CN105648481B - The method for adjusting zinc oxide three-dimensional hierarchical structure film morphology with trace metal salts - Google Patents
The method for adjusting zinc oxide three-dimensional hierarchical structure film morphology with trace metal salts Download PDFInfo
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- CN105648481B CN105648481B CN201610006003.5A CN201610006003A CN105648481B CN 105648481 B CN105648481 B CN 105648481B CN 201610006003 A CN201610006003 A CN 201610006003A CN 105648481 B CN105648481 B CN 105648481B
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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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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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
- C25D5/48—After-treatment of electroplated surfaces
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Abstract
The invention discloses a kind of methods adjusting zinc oxide three-dimensional hierarchical structure film morphology with trace metal salts, are as follows：Sample is made in copper sheet；Using galvanizing technique, respectively using copper sheet, zinc metal sheet as the cathode of circuit and anode, electroplating processes are carried out to copper sheet；Ammonium hydroxide and aqueous metal salt are added in autoclave liner, are stirred, then the copper sheet after above-mentioned electroplating processes is stood on by wall in autoclave liner；Closed autoclave is heated；Zinc oxide it is micro-/receive hierarchical structure film product.The pattern of ZnO is adjusted in the present invention using different metal salt, realize the controllable of ZnO three-dimensional hierarchical structures pattern on flexible substrate, in addition, since the copper base of electroplating processes is both the growth substrate of nano structure of zinc oxide, zinc source needed for zinc oxide growth is provided again, therefore can ensure good combination between the zinc oxide micro/nano structure and copper base of gained.
Description
Technical field
The present invention relates to zinc oxide hierarchical structure film manufacturing techniques fields, specifically adjust zinc oxide with trace metal salts
The method of three-dimensional hierarchical structure film morphology.
Background technology
Three-dimensional hierarchical structure refers to the complicated knot with specific dimensions and pattern formed by the structural unit of nanoscale
Structure.Compared with zero dimension, a peacekeeping two dimensional oxidation zinc nanostructure, three-dimensional hierarchical structure can not only provide the specific surface of bigger
Long-pending, high porosity, excellent anti-agglomeration ability, but also the respective advantage of humble structure is summarized to have good light
Absorption and light scattering ability, good charge-trapping ability and excellent electronics transfer capability, to make it have excellent urge
Change, air-sensitive and battery performance.
Zinc-oxide film good conductivity, chemically and thermally stability is high, is widely used in transparent conductive film, photoelectric device, the sun
Energy battery, air-sensitive, the energy and environment etc..In the wet chemical preparation method of zinc oxide micron/nano structure film, hydro-thermal method
Because of simple and effective and energy scale, occupy leading position in terms of zinc oxide films film preparation.For example, using acetate pyrolysismethod,
The methods of sol-gal process, magnetron sputtering method are in the first prefabricated one layer of zinc oxide crystal seed layer in growing substrate surface, then pass through hydro-thermal method
In matrix surface growth of zinc oxide nano linear array, this is the classical two-step method for preparing nano-wire array film, for example,
PeidongYang etc. [L.E.Greene, _ M.Law, _ D.H.Tan, _ M.Montano, _ J.Goldberger, _
G.Somorjai_and_P.Yang_General_route_to_vertical_ZnO_nano_wire_arrays_using_
textured_ZnO_seeds,_NanoLett.,_2005,_5(7):1231-1236] it is received first by spin coating zinc oxide colloid
The method of meter Jing is prepared for the seed layer of 50-200nm thickness, and then realizing zinc oxide nanowire in hydrothermal synthesis system exists
Prepare with scale on the silicon chip of 10cm sizes.But it is old that two-step method is only suitable for preparation simple structure such as nano wire, nanometer rods
Row film, though nanostructured morphologies can be changed by adding surfactant or structure directing agent in hydrothermal system, not
Easily realize the preparation of three-dimensional zinc oxide hierarchical structure film and its regulation and control of pattern.
