoted to 6.3 × 108A/cm2, while conductivity
10 can be reached5S/cm is having both good electric conductivity and current carrying capacity.However, the composite material system provided at present
Preparation Method process flow is complicated, and due to finally in CuSO4Plating is completed in solution, so that composite material surface Cu obtained is brilliant
Body grain graininess is larger and particle size is uneven.
It is, therefore, desirable to provide a kind of processing step more simplifies, while the surface C u crystal grain that conducting wire is made is more equal
Even preparation method.
Summary of the invention
The purpose of the present invention is to provide the preparation method of a kind of CNT based on single solutions and Cu compound wire,
This method can allow seed layer to be completed in same solution with conventional plating, avoid in traditional handicraft and need in different solutions
The problem of being electroplated simplifies plating step, avoids the oxidation of the internal Cu particle in replacement solution processes；In CuSO4
The Cu particle being electroplated in solution has apparent crystal boundary, and uses CNT/Cu composite conductor surface particles prepared by the present invention
More uniformly, the scattering of electric current can effectively be inhibited.
To achieve the above object, the technical scheme adopted by the invention is that:
CNT and the high current carrying conductor preparation method of Cu composite material based on single solutions, which is characterized in that including following steps
It is rapid:
1) one layer of SiO is grown in Si on piece2Insulating layer and as substrate；
2) orthogonal CNT spinning array is prepared in substrate, after densification, the both ends of CNT spinning array prepare respectively Ti with
Au plays the role of fixed CNT spinning array as electrode；
3) using photoresist as exposure mask, according to required conductor structure photoetching after, dispel not by photoresist protection CNT,
Dispel photoresist finally to obtain CNT spinning array conducting wire；
4) mixed solution of copper acetate, acetonitrile is configured, and is polarized with 0.001A electrical current to mixed solution, until mixing
Solution resistance≤10000 Ω；
5) using Cu as galvanic anode, the substrate with CNT spinning array conducting wire is as cathode, in the configured second of step 4)
In sour copper, acetonitrile mixed solution, 2h is electroplated according to electroplating current I；
6) electroplating current I is adjusted to electroplating current II, 2h is electroplated in copper acetate, acetonitrile mixed solution in continuation, and plating is made
CNT spinning array and Cu compound wire afterwards；Wherein, electroplating current II is 10 times of electroplating current I；
7) after cleaning the CNT spinning array after plating using acetonitrile with Cu compound wire, in H2Using 250 DEG C of annealing under environment
3h, wherein H2Throughput 150sccm, Ar throughput 200sccm；
8) to CNT spinning array and Cu compound wire load 2 × 105A/cm2Electric current obtained until resistance stabilization no longer declines
To final CNT spinning array and Cu compound wire.
Further, in step 1), the SiO of preparation2Thickness >=200nm of insulating layer.
In step 2, Ti layers are prepared respectively using electron beam evaporation with Au layers as electrode.
In step 3), using O2Ion bombardment dispels the CNT not protected by photoresist, using acetone, ethylene glycol or other
The solution immersion that photoresist can be dissolved dispels photoresist to obtain CNT spinning array conducting wire.
It is that concentration is that 27.5mmol/L configures mixed solution in acetonitrile according to copper acetate in step 4).
In step 5) and step 6), copper acetate, acetonitrile mixed solution are not contacted with the electrode of cathode contacts.
Electroplating current II in step 5) in electroplating current I and step 6) is the ratio of electroplating current and wire table area.
Electroplating current I is 2mA/cm2, electroplating current II is 20mA/cm2。
The relationship of the low current and area that load in step 8) is the relationship of size of current and wire sectional area.
Preparation process of the present invention simplifies plating step, and all electroplating process are complete in copper acetate, acetonitrile mixed solution
At the current-carrying capability of the CNT/Cu compound wire of preparation significantly improves, and surface C u grain graininess even compact.Through the invention
The compound wire being prepared may be applicable to microelectronic component, constraint and the original for regulating and controlling cold atom of carrying high current density
In sub- chip and other application fields required to big conducting wire current carrying density.
