CN102463351B - Methods for preparing silver nano-particles and conductive nano-film of silver nano-particles - Google Patents
Methods for preparing silver nano-particles and conductive nano-film of silver nano-particles Download PDFInfo
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- CN102463351B CN102463351B CN201010532873.9A CN201010532873A CN102463351B CN 102463351 B CN102463351 B CN 102463351B CN 201010532873 A CN201010532873 A CN 201010532873A CN 102463351 B CN102463351 B CN 102463351B
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- 238000006243 chemical reaction Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 18
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- 235000011164 potassium chloride Nutrition 0.000 claims description 18
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- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 5
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims description 2
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical group [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 229940096017 silver fluoride Drugs 0.000 claims description 2
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 2
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Abstract
The invention discloses methods for preparing silver nano-particles and a conductive film of the silver nano-particles. The method for preparing the silver nano-particles comprises the following steps of: 1) dripping an aqueous solution of sodium salt or potassium salt of ethylenediaminetetracetic acid into an aqueous solution of soluble silver salt until the solution is changed from turbidity to clarity, and stopping dripping to obtain a silver salt solution of an ethylenediaminetetracetic acid chelate ; and 2) dripping an aqueous solution of a reducing agent into the silver salt solution of the ethylenediaminetetracetic acid chelate under stirring condition, continuing reacting after the dripping is finished until the color of the solution is not changed, and thus obtaining the silver nano-particles. The method for preparing the conductive film comprises the following steps of: dispersing the silver nano-particles prepared by the method into water, coating a dispersion liquid on a substrate, and drying to obtain a silver nano-film; and soaking the silver nano-film in a strong electrolyte solution and treating for at least 3 seconds, taking out, and drying to obtain a film consisting of clinkery silver nano-particles. The silver nano-film has excellent electrical conductivity.
Description
Technical field
The present invention relates to a kind of method of preparing silver nano-grain and electrical-conductive nanometer film thereof.
Background technology
Silver nano-grain is a kind of broad-spectrum metal nano material.Especially its nano thin-film all has important application in fields such as flexible circuit, flexible electrode, SERS, reflectance coating, thin film transistor (TFT), Organic Light Emitting Diodes.A main method preparing at present silver nano-grain is wet chemistry method, its basic ideas are to obtain silver nano-grain with reducing agent reduction silver ion in the aqueous solution that contains little molecule or large molecule organic stabilizer, utilize organic stabilizer to be adsorbed in silver nano-grain surface and suppress it and reunite and growth, thereby obtaining silver nano-grain.The organic molecule that the nano thin-film that silver nano-grain prepared by said method forms a floor height insulation because of silver nano-grain surface coverage causes film resistor very high.Obtain the silver nanoparticle film of the high conductivity that is applicable to electronics application, the organic molecule on silver nano-grain surface must be removed.Conventional method is high temperature sintering, at the temperature of hundreds of degrees Celsius, organic molecule is decomposed, and because the fusing point of silver nano-grain is more much lower than body silver, is about 200 ℃ of left and right, thus when high temperature sintering nano-Ag particles also by clinkering.The silver nanoparticle film conductivity that utilizes sintering to obtain is very high, but the high temperature limit that sintering is required the application on Polymers substrate of this kind of method, because the normally polymer of poor heat resistance of flexible circuit and electrode Polymers substrate used, as polyphenyl dioctyl phthalate glycol ester.Except heat treatment, researcher has also proposed the methods such as laser ablation, microwave treatment, plasma treatment, high voltage sintering.Above method high temperature used and special installation have limited its range of application, are unfavorable for that the popularization of these methods is with practical.The people such as Wakuda utilize the organic solvents such as ethanol to wash away the lauryl amine that is adsorbed on silver nano-grain surface, caused silver nano-grain clinkering at normal temperatures, but the film resistor obtaining are very high.The people such as Magdassi utilize PDDA to process the silver nano-grain take polyacrylic acid as stabilizing agent, utilize the effect between poly-positive electrolyte and poly-cloudy electrolyte to cause silver nano-grain clinkering at normal temperatures, obtained the silver nanoparticle film of high conduction.The method of above two kinds of normal temperature clinkering silver nano-grains has been used organic solvent, organic stabilizer and special polymer, has improved cost and is unfavorable for environmental protection.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, proposed a kind of method of preparing silver nano-grain.In preparation process, without adding organic stabilizer, the silver nano-grain obtaining gets final product clinkering by conventional electrolyte solution processing, obtains the silver nanoparticle film of high conduction.
