CN106435542A - Ag-Cu film preparation method - Google Patents
Ag-Cu film preparation method Download PDFInfo
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- CN106435542A CN106435542A CN201610638112.9A CN201610638112A CN106435542A CN 106435542 A CN106435542 A CN 106435542A CN 201610638112 A CN201610638112 A CN 201610638112A CN 106435542 A CN106435542 A CN 106435542A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910017944 Ag—Cu Inorganic materials 0.000 title claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 97
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000001509 sodium citrate Substances 0.000 claims abstract description 21
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 6
- 239000010409 thin film Substances 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000010408 film Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000001069 Raman spectroscopy Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 15
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 15
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 229940112669 cuprous oxide Drugs 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 241000222065 Lycoperdon Species 0.000 description 5
- 241000768494 Polymorphum Species 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000013401 experimental design Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 229910018292 Cu2In Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The present invention provides an Ag-Cu film preparation method, which comprises: treating a Cu sheet, preparing a high-purity Cu sheet, preparing a copper sulfate solution containing a certain amount of SDS, inserting the treated Cu sheet into the solution, heating to a temperature of 40-60 DEG C, maintaining for 3-6 h, taking out to form a Cu2O-Cu sheet, inserting the Cu2O-Cu sheet into a sodium citrate solution having a certain concentration, adding a certain amount of a AgNO3 solution, stirring at a room temperature, rapidly adding a certain amount of ammonia water, continuously stirring for a certain time, and taking out the sample. According to the present invention, the method has characteristics of cheap and easily-available raw materials, simple synthesis process, low cost, short reaction period, and convenient reaction control; and the prepared sample is uniform, the Ag film is firm and does not easily shed, the surface forms the sheet-like structure, the hot spots are more, the surface Raman enhancing, the recycling and the device production are easily achieved, and no environment pollution is generated.
Description
Technical field
The invention belongs to the preparation field of nano thin-film, a kind of preparation method of specific design Ag-cu thin film.
Background technology
Ag nano-particle, because having good optically and electrically performance, can be applicable to chemistry and biosensor, surface
Strengthen the fields such as Raman scattering, light emitting diode and solaode.Many applications of silver nano-grain and its remaining light are mutually made
The surface plasma body resonant vibration that used time produces is closely related, when that is, illumination is mapped on silver nano-grain, the electrons of particle surface
There is collective vibration, when the frequency of incident illumination and the frequency of vibration of electronics are identical, covibration can be produced.This surface etc. from
Sub- excimer can produce strong scattering to light, and so that local field is strengthened.
At present, in a lot of fields, be required to support film dress, just can in order to preparing device part, the pattern of metallic film
Research causes the concern of Many researchers, its synthetic method also various inclusion self assembly, electro-deposition, PVD, electron number etching,
Nano impression and template etc., but above-mentioned synthetic method method complexity, apparatus expensive etc., limit its application.In recent years
Come, the method that Zhu et al. utilizes electro-deposition, the micron hemisphere that lamellar is self-assembled into successfully has been obtained on electro-conductive glass, and upper
The preparation method stating film type SERS substrate is compared, and electrochemical process synthesis device is simple, and the SERS substrate synthesizing shows
Preferably Repeatability, prepare the concern by Many researchers of the method for SERS substrate although electrification hence with electrochemistry
The method learning deposition can obtain uniform SERS substrate on a large scale, but preparation efficiency is low, therefore more simple, cheap
SERS FLOOR method remains the target that numerous researcheres are pursued.Zhan et al. reports for work using copper sheet recently is substrate, passes through
Electrochemical in-situ reacts, and is successfully prepared the thin film of Ag nanometer sheet assembling on copper sheet, but in this reaction system, Cu piece serves as a contrast
Bottom is too fast with the reaction of Ag ion, leads to the product morphology cannot finely regulating.In recent years, the reason cu is quick with Ag ionic reaction
It is Ag+/ Ag standard electrode EMF is 0.8V, significantly larger than Cu2+/ Cu standard electrode EMF is 0.34V if it is possible to reduce also
Former potential, then be conducive to the control of reaction rate.Cu2+/Cu+Standard electrode EMF is 0.16V, compares Cu2+/ Cu standard electrode EMF
Much lower, this would be possible to greatly reduce reaction rate, realizes the control of silver nanoparticle unit growth, and such as GAO et al. utilizes oxygen
Change cuprous Ag thin film of making to be studied, wherein using HNO3Reacted with sodium citrate, successfully prepared Ag nanometer
Piece thin film, its reaction is more gentle, and controllability is more completely reacted using Cu piece substrate and Ag ion than directly, however, said method
Or inconvenience controls, and man's activity is larger, and reaction time is longer, reactions steps are complicated, the Ag thin film of generation easy to fall off, unfavorable
In recycling, also it is unfavorable for making device etc. deficiency, limit its application.
