CN103693678A - Ito powder and method of producing same, dispersion liquid and method of ito film - Google Patents
Ito powder and method of producing same, dispersion liquid and method of ito film Download PDFInfo
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- CN103693678A CN103693678A CN201310287607.8A CN201310287607A CN103693678A CN 103693678 A CN103693678 A CN 103693678A CN 201310287607 A CN201310287607 A CN 201310287607A CN 103693678 A CN103693678 A CN 103693678A
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- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
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- C01G15/00—Compounds of gallium, indium or thallium
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Abstract
The present invention provides a kind of ITO power which turns into a compaction under low pressure and shows surface modification of high conductivity as well as the manufacturing method thereof, as well as the manufacturing methods of a kind of dispersion liquid and a membrane. When the compaction comprised by the ITO power of the present invention's surface modification is applied a pressure of 0.98MPa, an electrical resistivity of the compaction is below 0.50 Omego com; when the compaction is applied a pressure of 0.196 to 29.42MPa as well as a volume resistivity of the compaction sets to Y and the pressure sets to X,the relationship between the pressure and the volume resistivity are approximate to Y=Alpha Xn,and Alpha is below 5.00 and n is below -0.500.
Description
Technical field
The present invention relates to a kind of ito powder and manufacture method thereof that demonstrates the surface modification of high conductivity while under low pressure becoming pressed compact.In this specification sheets, ITO refers to indium tin oxide (Indium Tin Oxide).
Background technology
ITO is In
2o
3in doped with the compound of tin (Sn), have 10
20～10
21cm
-3high carrier concentration, in the ITO film with vapor phase process film forming such as sputtering methods, can obtain 1 * 10
-4the low-resistivity of Ω cm left and right.In the ITO film of being made by this ITO, in visible region, there is high transparent (for example referring to Patent Document 1).Therefore, ITO film is widely used in the transparency electrode (such as referring to Patent Document 2) of liquid-crystal display or the higher heat ray-shielding material (such as referring to Patent Document 3) of heat ray shielding effect etc. and requires in the field of excellent optical characteristics.As the film of this ITO film, studying one-tenth embrane method based on easy coating and replacing the physical film deposition methods (for example referring to Patent Document 4) such as vacuum vapour deposition that cost is higher and sputtering method.
Patent documentation 1: Japanese Patent Publication 2009-032699 communique ([0009] section)
Patent documentation 2: Japanese Patent Publication 2005-054273 communique ([0006] section)
Patent documentation 3: Japanese Patent Publication 2011-116623 communique ([0002] section)
Patent documentation 4: Japanese Patent Publication 2011-034708 communique ([0002] section)
As the film of the application type of the method for film forming ITO film, there is the utilising efficiency of material and productivity is higher, bendability is excellent and for the advantages such as less-restrictive of the substrate being coated with.Yet, to compare with physical film deposition method, the electroconductibility of particle itself is lower, and particle contact resistance is each other higher, therefore has on the contrary the shortcoming that electroconductibility is lower.
Summary of the invention
The object of the present invention is to provide a kind of resistivity can reduce with coating method film forming ITO film time to obtain ito powder and the manufacture method thereof of high conductivity.
The ito powder that the 1st viewpoint of the present invention is surface modification, it is following ito powder: the pressed compact consisting of described ito powder is applied to 0.98MPa(10kgf/cm
2) pressure time the volume specific resistance of described pressed compact be below 0.50 Ω cm, will apply 0.196～29.42MPa(2～300kgf/cm to described pressed compact
2) pressure time the volume specific resistance of described pressed compact when being made as Y and described pressure and being made as X, close like following formula (1) between described pressure and described volume specific resistance, in this formula (1), a is below 5.00, and n is below-0.500.
Y=aX
n （1）
And, the 2nd viewpoint of the present invention is the invention based on the 1st viewpoint, and it is the improvement that comprises the manufacture ito powder method of following operation: in the mixed aqueous solution of 3 valency indium compounds and divalent tin compound, the mixed-alkali aqueous solution generates the co-precipitation oxyhydroxide of indium and tin, with pure water or ion exchanged water, clean described throw out, remove described sedimentary supernatant liquor and prepare the slurry that is dispersed with indium tin hydroxide particle, dry described slurry, and burn till described dry indium tin hydroxide and obtain indium tin oxide, wherein, in described matting, clean the extremely resistivity of described supernatant liquor and at least reach 5000 Ω cm, in the preparation section of described slurry, the slurry of having removed described supernatant liquor is diluted with water so that the concentration of described hydroxide particles becomes after the scope of 10～30 quality %, when stirring, to adding in described slurry, with respect to described hydroxide particles 100 quality %, be the organic protective agent of the scope of 0.1～5 quality %, after described firing process, pulverize the aggregate of the ito powder having burnt till, the ito powder of this pulverizing be impregnated in after surface treatment liquid, under nitrogen atmosphere, the scope heating of 200～400 ℃ 0.5～5 hour.