The method of preparing silver nano-grain provided by the present invention, comprises the steps:
1) aqueous solution of disodium edta or sylvite is splashed in silver soluble saline solution, until solution becomes clarification from muddiness, stop dripping, obtain the silver salt solution of ethylenediamine tetra-acetic acid chelating; The pH value of the aqueous solution of described disodium edta or sylvite is 6-8;
2) under stirring, the reducing agent aqueous solution is splashed in the silver salt solution of described ethylenediamine tetra-acetic acid chelating, dropwise rear continuation reaction, until solution colour no longer changes, obtain silver nano-grain.
Wherein, step 1) described in soluble silver salt can be selected from following at least one: silver nitrate, silver acetate, silver fluoride and silver perchlorate; In described silver soluble saline solution, the mass concentration of soluble silver salt can be 0.001～10%, is preferably 0.01～1%; In the aqueous solution of described disodium edta or sylvite, the concentration of disodium edta or sylvite can be 0.5～1.5M.
Step 1) described in the aqueous solution of disodium edta or sylvite can prepare according to following two kinds of methods:
1) NaOH or KOH solution are joined in ethylenediamine tetra-acetic acid, limit edged stirs, until ethylenediamine tetra-acetic acid dissolves completely, then adds water and is settled to desired concn, obtains the edetate aqueous solution that pH value is 6-8; The concentration of described NaOH or KOH solution is 5～15M;
2) by soluble in water to disodium edta or sylvite, then its pH value is adjusted to pH=6～8, obtains the aqueous solution of described disodium edta or sylvite; Described disodium edta is specially disodium EDTA or tetrasodium salt of EDTA; Described ethylene diamine tetraacetic acid sylvite is specially EDTA Dipotassium salt or ethylenediamine tetra-acetic acid four sylvite.
Step 2) described in reducing agent can be catechol and/or hydroquinones; Consumption and the step 1 of described reducing agent) described in silver soluble saline solution the mol ratio of soluble silver salt can be 0.1: 1～10: 1, preferably 1: 1.
Step 2) described in reaction reaction temperature be 10-95 ℃; Step 2) described in rate of addition that the reducing agent aqueous solution is splashed in the silver salt solution of described ethylenediamine tetra-acetic acid chelating be 0.1-0.5mL/min, the rotating speed of described stirring is 500-1500rpm.
The present invention also provides a kind of method (being the method for silver nano-grain normal temperature clinkering) of preparing silver nanoparticle conductive film.
The present invention also provides a kind of method of preparing silver nanoparticle conductive film, comprises the steps:
A) prepare silver nano-grain according to method provided by the invention;
B) silver nano-grain of step a) being prepared is scattered in water, obtains silver nano-grain aqueous dispersions; Again described dispersion liquid is coated in substrate, dry, obtain silver nanoparticle film;
C) described silver nanoparticle film is dipped in strong electrolytic solution and processes at least 3 seconds, take out, be dried, obtained the conductive film being formed by the silver nano-grain of clinkering.
Wherein, step b) described in substrate without specific (special) requirements, can be any substrate, comprise polymer, glass, pottery, metal etc.Step c) described in strong electrolyte refer in the aqueous solution can complete full-ionized electrolyte; As various solubility salts, acid etc., its concentration is greater than 10
-4m.
The present invention compared with prior art tool has the following advantages:
1, gained silver nano-grain gets final product clinkering through general strong electrolytic solution processing, without need heat treatment just can make silver nano-grain clinkering as conventional method, energy-conservation quick again.
2, the method for preparing conductive silver nano thin-film provided by the invention can be carried out at normal temperatures, is particularly useful for preparing conducting film in the bad polymeric substrates of heat resistance.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph without the silver nano-grain film of electrolyte solution processing in embodiment 3.