The various flower-shaped, dendroids constructed by the low-dimensionals nanometer primitive such as nano wire, nanometer sheet, nano particle, forest shape, ball
The hierarchical structures nano-powders such as shape, hairbrush shape can utilize hydro-thermal method by adjusting hydrothermal condition such as reaction temperature, time, solvent
Component, the molar ratio of initial feed, solution pH etc. be prepared, corresponding research has many reports.Such as, Seungho
[S.Cho, _ J.W.Jang, _ J.S.Lee, _ K.H.Lee, _ Exposed_crystal_face_controlled_ such as Cho
synthesis_of_3D_ZnO_superstructures,_Langmuir_2010(26):14255-14262.] pass through change
The concentration and reaction temperature of reactant have obtained four kinds of three-dimensional zinc oxide nanostructures with specific morphology；Du etc. [G.Du, _
L.Zhang,_Y.Feng,Y.Xu,_Y.Sun,_B.Ding,_Q.Wang,_Controllable_synthesis_of_ZnO_
architectures_by_a_surfactant-free_hydrothermal_process,_Mater.Lett.2012(73):
86-88] in the water-heat process of surfactant-free, using different ammonia sources, obtain by nanometer rods, nano-nail or nanometer tower
The flower shape zinc oxide structure radially assembled and the radially zinc oxide structures microballoon by nanotube bundle together.But profit
The controlledly synthesis of hierarchical structure pattern is prepared based on growth ZnO hierarchical structures film on flexible substrate and realized with simple hydro-thermal method
Then have difficulties.Though hierarchical structure nano-powder substantially improves the dispersion performance of powder nanometer particle, to realize its with it is soft
Property substrate be bonded securely, there is also larger difficulties, even if taking such as coating, binder bonding in conjunction with low temperature, chemically sintered
Technique prepares film, remains on and there are problems that hierarchical structure powder film poor adhesive force on flexible substrates.
Invention content
The purpose of the present invention is to provide a kind of simply zinc oxide three-dimensional hierarchical structure film being adjusted with trace metal salts
The method of pattern, to solve the problems mentioned in the above background technology.
To achieve the above object, the present invention provides the following technical solutions：
The method for adjusting zinc oxide three-dimensional hierarchical structure film morphology with trace metal salts, is as follows：
(1) sample is made in copper sheet, is polished with sand paper, is rinsed with water, then with dilute hydrochloric acid, acetone, each ultrasound of deionized water
Clean 10min；
(2) galvanizing technique is utilized, respectively using copper sheet, zinc metal sheet as the cathode of circuit and anode, by controlling cathode current
Density is 0.1~0.13A/dm2, the electroplating processes more than 30min are carried out to copper sheet；
(3) the soluble metal saline solution of a concentration of 0.001 ± 0.0005mol/L of 40mL and 0.75 ± 0.25mL is dense
Ammonium hydroxide is mixed to get hydrothermal solution, and hydrothermal solution is added in autoclave liner, is stirred, then by above-mentioned electroplating processes
Copper sheet afterwards is stood on by wall in autoclave liner；
(4) closed autoclave is placed in air dry oven and is heated to 90 DEG C, and keep the temperature 6~9h；
(5) after reaction, it takes out reaction kettle and takes out sample from kettle after room temperature, respectively with anhydrous
Respectively sample three times, is finally dried in vacuo 2h by cleaning at 50 DEG C for ethyl alcohol, deionized water, obtain zinc oxide it is micro-/hierarchical structure of receiving is thin
Film product.
As a further solution of the present invention：The trace metal salts are soluble metallic salt, the metal of trace metal salts
Ion generates corresponding hydroxide precipitation under the alkaline condition that ammonium hydroxide provides.
As a further solution of the present invention：The size of step (1) the Chinese style sample ruler cun is 2cm × 4cm.
As a further solution of the present invention：Soluble metal saline solution is a concentration of in the step (3)
0.001mol/L。
As a further solution of the present invention：The volume of concentrated ammonia liquor is 0.75mL in the step (3).