The 3rd viewpoint of the present invention is the invention based on the 2nd viewpoint, and it is the following method of manufacturing ito powder: described organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl vitriol, polyvinyl alcohol or octyldimethyl ethyl ammonium sulfovinate.
And, the 4th viewpoint of the present invention is the invention based on the 1st viewpoint, and it is the improvement that comprises the manufacture ito powder method of following operation: in the mixed aqueous solution of 3 valency indium compounds and divalent tin compound, the mixed-alkali aqueous solution generates the co-precipitation oxyhydroxide of indium and tin; With pure water or ion exchanged water, clean described throw out; Remove described sedimentary supernatant liquor and prepare the slurry that is dispersed with indium tin hydroxide particle; Dry described slurry; And burn till described dry indium tin hydroxide and obtain indium tin oxide.Wherein, in described matting, clean the extremely resistivity of described supernatant liquor and at least reach 5000 Ω cm, in the preparation section of described slurry, the slurry of having removed described supernatant liquor is diluted with water so that the concentration of described hydroxide particles becomes after the scope of 10～30 quality %, when stirring, to adding in described slurry, with respect to described hydroxide particles 100 quality %, be the organic protective agent of the scope of 0.1～5 quality %, in described drying process, the slurry that is added with described organic protective agent and is dispersed with indium tin hydroxide is dried, in described firing process, in atmosphere, with the microwave of 2.45GHz～28GHz, heat and burn till, after described firing process, pulverize the aggregate of the ito powder having burnt till, the ito powder of this pulverizing be impregnated in after surface treatment liquid, under nitrogen atmosphere, the scope heating of 200～400 ℃ 0.5～5 hour.
The 5th viewpoint of the present invention is the invention based on the 4th viewpoint, and it is the following method of manufacturing ito powder: described organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl vitriol, polyvinyl alcohol or octyldimethyl ethyl ammonium sulfovinate.
And, the 6th viewpoint of the present invention is the invention based on the 1st viewpoint, and it is the improvement that comprises the manufacture ito powder method of following operation: in the mixed aqueous solution of 3 valency indium compounds and divalent tin compound, the mixed-alkali aqueous solution generates the co-precipitation oxyhydroxide of indium and tin; With pure water or ion exchanged water, clean described throw out; Remove described sedimentary supernatant liquor and prepare the slurry that is dispersed with indium tin hydroxide particle; Dry described slurry; And burn till described dry indium tin hydroxide and obtain indium tin oxide.Wherein, in described matting, clean the extremely resistivity of described supernatant liquor and at least reach 5000 Ω cm, in the preparation section of described slurry, the slurry of having removed described supernatant liquor is diluted with alcohol so that the concentration of described hydroxide particles becomes after the scope of 1～5 quality %, when stirring, to adding in described slurry, with respect to described hydroxide particles 100 quality %, be the organic protective agent of the scope of 0.1～5 quality %, in described firing process, to the inside of tube furnace that is heated to the scope of 250～800 ℃, under the state that makes nitrogen with the linear velocity circulation of the scope of 0.5～5m/s, to spray with the dilution of described alcohol and the slurry that is added with described organic protective agent and is dispersed with indium tin hydroxide particle, thereby thermolysis burn till indium tin hydroxide particle and obtain indium tin oxide particles in described tube furnace.
The 7th viewpoint of the present invention is the invention based on the 6th viewpoint; it is the following method of manufacturing ito powder: described alcohol is ethanol, methyl alcohol or propyl alcohol, and described organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl vitriol, polyvinyl alcohol or octyldimethyl ethyl ammonium sulfovinate.
And the 8th viewpoint of the present invention is for being scattered in by the ito powder of the 1st viewpoint or the ito powder that produces by any method in the 2nd～7th method of manufacturing dispersion liquid in solvent.
And the 9th viewpoint of the present invention is the method for ITO film of being manufactured by the dispersion liquid of the 8th viewpoint.