Fig. 2 is the stereoscan photograph of the silver nano-grain film of process electrolyte solution processing in embodiment 3.
Fig. 3 is the photo of the conductive silver nano thin-film prepared in PET substrate in embodiment 3.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels." wt% " in following embodiment refers to " quality percentage composition ".
Embodiment 1, prepare silver nano-grain and silver nanoparticle film
By the edetate solution of 1M (pH=7.0, EDTA is dissolved in 10M NaOH solution, then add water be settled to 1M) dropwise join the AgNO of 70g 0.1wt% (0.0004mol)
3in the aqueous solution, until solution becomes clarification from muddiness, consume altogether edetate solution 0.61mL.0.0454g (0.0004mol) catechol is dissolved in and in 20g water, obtains catechol solution.Catechol solution is dropwise added to the AgNO of the EDTA chelating preparing
3in the middle of solution, impose stirring, speed is 600rpm simultaneously, and reaction temperature is 25 ℃.Within 1 hour, dropwise, continue reaction and within 1 hour, stop reaction, solution becomes grey black.Products therefrom centrifugation, with water washing, three times repeatedly.Gained silver nano-grain is scattered in 30mL water again, is coated in substrate of glass, 60 ℃ are dried to obtain silver nanoparticle film, and surveying its sheet resistance is 35k Ω/mouth.Gained silver nanoparticle film is soaked in to the CaCl of 0.1M
210s in the aqueous solution, takes out with water and rinses, and nitrogen dries up, and obtains the good silver nanoparticle film of electric conductivity, and surveying its sheet resistance is 1.02 Ω/.
Embodiment 2, prepare silver nano-grain and silver nanoparticle film
By the edetate solution of 1M (pH=7.0, EDTA is dissolved in 10M NaOH solution, then add water be settled to 1M) dropwise join the AgNO of 70g 0.2wt% (0.0008mol)
3in the aqueous solution, until solution becomes clarification from muddiness, consume altogether edetate solution 1.34mL.0.0908g (0.0008mol) catechol is dissolved in and in 20g water, obtains catechol solution.By the slow catechol solution AgNO that splashes into the EDTA chelating preparing
3in the middle of solution, impose stirring, speed is 800rpm simultaneously, and reaction temperature is 40 ℃.Within 1 hour, dropwise, continue reaction and within 1 hour, stop reaction, solution becomes grey black.Products therefrom centrifugation, with water washing, three times repeatedly.Gained silver nano-grain is scattered in 30mL water again, is coated in ceramic bases, 60 ℃ dry obtains silver nanoparticle film, and surveying its sheet resistance is 15.47k Ω/mouth.Gained silver nanoparticle film is soaked in to the MgCl of 0.1M
215s in the aqueous solution, takes out and rinses with water.Nitrogen dries up, and obtains the good silver nanoparticle film of electric conductivity, and surveying its sheet resistance is 0.57 Ω/.
Embodiment 3, prepare silver nano-grain and silver nanoparticle film
The edetate solution of 1.5M (tetrasodium ethylenediamine tetraacetate is soluble in water, then regulates its pH value to 7.0) is dropwise joined to the AgNO of 70g 0.4wt% (0.0016mol)
3in the aqueous solution, until solution becomes clarification from muddiness, consume altogether edetate solution 1.83mL.0.1816g (0.0016mol) catechol is dissolved in and in 40g water, obtains catechol solution.Catechol solution is dropwise added to the AgNO of the EDTA chelating preparing
3in the middle of solution, impose stirring, speed is 900rpm simultaneously, and reaction temperature is 80 ℃.Within 1.5 hours, dropwise, continue reaction and within one hour, stop reaction, solution becomes grey black.Products therefrom centrifugation, with water washing, three times repeatedly.Gained silver nano-grain is scattered in 30mL water again, is coated in PET (polyester) substrate, 65 ℃ are dried to obtain silver nanoparticle film, and its electromicroscopic photograph is shown in Fig. 1, and surveying its sheet resistance is 9.42k Ω/.Gained silver nanoparticle film is soaked in to 5s in the NaCl aqueous solution of 0.2M, takes out with water and rinse, nitrogen dries up, and obtains the good silver nanoparticle film of electric conductivity, and surveying its sheet resistance is 0.47k Ω/.The electromicroscopic photograph of the silver nanoparticle film after electrolyte treatment is shown in Fig. 2, and as shown in Figure 2, silver nano-grain is clinkering.