Content of the invention
The present invention provides a kind of method simple, controlled, firm, beneficial to the preparation method of the Ag-Cu thin film recycling.
A kind of preparation method of Ag-cu thin film is it is characterised in that include following preparation process：
Step one, processes Cu piece, prepares high-purity Cu piece；
Step 2, the copper-bath containing a certain amount of SDS for the configuration, and the Cu piece after processing is inserted above-mentioned solution
In；
Step 3, is heated to 40-60 DEG C, keeps 3-6 hour, takes out Cu piece, that is, form Cu2O-Cu piece；
Step 4, by above-mentioned Cu2O-Cu piece immerses in certain density sodium citrate solution；
Step 5, adds a certain amount of AgNO3Solution, is stirred at room temperature；
Step 6, rapidly joins a certain amount of ammonia on the basis of above-mentioned steps five, continues stirring certain time, takes out
Sample.
Specifically, process Cu piece in described step one to include, clean removing surface respectively with acetone and EtOH Sonicate organic
Thing, then through dilute HNO3Soak and remove surface film oxide, then clean removing surface impurity through deionized water.
Further, the time of described acetone and EtOH Sonicate cleaning is respectively 8-12 minute；Described dilute HNO3 invades bubble
Time is 3-8 minute.
Preferably, the concentration of described copper-bath is 0.005-0.017g/mL.
Further, described SDS and the mass ratio of copper sulfate are (0.1-0.5)：1.
Further, the concentration of described sodium citrate is (1 × 10-3-4.2×10-3)g/ml.
Preferably, described AgNO3Mass ratio with copper sulfate is (0.67-5)：1.
Preferably, the volume of described ammonia is (0.1-0.2) with the volume ratio of copper-bath: 1.
Specifically, the bare area of described Cu piece is 0.04-0.2cm2.
Present invention additionally comprises a kind of Ag-Cu thin film, the Ag-Cu preparing gained by the preparation method of any of the above-described is thin
Film.
Technique scheme has the advantages that, method is easy to control, with low cost, decreases method and step, obtains
The sample arriving is more firm, is easy to cycle applications.
The preparation method of the present invention, is broadly divided into two steps, copper sheet is immersed in the CuSO of finite concentration volume first4
In solution, it is being heated to uniform temperature, one layer of evengranular Cu of growth in situ on copper sheet2O reducing zone, we pass through rationally
Experimental design, making Cu2In O films Step, improved, from original soaking at room temperature, be changed to heat treated, bright
Aobvious shortening generates Cu2The control of the reaction time of O thin film, more conducively time cost；Then again by using Cu2O is reduction
Agent, sodium citrate is structure directing agent and stabilizer, and ammonia is reacting substance, obtains uniformly being become by flake-assembly mode on copper sheet
Ag thin film.
The experimental design of technical solution of the present invention, reactions steps are comparatively easy to control, and man's activity is less, reaction time
Shorter, with low cost, most important for generate Ag thin film difficult for drop-off, ratio is stronger, and its surface also generate lamellar knot
Structure, and focus is more, beneficial to surface Raman enhancement, beneficial to recycling, is also beneficial to make device.
Brief description
Fig. 1 is scanning electron microscope (SEM) photo of Ag/Cu thin film prepared by example 1.
Fig. 2 is the X ray diffracting spectrum of Cu piece in Ag/Cu thin-film process prepared by example 1.
Fig. 3 is Cu in Ag/Cu thin-film process prepared by example 12The X ray diffracting spectrum of O/cu thin film.
Fig. 4 is the X ray diffracting spectrum of Ag/Cu thin film prepared by example 1.
Fig. 5 is the EDS figure of Ag/Cu thin film prepared by example 1.