The ito powder of the 1st viewpoint of the present invention, applies 0.98MPa(10kgf/cm
2) pressure time the volume specific resistance of pressed compact of ito powder be below 0.50 Ω cm, will apply 0.196～29.42MPa(2～300kgf/cm to described pressed compact
2) pressure time the volume specific resistance of described pressed compact when being made as Y and described pressure being made as to X, be similar to above-mentioned formula (1), a in formula (1) is below 5.00 and n is below-0.500, the resistivity that therefore, can reduce while utilizing this ito powder with coating method film forming ITO film obtains high conductivity.
And, in the manufacture method of the ito powder of the 2nd viewpoint of the present invention, in matting, clean to the resistivity of supernatant liquor and at least reach 5000 Ω cm, in the preparation section of slurry, the slurry of having removed supernatant liquor is diluted with water so that the concentration of hydroxide particles becomes after the scope of 10～30 quality %, when stirring, to adding in described slurry, with respect to described hydroxide particles 100 quality %, be the organic protective agent of the scope of 0.1～5 quality %, after firing process, pulverize the aggregate of the ito powder having burnt till, the ito powder of this pulverizing be impregnated in after surface treatment liquid, under nitrogen atmosphere, the scope heating of 200～400 ℃ 0.5～5 hour.The hydroxide particles higher organic protective agent of temperature that is decomposed is coated, and therefore, in sintering process, the contact each other of ITO particle is prevented from, particle growth difficulty.This organic protective agent is final thermolysis by burning till.Thus, the surface of ito powder is modified, and the resistivity that can reduce while utilizing this ito powder with coating method film forming ITO film obtains high conductivity.
And, in the manufacture method of the ito powder of the 4th viewpoint of the present invention, in matting, clean to the resistivity of supernatant liquor and at least reach 5000 Ω cm, in the preparation section of slurry, the slurry of having removed supernatant liquor is diluted with water so that the concentration of hydroxide particles becomes after the scope of 10～30 quality %, when stirring, to adding in described slurry, with respect to described hydroxide particles 100 quality %, be the organic protective agent of the scope of 0.1～5 quality %, in drying process, the slurry that is added with organic protective agent and is dispersed with indium tin hydroxide is dried, in firing process, in atmosphere, with the microwave of 2.45GHz～28GHz, heat and burn till, after firing process, pulverize the aggregate of the ito powder having burnt till, the ito powder of this pulverizing be impregnated in after surface treatment liquid, under nitrogen atmosphere, the scope heating of 200～400 ℃ 0.5～5 hour.The hydroxide particles higher organic protective agent of temperature that is decomposed is coated, and therefore, in sintering process, the contact each other of ITO particle is prevented from, particle growth difficulty.This organic protective agent is final thermolysis by burning till.Thus, the surface of ito powder is modified, and the resistivity that can reduce while utilizing this ito powder with coating method film forming ITO film obtains high conductivity.
And, in the manufacture method of the ito powder of the 6th viewpoint of the present invention, in matting, clean to the resistivity of supernatant liquor and at least reach 5000 Ω cm, in the preparation section of slurry, the slurry of having removed supernatant liquor is diluted with alcohol so that the concentration of hydroxide particles becomes after the scope of 1～5 quality %, when stirring, to adding in described slurry, with respect to hydroxide particles 100 quality %, be the organic protective agent of the scope of 0.1～5 quality %, in described firing process, to the inside of tube furnace that is heated to the scope of 250～800 ℃, so that under the state of nitrogen with the linear velocity circulation of the scope of 0.5～5m/s, to spray with alcohol dilution and the slurry that is added with organic protective agent and is dispersed with indium tin hydroxide particle, thereby thermolysis burn till indium tin hydroxide particle and obtain indium tin oxide particles in tube furnace.The hydroxide particles higher organic protective agent of temperature that is decomposed is coated, and therefore, in sintering process, the contact each other of ITO particle is prevented from, particle growth difficulty.This organic protective agent is final thermolysis by burning till.Thus, the surface of ito powder is modified, and the resistivity that can reduce while utilizing this ito powder with coating method film forming ITO film obtains high conductivity.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of device of resistivity of measuring the pressed compact of ito powder.
Fig. 2 means the figure of the relation between the resistivity of pressed compact of impressed pressure and ito powder.
Embodiment
Then, embodiment is described.