Embodiment 4, prepare silver nano-grain and silver nanoparticle film
The edetate solution of 0.5M (pH=6.5, tetrasodium ethylenediamine tetraacetate is soluble in water, then regulates its pH value to 6.5) is dropwise joined to the CH of 70g 0.05wt% (0.0002mol)
3in the COOAg aqueous solution, until solution becomes clarification from muddiness.Consume altogether edetate solution 0.70mL.0.0277g (0.0002mol) hydroquinones is dissolved in and in 30g water, obtains catechol solution.By the slow hydroquinones solution CH that splashes into the EDTA chelating preparing
3in the middle of COOAg solution, impose stirring, speed is 1000rpm simultaneously, and reaction temperature is 25 ℃.Within one hour, dropwise, continue reaction and within one hour, stop reaction, solution becomes grey black.Products therefrom centrifugation, with water washing, three times repeatedly.Gained silver nano-grain is scattered in 30mL water again, be coated at the bottom of silicon wafer-based on, 60 ℃ of dry silver nanoparticle films that to obtain, surveying its sheet resistance is 50k Ω/.Gained silver nanoparticle film is soaked in to 10
-3the CaCl of M
220s in the middle of the aqueous solution, takes out with water and rinses, and nitrogen dries up, and obtains the good silver nanoparticle film of electric conductivity, and surveying its sheet resistance is 15.45 Ω/mouths.
Embodiment 5, prepare silver nano-grain and silver nanoparticle film
By the edetate solution of 1M (pH=7.5, EDTA is dissolved in 10M KOH solution, then add water be settled to 1M) dropwise join the AgClO of 60g 0.8wt% (0.0023mol)
4in the aqueous solution, until solution becomes clarification from muddiness.Consume altogether edetate solution 5.05mL.0.3632g (0.0032mol) catechol is dissolved in and in 20g water, obtains catechol solution.By the slow catechol solution AgClO that splashes into the EDTA chelating preparing
4in the middle of solution, impose stirring, speed is 800rpm simultaneously, and reaction temperature is 60 ℃.Within one hour, dropwise, continue reaction and within 1 hour, stop reaction, solution becomes grey black.Products therefrom centrifugation, with water washing, three times repeatedly.Gained silver nano-grain is scattered in 30mL water again, is coated in PTFE (polytetrafluoroethylene (PTFE)) substrate, 60 ℃ are dried to obtain silver nanoparticle film, and surveying its sheet resistance is 6k Ω/.Gained silver nanoparticle film is soaked in to 40s in the HCl aqueous solution of 0.1M, takes out with water and rinse, nitrogen dries up, and obtains the good silver nanoparticle film of electric conductivity, and surveying its sheet resistance is 0.45 Ω/.
Embodiment 6, prepare silver nano-grain and silver nanoparticle film
By the edetate solution of 1M (pH=7.0, EDTA is dissolved in 10M NaOH solution, then add water be settled to 1M) dropwise join the AgNO of 70g 0.1wt% (0.0004mol)
3in the aqueous solution, until solution becomes clarification from muddiness, consume altogether edetate solution.0.0454g (0.0004mol) catechol is dissolved in and in 20g water, obtains catechol solution.Hydroquinones solution is delayed to splash into the AgNO of the EDTA chelating preparing
3in the middle of solution, impose stirring, speed is 600rpm simultaneously, and reaction temperature is 20 ℃.Within 1 hour, dropwise, continue reaction and within 1 hour, stop reaction, solution becomes grey black.Products therefrom centrifugation, with water washing, three times repeatedly.Gained silver nano-grain is scattered in 30mL water again, is coated in PP (polypropylene) substrate, 60 ℃ are dried to obtain silver nanoparticle film, and surveying its sheet resistance is 37k Ω/.Gained silver nanoparticle film is soaked in to the MgSO of 0.1M
420s in the middle of the aqueous solution, takes out and rinses with water.Nitrogen dries up, and obtains the good silver nanoparticle film of electric conductivity, and surveying its sheet resistance is 0.95 Ω/.