As further scheme of the invention：Soaking time in the step (4) is 6h.
Compared with prior art, the beneficial effects of the invention are as follows：
It is proposed by the present invention prepared on copper base zinc oxide it is micro-/receive hierarchical structure, including first with electroplating technology, clear
The zinc micron film display of clean copper sheet surface plating last layer densification；Then hydro-thermal method is utilized, by adding into ammonium hydroxide-hydrothermal system
Enter micro soluble metallic salt, the metal ion dissolved need to generate corresponding dissolving under the alkaline condition that ammonium hydroxide provides
Little hydroxide is spent, hydroxide deposition serves as the seed of zinc oxide nucleating growth, induced oxidation on zinc micron film surface
The a large amount of out-phase forming cores of zinc, excessive or very few hydroxide precipitation can inhibit forming core and the growth of zinc oxide under certain condition.
In the methods of the invention, due to the differences such as the ionic radius of different metal element, electronegativity, the solubility and knot of hydroxide
Crystalline substance is also different, to influence the forming core speed of growth and nanostructure and pattern of zinc oxide.
In the present invention, by the regulation and control of metal salt, the regulation and control of zinc oxide hierarchical structure film morphology are realized；It is added in reaction
Trace metal ion also be used as doped chemical the physical and chemical properties of zinc oxide can be played into zinc oxide lattice
Certain adjustment effect；The flexible copper base used in the present invention is not only alleviated compared to the conducting glass substrate and Si pieces of rigidity
Film weight also reduces the cost of manufacture of film, while because of its flexible deformation, can expand zinc-oxide film applies model
It encloses；In addition, in the method for the present invention, due to the copper base of electrogalvanizing processing be both nano structure of zinc oxide growth substrate and
For the zinc source needed for zinc oxide growth, thus can ensure gained zinc oxide micro/nano structure and copper base between it is good
In conjunction with.
Description of the drawings
Fig. 1 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L zinc nitrate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
Zinc oxide it is micro-/hierarchical structure of receiving amplify SEM schematic diagrames, wherein a be amplification 2000 times, b be amplification be 10000 times.
Fig. 2 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L magnesium nitrate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
Zinc oxide it is micro-/hierarchical structure of receiving amplify SEM schematic diagrames, wherein a be amplification 2000 times, b be amplification 10000 times.
Fig. 3 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L barium nitrate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
Zinc oxide it is micro-/hierarchical structure of receiving amplify SEM schematic diagrames, wherein a be amplification 1000 times, b be amplification 5000 times.
Fig. 4 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L strontium nitrate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
Zinc oxide it is micro-/hierarchical structure of receiving amplify SEM schematic diagrames.Wherein a is 2000 times of amplification, and b is 10000 times of amplification.
Fig. 5 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L ferrous sulfate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
To zinc oxide it is micro-/hierarchical structure of receiving amplify SEM schematic diagrames, wherein a be amplification 500 times, b be amplification 2000 times.
Fig. 6 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L cobalt nitrate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
Zinc oxide it is micro-/hierarchical structure of receiving amplify SEM schematic diagrames, wherein a be amplification 1000 times, b be amplification 10000 times.
Fig. 7 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L nickel nitrate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
Zinc oxide it is micro-/hierarchical structure of receiving amplify SEM schematic diagrames, wherein a be amplification 1000 times, b be amplification 10000 times.
Fig. 8 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L lanthanum nitrate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
Zinc oxide it is micro-/hierarchical structure of receiving amplify SEM schematic diagrames, wherein a be amplification 1000 times, b be amplification 5000 times.
Fig. 9 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L aqueous neodymium nitrate, and 90 DEG C, hydro-thermal reaction 9h is obtained
Zinc oxide it is micro-/hierarchical structure of receiving amplify SEM schematic diagrames, wherein a be amplification 1000 times, b be amplification 5000 times.
