CN109637975B - Preparation method of CNT and Cu composite wire based on single solution electroplating - Google Patents
Preparation method of CNT and Cu composite wire based on single solution electroplating Download PDFInfo
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- CN109637975B CN109637975B CN201811332249.7A CN201811332249A CN109637975B CN 109637975 B CN109637975 B CN 109637975B CN 201811332249 A CN201811332249 A CN 201811332249A CN 109637975 B CN109637975 B CN 109637975B
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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 a preparation method of a CNT and Cu composite wire based on single solution electroplating, which comprises the steps of preparing a CNT array, preparing an electrode, etching and electroplatingPlating, hydrogen annealing and current annealing to obtain the composite material wire with high current carrying capacity. In the process of forming the CNT/Cu composite wire, the seed layer and the conventional electroplating are finished in the same solution, so that the situation that the seed layer is electroplated in an acetonitrile/copper acetate mixed solution and then CuSO is adopted in the traditional process is avoided4The problem of electroplating in the solution simplifies the electroplating step, avoids the oxidation of the Cu particles in the solution replacing process, and the granularity of the prepared surface Cu particles is larger than that of the prepared surface Cu particles by adopting CuSO4The prepared sample is more uniform and compact. The CNT/Cu composite wire prepared by the invention can effectively improve the current carrying capacity of the wire, so that the wire is not easy to fuse when a circuit works under a large current.
Description
Technical Field
The invention belongs to the technical field of microelectronics and microsystems, and particularly relates to a preparation method of a CNT and Cu composite wire based on single-solution electroplating.
Background
The atomic chip is a micro-system on a chip which can realize the control of cold atoms, one of the common methods is to lead large current to generate a magnetic trap on a lead with a specific shape to realize the functions, thus greatly reducing the volume and the complexity of a cold atom experimental device and having important significance for the practicability of the cold atom system. In order to generate deep potential wells to tightly bind cold atomic groups, a few amperes of current needs to be loaded on micron-sized wires of an atomic chip for a long time, and the current density of the wires is required to reach 106A/cm2Above the order of magnitude. Meanwhile, in order to reduce ohmic heat when the wire is energized, the wire needs to have a large electrical conductivity. In addition, as the integration of electronic devices is continuously increased, the wires need to be supported on the premise of limiting the size of the wiresThe carrier current density also increases.
At present, the theoretical values of the electrical conductivity and the current carrying capacity of metal materials Cu and Ag with relatively high electrical conductivity and current carrying capacity are respectively 105S/cm and 106A/cm2Magnitude. In contrast, graphene and Carbon Nanotubes (CNTs) have a conductivity of 109A/cm, although lower, only on the order of 103S/cm2Magnitude of current carrying capacity. Foreign research institutions propose that the CNT and Cu are prepared into a uniform composite material so that the current carrying capacity of the wire can be changed from 10 of Cu6A/cm2To 6.3 × 108A/cm2While the conductivity can reach 105S/cm, namely, the conductive material has good conductivity and current carrying capacity. However, the preparation method of the composite material provided at present is complex in process flow and is finally CuSO4And electroplating is finished in the solution, so that the Cu crystal particles on the surface of the prepared composite material have larger particle size and uneven particle size.
Therefore, a method for manufacturing a conductive wire with more uniform Cu crystal particles on the surface thereof, which simplifies the process steps, is needed.
Disclosure of Invention
The invention aims to provide a preparation method of a CNT and Cu composite wire based on single solution electroplating, which can enable a seed layer and conventional electroplating to be completed in the same solution, avoid the problem that electroplating needs to be performed in different solutions in the traditional process, simplify the electroplating step and avoid the oxidation of Cu particles inside in the process of replacing the solution; in CuSO4The Cu particles electroplated in the solution have obvious grain boundaries, and the CNT/Cu composite material wire prepared by the method has more uniform surface particles and can effectively inhibit the scattering of current.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the CNT and Cu composite material high current-carrying wire based on single solution electroplating is characterized by comprising the following steps of:
1) growing a layer of SiO on a Si wafer2An insulating layer as a substrate;
2) preparing an orthogonal CNT spinning array on a substrate, after densification, respectively preparing Ti and Au at two ends of the CNT spinning array as electrodes, and simultaneously playing a role in fixing the CNT spinning array;
3) the method comprises the following steps of (1) taking photoresist as a mask, removing CNT which is not protected by the photoresist after photoetching according to a required wire structure, and finally removing the photoresist to obtain a CNT spinning array wire;
4) preparing a mixed solution of copper acetate and acetonitrile, and polarizing the mixed solution by electrifying current of 0.001A until the resistance of the mixed solution is less than or equal to 10000 omega;
5) adopting Cu as an electroplating anode and a substrate with a CNT spinning array wire as a cathode, and electroplating for 2 hours in the prepared mixed solution of copper acetate and acetonitrile in the step 4) according to an electroplating current I;
6) adjusting the electroplating current I to be an electroplating current II, and continuously electroplating for 2 hours in a mixed solution of copper acetate and acetonitrile to prepare an electroplated CNT spinning array and a Cu composite wire; wherein the electroplating current II is 10 times of the electroplating current I;
7) cleaning the electroplated CNT spinning array and the Cu composite wire by adopting acetonitrile, and then cleaning the cleaned CNT spinning array and the Cu composite wire in H2Annealing at 250 deg.C for 3H under ambient conditions, wherein H2The gas flow rate is 150sccm, and the Ar gas flow rate is 200 sccm;
8) loading of CNT spin arrays and Cu composite wires 2 × 105A/cm2Until the resistance is stable and does not decrease any more, and the final CNT spinning array and the Cu composite wire are obtained.