Claims (6)
1. a method of preparing silver nano-grain, comprises the steps:
1) aqueous solution of disodium edta or sylvite is splashed in silver soluble saline solution, until solution becomes clarification from muddiness, stop dripping, obtain the silver salt solution of ethylenediamine tetra-acetic acid chelating; The pH value of the aqueous solution of described disodium edta or sylvite is 6-8;
2) under stirring, the reducing agent aqueous solution is splashed in the silver salt solution of described ethylenediamine tetra-acetic acid chelating, dropwise rear continuation reaction, until solution colour no longer changes, obtain silver nano-grain; Described reducing agent is catechol and/or hydroquinones;
Step 1) described in soluble silver salt be selected from following at least one: silver nitrate, silver acetate, silver fluoride and silver perchlorate; In described silver soluble saline solution, the mass concentration of soluble silver salt is 0.01～1%;
Step 1) described in the aqueous solution of disodium edta or sylvite the concentration of disodium edta or sylvite be 0.5～1.5M;
Step 2) described in consumption and the step 1 of reducing agent) described in silver soluble saline solution the mol ratio of soluble silver salt be 1: 1; The reaction temperature of described reaction is 10-95 ℃.
2. method according to claim 1, is characterized in that: step 1) described in the compound method of the aqueous solution of disodium edta or sylvite be following a) or b):
A) NaOH or KOH solution are joined in ethylenediamine tetra-acetic acid, limit edged stirs, until ethylenediamine tetra-acetic acid dissolves completely, then adds water and is settled to desired concn, obtains the edetate aqueous solution that pH value is 6-8; The concentration of described NaOH or KOH solution is 5～15M;
B) by soluble in water to disodium edta or sylvite, then its pH value is adjusted to pH=6～8, obtains the aqueous solution of described disodium edta or sylvite; Described disodium edta is disodium EDTA or tetrasodium salt of EDTA; Described ethylene diamine tetraacetic acid sylvite is EDTA Dipotassium salt or ethylenediamine tetra-acetic acid four sylvite.
3. according to the method described in 1 or 2 of claims, it is characterized in that: step 2) described in rate of addition that the reducing agent aqueous solution is splashed in the silver salt solution of described ethylenediamine tetra-acetic acid chelating be 0.1-0.5mL/min, the rotating speed of described stirring is 500-1500rpm.
4. a method of preparing conductive silver nano thin-film, comprises the steps:
A) prepare silver nano-grain according to arbitrary described method in claim 1-3;
B) silver nano-grain of step a) being prepared is scattered in water, obtains silver nano-grain aqueous dispersions; Again described dispersion liquid is coated in substrate, dry, obtain silver nanoparticle film;
C) described silver nanoparticle film is dipped in strong electrolytic solution and processes at least 3 seconds, take out, be dried, obtain conductive silver nano thin-film.
5. method according to claim 4, is characterized in that: step b) described in substrate comprise polymer, glass, pottery or metal.
6. according to the method described in claim 4 or 5, it is characterized in that: step c) described in strong electrolyte refer in the aqueous solution can complete full-ionized electrolyte; In described strong electrolytic solution, the concentration of strong electrolyte is greater than 10
-4m.
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| CN102990083B (en) * | 2012-12-25 | 2015-03-25 | 中国科学院合肥物质科学研究院 | Preparation method of silver nanometer particle film |
| CN103600082B (en) * | 2013-11-26 | 2015-11-18 | 清华大学 | Silver nano-particle layer and preparation method thereof and application |
| CN109487250B (en) * | 2017-09-13 | 2020-02-18 | 北京化工大学 | Method for preparing surface silver-plated composite material |
| CN109128211B (en) * | 2018-08-16 | 2021-10-26 | 山东大学 | Method for preparing micro-nano silver particles in aqueous solution system |
| CN111633217B (en) * | 2020-06-08 | 2022-09-02 | 内蒙古工业大学 | Metal composite nano material and preparation method and application thereof |
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