CN105776321A - An indium tin oxide nanometer crystal composite solution, and a preparing method and applications thereof - Google Patents
An indium tin oxide nanometer crystal composite solution, and a preparing method and applications thereof Download PDFInfo
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- CN105776321A CN105776321A CN201410809742.9A CN201410809742A CN105776321A CN 105776321 A CN105776321 A CN 105776321A CN 201410809742 A CN201410809742 A CN 201410809742A CN 105776321 A CN105776321 A CN 105776321A
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Abstract
The invention discloses an indium tin oxide (ITO) nanometer crystal composite solution, and a preparing method and applications thereof. The preparing method includes a step of preparing an ITO nanometer crystal dispersion liquid, namely a step of directly dispersing ITO crystals into a polar organic solvent to form the ITO nanometer crystal dispersion liquid; a step of preparing an ITO precursor liquid, namely a step of mixing an In precursor liquid and a Sn precursor liquid, and fully stirring at room temperature to form the ITO precursor liquid; and a step of fully mixing the ITO nanometer crystal dispersion liquid and the ITO precursor liquid, shearing, and dispersing to form the indium tin oxide nanometer crystal composite solution. The ITO nanometer crystal composite solution which is stable is prepared through synthesizing the ITO nanometer crystal dispersion liquid and an ITO precursor and mixing the ITO nanometer crystal dispersion liquid and the ITO precursor simply. ITO films which are high in conductivity at low temperatures and high in stability in the atmospheric environment can be prepared through subjecting the composite solution to simple coating, film formation and annealing, and can meet requirements on electrical properties. The preparing method is simple and easy to operate.
Description
Technical field
The present invention be more particularly directed to a kind of indium tin oxide (ITO) nanocomposite solution, its preparation method and application thereof, for instance in the application prepared in laminated film, belong to field of nanometer material technology.
Background technology
The main component of tin indium oxide (ITO) is the composite oxides that stannum oxide is solid-solubilized in Indium sesquioxide..ITO is widely used in the fields such as liquid crystal display, electroluminescent, solaode because it has the optically and electrically performance of excellence.The method preparing ito thin film has a lot, including magnetron sputtering method, vacuum vapor deposition and solwution method etc..Solwution method refers to the method adopting solvent to dissolve reaction material when preparing ito thin film, and sol-gal process and nanoparticle membrane formation process are two kinds of methods that it is common.Now it has been reported that use the ITO precursor liquid of spontaneous combustion formula, prepare ito thin film by sol-gal process, the Low Temperature Heat Treatment below 300 DEG C, just can obtain the ito thin film of conduction, and the structure comparison of film is fine and close.Nanoparticle membrane formation process is first to obtain the dispersion liquid of ITO nano-powder, then by the method film forming of various coatings or printing.The ito thin film that both approaches is obtained, all has certain conductance at low temperatures, but conductance ratio is relatively low, it is impossible to meet actual demand.And thin film puts in atmosphere after a period of time, conductance is unstable, presents obvious downward trend.
Summary of the invention
Present invention is primarily targeted at a kind of indium tin oxide (ITO) nanocomposite solution with low temperature high conductivity of offer, to overcome deficiency of the prior art.
The method that another object of the present invention is to provide one to prepare described indium tin oxide (ITO) nanocomposite solution, it has the features such as technique is simple.
A further object of the present invention is in that to provide the purposes of aforementioned indium tin oxide (ITO) nanocomposite solution, the such as purposes in preparing ITO laminated film, this ITO laminated film has high conductance and atmospheric environment stability inferior high at low temperatures, and its technique is simply easily operated simultaneously.
For realizing aforementioned invention purpose, technical scheme includes:
A kind of preparation method of indium tin oxide nanocomposite solution, including:
I, the nanocrystalline dispersion liquid of ITO is provided, including: it is directly dispersing in polar organic solvent forms the nanocrystalline dispersion liquid of ITO by nanocrystalline for ITO；
II, ITO precursor liquid is provided, including: the precursor liquid of In is mixed with the precursor liquid of Sn, and is at room temperature sufficiently stirred for, form ITO precursor liquid；
III, nanocrystalline for ITO dispersion liquid is mixed homogeneously with ITO precursor liquid, shear dispersion, form described indium tin oxide nanocomposite solution.