Figure 10 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L aqueous bismuth nitrate solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
To zinc oxide it is micro-/hierarchical structure of receiving amplify SEM schematic diagrames, wherein a be amplification 1000 times, b be amplification 10000 times.
Figure 11 is that 0.5mL concentrated ammonia liquors are added in 40mL, 0.001mol/L barium nitrate aqueous solution, 90 DEG C, hydro-thermal reaction 6h
Obtained zinc oxide is micro-/hierarchical structure of receiving amplification SEM schematic diagrames, wherein a is 1000 times of amplification, and b is 5000 times of amplification.
Figure 12 is that 0.5mL concentrated ammonia liquors are added in 40mL, 0.001mol/L aqueous neodymium nitrate, 90 DEG C, hydro-thermal reaction 6h
Obtained zinc oxide is micro-/hierarchical structure of receiving amplification SEM schematic diagrames, wherein a is 1000 times of amplification, and b is 10000 times of amplification.
Figure 13 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L magnesium nitrate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
To zinc oxide it is micro-/receive the XRD spectra of hierarchical structure.
Figure 14 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L cobalt nitrate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
To zinc oxide it is micro-/receive the XRD spectra of hierarchical structure.
Figure 15 is that 1mL concentrated ammonia liquors are added in 40mL, 0.001mol/L lanthanum nitrate aqueous solution, and 90 DEG C, hydro-thermal reaction 9h is obtained
To zinc oxide it is micro-/receive the XRD spectra of hierarchical structure.
Figure 16 is that 0.5mL concentrated ammonia liquors are added in 40mL, 0.001mol/L cobalt nitrate aqueous solution, 90 DEG C, hydro-thermal reaction 6h
Obtained zinc oxide is micro-/receive the XRD spectra of hierarchical structure.
Figure 17 is that 1mL concentrated ammonia liquors, the hydro-thermal reaction 9h at 90 DEG C are added in 40mL, 0.001mol/L aqueous neodymium nitrate
Obtained zinc oxide is micro-/receive the X-ray energy spectrogram (EDS spectrograms) of hierarchical structure.
Figure 18 is that 1mL concentrated ammonia liquors, the hydro-thermal reaction 9h at 90 DEG C are added in 40mL, 0.001mol/L lanthanum nitrate aqueous solution
Obtained zinc oxide is micro-/receive the x-ray photoelectron spectroscopy figure (XPS spectrum figure) of hierarchical structure, wherein a is the full spectrograms of XPS, b La
Narrow scan figure.
Figure 19 is that 1mL concentrated ammonia liquors, the hydro-thermal reaction 9h at 90 DEG C are added in 40mL, 0.001mol/L cobalt nitrate aqueous solution
Obtained zinc oxide is micro-/receive the XPS spectrum figure of hierarchical structure, wherein a is the full spectrograms of XPS, and b is Co narrow scan figures.
Specific implementation mode
The technical solution of this patent is described in more detail With reference to embodiment.
Embodiment 1
Please refer to Fig.1-19, in the embodiment of the present invention, a kind of with trace metal salts to adjust zinc oxide three-dimensional hierarchical structure thin
The method of film pattern, is as follows：
The method for adjusting zinc oxide three-dimensional hierarchical structure film morphology with trace metal salts, is as follows：
(1) sample that size is 2cm × 4cm is made in copper sheet, is polished, be rinsed with water with sand paper, then with dilute hydrochloric acid, third
Ketone, deionized water are respectively cleaned by ultrasonic 10min；
(2) galvanizing technique is utilized, respectively using copper sheet, zinc metal sheet as the cathode of circuit and anode, by controlling cathode current
Density is 0.1~0.13A/dm2, the electroplating processes more than 30min are carried out to copper sheet；
(3) the soluble metal saline solution of a concentration of 0.001mol/L of 40mL and 1mL concentrated ammonia liquors are mixed to get hydro-thermal
Hydrothermal solution is added in autoclave liner, is stirred by solution, then the copper sheet after above-mentioned electroplating processes is upright by wall
In autoclave liner；
(4) closed autoclave is placed in air dry oven and is heated to 90 DEG C, and keep the temperature 9h；
(5) after reaction, it takes out reaction kettle and takes out sample from kettle after room temperature, respectively with anhydrous
Respectively cleaning three times, removes the reactant and solvent of surface, is finally dried in vacuo sample at 50 DEG C for ethyl alcohol, deionized water
2h, obtain zinc oxide it is micro-/receive hierarchical structure film product.
