CN109355685A - A kind of preparation method of the micro-nano periodic structure material of the copper of ring-segment-like - Google Patents
A kind of preparation method of the micro-nano periodic structure material of the copper of ring-segment-like Download PDFInfo
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- CN109355685A CN109355685A CN201811484587.2A CN201811484587A CN109355685A CN 109355685 A CN109355685 A CN 109355685A CN 201811484587 A CN201811484587 A CN 201811484587A CN 109355685 A CN109355685 A CN 109355685A
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- copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
Abstract
This application discloses a kind of preparation methods of the micro-nano periodic structure material of the copper of ring-segment-like, are prepared in closed reaction chamber, and reaction chamber is connected with circulation waters, control growth room temperature, growth power supply control deposition velocity and structure by waters；A piece of silicon wafer is chosen to be put into growth room as substrate；Using copper as cathode and anode, the cathode and the anode certain distance parallel to each other that pulls open are placed in the deposition substrate, and the cathode and anode are connected with applying electrical potential；Copper-bath is instilled in the deposition substrate, then covered；The lid of the growth room is sealed to completely cut off ambient temperature.The application has the copper micro nano structure of ring-segment-like structure in the seal chamber under water bath with thermostatic control control using electrochemical deposition method preparation；Experimental method is simply easily operated, and experiment condition is content with very little, reproducible, is convenient for large-scale production；Accuracy controlling copper micro-nano structure can be realized by appositional growth condition.
Description
Technical field
The invention belongs to the technical fields of nano material preparation, are related to the copper nanometer week of electrochemical deposition ring-segment-like at room temperature
The preparation method of phase structural material.
Background technique
Periodic function nano structural material is since it is in nanophotonics, bio-sensing, chemical analysis, photovoltaic power generation etc.
There is huge application potential in field, becomes the research hotspot in nano science field.In the preparation method of numerous nano materials,
The ordered structure that electro-deposition method prepares nanometer scale has at low cost, and equipment is simple, easily operated, high production efficiency, is easy
The advantages that realizing industrialization.Meanwhile using the voltage conditions of periodic swinging, may be implemented to the controllable from group of nano material
Dress.
In addition, the building process of ultra-thin liquid layer equally affects the deposition process and its growthform of metal ion.Super
In thin liquid layer in the chemical deposition process of metal ion, ion migrates in extra electric field, and electrochemical reaction is in cathode and anode
Nearby occur, there are changes in spatial distribution for the ion concentration for causing near electrode.The changes in distribution of this ion concentration can be with
Trigger new electrochemical process.The deposition of metal ion can also be controlled by nucleation process, and nucleation process is to ion concentration
It is very sensitive with the variation of electric field.Therefore, the growth course and mechanism of understanding nano material in depth are helped preferably to control
The structure and growth of material.
Copper nano material is a kind of important raw material of industry, is added preparing conductive material, effective catalyst and lubricating oil
Add agent etc., it can be used as the material instead of noble metal Au, Ag, substantially reduce cost, have broad application prospects.
Summary of the invention
In view of drawbacks described above in the prior art or deficiency, it is intended to provide a kind of micro-nano periodic structure material of copper of ring-segment-like
The preparation method of material.
In a first aspect,
According to technical solution provided by the embodiments of the present application, a kind of preparation of the micro-nano periodic structure material of the copper of ring-segment-like
Method,
Preparation step are as follows:
It is carried out in closed reaction chamber, reaction chamber is connected with circulation waters, controls growth room temperature, growth by waters
Power supply controls deposition velocity and structure；
A. a piece of silicon wafer is chosen to be put into growth room as substrate；
B. using copper as cathode and anode, the cathode and the anode certain distance parallel to each other that pulls open are placed on described sink
On product substrate, and the cathode and anode are connected with applying electrical potential；
C. copper-bath is instilled in the deposition substrate, then covered；
D. the lid of the growth room is sealed to completely cut off ambient temperature.
In the application, the indoor temperature of growth is controlled by the circulation waters, and temperature reduction makes CuSO4Solution is gradually
It freezes, is mingled between ice sheet and the deposition substrate from CuSO4The solute being precipitated in solution, so as to form quasi- two dimension
CuSO4The ultra-thin liquid layer of solution.
In the application, the concentration by regulating and controlling electrolyte controls the building of the ultra-thin liquid layer, and then determines described ultra-thin
Cu in liquid layer2+Concentration.