Further, step I includes:
1) containing indium compound, stannide mixed aqueous solution in add alkali, regulate pH value be 8.0～9.0, make described indium compound, stannide be converted into indium hydroxide, stannum precipitation of hydroxide；
2) repeatedly clean described indium hydroxide, stannum precipitation of hydroxide, then solid-liquid separation with deionized water, alcoholic solvent respectively, obtain the presoma of indium hydroxide, stannum hydroxide；
3) described presoma and ethanol being mixed to form presoma-alcoholic solution that concentration is 0.02～0.1g/mL, add polyvinylpyrrolidone, shear and be dispersed into suspension, wherein polyvinylpyrrolidone is 2～10 with the mass ratio of described presoma；
4) described suspension is inserted heat treatment in autoclave, obtain blue precipitate, obtain described ITO after repeatedly cleaning described blue precipitate with acetone, alcoholic solvent respectively nanocrystalline；
5) in nanocrystalline for described ITO dispersion polar organic solvent, the nanocrystalline dispersion liquid of described ITO will be obtained after shearing dispersion and/or supersound process.
As comparatively one of preferred embodiment, step 1) in, described containing indium compound, stannide mixed aqueous solution in the amount of substance of tin element account for indium, the total amount of substance sum of tin element 5～10%.
Further, described indium compound is selected from but any one or any one the hydrate that is not limited in indium chloride, indium nitrate.
Further, described stannide is selected from but is not limited to the hydrate of butter of tin or butter of tin.
Further, described alkali is selected from but is not limited to sodium hydroxide, potassium hydroxide or ammonia.
Further, described polyvinylpyrrolidone preferably is selected from but any one or the two or more combination that are not limited in K-15, K-30, K-60, K-90.
As comparatively one of preferred embodiment, step 2) including: after indium compound, stannide are converted into indium hydroxide, stannum precipitation of hydroxide, it is carried out within 30min.
As comparatively one of preferred embodiment, step 4) in, in autoclave, heat treated temperature is 220～260 DEG C, and the time is 12～28 hours.
Further, step II includes:
1. the nitrate of indium is dissolved under room temperature in polar organic solvent and forms indium nitrate solution, described indium nitrate solution adds acetylacetone,2,4-pentanedione and strong aqua ammonia, reaction more than 12h is stirred at room temperature, it is thus achieved that the precursor liquid of the In of spontaneous combustion formula；
2. stannous chloride and ammonium nitrate that mol ratio is 1:1 are dissolved in organic solvent, are stirred at room temperature to abundant dissolving, add acetylacetone,2,4-pentanedione and strong aqua ammonia, reaction more than 12h is stirred at room temperature, it is thus achieved that the precursor liquid of the Sn of spontaneous combustion formula；
3. the precursor liquid of In is mixed according to the thing mass ratio of 19:1-9:1 with the precursor liquid of Sn, and at room temperature more than stirring reaction 1h, form described ITO precursor liquid.
As comparatively one of preferred embodiment, step 1. in, indium: acetylacetone,2,4-pentanedione: the molal volume of strong aqua ammonia is than for 1mol:200ml:114ml.
As comparatively one of preferred embodiment, step 2. in, stannum: acetylacetone,2,4-pentanedione: the molal volume of strong aqua ammonia is than for 1mol:200ml:114ml.
As comparatively one of preferred embodiment, step 3. in, the thing mass ratio of the precursor liquid of In and the precursor liquid of Sn is 19:1-9:1.
Further, described polar organic solvent preferably is selected from but is not limited to ethanol, ethylene glycol monomethyl ether or ethylene glycol.
As comparatively one of preferred embodiment, in the solution of indium tin oxide nanocomposite described in step III, the amount of substance of the nanocrystalline contained In element of ITO accounts in described indium tin oxide nanocomposite solution more than the 50% of the total material amount of In element.
As comparatively one of preferred embodiment, the concentration of the nanocrystalline dispersion liquid of described ITO is 0.1-1moL/L.
As comparatively one of preferred embodiment, the concentration of described ITO precursor liquid is 0.1-1moL/L.
The indium tin oxide nanocomposite solution prepared by any one method aforementioned.
A kind of preparation method of ITO laminated film, including: by described indium tin oxide nanocomposite solution film forming in substrate, afterwards at 150 DEG C-300 DEG C, particularly in air atmosphere annealing more than 1h when lower than 300 DEG C, it is thus achieved that described ITO laminated film.
As one of viable solution, described preparation method may include that and adds polar organic solvent dilution to described indium tin oxide nanocomposite solution, repaste and be distributed in substrate film forming, wherein the consumption of polar solvent is the 0-20% of described indium tin oxide nanocomposite overall solution volume, and described polar organic solvent includes diglycol, ethylene glycol or triethylene glycol.