Embodiment 2
It please refers to Fig.1-19, in the embodiment of the present invention, zinc oxide three-dimensional hierarchical structure film shape is adjusted with trace metal salts
The method of looks, is as follows：
(1) sample that size is 2cm × 4cm is made in copper sheet, is polished, be rinsed with water with sand paper, then with dilute hydrochloric acid, third
Ketone, deionized water are respectively cleaned by ultrasonic 10min；
(2) galvanizing technique is utilized, respectively using copper sheet, zinc metal sheet as the cathode of circuit and anode, by controlling cathode current
Density is 0.1~0.13A/dm2, the electroplating processes more than 30min are carried out to copper sheet；
(3) the soluble metal saline solution of a concentration of 0.001mol/L of 40mL and 0.5mL concentrated ammonia liquors are mixed to get water
Hydrothermal solution is added in autoclave liner, is stirred by hot solution, then the copper sheet after above-mentioned electroplating processes is straight by wall
It stands in autoclave liner；
(4) closed autoclave is placed in air dry oven and is heated to 90 DEG C, and keep the temperature 6h；
(5) after reaction, it takes out reaction kettle and takes out sample from kettle after room temperature, respectively with anhydrous
Respectively cleaning three times, removes the reactant and solvent of surface, is finally dried in vacuo sample at 50 DEG C for ethyl alcohol, deionized water
2h, obtain zinc oxide it is micro-/receive hierarchical structure film product.
Embodiment 3
It please refers to Fig.1-19, in the embodiment of the present invention, zinc oxide three-dimensional hierarchical structure film shape is adjusted with trace metal salts
The method of looks, is as follows：
(1) sample that size is 2cm × 4cm is made in copper sheet, is polished, be rinsed with water with sand paper, then with dilute hydrochloric acid, third
Ketone, deionized water are respectively cleaned by ultrasonic 10min；
(2) galvanizing technique is utilized, respectively using copper sheet, zinc metal sheet as the cathode of circuit and anode, by controlling cathode current
Density is 0.1~0.13A/dm2, the electroplating processes more than 30min are carried out to copper sheet；
(3) the soluble metal saline solution of a concentration of 0.0005mol/L of 40mL and 0.5mL concentrated ammonia liquors are mixed to get water
Hydrothermal solution is added in autoclave liner, is stirred by hot solution, then the copper sheet after above-mentioned electroplating processes is straight by wall
It stands in autoclave liner；
(4) closed autoclave is placed in air dry oven and is heated to 100 DEG C, and keep the temperature 7h；
(5) after reaction, it takes out reaction kettle and takes out sample from kettle after room temperature, respectively with anhydrous
Respectively cleaning three times, removes the reactant and solvent of surface, is finally dried in vacuo sample at 50 DEG C for ethyl alcohol, deionized water
2h, obtain zinc oxide it is micro-/receive hierarchical structure film product.