In the application, by the change of the pH value of the electrolyte influence the ultra-thin liquid layer building and deposit at
Part.
In conclusion the application has the beneficial effect that
1) there is in the seal chamber under water bath with thermostatic control control using electrochemical deposition method preparation the copper of ring-segment-like structure
Micro nano structure；
2) experimental method is simply easily operated, and experiment condition is content with very little, reproducible, is convenient for large-scale production；
3) accuracy controlling copper micro-nano structure can be realized by appositional growth condition.
Detailed description of the invention
By reading a detailed description of non-restrictive embodiments in the light of the attached drawings below, the application's is other
Feature, objects and advantages will become more apparent upon:
Fig. 1 is the experimental provision schematic diagram of the preparation ring-segment-like copper micro-nanometer structural material of use for laboratory of the invention；
Fig. 2 is the XRD spectrum of ring-segment-like copper micro-nanometer structural material in embodiment 2；
Fig. 3 is the shape appearance figure SEM of ring-segment-like copper micro-nanometer structural material in embodiment 2；
Fig. 4 is the AFM map of ring-segment-like copper micro-nanometer structural material made from embodiment 2；
Fig. 5 is ring-segment-like periodicity copper micro-nanometer structural material obtained after the amplitude for changing growth voltage in embodiment 3
AFM map.
Specific embodiment
The application is described in further detail with reference to the accompanying drawings and examples.It is understood that this place is retouched
The specific embodiment stated is used only for explaining related invention, rather than the restriction to the invention.It also should be noted that in order to
Convenient for description, part relevant to invention is illustrated only in attached drawing.
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The application is described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
A kind of preparation method of the micro-nano periodic structure material of the copper of ring-segment-like,
Preparation step are as follows:
It is carried out in closed reaction chamber, reaction chamber is connected with circulation waters, controls growth room temperature, growth by waters
Power supply controls deposition velocity and structure；
A. a piece of silicon wafer is chosen to be put into growth room as substrate；
B. using copper as cathode and anode, the cathode and the anode certain distance parallel to each other that pulls open are placed on described sink
On product substrate, and the cathode and anode are connected with applying electrical potential；
C. copper-bath is instilled in the deposition substrate, then covered；
D. the lid of the growth room is sealed to completely cut off ambient temperature.
The indoor temperature of growth is controlled by the circulation waters, and temperature reduction makes CuSO4Solution gradually freezes, in ice
It is mingled between layer and the deposition substrate from CuSO4The solute being precipitated in solution, so as to form quasi- two dimension CuSO4Solution
Ultra-thin liquid layer, growth potential make the Cu in ultra-thin liquid layer2+It is reduced to Cu atom to movable cathode, and in cathode, thus in yin
Extremely upper deposition；The Cu atom of anode is oxidized to Cu due to losing electronics simultaneously2+, it is continuously replenished in ultra-thin liquid layer, so that
Cu in liquid layer2+Dynamic equilibrium is kept on the whole, it is ensured that the continuous deposition of Cu.Pass through the dense of regulation electrolyte in experimentation
Degree controls the building of the ultra-thin liquid layer, and then determines Cu in the ultra-thin liquid layer2+Concentration.Pass through the pH value of the electrolyte
Change influence the building of the ultra-thin liquid layer and the composition of deposit.The thickness and concentration of ultra-thin liquid layer are to influence copper nanometer material
Expect the key factor of structure and morphology.Ultra-thin deposition liquid layer is precipitated when solution freezes, that is, solute segregation process；Analysis
The concentration of ultra-thin liquid layer solution is related with freezing temperature out, therefore freezing process is very crucial to ultra-thin liquid layer is constructed, to ultra-thin
The self assembly of liquid layer is the essential step of realization link shape structure.It is by semi-conductor thermoelectric material that solution is rapid with larger current
It is frozen into ice, regulating thermostatic bath temperature controls ice sheet, then is slowly dissolved ice with low current, finally retains near electrode
Multiple ice-nucleus.Impressed current is disconnected, ice-nucleus growth is controlled by water bath with thermostatic control, notices that the ice-nucleus speed of growth should not be excessively slow.Pass through
Optical microscopy freezing process from window heats stimulation disturbance ice sheet with low current, grasps repeatedly every or so half a minute
Make, ice sheet is made to form orderly ice crack, keeps ultra-thin liquid layer thickness uneven, interface solute concentration is higher, and deposition velocity is very fast.?