The ITO laminated film prepared by any one method aforementioned.
A kind of opto-electronic device, comprises described ITO laminated film.
Compared with prior art, the positive effect of the present invention includes: by synthesizing, the ITO with superior dispersibility is nanocrystalline to be mixed with ITO precursor liquid, obtains the ITO nanocomposite solution of stable existence；nullAnd，By being simply coated with or print film forming and the process annealing not higher than 300 DEG C，Obtain a kind of novel I TO laminated film，This laminated film demonstrates great conductance advantage compared to the nanocrystalline dispersion liquid of independent ITO or the become thin film of ITO precursor liquid，Also show good conductance stability and visible region transmitance (such as simultaneously，Mean transmissivity (550nm place) in visible ray 300 800nm is more than 90%)，Such as，The electrical conductivity (3.2S/cm) of the become thin film of composite nanocrystalline solution of 200 DEG C of air anneal is 6 times of the become film conductivity of the nanocrystalline dispersion liquid of independent ITO (0.52S/cm)，It it is 213 times of the become film conductivity of ITO precursor liquid (0.015S/cm)，And compound ito thin film places one week in atmosphere，Sheet resistance changes hardly.
Detailed description of the invention
The preparation method of a kind of indium tin oxide (ITO) the nanocomposite solution provided among a typical embodiments of the present invention comprises the steps:
The preparation of ITO nanocomposite solution includes the nanocrystalline dispersion liquid of ITO (B) and ITO precursor liquid (C) respective preparation method and B and the C mixing between them.
Step one: containing indium compound, butter of tin mixed aqueous solution in add alkali, regulate pH value be 8.0～9.0, make described indium compound, butter of tin be converted into indium hydroxide, stannum precipitation of hydroxide；
Step 2: repeatedly clean described indium hydroxide, stannum precipitation of hydroxide, then solid-liquid separation with deionized water, alcoholic solvent respectively, obtain the presoma of indium hydroxide, stannum hydroxide；
Step 3: mixed with ethanol by described presoma, adds polyvinylpyrrolidone (PVP), shears and is dispersed into suspension；Described presoma is 0.02～0.1g/mL in the concentration of ethanol, and the mass ratio adding PVP mass and presoma is 2～10；
Step 4: described suspension is inserted heat treatment in autoclave, obtains blue precipitate；The nanocrystalline A of tin indium oxide is obtained after repeatedly cleaning described blue precipitate with acetone, alcoholic solvent respectively；
Step 5: nanocrystalline A is distributed in ethanol, ethylene glycol monomethyl ether, ethylene glycol or its mixed solvent, obtains the nanocrystalline dispersion liquid B of ITO after shearing dispersion and supersound process.
Step 6: by the nitrate of indium, it is dissolved in ethylene glycol monomethyl ether, ethanol, ethylene glycol or its mixed solvent through being stirred at room temperature, it is configured to indium nitrate solution, above-mentioned solution adds the strong aqua ammonia of acetylacetone,2,4-pentanedione and 14.5moL/L, indium: acetylacetone,2,4-pentanedione: the ratio of strong aqua ammonia is 1mol:200ml:114ml, 12h is stirred at room temperature, namely obtains the precursor liquid of the In of spontaneous combustion formula；
Step 7: weigh the stannous chloride (SnCl that mol ratio is 1:12) and ammonium nitrate (NH4NO3), it is dissolved in ethylene glycol monomethyl ether, ethanol, ethylene glycol or its mixed solvent, it is stirred at room temperature to abundant dissolving, add the strong aqua ammonia of acetylacetone,2,4-pentanedione and 14.5moL/L, wherein stannum: acetylacetone,2,4-pentanedione: the ratio of strong aqua ammonia is 1mol:200ml:114ml, 12h is stirred at room temperature, namely obtains the precursor liquid of the Sn of spontaneous combustion formula；
Step 8: the precursor liquid of In and Sn is mixed than 19:1-9:1 with amount of substance, is stirred at room temperature more than 1 hour, obtains the precursor liquid C of ITO.
Step 9: by B and C with certain volume ratio mixing, stir, shear dispersion, namely obtain ITO nanocomposite solution D.
Meanwhile, the preparation method additionally providing a kind of ITO laminated film among a typical embodiments of the present invention, comprising:
Step S1: add in above-mentioned composite solution D and account for the cumulative volume ethylene glycol than 0-20% or triethylene glycol, stir and shear dispersion, obtaining the solution E for preparing thin film.