The resistivity of ito powder is the important indicator when the characteristic of the ITO film to being made by this ito powder is evaluated.Especially when ITO film is used as to conductive sheet or electrode, requiring high conductivity is low-resistivity.The resistivity of this ito powder is obtained by ito powder being become measure its volume specific resistance after the form of pressed compact.On the other hand, the volume specific resistance of pressed compact changes along with additional pressure.Therefore, although the volume specific resistance of the pressed compact under a certain both constant-pressures becomes tentative benchmark, if but by shape and the specific surface area of ito powder, under the state that changes over high pressure from low pressure, obtain volume specific resistance and be made as the resistivity of ito powder, can obtain the resistivity of the better ito powder of tolerance range.The present invention completes based on this opinion.
Ito powder of the present invention is the ito powder of surface modification, and the pressed compact consisting of this ito powder is applied to 0.98MPa(10kgf/cm
2) pressure time the volume specific resistance of pressed compact be below 0.50 Ω cm, will apply 0.196～29.42MPa(2～300kgf/cm to pressed compact
2) pressure time the volume specific resistance of pressed compact when being made as Y and pressure and being made as X, close like following formula (1) between pressure and volume specific resistance.Wherein, a of formula (1) is below 5.00, and n is below-0.500.
Y=aX
n （1）
This formula is that the result of measuring with the state of pressed compact according to effects on surface modification and the lower ito powder of volume specific resistance is derived.If above-mentioned a surpass 5.00 or n surpass-0.500, even if exist the impressed pressure of powder is become and greatly, strengthens the trend that particle contact each other is also difficult to improve electroconductibility, there is unfavorable condition.
For the manufacture of the ito powder of the ITO film of the present invention ito powder that carries out surface modification treatment that following 3 kinds of methods produce of serving as reasons.By carrying out surface modification treatment, can improve utilizing the electroconductibility of the ITO film that this ito powder produces.
(1) the 1st manufacture method
In the mixed aqueous solution of 3 valency indium compounds and divalent tin compound, the mixed-alkali aqueous solution generates the co-precipitation oxyhydroxide of indium and tin, after this precipitation is dried, is burnt till, pulverizes the indium tin oxide obtaining and obtains ito powder.As 3 valency indium compounds, can enumerate Indium-111 chloride (InCl
3), indium nitrate (In(NO
3)
3), indium acetate (In(CH
3cOO)
3) etc., as divalent tin compound, can enumerate tindichloride (SnCl
22H
2o), tin sulphate (SnSO
4), Tin tetrabromide (SnBr
2) etc.As alkaline aqueous solution, can enumerate ammonia (NH
3) water, bicarbonate of ammonia (NH
4hCO
3) water etc.By by make indium and tin oxyhydroxide co-precipitation time the final pH of reaction soln be adjusted into 3.5～9.3, preferably be adjusted into pH5.0～8.0, solution temperature is adjusted into more than 5 ℃, is preferably adjusted into 10 ℃～80 ℃ of solution temperatures, can make the co-precipitation precipitation of hydroxide of indium and tin.The mixing of alkaline aqueous solution can splash into alkaline aqueous solution when being adjusted into above-mentioned pH scope in above-mentioned mixed aqueous solution to be carried out, or also above-mentioned mixed aqueous solution and alkaline aqueous solution can be splashed into when Yu Shuizhong is adjusted into above-mentioned pH scope simultaneously and carry out.
Generate after above-mentioned co-precipitation indium tin hydroxide, with pure water or ion exchanged water, clean this throw out, clean to the resistivity of supernatant liquor and at least reach 5000 Ω cm, preferably at least reach 50000 Ω cm.If the resistivity of supernatant liquor is lower than 5000 Ω cm, the impurity such as chlorine is not fully removed, and cannot obtain highly purified In-Sn oxide powder.Remove resistivity and reach above-mentioned sedimentary supernatant liquors more than 5000 Ω cm, obtain the higher slurry of viscosity that is dispersed with indium tin hydroxide particle.With pure water or ion exchanged water, this slurry is diluted so that the concentration of hydroxide particles becomes the scope of 10～30 quality %; preferably become the scope of 15～25 quality %; afterwards, when stirring, in slurry, add for being adsorbed in the dispersed organic protective agent that this particle is improved on hydroxide particles surface.When above-mentioned dilution range is less than lower value, there is unfavorable condition consuming time in slurry dry, if surpass higher limit, can under the state higher in the viscosity of slurry, mix organic protective agent, therefore have the unfavorable condition of the undercompounding of organic protective agent.With respect to hydroxide particles 100 quality %, the addition of this organic protective agent is the scope of 0.1～5 quality %.The viewpoint of the sintering of the ito powder from this organic protective agent suppresses thermolysis, preferably the decomposition temperature of organic protective agent is in the scope of 250～500 ℃.As this organic protective agent, can enumerate palmityl dimethyl ethyl QAE quaternary aminoethyl vitriol, polyvinyl alcohol or octyldimethyl ethyl ammonium sulfovinate etc.When the addition of organic protective agent is less than the lower value of above-mentioned scope, cannot fully carry out the protection on hydroxide particles surface, the dispersiveness of particle is poor.And, if surpass higher limit, can there is an organic part or from the residual unfavorable condition of organic carbon component.