Embodiment 4
It please refers to Fig.1-19, in the embodiment of the present invention, zinc oxide three-dimensional hierarchical structure film shape is adjusted with trace metal salts
The method of looks, is as follows：
(1) sample that size is 2cm × 4cm is made in copper sheet, is polished, be rinsed with water with sand paper, then with dilute hydrochloric acid, third
Ketone, deionized water are respectively cleaned by ultrasonic 10min；
(2) galvanizing technique is utilized, respectively using copper sheet, zinc metal sheet as the cathode of circuit and anode, by controlling cathode current
Density is 0.1~0.13A/dm2, the electroplating processes more than 30min are carried out to copper sheet；
(3) the soluble metal saline solution of a concentration of 0.001mol/L of 40mL and 0.75mL concentrated ammonia liquors are mixed to get water
Hydrothermal solution is added in autoclave liner, is stirred by hot solution, then the copper sheet after above-mentioned electroplating processes is straight by wall
It stands in autoclave liner；
(4) closed autoclave is placed in air dry oven and is heated to 90 DEG C, and keep the temperature 8h；
(5) after reaction, it takes out reaction kettle and takes out sample from kettle after room temperature, respectively with anhydrous
Respectively cleaning three times, removes the reactant and solvent of surface, is finally dried in vacuo sample at 50 DEG C for ethyl alcohol, deionized water
2h, obtain zinc oxide it is micro-/receive hierarchical structure film product.
Embodiment 5
It please refers to Fig.1-19, in the embodiment of the present invention, zinc oxide three-dimensional hierarchical structure film shape is adjusted with trace metal salts
The method of looks, is as follows：
(1) sample that size is 2cm × 4cm is made in copper sheet, is polished, be rinsed with water with sand paper, then with dilute hydrochloric acid, third
Ketone, deionized water are respectively cleaned by ultrasonic 10min；
(2) galvanizing technique is utilized, respectively using copper sheet, zinc metal sheet as the cathode of circuit and anode, by controlling cathode current
Density is 0.1~0.13A/dm2, the electroplating processes more than 30min are carried out to copper sheet；
(3) the soluble metal saline solution of a concentration of 0.0015mol/L of 40mL and 1mL concentrated ammonia liquors are mixed to get hydro-thermal
Hydrothermal solution is added in autoclave liner, is stirred by solution, then the copper sheet after above-mentioned electroplating processes is upright by wall
In autoclave liner；
(4) closed autoclave is placed in air dry oven and is heated to 100 DEG C, and keep the temperature 9h；
(5) after reaction, it takes out reaction kettle and takes out sample from kettle after room temperature, respectively with anhydrous
Respectively cleaning three times, removes the reactant and solvent of surface, is finally dried in vacuo sample at 50 DEG C for ethyl alcohol, deionized water
2h, obtain zinc oxide it is micro-/receive hierarchical structure film product.
Hydrothermal condition such as hydrothermal temperature, time, ammonia vol and the metallic element of addition amount etc. influences zinc oxide in the present invention
Forming core growth, if fixed above-mentioned condition, metallic element type is micro- to zinc oxide/the final pattern of hierarchical structure received rises and determine to make
With.Metallic element salt used in the present invention, refers to metallic element soluble-salt, and the metal ion under solution condition can be in alkalinity
Under the conditions of form the little corresponding hydroxide of solubility.The addition of trace metal ion is in control crystallization kinetics in the present invention
It plays an important role on the last pattern of classification micro nano structure, different metal type acts on the nucleating growth of zinc oxide
Difference, induce different-shape, size, length nano structure of zinc oxide formation, finally obtain different shape zinc oxide three-dimensional it is micro-/
Receive hierarchical structure.
It is proposed by the present invention prepared on copper base zinc oxide it is micro-/receive hierarchical structure, including first with electroplating technology, clear
The zinc micron film display of clean copper sheet surface plating last layer densification；Then hydro-thermal method is utilized, by adding into ammonium hydroxide-hydrothermal system
Enter micro soluble metallic salt, the metal ion dissolved need to generate corresponding dissolving under the alkaline condition that ammonium hydroxide provides
Little hydroxide is spent, hydroxide deposition serves as the seed of zinc oxide nucleating growth, induced oxidation on zinc micron film surface
The a large amount of out-phase forming cores of zinc.Excessive or very few hydroxide precipitation can inhibit forming core and the growth of zinc oxide under certain condition,
In the methods of the invention, due to the differences such as the ionic radius of different metal element, electronegativity, the solubility and knot of hydroxide
Crystalline substance is also different, to influence the forming core speed of growth and nanostructure and pattern of zinc oxide.In the methods of the invention, micro
Metal ion is also used as doped chemical, enters in zinc oxide lattice, will adjust zinc oxide physics and chemistry to a certain extent
Performance.