Detailed description of the invention
Fig. 1 is preparation flow schematic diagram of the invention.
Fig. 2 is electroplating technology schematic diagram of the invention.
Fig. 3 is the electron scanning micrograph of CNT spinning array conducting wire prepared by the embodiment of the present invention 1.
Fig. 4 is the scanning electron microscope photograph on CNT spinning array prepared by the embodiment of the present invention 1 and Cu compound wire surface
Piece.
Fig. 5 is the scanning electron microscope photograph on CNT spinning array prepared by the embodiment of the present invention 1 and Cu compound wire surface
Piece.
In figure: 1 is to be prepared for SiO2The Si substrate of layer, 2 be the spinning CNT array that preparation is completed, and 3 be the electricity that preparation is completed
Pole, 4 be the spinning CNT array conducting wire after etching, and 5 be that the compound wire after Cu has been electroplated, and 6 is with spinning CNT gusts after etching
The substrate of column wire, 7 be copper sheet, and 8 be the mixed solution of copper acetate, acetonitrile, and 9 be electroplating cathode, and 10 be galvanic anode.
Specific embodiment
As shown in Figs. 1-2, the present embodiment includes the following steps:
1) SiO of one layer of 200nm thickness is grown in Si on piece by PECVD2Insulating layer and as substrate；
2) the orthogonal CNT spinning array that eight layers are prepared in substrate after densification, uses electronics at CNT spinning array both ends
Beam evaporation is sequentially prepared 2nmTi and 5nmAu as electrode, while playing the role of fixed CNT spinning array；
3) using AZ5214 photoresist as exposure mask, according to mask structure being photoetching after (wire glass is about 0.01cm2),
Using 300W power, O2Ion bombardment 8min dispels the part CNT that do not protected by photoresist, and last acetone soak 2h removes photoetching
Glue obtains CNT spinning array conducting wire；
4) mixed solution is configured using 0.827g copper acetate and 150ml acetonitrile, mixed solution is stirred at 70 DEG C until
Copper acetate is dissolved completely in acetonitrile.Positive and negative anodes are all made of Cu, are polarized by current source to mixed solution, and setting electric current is
0.001A, until output voltage is reduced to 10V；
5) using Cu as galvanic anode, the substrate with CNT spinning array conducting wire obtained in step 3) is as cathode, in step
It is rapid 5) in configured copper acetate, in acetonitrile mixed solution, 2h is electroplated by the electroplating current I of 2mA, pays attention to and the electricity of cathode contacts
Pole not contact solution；
6) after completing step 5), electroplating current I is adjusted to the electroplating current II of 20mA, is continued molten in copper acetate, acetonitrile mixing
2h is electroplated in liquid, CNT spinning array and Cu compound wire after plating is made；
7) after cleaning the CNT spinning array after obtained plating using acetonitrile with Cu compound wire, in H2250 DEG C are used under environment
Anneal 3h, wherein H2 throughput 150sccm, Ar throughput 200sccm；
8) using constant-current source to conducting wire load 2 × 105A/cm2Electric current, until output voltage stabilization no longer declines.
By above-mentioned specific implementation step, the CNT spinning array conducting wire being prepared, as shown in Figure 3.
The CNT spinning array being prepared by above-mentioned specific implementation step and Cu compound wire surface, such as Fig. 4-5 institute
Show.