In atmosphere, preferably under the inert gas atmospheres such as nitrogen or argon, the indium tin hydroxide that surface adsorption is had to an organic protective agent is the scope of 100～200 ℃ after dry 2～24 hours, and the scope at 250～800 ℃ in atmosphere is burnt till 0.5～6 hour with firing furnace.Utilize hammer mill or ball mill etc., will burn till formed aggregate by this and pulverize and decompose to obtain ito powder.After this ito powder is put into the surface treatment liquid that is mixed with the dehydrated alcohol of 50～95 quality % and the distilled water of 5～50 quality % and is flooded, put into glass dish, scope at 200～400 ℃ under nitrogen atmosphere heats 0.5～5 hour, can obtain the ito powder that carries out surface modification treatment.
(2) the 2nd manufacture method
The solid-liquid separating method of slurry and heating process for calcining are different from the 1st manufacture method.First, the slurry that is added with organic protective agent and is dispersed with indium tin hydroxide obtaining with the 1st manufacture method is dried.As an example of this drying means, with force (forcing) pump, slurry is pressed into the mud cake that obtains oxyhydroxide in pressure filter, dry this mud cake.Then dry thing is heated and burnt till with the microwave of 2.45GHz～28GHz in atmosphere.This microwave heating treatment is for example filled in above-mentioned mud cake in the microwave oven of CMC technological development company limited system, and utilizes the microwave heating treatment of the 2.45GHz of the industrial μ-reactor making of four countries' instrumentation to carry out.
Microwave heating is in the scope of 250～800 ℃, preferably in the scope of 350～600 ℃, to heat up to carry out with the interior speed that reaches target temperature at 10 minutes, to burn till by keep the scope of 5～120 minutes at target temperature, the scope preferably keeping 10～60 minutes is carried out.When Heating temperature is less than lower value, exist oxyhydroxide incomplete decomposing to become the unfavorable condition of oxide compound, if surpass higher limit, have the unfavorable condition of ITO particle coarsening.If the heating-up time till target temperature surpasses 10 minutes, there is the unfavorable condition of the effect disappearance heating up rapidly.If the hold-time under target temperature is less than lower value, exist oxyhydroxide incomplete decomposing to become the unfavorable condition of oxide compound, if surpass higher limit, there is the unfavorable condition of ITO particle coarsening.Utilize hammer mill or ball mill etc. that burned material is pulverized and decompose to obtain ito powder.Below, similarly obtain with the 1st manufacture method the ito powder that carries out surface modification treatment.
(3) the 3rd manufacture method
Without pulverize indium tin oxide after burning till indium tin hydroxide, this point is different from the 1st and the 2nd manufacture method.
The higher slurry of the viscosity that is dispersed with indium tin hydroxide particle obtaining with the 1st manufacture method is diluted with alcohol so that the concentration of hydroxide particles becomes the scope of 1～5 quality %; preferably become the scope of 1～3 quality %, and in slurry, add for being adsorbed in the dispersed organic protective agent that this particle is improved on hydroxide particles surface when stirring.With respect to hydroxide particles 100 quality %, the addition of this organic protective agent is the scope of 0.1～5 quality %.Each lower value of addition scope and the reason of each higher limit of stipulating above-mentioned dilution range and above-mentioned organic protective agent are identical with the 1st manufacture method.The viewpoint of the sintering of the ito powder from this organic protective agent suppresses thermolysis, preferably the decomposition temperature of organic protective agent is in the scope of 250～500 ℃.As this alcohol, can enumerate ethanol, propyl alcohol or methyl alcohol etc., as organic protective agent, can enumerate palmityl dimethyl ethyl QAE quaternary aminoethyl vitriol, polyvinyl alcohol or octyldimethyl ethyl ammonium sulfovinate etc.