Step S2: by solution E spin-coating film in a substrate；
Step S3: the ito thin film obtained, air atmosphere annealing at 150 DEG C-300 DEG C, annealing time is not less than 1h, namely obtains ITO laminated film.
First the present invention obtains a kind of novel ITO nanocomposite solution, this composite solution can obtain ITO laminated film by being coated with or printing, the ITO laminated film of this new structure, Low Temperature Heat Treatment in atmosphere, it is obtained with the conductance that comparison is high, and its electrical conductivity varies less in atmospheric atmosphere, and also there is the transmitance that comparison is high visible region.
Further, technical solution of the present invention is elaborated by the preparation process below in conjunction with table 1 and the preferred nanocrystalline dispersion liquid of ITO and ITO precursor liquid.
The preparation process of the nanocrystalline dispersion liquid of ITO and ITO precursor liquid is as follows:
Step one: containing indium compound, the mixed aqueous solution of butter of tin adds alkali, indium compound includes indium chloride, one or more in indium nitrate and their hydrate, butter of tin includes itself and one or more in its hydrate, indium compound, in the mixed aqueous solution of butter of tin, the amount of substance of tin element accounts for indium, the 5～10% of the total amount of substance sum of tin element, alkali can be sodium hydrate aqueous solution, potassium hydroxide aqueous solution or ammonia, regulating pH value is 8.0～9.0, make described indium compound, butter of tin is converted into indium hydroxide, stannum precipitation of hydroxide；
Step 2: after indium compound and butter of tin are converted into indium hydroxide, stannum precipitation of hydroxide, it is sufficiently stirred for, it is carried out within 30min, described indium hydroxide, stannum precipitation of hydroxide is repeatedly cleaned respectively with deionized water, alcoholic solvent, then solid-liquid separation, obtains the presoma of indium hydroxide, stannum hydroxide；
Step 3: mixed with ethanol by described presoma, adds polyvinylpyrrolidone (PVP), and polyvinylpyrrolidone is selected from any one or two or more combination in K-15, K-30, K-60, K-90, shears and is dispersed into suspension；Described presoma is 0.02～0.1g/mL in the concentration of ethanol, and the mass ratio adding PVP mass and presoma is 2～10；
Step 4: described suspension is inserted heat treatment in autoclave, heat treatment temperature is 220～260 DEG C, and the time is 12～28 hours, obtains blue precipitate；Respectively with blue precipitate described in acetone, alcoholic solvent eccentric cleaning repeatedly, centrifugal rotational speed 8000rpm～15000rpm, centrifugation time 5～10min, centrifugal number of times 3～8 times, obtain the nanocrystalline A of tin indium oxide afterwards；
Step 5: nanocrystalline A is distributed in ethanol or ethylene glycol monomethyl ether solvent, shears dispersion and supersound process, shears dispersion rotating speed 12000rpm～20000rpm, time 30s～60s, ultrasonic power 50～100W, time 5～60min, obtain the nanocrystalline dispersion liquid B of ITO afterwards.
Step 6: weigh the nitrate (In (NO of the indium of 0.001moL3)3), it is dissolved in the ethylene glycol monomethyl ether (analytical pure) of 1mL or ethanol (analytical pure) or ethylene glycol (analytical pure) or its mixed solvent, it is stirred at room temperature to abundant dissolving, add the acetylacetone,2,4-pentanedione (analytical pure) of 0.2mL and the strong aqua ammonia of the 14.5moL/L of 114 μ L, 12h is stirred at room temperature, namely obtains the precursor liquid of the In of the 1moL/L of spontaneous combustion formula；
Step 7: weigh the stannous chloride (SnCl of 0.001moL2) and the ammonium nitrate (NH of 0.001moL4NO3), it is dissolved in the ethylene glycol monomethyl ether (analytical pure) of 1mL or ethanol (analytical pure) or ethylene glycol (analytical pure) or its mixed solvent, it is stirred at room temperature to abundant dissolving, add the acetylacetone,2,4-pentanedione (analytical pure) of 0.2mL and the strong aqua ammonia of the 14.5moL/L of 57 μ L, 12h is stirred at room temperature, namely obtains the precursor liquid of the Sn of the 1moL/L of spontaneous combustion formula；
Step 8: the precursor liquid of In and Sn is mixed than 19:1-9:1 with amount of substance, is stirred at room temperature more than 1 hour, obtains the precursor liquid C of ITO.
Step 9: by B and C with certain volume ratio mixing, stir, shear dispersion, namely obtain ITO nanocomposite solution D.