Further, in step 1), SiO is prepared2The thickness of the insulating layer is more than or equal to 200 nm.
In the step 2), a Ti layer and an Au layer are respectively prepared as electrodes by adopting electron beam evaporation.
In step 3), O is used2And removing the CNT not protected by the photoresist by ion bombardment, and soaking and removing the photoresist by using acetone, glycol or other solution capable of dissolving the photoresist to obtain the CNT spinning array wire.
In the step 4), a mixed solution is prepared according to the concentration of the copper acetate in the acetonitrile, wherein the concentration of the copper acetate is 27.5 mmol/L.
In the steps 5) and 6), the electrode in contact with the cathode does not contact with the mixed solution of copper acetate and acetonitrile.
The electroplating current I in the step 5) and the electroplating current II in the step 6) are in the ratio relation between the electroplating current and the surface area of the lead. The plating current I is 2mA/cm2The plating current II is 20mA/cm2。
Step 8) load 2 × 105A/cm2The current of (a) is a ratio relation of the current magnitude and the cross-sectional area of the wire.
The preparation process simplifies the electroplating steps, all the electroplating processes are completed in the mixed solution of copper acetate and acetonitrile, the current carrying capacity of the prepared CNT/Cu composite wire is obviously improved, and the granularity of surface Cu particles is uniform and compact. The composite wire prepared by the invention can be applied to microelectronic devices needing to bear large current density, atomic chips for restraining and regulating cold atoms and other application fields having requirements on the current-carrying density of the large wire.
Drawings
FIG. 1 is a schematic view of the preparation process of the present invention.
FIG. 2 is a schematic diagram of an electroplating process according to the present invention.
Fig. 3 is a scanning electron microscope photograph of the CNT spinning array wire prepared in example 1 of the present invention.
Fig. 4 is a scanning electron microscope photograph of the CNT spinning array and the Cu composite wire surface prepared in example 1 of the present invention.
Fig. 5 is a scanning electron microscope photograph of the CNT spinning array and the Cu composite wire surface prepared in example 1 of the present invention.
In the figure: 1 is to prepare SiO2The Si substrate of the layer, 2 is a prepared spinning CNT array, 3 is a prepared electrode, 4 is an etched spinning CNT array conductor, 5 is a composite conductor after Cu plating, 6 is a substrate with the etched spinning CNT array conductor, 7 is a copper sheet, 8 is a mixed solution of copper acetate and acetonitrile, 9 is an electroplating cathode, and 10 is an electroplating anode.