Inside to the vertical tube furnace that is heated to 250～800 ℃ of scopes configuring of the long side direction that makes pipe; make the linear velocity with 0.5～5m/s scope as the nitrogen of carrier gas; preferably under the state with the linear velocity circulation of 1～3m/s scope; by utilizing two-fluid spray nozzle to spray with alcohol dilution and the slurry that is added with organic protective agent and is dispersed with indium tin hydroxide particle, be together directed in tube furnace with nitrogen.When linear velocity is less than lower value, the harvest yield of ito powder reduces, if surpass higher limit, cannot fully heat the slurry of spraying.Thus, the thermolysis burning till in tube furnace of indium tin hydroxide particle, can obtain from the relief outlet of tube furnace the ito powder that carries out surface modification treatment.
[embodiment]
Then, embodiments of the invention and comparative example are together elaborated.
< embodiment 1 >
[method of the ito powder of surface modification treatment is carried out in manufacture]
At In metal concentration, be the indium chloride (InCl of 24 quality %
3) in aqueous solution 163g, add and mix tin dichloride powder (SnCl
22H
2o powder) 4g, is stirred to after tin dichloride powder all dissolves, and all amounts is joined in the pure water of 1000ml and is used as material solution.By the ammonia (NH of 25 quality %
3) aqueous solution splashes into 90 minutes to this material solution.Now temperature of reaction is adjusted into 80 ℃, the pH of end reaction solution is adjusted into 8.0.By generated indium tin co-precipitation oxyhydroxide, be that throw out carries out gradient cleaning repeatedly by ion exchanged water.In the resistivity of supernatant liquor, reach 5000 Ω cm when above, remove above-mentioned sedimentary supernatant liquor and obtain the higher slurry of viscosity that is dispersed with indium tin hydroxide particle.
When stirring this slurry, this slurry is diluted with pure water so that after the concentration of hydroxide particles becomes 20 quality %, the organic protective agent of adding 1.3g is polyvinyl alcohol.The addition of this organic protective agent is 1.0 quality % with respect to indium tin hydroxide.This slurry, is burnt till 2 hours at 700 ℃, and aggregate pulverized and decomposed after dry 10 hours at 110 ℃ in atmosphere in atmosphere, thereby obtain the ito powder of about 70g.The ito powder of this 70g is put into and is mixed with the surface treatment liquid of dehydrated alcohol and distilled water (mixture ratio is, with respect to alcohol 95 quality %, distilled water is 5 quality %) in flooded after, put into glass dish, under nitrogen atmosphere, at 330 ℃, heat 2 hours, thereby obtain the ito powder that carries out surface modification treatment.
[manufacture of ITO film]
The ito powder 20g that this is carried out to surface modification treatment puts into distilled water (0.020g), two (2 ethyl hexanoic acid) triglycol ester [3G] (23.8g), make its dispersion in the mixed solution of dehydrated alcohol (2.1g), phosphoric acid polyester (1.0g), 2 ethyl hexanoic acid (2.0g) and 2,4-pentane diketone (0.5g).It is that the content of ito powder becomes 10 quality % that prepared dispersion liquid is diluted to solid substance with dehydrated alcohol.The dispersion liquid that this is diluted, by spin application film forming on quartz glass plate, is the ITO film of 0.2 μ m thereby obtain thickness.
< embodiment 2 >
At In metal concentration, be the indium chloride (InCl of 24 quality %
3) in aqueous solution 135g, add and mix tin dichloride powder (SnCl
22H
2o powder) 16g, is stirred to after tin dichloride powder all dissolves, and all amounts is joined in the pure water of 1000ml and is used as material solution.By the ammonia (NH of 25 quality %
3) aqueous solution splashes into 90 minutes to this material solution.Now temperature of reaction is adjusted into 60 ℃, the pH of end reaction solution is adjusted into 5.0.By generated indium tin co-precipitation oxyhydroxide, be that throw out carries out gradient cleaning repeatedly by ion exchanged water.In the resistivity of supernatant liquor, reach 5000 Ω cm when above, remove above-mentioned sedimentary supernatant liquor, thereby obtain the higher slurry of viscosity that is dispersed with indium tin hydroxide particle.When stirring this slurry, this slurry is diluted with pure water so that the concentration of hydroxide particles becomes after 15 quality %, adding organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl vitriol (70 quality %) 4.5g.The addition of this organic protective agent is 3.0 quality % with respect to indium tin hydroxide.