Specific embodiment
Embodiment 1
Cu2O thin film：
Step one, processes Cu piece, Cu piece acetone and ethanol are cleaned by ultrasonic 10 minutes removing surface organic matters respectively, then warp
Dilute HNO3Soak 5 minutes and remove surface film oxide, then clean 3 removing surface impurities through deionized water, dry, stand-by 0.2*
0.2cm, i.e. high-purity Cu piece；
Step 2, prepares in 100ml beaker and adds 0.3g CuSO4(form CuSO with 50ml deionized water4Solution
Concentration is 0.006g/mL), and add 0.08g SDS (i.e. SDS and the mass ratio of copper sulfate are 0.27: 1), by step one
High-purity Cu piece is put in above-mentioned solution, and is heated to 60 DEG C, keeps 6 hours, takes out, and is cleaned with ethanol and deionized water 3 times,
Obtain Chinese red Cu2O thin film, that is, form Cu2O-Cu piece：
Ag/Cu thin film：
Step 3, adds 0.12g sodium citrate as structure directing agent in 100ml beaker, adds 80ml deionization
Water, is stirred at room temperature 20 minutes, that is, forming concentration is 1.5 × 10-3The sodium citrate solution of g/mL；
Step 4, by the Cu handling well in step 22O-Cu piece againsts walls of beaker and is completely immersed in the lemon that step 3 prepares
Lemon acid sodium solution, stirs 10 minutes；
Step 5, adds the AgNO of 5ml 0.016g/mL3Solution, is stirred at room temperature 5 minutes；
Step 6, rapidly joins the ammonia that 5mL concentration is 30% on the basis of above-mentioned steps five, continues stirring 20 minutes
Afterwards, take out sample it can be seen that Chinese red thin film before becomes Lycoperdon polymorphum Vitt thin film.Accompanying drawing 1-3 is system in the present embodiment respectively
The SEM figure of the Ag/Cu thin film becoming, from accompanying drawing 1 it can be seen that the Ag of the Ag/Cu thin film made is laminated structure, and structure is more
Fine and close.By the XRD figure of accompanying drawing 2-4 it can be seen that the situation of change of the sample made in each step, Fig. 2 is the XRD figure of copper sheet
Spectrum, Fig. 3 is to make Cu on copper sheet2The XRD spectrum of O thin film, Fig. 4 is by the Cu on Cu2O thin film makes the XRD figure of Ag thin film
Spectrum；Be can be seen that according to above-mentioned collection of illustrative plates and be successfully made Cu2O thin film, is made for Ag thin film further.The product that Fig. 5 makes for Fig. 4
Product corresponding EDS collection of illustrative plates, from collection of illustrative plates it can be seen that generate for Ag simple substance.The Ag/Cu thin film finally obtaining, thin film is very firm
Gu, it is not easily broken and comes off, beneficial to recycling.
Embodiment 2
Cu2O thin film：
(1) process Cu piece, Cu piece acetone and EtOH Sonicate clean 10 minutes and remove surface organic matter, then through dilute HNO3Leaching
Bubble removes surface film oxide in 5 minutes, then cleans 3 removing surface impurities through deionized water, dries, stand-by, Cu chip size is
0.2*0.2cm, i.e. high-purity Cu piece；
(2) add 0.1g CuSO in 100ml beaker4With 50mL deionized water, and add 0.05gSDS, by (1)
High-purity Cu piece after process is put in above-mentioned solution, is heated to 60 DEG C, keeps 6 hours, takes out, is cleaned with ethanol and deionized water
3 times, obtain Chinese red cuprous oxide film, that is, form Cu2O-Cu piece；
Ag/Cu thin film：
(3) add 0.1 gram of sodium citrate as structure directing agent in 100ml beaker, add in 60ml deionized water, room
Temperature stirring 20 minutes, forms 1.67 × 10-3The sodium citrate solution of g/mL；
(4) the cuprous oxide film piece handled well in (2) is against walls of beaker and be completely immersed in the sodium citrate that (3) prepare
Solution, stirs 10 minutes；
(5) add the AgNO of 5mL 0.016g/mL3Solution, is stirred at room temperature 5 minutes；
(6) rapidly join the ammonia that 5mL concentration is 20% on the basis of (5), after continuing stirring 20 minutes, take out sample
Product it can be seen that Chinese red thin film before becomes Lycoperdon polymorphum Vitt thin film, that is, obtain Ag/Cu thin film.Embodiment 3
Cu2O thin film：
(1) Cu piece acetone and EtOH Sonicate cleans 10 minutes and removes surface organic matter, then through dilute HNO3Soak and remove for 5 minutes