The preparation process of the nanocrystalline dispersion liquid of preferred ITO and ITO precursor liquid is as follows:
Step one: be 12:1 by the ratio of indium, the amount of substance of tin element, weighs 2gInCl3·4H2O and 0.194gSnCl4·5H2O, is dissolved in the deionized water of 20mL, after stirring, adds strong aqua ammonia in mixed aqueous solution, and regulating pH value is 9, makes indium ion, tin ion be fully converted to indium hydroxide (In (OH)3), stannic hydroxide (Sn (OH)4) precipitation.
Step 2: after the indium hydroxide of step one, stannum precipitation of hydroxide centrifugation, repeatedly clean 4 times with deionized water and remove foreign ion, remove the residual moisture in precipitation with dehydrated alcohol (analytical pure) cyclic washing 3 times again, it is thus achieved that indium hydroxide, stannum hydroxide presoma.
Step 3: add 60mL dehydrated alcohol, stirring in described presoma, shear and be dispersed into mixed liquor, parallel is divided into 2 parts of mixed solutions, every part of about 30mL.Then in every part of mixed solution, it is separately added into the PVP (K30, MW40000) of 3g, stirring, and shear dispersion, make PVP fully dissolve, obtain mixing suspension.
Step 4: be respectively put in the autoclave of 50mL by suspension, through 250 DEG C of heat treatment 24h, obtains blue precipitate.Obtained blue precipitate through 1 washing with acetone, centrifugal rotational speed 15000rpm, time 10min, after 4 ethanol purge, each centrifugal rotational speed 12000rpm, time 5min, obtain blue colored crystal A.
Step 5: be distributed in alcohol solvent by nanocrystalline A, obtains the nanocrystalline dispersion liquid B of ITO after shearing dispersion and supersound process, the substance withdrawl syndrome of B is transferred to 0.3moL/L.
Step 6: weigh the nitrate (In (NO of the indium of 0.382g3)3·4.5H2O), it is dissolved in the ethylene glycol monomethyl ether (analytical pure) of 2.5mL, is stirred at room temperature to being completely dissolved, add the acetylacetone,2,4-pentanedione of 0.2mL and the strong aqua ammonia of the 14.5moL/L of 114 μ L, 12h is stirred at room temperature, namely obtains the precursor liquid of the In of the 0.4moL/L of spontaneous combustion formula.
Step 7: weigh the stannous chloride (SnCl of 0.226g2·2H2And the ammonium nitrate (NH of 0.08g O)4NO3), it is dissolved in the ethylene glycol monomethyl ether (analytical pure) of 2.5mL, is stirred at room temperature to abundant dissolving, add the acetylacetone,2,4-pentanedione (analytical pure) of 0.2mL and the strong aqua ammonia of the 14.5moL/L of 57 μ L, 12h is stirred at room temperature, namely obtains the precursor liquid of the Sn of the 0.4moL/L of spontaneous combustion formula.
Step 8: the precursor liquid of the precursor liquid of the In of 0.4moL/L and the Sn of 0.4moL/L is mixed with the volume ratio of 92.5:7.5, and add the dilution of a certain amount of ethylene glycol monomethyl ether, obtain the ITO precursor liquid of 0.3moL/L.
According to the preparation technology of aforementioned ITO laminated film, take preferred ITO precursor liquid, the nanocrystalline dispersion liquid of ITO and ITO nanocomposite solution respectively and make ito thin film, and its performance is tested respectively, table 1 data can be obtained.
Table 1:ITO precursor liquid, the nanocrystalline dispersion liquid of ITO and ITO nanocomposite solution spin coating respectively become ito thin film conductance correction data after 200 DEG C, 250 DEG C and 300 DEG C are annealed
Embodiment 1:
The preparation process of ITO composite solution and ITO laminated film is as follows:
Step one: the ITO precursor liquid of the nanocrystalline dispersion liquid of ITO of the 0.3moL/L of above-mentioned preferred preparation and 0.3moL/L is mixed with the ratio of volume ratio 2/1, is sufficiently stirred for shearing, obtain ITO composite solution D1；
Step 2: by ITO composite solution D1, spin-coating film on alkali-free glass, spin coating rotating speed 2000rpm, time 1min, before spin coating, alkali-free glass substrate first passes through the O of 100W1min2Cement Composite Treated by Plasma；
Step 3: after a spin coating is complete, substrate is first dried on hot plate, and the temperature that hot plate is arranged is 200 DEG C, time 20min；
Step 4: the same so plasma spin coating is dried and repeated 4 times, obtains ito thin film, and at 200 DEG C air atmosphere annealing 2h.