This slurry, is burnt till 3 hours at 800 ℃, and aggregate pulverized and decomposed after dry 10 hours at 110 ℃ in atmosphere in atmosphere, thereby obtain the ito powder of about 75g.The ito powder of this 75g is put into the surface treatment liquid (mixture ratio: with respect to alcohol 95 quality % that is mixed with dehydrated alcohol and distilled water, distilled water is 5 quality %) in flooded after, put into glass dish under nitrogen atmosphere, 330 ℃ of heating 2 hours, thereby obtain the ito powder that carries out surface modification treatment.And, utilize this ito powder to produce similarly to Example 1 ITO film.
< embodiment 3 >
At In metal concentration, be the indium chloride (InCl of 24 quality %
3) in aqueous solution 154g, add and mix tin dichloride powder (SnCl
22H
2o powder) 8g, is stirred to after tin dichloride powder all dissolves, and all amounts is joined in the pure water of 1000ml and is used as material solution.By the ammonia (NH of 25 quality %
3) aqueous solution splashes into 90 minutes to this material solution.Now temperature of reaction is adjusted into 20 ℃, the pH of end reaction solution is adjusted into 7.0.By generated indium tin co-precipitation oxyhydroxide, be that throw out carries out gradient cleaning repeatedly by ion exchanged water.In the resistivity of supernatant liquor, reach 5000 Ω cm when above, remove above-mentioned sedimentary supernatant liquor, thereby obtain the higher slurry of viscosity that is dispersed with indium tin hydroxide particle.When stirring this slurry, this slurry is diluted with ethanol so that after the concentration of hydroxide particles becomes 1.0 quality %, adding organic protective agent is octyldimethyl ethyl ammonium sulfovinate (50 quality %) 10g.The addition of this organic protective agent is 5.0 quality % with respect to indium tin hydroxide.
To the vertical inside that is heated to the tube furnace of 500 ℃ configuring of the long side direction that makes pipe, make as the nitrogen of carrier gas under the state with the linear velocity circulation of 1m/s scope, utilize two-fluid spray nozzle to spray in this slurry, and be together directed in tube furnace with nitrogen.Thus, the thermolysis burning till in tube furnace of indium tin hydroxide particle, obtains from the relief outlet of tube furnace the ito powder that carries out surface modification treatment.And utilize this ito powder to produce similarly to Example 1 ITO film.
< comparative example 1 >
At In metal concentration, be the indium chloride (InCl of 24 quality %
3) in aqueous solution 245g, adding melting concn is the tin tetrachloride (SnCl of 55 quality %
4) aqueous solution 11.5g, prepare InCl
3-SnCl
4mixing solutions.Then, by bicarbonate of ammonia (NH
4hCO
3) water 500g is dissolved in ion exchanged water, being prepared into total amount is that 1000ml and temperature are 70 ℃.In this aqueous solution, by above-mentioned InCl
3-SnCl
4all amounts of mixing solutions splash into 20 minutes when stirring and generate indium tin co-precipitation oxyhydroxide.With this state, stir again 30 minutes.The final pH of reaction soln is now 9.0.Reclaiming throw out is indium tin hydroxide, after centrifuge dewatering, carries out centrifuging when adding ion exchanged water to clean, and reaches 5000 Ω cm finish centrifuging when above in the resistivity of filtrate.Then this throw out is dried after the night at 100 ℃, at 600 ℃, burns till 3 hours, and aggregate is pulverized and decomposed, thus the ito powder of acquisition 75g.
The ito powder of this 75g is put into and is mixed with the surface treatment liquid of dehydrated alcohol and distilled water (mixture ratio is, with respect to alcohol 95 quality %, distilled water is 5 quality %) in flooded after, put into glass dish, under nitrogen atmosphere, at 330 ℃, heat 3 hours, thereby obtain the ito powder that carries out surface modification treatment.And, utilize this ito powder to produce similarly to Example 1 ITO film.