By Fig. 1-12 it is found that under conditions of other conditions are identical, the one-dimension zinc oxide grown on zinc micron film is received
Rice noodles have different patterns, size and length because the metal salt type being added in hydrothermal system is different, finally obtain pattern
Entirely different zinc oxide three-dimensional hierarchical structure, by comparison diagram 3, Figure 11, Fig. 9 and Figure 12 it is found that fixing metal salt type, adding
Enter amount and hydrothermal temperature, the final pattern of zinc oxide three-dimensional hierarchical structure also can be changed in change ammonium hydroxide addition and hydro-thermal time.
From Figure 13-15 as can be seen that diffraction spectral peak is nearly identical in three figures, all diffraction maximums in each figure remove
The diffraction maximum corresponding to Zn micron films and Copper substrate (JCPDS standard cards number are 04-0836) not being completely dissolved, remaining spreads out
The zinc oxide of hexagonal wurtzite structure (JCPDS standard cards number are 36-1451) can be belonged to by penetrating peak, not see that reaction is introduced
The corresponding diffraction maximum of metal species, show in hydrothermal system be added different metal salting liquid, copper base growth be all
The higher hexagonal wurtzite nano structure of zinc oxide of purity.Compares figure 16 is with Figure 14 it is found that the corresponding diffraction peak intensity of zinc oxide
It is apparent to weaken, and the corresponding diffraction peak intensity of zinc micron film is remarkably reinforced, and almost loses the corresponding diffraction maximum of copper base, shows
0.5mL concentrated ammonia liquors are added in 40mL, 0.001M cobalt nitrate aqueous solution, 90 DEG C, under 6h hydrothermal reaction conditions, the zinc on copper base is micro-
Rice piece, which has, more is converted into zinc oxide.
Figure 17 is 40mL, 1mL concentrated ammonia liquors is added in 0.001M aqueous neodymium nitrates, hydro-thermal reaction 9h is obtained at 90 DEG C
Zinc oxide is micro-/receive the energy spectrum diagram of hierarchical structure, there are the corresponding peak of Zn and O elements, the result of quantitative analysis to show Zn in spectrogram:O
≈ 1 shows that zinc micron film has been converted into fine and close zinc oxide nanowire completely in this product.Because the doping of neodymium is few, spectrogram
In have no the corresponding peak of neodymium.
As shown in a figures in Figure 18, in XPS full scan spectrograms, in addition to the corresponding spectral peaks of C1s, separately there is Zn, O and La
The main peak and secondary peak of three kinds of elements, illustrate that La has been incorporated into zinc oxide lattice, in Figure 18 shown in b figures, illustrate four of La
The combination of feature spectral peak can be La in 834.08eV, 836.08eV, 849.08eV, 854.08eV, with standard spectrum respectively2O3Spy
Sign spectral line is consistent, and illustrates that the chemical valence for the La being entrained in nano zine oxide is+3.
As shown in a figures in Figure 19, in XPS full scan spectrograms, only there is the spectral peak of tri- kinds of elements of Zn, O and C, Figure 19
Co can occur for 779.2eV in combination in middle b figures2p3/2Corresponding spectral peak illustrates there are Co elements in sample, in the form of+3
It is present in zinc oxide lattice.
The flexible copper base used in the present invention not only alleviates film weight, also reduces the cost of manufacture of film, together
The flexible deformations of Shi Yinqi, can expand the application range of zinc-oxide film, in addition, in the method for the present invention, due to electroplating processes
Copper base is both the growth substrate of nano structure of zinc oxide and the zinc source needed for zinc oxide growth, therefore can ensure institute
Good combination between the zinc oxide micro/nano structure obtained and copper base.