Claims (9)
1. the preparation method of the CNT and Cu compound wire based on single solutions, it is characterised in that include the following steps:
1) one layer of SiO is grown in Si on piece2Insulating layer and as substrate；
2) orthogonal CNT spinning array is prepared in substrate, after densification, prepares Ti layers respectively at the both ends of CNT spinning array
It is used as electrode with Au layers, while playing the role of fixed CNT spinning array；
3) using photoresist as exposure mask, according to required conductor structure photoetching after, dispel not by photoresist protection CNT,
Dispel photoresist again to obtain CNT spinning array conducting wire；
4) mixed solution of copper acetate, acetonitrile is configured, and is polarized with 0.001A electrical current to mixed solution, until mixing
Solution resistance≤10000 Ω；
5) using Cu as galvanic anode, the substrate with CNT spinning array conducting wire is as cathode, in the configured second of step 4)
Sour copper, acetonitrile mixed solution in, according to electroplating current I be electroplated 2h, wherein in substrate with cathode connection electrode not contact
Mixed solution；
6) electroplating current I is adjusted to electroplating current II, 2h is electroplated in copper acetate, acetonitrile mixed solution in continuation, and plating is made
CNT spinning array and Cu compound wire afterwards；The electroplating current II is 10 times of electroplating current I；Wherein, in substrate with cathode
The electrode of connection not contact mixed solution；
7) after cleaning the CNT spinning array after plating using acetonitrile with Cu compound wire, in H2Using 250 DEG C of annealing under environment
3h, wherein H2Throughput 150sccm, Ar throughput 200sccm；
8) to CNT spinning array and Cu compound wire load 2 × 105A/cm2Electric current obtained until resistance stabilization no longer declines
Final CNT spinning array and Cu compound wire.
2. the preparation method of the CNT and Cu compound wire based on single solutions as described in claim 1, which is characterized in that
In step 1), the SiO of preparation2Thickness >=200nm of insulating layer.
3. the preparation method of the CNT and Cu compound wire based on single solutions as described in claim 1, which is characterized in that
In step 2, CNT spinning array the preparation method comprises the following steps: first layer CNT array is first pulled out in substrate, then perpendicular to first layer
The arragement direction of CNT array pulls out second layer CNT array, repeatedly, to obtain the CNT spinning array of orthogonal multilayer.
4. the preparation method of the CNT and Cu compound wire based on single solutions as described in claim 1, which is characterized in that
In step 2, Ti layers are prepared respectively using electron beam evaporation with Au layers as electrode.
5. the preparation method of the CNT and Cu compound wire based on single solutions as described in claim 1, which is characterized in that
In step 3), using O2Ion bombardment dispels the CNT not protected by photoresist.
6. the preparation method of the CNT and Cu compound wire as described in claim 1 or 5 based on single solutions, feature exist
In using acetone soak to dispel photoresist to obtain CNT spinning array conducting wire in step 3).
7. the preparation method of the CNT and Cu compound wire based on single solutions as described in claim 1, which is characterized in that
It is that concentration is that 27.5mmol/L configures mixed solution in acetonitrile according to copper acetate in step 4).
8. the preparation method of the CNT and Cu compound wire based on single solutions as described in claim 1, which is characterized in that
The current ratio uniformly-coating electric current of electroplating current II in step 5) in electroplating current I and step 6) and conducting wire upper surface face
Product.
9. the preparation method of the CNT and Cu compound wire based on single solutions as described in claim 1, which is characterized in that
The relationship of the low current and area that load in step 8) is the relationship of size of current and wire sectional area.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113889294A (en) * | 2021-09-14 | 2022-01-04 | 中南大学 | Cu-CNTs composite nano-wire and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1941289A (en) * | 2005-09-26 | 2007-04-04 | 财团法人工业技术研究院 | Method for forming interconnected electroplating lead wire of nano-carbon tube and metal composite material |
| US20130299212A1 (en) * | 2010-12-28 | 2013-11-14 | National Institute Of Advanced Industrial Science And Technology | Cnt metal composite and method of manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1941289A (en) * | 2005-09-26 | 2007-04-04 | 财团法人工业技术研究院 | Method for forming interconnected electroplating lead wire of nano-carbon tube and metal composite material |
| US20130299212A1 (en) * | 2010-12-28 | 2013-11-14 | National Institute Of Advanced Industrial Science And Technology | Cnt metal composite and method of manufacturing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113889294A (en) * | 2021-09-14 | 2022-01-04 | 中南大学 | Cu-CNTs composite nano-wire and preparation method and application thereof |
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Granted publication date: 20200918 Termination date: 20211109 |