Detailed Description
As shown in fig. 1-2, the present embodiment includes the following steps:
1) growing a layer of SiO with the thickness of 200nm on a Si wafer by PECVD2An insulating layer as a substrate;
2) preparing eight layers of orthogonal CNT spinning arrays on a substrate, after densification, sequentially preparing 2nmTi and 5nmAu as electrodes at two ends of the CNT spinning arrays by adopting electron beam evaporation, and simultaneously playing a role in fixing the CNT spinning arrays;
3) using AZ5214 photoresist as mask, and photoetching according to the mask structure (the area of the conducting wire is about 0.01 cm)2) With 300W of power, O2Removing the CNT part which is not protected by the photoresist by ion bombardment for 8min, and finally soaking the CNT part in acetone for 2h to remove the photoresist to obtain a CNT spinning array wire;
4) a mixed solution was prepared from 0.827g of copper acetate and 150ml of acetonitrile, and the mixed solution was stirred at 70 ℃ until the copper acetate was completely dissolved in the acetonitrile. The positive electrode and the negative electrode are both made of Cu, the mixed solution is polarized through a current source, and the current is set to be 0.001A until the output voltage is reduced to 10V;
5) adopting Cu as an electroplating anode, taking the substrate with the CNT spinning array wire obtained in the step 3) as a cathode, electroplating for 2h in the prepared copper acetate and acetonitrile mixed solution in the step 5) according to an electroplating current I of 2mA, and paying attention to the electrode in contact with the cathode not to contact with the solution;
6) after the step 5) is finished, adjusting the electroplating current I to be 20mA of electroplating current II, and continuously electroplating for 2h in the mixed solution of copper acetate and acetonitrile to prepare the electroplated CNT spinning array and Cu composite wire;
7) cleaning the prepared electroplated CNT spinning array and the Cu composite wire by adopting acetonitrile, and then washing the cleaned CNT spinning array and the Cu composite wire in H2Annealing for 3H at 250 ℃ in the environment, wherein the gas flow of H2 is 150sccm, and the gas flow of Ar is 200 sccm;
8) 2 × 10 load wire by constant current source5A/cm2Until the output voltage stabilizes and does not drop any more.
Through the above specific implementation steps, the obtained CNT spun array wire is prepared, as shown in fig. 3.
Through the above specific implementation steps, the obtained CNT spinning array and the surface of the Cu composite wire are prepared, as shown in fig. 4-5.
Claims (7)
1. The preparation method of the CNT and Cu composite wire based on single solution electroplating is characterized by comprising the following steps:
1) growing a layer of SiO on a Si wafer2An insulating layer as a substrate;
2) preparing an orthogonal CNT spinning array on a substrate, after densification, respectively preparing a Ti layer and an Au layer at two ends of the CNT spinning array as electrodes, and simultaneously playing a role in fixing the CNT spinning array;
3) the photoresist is used as a mask, CNT which is not protected by the photoresist is removed after photoetching according to a required wire structure, and the photoresist is removed to obtain the CNT spinning array wire;
4) preparing a mixed solution of copper acetate and acetonitrile, and polarizing the mixed solution by electrifying current of 0.001A until the resistance of the mixed solution is less than or equal to 10000 omega;
5) adopting Cu as an electroplating anode and a substrate with a CNT spinning array wire as a cathode, and electroplating for 2h in the mixed solution of copper acetate and acetonitrile prepared in the step 4) according to an electroplating current I, wherein an electrode connected with the cathode on the substrate does not need to contact the mixed solution;
6) adjusting the electroplating current I to be an electroplating current II, and continuously electroplating for 2 hours in a mixed solution of copper acetate and acetonitrile to prepare an electroplated CNT spinning array and a Cu composite wire; the electroplating current II is 10 times of the electroplating current I; wherein an electrode connected to the cathode on the substrate does not contact the mixed solution;
7) cleaning the electroplated CNT spinning array and the Cu composite wire by adopting acetonitrile, and then cleaning the cleaned CNT spinning array and the Cu composite wire in H2Annealing at 250 deg.C for 3H under ambient conditions, wherein H2The gas flow rate is 150sccm, and the Ar gas flow rate is 200 sccm;
8) loading of CNT spin arrays and Cu composite wires 2 × 105A/cm2Until the resistance is stable and does not decrease any more, and the final CNT spinning array and the Cu composite wire are obtained.
2. Such as rightThe method for preparing CNT and Cu composite wires based on single solution plating according to claim 1, wherein SiO prepared in step 1) is2The thickness of the insulating layer is more than or equal to 200 nm.
3. The method for preparing the CNT and Cu composite wire based on single solution plating according to claim 1, wherein in the step 2), the method for preparing the CNT spinning array comprises the following steps: and drawing a first layer of CNT array on the substrate, then drawing a second layer of CNT array perpendicular to the arrangement direction of the first layer of CNT array, and repeating the steps to obtain an orthogonal multilayer CNT spinning array.
4. The method for preparing CNT and Cu composite wires based on single solution plating according to claim 1, wherein in step 2), a Ti layer and an Au layer are prepared as electrodes by electron beam evaporation, respectively.
5. The method for preparing CNT and Cu composite wires based on single solution plating according to claim 1, wherein O is used in step 3)2Ion bombardment removes CNTs unprotected by the photoresist.
6. The method for preparing CNT and Cu composite wires based on single solution plating according to claim 1 or 5, wherein the photoresist is removed by soaking in acetone in step 3) to obtain CNT spun array wires.
7. The method of claim 1, wherein the step 4) is performed by preparing a mixed solution of copper acetate in acetonitrile at a concentration of 27.5 mmol/L.
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