The better embodiment of this patent is explained in detail above, but this patent is not limited to above-mentioned embodiment party
Formula, one skilled in the relevant art within the scope of knowledge, can also be under the premise of not departing from this patent objective
Various changes can be made.
Claims (5)
1. the method for adjusting zinc oxide three-dimensional hierarchical structure film morphology with trace metal salts, which is characterized in that the micro gold
Category salt is soluble metallic salt, and corresponding hydrogen is generated under the alkaline condition that ammonium hydroxide provides by the metal ion of trace metal salts
Oxide precipitation, which is realized, adjusts zinc oxide three-dimensional hierarchical structure film morphology；It is as follows：
(1) sample is made in copper sheet, is polished with sand paper, is rinsed with water, then be respectively cleaned by ultrasonic with dilute hydrochloric acid, acetone, deionized water
10min；
(2) galvanizing technique is utilized, respectively with cathode and anode that copper sheet, zinc metal sheet are plating, by controlling cathode-current density
For 0.1~0.13A/dm2, the electroplating processes more than 30min are carried out to copper sheet；
(3) by the soluble metal saline solution and 0.75 ± 0.25mL concentrated ammonia liquors of a concentration of 0.001 ± 0.0005mol/L of 40mL
It is mixed to get hydrothermal solution, hydrothermal solution is added in autoclave liner, is stirred, then will be after above-mentioned electroplating processes
Copper sheet is stood on by wall in autoclave liner；The soluble metallic salt is trace metal salts；
(4) closed autoclave is placed in air dry oven and is heated to 80-100 DEG C, and keep the temperature 6~9h；
(5) after reaction, it takes out reaction kettle and takes out sample from kettle after room temperature, respectively with anhydrous second
Respectively sample three times, is finally dried in vacuo 2h by cleaning at 50 DEG C for alcohol, deionized water, obtain zinc oxide it is micro-/receive hierarchical structure film
Product.
2. the method according to claim 1 for adjusting zinc oxide three-dimensional hierarchical structure film morphology with trace metal salts,
It is characterized in that, the size of step (1) the Chinese style sample ruler cun is 2cm × 4cm.
3. the method according to claim 1 for adjusting zinc oxide three-dimensional hierarchical structure film morphology with trace metal salts,
It is characterized in that, a concentration of 0.001mol/L of soluble metal saline solution in the step (3).
4. the method according to claim 1 for adjusting zinc oxide three-dimensional hierarchical structure film morphology with trace metal salts,
It is characterized in that, the volume of concentrated ammonia liquor is 0.75mL in the step (3).
5. the method according to claim 1 for adjusting zinc oxide three-dimensional hierarchical structure film morphology with trace metal salts,
It is characterized in that, the soaking time in the step (4) is 6h.
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| CN102024573A (en) * | 2010-12-18 | 2011-04-20 | 西南交通大学 | Method for preparing sensitized ZnO nano-plate photo-anode of PbS quantum dot |
| CN102417201A (en) * | 2011-08-31 | 2012-04-18 | 北京大学 | Method for preparing one-dimensional self-assembly material with ZnO nanorod array as template |
| CN105088344A (en) * | 2015-08-05 | 2015-11-25 | 广西科技大学 | Method for preparing PbS sensitization ZnO nanorod arrays on zinc sheet |
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| CN102024573A (en) * | 2010-12-18 | 2011-04-20 | 西南交通大学 | Method for preparing sensitized ZnO nano-plate photo-anode of PbS quantum dot |
| CN102417201A (en) * | 2011-08-31 | 2012-04-18 | 北京大学 | Method for preparing one-dimensional self-assembly material with ZnO nanorod array as template |
| CN105088344A (en) * | 2015-08-05 | 2015-11-25 | 广西科技大学 | Method for preparing PbS sensitization ZnO nanorod arrays on zinc sheet |
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| "Zn基ZnO纳米线的水热合成及其光催化性能";傅凤鸣等;《人工晶体学报》;20150131;第44卷(第1期);第109-110页 * |
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