Four probe sheet resistance instrument testing film sheet resistances are 12100 Ω/, and step instrument test thickness is 256nm, therefore electrical conductivity is 3.227S/cm.
Contrast experiment: by the ITO precursor liquid of the nanocrystalline dispersion liquid of ITO of the 0.3moL/L of above-mentioned preferred preparation and 0.3moL/L spin-coating film respectively.Specifically comprise the following steps that
Step one: by nanocrystalline for the ITO of 0.3moL/L dispersion liquid spin-coating film on alkali-free glass, spin coating rotating speed 2000rpm, time 1min, by the ITO precursor liquid of 0.3moL/L spin-coating film on alkali-free glass respectively, spin coating rotating speed 1000rpm, time 1min, before spin coating, alkali-free glass substrate first passes through the O of 100W1min2Cement Composite Treated by Plasma；
Step 2: after a spin coating is complete, substrate is first dried on hot plate, and the temperature that hot plate is arranged is 200 DEG C, time 20min；
Step 3: the respectively the same so plasma spin coatings of two ITO solution are dried and repeated 4 times, obtains ito thin film, and at 200 DEG C air atmosphere annealing 2h.
Four probe sheet resistance instrument test the become sheet resistances of ITO precursor liquid are 2.5 × 106Ω/, it is 260nm that ellipsometer tests its thickness, therefore electrical conductivity is 0.015S/cm；Four probe sheet resistance instrument test nanocrystalline the become sheet resistances of ITO are 68400 Ω/, and step instrument test thickness is 280nm, therefore electrical conductivity is 0.521S/cm.
As can be seen here, in the present embodiment, anneal 200 DEG C of air atmosphere, under identical spin coating proceeding, the conductance of the laminated film that ITO composite solution obtains, hence it is evident that be better than independent ITO precursor solution or the become thin film of the nanocrystalline dispersion liquid of ITO, can also significantly find out from table.The novel laminated film that this composite solution spin coating obtains, carrier transport is greatly enhanced, and conductance increases.
Embodiment 2:
The preparation process of ITO composite solution and ITO laminated film is as follows:
Step one: the ITO precursor liquid of the nanocrystalline dispersion liquid of ITO of the 0.3moL/L of above-mentioned preferred preparation and 0.3moL/L is mixed with the ratio of volume ratio 2/1, and is accounted for the cumulative volume ethylene glycol than 20%, be sufficiently stirred for shearing, obtain ITO composite solution D2；
Step 2: by ITO composite solution D2, spin-coating film on alkali-free glass, spin coating rotating speed 2000rpm, time 1min, before spin coating, alkali-free glass substrate first passes through the O of 100W1min2Cement Composite Treated by Plasma；
Step 3: after a spin coating is complete, substrate is first dried on hot plate, and the temperature that hot plate is arranged is 250 DEG C, time 20min；
Step 4: the same so plasma spin coating is dried and repeated 4 times, obtains ito thin film, and at 250 DEG C air atmosphere annealing 2h.
Four probe sheet resistance instrument testing film sheet resistances are 8790 Ω/, and step instrument test thickness is 200nm, therefore electrical conductivity is 5.657S/cm.
Contrast experiment: by the ITO precursor liquid of the nanocrystalline dispersion liquid of ITO of the 0.3moL/L of above-mentioned preferred preparation and 0.3moL/L spin-coating film respectively.Specifically comprise the following steps that
Step one: by nanocrystalline for the ITO of 0.3moL/L dispersion liquid spin-coating film on alkali-free glass, spin coating rotating speed 2000rpm, time 1min, by the ITO precursor liquid of 0.3moL/L spin-coating film on alkali-free glass respectively, spin coating rotating speed 1000rpm, time 1min, before spin coating, alkali-free glass substrate first passes through the O of 100W1min2Cement Composite Treated by Plasma；
Step 2: after a spin coating is complete, substrate is first dried on hot plate, and the temperature that hot plate is arranged is 250 DEG C, time 20min；
Step 3: the respectively the same so plasma spin coatings of two ITO solution are dried and repeated 4 times, obtains ito thin film, and at 250 DEG C air atmosphere annealing 2h.
Four probe sheet resistance instrument test the become sheet resistances of ITO precursor liquid are 1.9 × 104Ω/, it is 290nm that ellipsometer tests its thickness, therefore electrical conductivity is 1.821S/cm；Four probe sheet resistance instrument test nanocrystalline the become sheet resistances of ITO are 18800 Ω/, and step instrument test thickness is 270nm, therefore electrical conductivity is 1.977S/cm.