In this technology, the micro-nano periodic structure material of copper of Bamboo-shaped can also be produced.
During the experiment, it needs to prepare to reaction solution first: anhydrous cupric sulfate and deionized water being uniformly mixed, magnetic is used
The stirring of power blender, is configured to reaction solution；The deposition solution of 50-60mmol/L is configured, and measuring its pH value is 4-4.6；
Secondly the electrode and deposition substrate for preparing electro-deposition choose the thin copper wire that diameter is 50 μm, by table using copper as cathode and anode
Face is gently polished smooth with sand paper, to remove the insulated paint of its appearance, is cleaned after being impregnated 5 hours with alcohol with ultrapure water spare；
Using silicon as deposition substrate, silicon wafer is cut into the small square piece of 2cm × 2cm, the impurity of cleaning silicon chip surface attachment (molecule-type, from
Subtype, atomic impurity).Molecule-type impurity is readily cleaned, and ionic and atomic impurity belong to chemisorption type impurity, difficult
In cleaning.It is general first to be cleaned once using acid, aqueous slkali or alkaline hydrogen peroxide, then remaining is removed with chloroazotic acid or acid hydrogen peroxide
Ionic and atomic impurity.It is finally rinsed well, is dried with spare with deionized water.
Embodiment 1: referring to FIG. 1, illustrate laboratory of the present invention preparation ring-segment-like copper micro-nanometer structural material device and
Preparation process.
The present invention when preparing ring-segment-like copper period micro-nanometer structural material using a kind of simple easily controllable device,
As shown in Figure 1.
In Fig. 1, top half device is the window and microscope of observation growth；Lower half portion is deposition seal chamber, internal
It is ultra-thin liquid layer building device.Chamber is connect with thermostatic circulation bath, the building of ultra-thin liquid layer and deposition growing in control chamber room
Temperature environment.
Embodiment 2: Fig. 2, Fig. 3 and Fig. 4 are please referred to:
The copper period micro-nanometer structural material (1) of ring-segment-like
Configuration is to reaction solution first: anhydrous cupric sulfate and deionized water are hybridly prepared into deposition liquid, concentration 50-
60mmol/L, pH value 4-4.6；Anode and cathode is placed on substrate, then instills deposition solution, covers coverslip, sealing reflection chamber.
It opens circulator bath and mixes up -1--3 DEG C of control temperature, construct ultra-thin liquid layer.Next, electrodeposition process is just in this quasi- two dimension
It is carried out in space.Under the action of periodic voltage, frequency 0.3Hz, amplitude 0.35V, the Cu in ultra-thin liquid layer2+In cathode
It is reduced to Cu atom, is deposited on cathode；The Cu atom of anode is oxidized to Cu simultaneously2+, so that the Cu in liquid layer2+
Keep dynamic equilibrium, it is ensured that the deposition growing of Cu.
Deposit is rinsed with deionized water after reaction, being put into prevents from aoxidizing in the glove box vacuumized.
The XRD spectrum of sample obtained is shown in that Fig. 2, SEM curve are shown in that Fig. 3, the surface texture AFM map of material are shown in Fig. 4.
Embodiment 3: Fig. 5 is please referred to:
The copper period micro-nanometer structural material (2) of ring-segment-like
Configuration is to reaction solution first: anhydrous cupric sulfate and deionized water are hybridly prepared into deposition liquid, concentration 50-
60mmol/L, pH value 4-4.6；Anode and cathode is placed on substrate, then instills deposition solution, covers coverslip, sealing reflection chamber.
It opens circulator bath and mixes up -1--3 DEG C of control temperature, construct ultra-thin liquid layer.Next, electrodeposition process is just in this quasi- two dimension
It is carried out in space.Under the action of periodic voltage, frequency 0.3Hz, amplitude 0.3V, the Cu in ultra-thin liquid layer2+In cathode
It is reduced to Cu atom, is deposited on cathode；The Cu atom of anode is oxidized to Cu simultaneously2+, so that the Cu in liquid layer2+
Keep dynamic equilibrium, it is ensured that the deposition growing of Cu.
Deposit is rinsed with deionized water after reaction, being put into prevents from aoxidizing in the glove box vacuumized.
The surface texture AFM map of material obtained is shown in Fig. 5.