Remove surface film oxide, then clean 3 removing surface impurities through deionized water, dry, stand-by, that is, form high-purity Cu piece, Cu piece chi
Very little for 0.2*0.2cm；
(2) add 0.5g CuSO in 100ml beaker4With 50mL deionized water, and add 0.1g SDS, by (1)
High-purity Cu piece is put in above-mentioned solution, is heated to 50 DEG C, keeps 6 hours, takes out, is cleaned with ethanol and deionized water 3 times, obtain
Chinese red cuprous oxide film, that is, form Cu2O-Cu piece；
Ag/Cu thin film：
(3) add 0.25 gram of sodium citrate in 100ml beaker as structure directing agent, and add 100ml deionized water
In, it is stirred at room temperature 20 minutes, forming concentration is 2.5 × 10-3The sodium citrate solution of g/mL；
(4) the cuprous oxide film piece handled well in (2) is against walls of beaker and be completely immersed in the sodium citrate that (3) prepare
Solution, stirs 10 minutes；
(5) add 5mL 0.04g/mL AgNO3Solution, is stirred at room temperature 5 minutes；
(6) rapidly join the ammonia that 5mL concentration is 30% in (5), after continuing stirring 20 minutes, take out sample, permissible
Chinese red thin film before seeing becomes Lycoperdon polymorphum Vitt thin film, that is, obtain Ag/Cu thin film.
Embodiment 4：
Cu2O thin film：
Step one, processes Cu piece, Cu piece acetone and ethanol are cleaned by ultrasonic 8 minutes removing surface organic matters respectively, then warp
Dilute HNO3Soak 3 minutes and remove surface film oxide, then clean 3 removing surface impurities through deionized water, dry, stand-by, obtain final product
High-purity Cu piece, the size of Cu piece is 0.2cm2；
Step 2, the copper-bath containing a certain amount of SDS for the configuration, prepare in 100ml beaker and add 0.5g
CuSO4With 30ml deionized water, and add 0.25g SDS, and the Cu piece after processing inserts in above-mentioned solution；It is heated to temperature
For 40 DEG C, keep 3 hours；Take out, cleaned with ethanol and deionized water 3 times, obtain Chinese red cuprous oxide film, formed
Cu2O-Cu piece；
Ag/Cu thin film：
Step 3, adds 0.42g sodium citrate as structure directing agent in 100ml beaker, adds 100ml deionization
Water, is stirred at room temperature 20 minutes, that is, forming concentration is 4.2 × 10-3The sodium citrate solution of g/mL, by above-mentioned Cu2O-Cu piece againsts
Walls of beaker is completely immersed in this sodium citrate solution, stirs 10 minutes；
Step 4, adds the AgNO of 10ml0.25g/mL3Solution, is stirred at room temperature 5 minutes；
Step 5, rapidly joins the ammonia that 6mL concentration is 30% on the basis of above-mentioned step 4, continues stirring 20 minutes
Afterwards, take out sample.Chinese red thin film before can seeing becomes Lycoperdon polymorphum Vitt thin film, that is, obtain Ag/Cu thin film.
Embodiment 5：
Cu2O thin film：
Step one, processes Cu piece, Cu piece acetone and ethanol are cleaned by ultrasonic 12 minutes removing surface organic matters respectively, then warp
Dilute HNO3Soak 8 minutes and remove surface film oxide, then clean 3 removing surface impurities through deionized water, dry, stand-by, obtain final product
High-purity Cu piece, the size of Cu piece is 0.04cm2；
Step 2, the copper-bath containing a certain amount of SDS for the configuration, prepare in 100ml beaker and add 0.2g
CuSO4With 40ml deionized water, and add 0.02g SDS；And insert the Cu piece after processing in above-mentioned solution；It is heated to 45
DEG C, keep 6 hours；Take out, cleaned with ethanol and deionized water 3 times, obtain Chinese red cuprous oxide film, form Cu2O-Cu
Piece；
Ag/Cu thin film：
Step 3, adds 0.1g sodium citrate as structure directing agent in 100ml beaker, adds 100ml deionization
Water, is stirred at room temperature 20 minutes, that is, forming concentration is 1 × 10-3The sodium citrate solution of g/mL, by above-mentioned Cu2O-Cu piece againsts burning
Wall of cup is completely immersed in this sodium citrate solution, stirs 10 minutes；
Step 4, adds the AgNO of 3.2ml 0.1g/mL3Solution, is stirred at room temperature 5 minutes；
Step 5, rapidly joins the ammonia that 8mL concentration is 30% on the basis of above-mentioned step 4, continues stirring 20 minutes
Afterwards, take out sample.Chinese red thin film before can seeing becomes Lycoperdon polymorphum Vitt thin film, Ag/Cu thin film.