As can be seen here, in the present embodiment, anneal 250 DEG C of air atmosphere, under identical spin coating proceeding, the conductance of the laminated film that ITO composite solution obtains, compares and is better than independent ITO precursor solution or the become thin film of the nanocrystalline dispersion liquid of ITO, can also significantly find out from table.The novel laminated film that this composite solution spin coating obtains, carrier transport is greatly enhanced, and conductance increases.
Embodiment 3:
The preparation process of ITO composite solution and ITO laminated film is as follows:
Step one: the ITO precursor liquid of the nanocrystalline dispersion liquid of ITO of the 0.3moL/L of above-mentioned preferred preparation and 0.3moL/L is mixed with the ratio of volume ratio 3/1, and is accounted for the cumulative volume ethylene glycol than 20%, be sufficiently stirred for shearing, obtain ITO composite solution D3；
Step 2: by ITO composite solution D3, spin-coating film on alkali-free glass, spin coating rotating speed 2000rpm, time 1min, before spin coating, alkali-free glass substrate first passes through the O of 100W1min2Cement Composite Treated by Plasma；
Step 3: after a spin coating is complete, substrate is first dried on hot plate, and the temperature that hot plate is arranged is 300 DEG C, time 20min；
Step 4: the same so plasma spin coating is dried and repeated 4 times, obtains ito thin film, and at 300 DEG C air atmosphere annealing 2h.
Four probe sheet resistance instrument testing film sheet resistances are 11000 Ω/, and step instrument test thickness is 210nm, therefore electrical conductivity is 3.968S/cm.
Contrast experiment: by the ITO precursor liquid of the nanocrystalline dispersion liquid of ITO of the 0.3moL/L of above-mentioned preferred preparation and 0.3moL/L spin-coating film respectively.Specifically comprise the following steps that
Step one: by nanocrystalline for the ITO of 0.3moL/L dispersion liquid spin-coating film on alkali-free glass, spin coating rotating speed 1000rpm, time 1min, by the ITO precursor liquid of 0.3moL/L spin-coating film on alkali-free glass respectively, spin coating rotating speed 1000rpm, time 1min, before spin coating, alkali-free glass substrate first passes through the O of 100W1min2Cement Composite Treated by Plasma；
Step 2: after a spin coating is complete, substrate is first dried on hot plate, and the temperature that hot plate is arranged is 300 DEG C, time 20min；
Step 3: the respectively the same so plasma spin coatings of two ITO solution are dried and repeated 4 times, obtains ito thin film, and at 300 DEG C air atmosphere annealing 2h.
Four probe sheet resistance instrument test the become sheet resistances of ITO precursor liquid are 5900 Ω/, and it is 150nm that ellipsometer tests its thickness, therefore electrical conductivity is 11.119S/cm；Four probe sheet resistance instrument test nanocrystalline the become sheet resistances of ITO are 10000 Ω/, and step instrument test thickness is 450nm, therefore electrical conductivity is 2.222S/cm.
As can be seen here, in the present embodiment, anneal 300 DEG C of air atmosphere, under identical spin coating proceeding, the conductance of the laminated film that ITO composite solution obtains, compared to independent ITO precursor solution or the become thin film of the nanocrystalline dispersion liquid of ITO, do not demonstrate advantage, can also significantly find out from table 1.The novel laminated film that this composite solution spin coating obtains, although carrier transport strengthens, but at this temperature, the PVP of ITO nanocrystal surface decomposes in a large number, causes that hole increases in a large number, and interparticle contact resistance becomes big, and electrical conductance is not as strong.
Technical scheme and beneficial effect have been described in detail by embodiment described above; it it should be understood that; the foregoing is only specific embodiments of the invention; it is not limited to the present invention; all any amendments made in the spirit of the present invention and improvement etc., should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of an indium tin oxide nanocomposite solution, it is characterised in that including:
I, the nanocrystalline dispersion liquid of ITO is provided, including: it is directly dispersing in polar organic solvent forms the nanocrystalline dispersion liquid of ITO by nanocrystalline for ITO；
II, ITO precursor liquid is provided, including: the precursor liquid of In is mixed with the precursor liquid of Sn, and is at room temperature sufficiently stirred for, form ITO precursor liquid；
III, nanocrystalline for ITO dispersion liquid is mixed homogeneously with ITO precursor liquid, shear dispersion, form described indium tin oxide nanocomposite solution.