Above description is only the preferred embodiment of the application and the explanation to institute's application technology principle.Those skilled in the art
Member is it should be appreciated that invention scope involved in the application, however it is not limited to technology made of the specific combination of above-mentioned technical characteristic
Scheme, while should also cover in the case where not departing from the inventive concept, it is carried out by above-mentioned technical characteristic or its equivalent feature
Any combination and the other technical solutions formed.Such as features described above has similar function with (but being not limited to) disclosed herein
Can technical characteristic replaced mutually and the technical solution that is formed.
Claims (4)
1. a kind of preparation method of the micro-nano periodic structure material of the copper of ring-segment-like, it is characterized in that:
Preparation step are as follows:
It is carried out in closed reaction chamber, reaction chamber is connected with circulation waters, controls growth room temperature by waters, grows power supply
Control deposition velocity and structure；
A. a piece of silicon wafer is chosen to be put into growth room as substrate；
B. using copper as cathode and anode, the cathode and the anode certain distance parallel to each other that pulls open are placed on the deposition lining
On bottom, and the cathode and anode are connected with applying electrical potential；
C. copper-bath is instilled in the deposition substrate, then covered；
D. the lid of the growth room is sealed to completely cut off ambient temperature.
2. a kind of preparation method of the micro-nano periodic structure material of the copper of ring-segment-like according to claim 1, it is characterized in that:
The indoor temperature of growth is controlled by the circulation waters, and temperature reduction makes CuSO4Solution gradually freezes, ice sheet with it is described
It is mingled between deposition substrate from CuSO4The solute being precipitated in solution, so as to form quasi- two dimension CuSO4The ultra-thin liquid layer of solution.
3. a kind of preparation method of the micro-nano periodic structure material of the copper of ring-segment-like according to claim 2, it is characterized in that:
Concentration by regulating and controlling electrolyte controls the building of the ultra-thin liquid layer, and then determines Cu in the ultra-thin liquid layer2+Concentration.
4. a kind of preparation method of the micro-nano periodic structure material of the copper of ring-segment-like according to claim 3, it is characterized in that:
The building of the ultra-thin liquid layer and the composition of deposit are influenced by the change of the pH value of the electrolyte.
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| CN201811484587.2A CN109355685A (en) | 2018-12-06 | 2018-12-06 | A kind of preparation method of the micro-nano periodic structure material of the copper of ring-segment-like |
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| CN201811484587.2A CN109355685A (en) | 2018-12-06 | 2018-12-06 | A kind of preparation method of the micro-nano periodic structure material of the copper of ring-segment-like |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272685A (en) * | 1999-05-03 | 2000-11-08 | 摩托罗拉公司 | Method for forming copper layer on semiconductor chip |
| CN102747398A (en) * | 2012-07-02 | 2012-10-24 | 吉林大学 | Functional material with CuO and In2O3 micro-nano heterogeneous periodic structure and preparation method thereof |
| CN104928737A (en) * | 2015-06-19 | 2015-09-23 | 临沂大学 | Method of modifying two-dimensional spatial electrochemically-deposited nano-micro ordered structural material |
| CN105671604A (en) * | 2016-01-26 | 2016-06-15 | 临沂大学 | Improved method for two-dimensional electrochemical construction of nano-micro electrical component |
-
2018
- 2018-12-06 CN CN201811484587.2A patent/CN109355685A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272685A (en) * | 1999-05-03 | 2000-11-08 | 摩托罗拉公司 | Method for forming copper layer on semiconductor chip |
| CN102747398A (en) * | 2012-07-02 | 2012-10-24 | 吉林大学 | Functional material with CuO and In2O3 micro-nano heterogeneous periodic structure and preparation method thereof |
| CN104928737A (en) * | 2015-06-19 | 2015-09-23 | 临沂大学 | Method of modifying two-dimensional spatial electrochemically-deposited nano-micro ordered structural material |
| CN105671604A (en) * | 2016-01-26 | 2016-06-15 | 临沂大学 | Improved method for two-dimensional electrochemical construction of nano-micro electrical component |
Non-Patent Citations (3)
| Title |
|---|
| CHANG LIU等: "Fabrication of the Pattern of Copper Nanowires with Adjustable Density on Oxidized Si Substrate", 《J. PHYS. CHEM. C 》 * |
| ZHAOCUN ZONG等: "Potential-induced copper periodic micro-/nanostructures by electrodeposition on silicon substrate", 《NANOTECHNOLOGY》 * |
| 姚彬彬: "准二维铜周期薄膜化学沉积及其线阵列湿刻制备", 《工程科技I辑》 * |
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Application publication date: 20190219 |