Claims (10)
1. a kind of preparation method of Ag-Cu thin film is it is characterised in that include following preparation process：
Step one, processes Cu piece, prepares high-purity Cu piece；
Step 2, the copper-bath containing a certain amount of SDS for the configuration, and the Cu piece after processing is inserted in above-mentioned solution；
Step 3, under the conditions of temperature is for 40-60 DEG C, keeps 3-6 hour, takes out, that is, form Cu2O-Cu piece；
Step 4, by above-mentioned Cu2O-Cu piece immerses in certain density sodium citrate solution；
Step 5, adds a certain amount of AgNO3Solution, is stirred at room temperature；
Step 6, rapidly joins a certain amount of ammonia on the basis of above-mentioned steps five, continues stirring certain time, takes out sample
Product.
2. preparation method as claimed in claim 1 includes, respectively with third it is characterised in that processing Cu piece in described step one
Ketone and EtOH Sonicate cleaning remove surface organic matter, then through dilute HNO3Soak and remove surface film oxide, then through deionized water cleaning
Remove surface impurity.
3. preparation method as claimed in claim 2 it is characterised in that described acetone and EtOH Sonicate cleaning time be respectively
8-12 minute；Described dilute HNO3The time invading bubble is 3-8 minute.
4. preparation method as claimed in claim 1 is it is characterised in that the concentration of described copper-bath is 0.005-
0.017g/mL.
5. preparation method as claimed in claim 1 is it is characterised in that described SDS is (0.1-0.5) with the mass ratio of copper sulfate
∶1.
6. preparation method as claimed in claim 1 is it is characterised in that the concentration of described sodium citrate is (1 × 10-3-4.2×
10-3)g/mL.
7. the preparation method as described in claim 1 or 4 or 5 or 6 is it is characterised in that described AgNO3Mass ratio with copper sulfate
For (0.16-5): 1.
8. the preparation method as described in claim 1 or 4 is it is characterised in that the body of the volume of described ammonia and copper-bath
Long-pending ratio is (0.1-0.2): 1.
9. preparation method as claimed in claim 1 is it is characterised in that the bare area of described Cu piece is 0.04-0.2cm2.
10. a kind of Ag-Cu thin film is it is characterised in that prepare gained by the preparation method of described any one of claim 1-7
Ag-Cu thin film.
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| CN102002694A (en) * | 2010-12-14 | 2011-04-06 | 江西理工大学 | Method for preparing uniform silver conducting layer on surface of metal or nonmetal material |
| CN104141159A (en) * | 2014-08-22 | 2014-11-12 | 西北大学 | Method for controlling conduction type of cuprous oxide semiconductor based on concentration of surface active agent in electroplating liquid |
| CN104569096A (en) * | 2015-02-05 | 2015-04-29 | 盐城工学院 | Construction method and detection method of cuprous oxide membrane-based enzyme free-oxygen sensitive glucose photo electrochemical sensor |
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| CN102002694A (en) * | 2010-12-14 | 2011-04-06 | 江西理工大学 | Method for preparing uniform silver conducting layer on surface of metal or nonmetal material |
| CN104141159A (en) * | 2014-08-22 | 2014-11-12 | 西北大学 | Method for controlling conduction type of cuprous oxide semiconductor based on concentration of surface active agent in electroplating liquid |
| CN104569096A (en) * | 2015-02-05 | 2015-04-29 | 盐城工学院 | Construction method and detection method of cuprous oxide membrane-based enzyme free-oxygen sensitive glucose photo electrochemical sensor |
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