2. the preparation method of indium tin oxide nanocomposite solution according to claim 1, it is characterised in that step I includes:
1) containing indium compound, stannide mixed aqueous solution in add alkali, regulating pH value is 8.0～9.0, make described indium compound, stannide be converted into indium hydroxide, stannum precipitation of hydroxide, described containing indium compound, stannide mixed aqueous solution in the amount of substance of tin element account for indium, the total amount of substance sum of tin element 5～10%；
2) repeatedly clean described indium hydroxide, stannum precipitation of hydroxide, then solid-liquid separation with deionized water, alcoholic solvent respectively, obtain the presoma of indium hydroxide, stannum hydroxide；
3) described presoma and ethanol being mixed to form presoma-alcoholic solution that concentration is 0.02～0.1g/mL, add polyvinylpyrrolidone, shear and be dispersed into suspension, wherein polyvinylpyrrolidone is 2～10 with the mass ratio of described presoma；
4) described suspension being inserted heat treatment in autoclave, heat treatment temperature is 220 ~ 260 DEG C, and the time is 12 ~ 28 hours, obtains blue precipitate, obtains described ITO nanocrystalline after repeatedly cleaning described blue precipitate with acetone, alcoholic solvent respectively；
5) in nanocrystalline for described ITO dispersion polar organic solvent, the nanocrystalline dispersion liquid of described ITO will be obtained after shearing dispersion and/or supersound process.
3. the preparation method of indium tin oxide nanocomposite solution according to claim 2, it is characterized in that: described indium compound includes any one or any one the hydrate in indium chloride, indium nitrate, described stannide includes the hydrate of butter of tin or butter of tin, described alkali includes sodium hydroxide, potassium hydroxide or ammonia, described polyvinylpyrrolidone includes K-15, any one or two or more combination in K-30, K-60, K-90.
4. the preparation method of indium tin oxide nanocomposite solution according to claim 1, it is characterised in that step II includes:
1. the nitrate of indium is dissolved under room temperature in polar organic solvent and forms indium nitrate solution, described indium nitrate solution adds acetylacetone,2,4-pentanedione and strong aqua ammonia, and make indium: acetylacetone,2,4-pentanedione: the molal volume of strong aqua ammonia is than for 1mol:200ml:114ml, reaction 12h more than is stirred at room temperature, it is thus achieved that the precursor liquid of the In of spontaneous combustion formula；
2. stannous chloride and ammonium nitrate that mol ratio is 1:1 are dissolved in organic solvent, it is stirred at room temperature to abundant dissolving, add acetylacetone,2,4-pentanedione and strong aqua ammonia, and make stannum: acetylacetone,2,4-pentanedione: the molal volume of strong aqua ammonia is than for 1mol:200ml:114ml, reaction 12h more than is stirred at room temperature, it is thus achieved that the precursor liquid of the Sn of spontaneous combustion formula；
3. the precursor liquid of In is mixed according to the thing mass ratio of 19:1-9:1 with the precursor liquid of Sn, and at room temperature more than stirring reaction 1h, form described ITO precursor liquid.
5. the preparation method of indium tin oxide nanocomposite solution according to any one of claim 1-4, it is characterised in that described polar organic solvent includes ethanol, ethylene glycol monomethyl ether or ethylene glycol；
In the solution of indium tin oxide nanocomposite described in step III, the amount of substance of the nanocrystalline contained In element of ITO accounts in described indium tin oxide nanocomposite solution more than the 50% of the total material amount of In element；
The concentration of the nanocrystalline dispersion liquid of described ITO is 0.1-1moL/L, and the concentration of described ITO precursor liquid is 0.1-1moL/L.
6. the indium tin oxide nanocomposite solution that prepared by method according to any one of claim 1-5.
7. the preparation method of an ITO laminated film, it is characterised in that including: by the indium tin oxide nanocomposite solution film forming in substrate described in claim 6, afterwards air atmosphere annealing more than 1h at 150 DEG C-300 DEG C, it is thus achieved that described ITO laminated film.
8. the preparation method of ITO laminated film according to claim 7, it is characterized in that including: in described indium tin oxide nanocomposite solution, add polar organic solvent, repaste and be distributed in substrate film forming, wherein the consumption of polar solvent is the 0-20% of described indium tin oxide nanocomposite overall solution volume, and described polar organic solvent includes diglycol, ethylene glycol or triethylene glycol.
9. the ITO laminated film that prepared by method according to any one of claim 7-8.
10. an opto-electronic device, it is characterised in that comprise the ITO laminated film described in claim 9.
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