< comparison test >
[evaluation of ito powder]
The pressed compact that each ito powder obtaining in embodiment 1～3 and comparative example 1 is formed is applied to 0.98MPa(10kgf/cm
2) pressure time the volume specific resistance of this pressed compact be shown in following table 1.Utilize the determinator shown in Fig. 1 (Mitsubishi Chemical Analytech Co., Ltd. MCP-PD51 processed) to be determined at the volume specific resistance of each ito powder obtaining in this embodiment 1～3 and comparative example 1.Particularly, the ito powder of filling 2.00g in the cylinder body 1 that is 25mm at the internal diameter φ shown in Fig. 1, at 0.196～29.42MPa(2～300kgf/cm
2) scope in change pressure, be determined at respectively at the same time 10 above resistivity and test portion thickness in the ito powder obtaining in embodiment 1～3 and comparative example 1.Pressure is by not shown determination of pressure sensor, and resistivity is measured with direct current four-terminal method.In Fig. 1,2 pressed compacts that are ito powder.
What shown in Fig. 2, put on test portion powder is converted into the relation between the pressure (transverse axis) of power and the volume specific resistance (longitudinal axis) of the pressed compact of ito powder according to unit surface.This relation is similar to the formula (1) of following power by least square method.In addition, the volume specific resistance of powder calculates by the attached correction coefficient of mensuration system is multiplied by the value determining.The a of the rough and ready formula (1) obtaining in embodiment 1～3 and comparative example 1 shown in table 1 and the value of n.
Y=aX
n （1）
By Instrument of Electrical Resistivity Measurement (MCP-T400 processed of oiling company of Mitsubishi), determine the surface resistivity (Ω/) of each ITO film obtaining in embodiment 1～3 and comparative example 1.The results are shown in table 1.
[table 1]
< evaluates >
As seen from Table 1, be below 5.00 to a by formula (1) and the pressed compact that forms of the n ito powder that is embodiment 1～3 below-0.500 applies 0.98MPa(10kgf/cm
2) pressure time the volume specific resistance of this pressed compact be below 0.500 Ω cm.And the surface resistivity of the ITO film of being made by these ito powders is 1.0 * 10
6below Ω/.With respect to this, to a by formula (1), be below 5.00 but n surpasses the pressed compact that the ito powder of-0.500 comparative example 1 forms applies 0.98MPa(10kgf/cm
2) pressure time the volume specific resistance of this pressed compact surpass 0.5 Ω cm.And the surface resistivity of the ITO film of being made by the ito powder of comparative example 1 has surpassed 1.0 * 10
6Ω/.More than verified the embodiment 1～3 with the relation that is similar to formula (1), the resistivity while reducing with coating method film forming ITO film obtains high conductivity.
Claims (9)
1. an ito powder for surface modification, is characterized in that,
The volume specific resistance of the described pressed compact when pressed compact consisting of described ito powder is applied to the pressure of 0.98MPa is below 0.50 Ω cm, by described pressed compact is applied to 0.196～29.42MPa pressure time the volume specific resistance of described pressed compact when being made as Y and described pressure and being made as X, relation between described pressure and described volume specific resistance is carried out matching with following formula (1), in this formula (1), a is below 5.00, and n is below-0.500
Y=aX
n （1）。
2. a manufacture method for ito powder, its manufacture method that is ito powder claimed in claim 1, it comprises following operation:
In the mixed aqueous solution of 3 valency indium compounds and divalent tin compound, the mixed-alkali aqueous solution generates the co-precipitation oxyhydroxide of indium and tin; With pure water or ion exchanged water, clean described co-precipitation oxyhydroxide; Remove the supernatant liquor of described co-precipitation oxyhydroxide and prepare the slurry that is dispersed with indium tin hydroxide particle; Dry described slurry; And burn till described dry indium tin hydroxide and obtain indium tin oxide,
The method of described manufacture ito powder is characterised in that,
In the operation of described cleaning, clean the extremely resistivity of described supernatant liquor and at least reach 5000 Ω cm,
In the preparation section of described slurry; the slurry of having removed described supernatant liquor is diluted with water so that the concentration of described hydroxide particles becomes after the scope of 10～30 quality %; when stirring, to adding in described slurry, with respect to described hydroxide particles 100 quality %, be the organic protective agent of the scope of 0.1～5 quality %
After described operation of burning till, pulverize the aggregate of the ito powder having burnt till, the ito powder of this pulverizing be impregnated in after surface treatment liquid, under nitrogen atmosphere, the scope heating of 200～400 ℃ 0.5～5 hour.
3. manufacture method according to claim 2, wherein,
Described organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl vitriol, polyvinyl alcohol or octyldimethyl ethyl ammonium sulfovinate.
4. a manufacture method for ito powder, its manufacture method that is ito powder claimed in claim 1, it comprises following operation:
In the mixed aqueous solution of 3 valency indium compounds and divalent tin compound, the mixed-alkali aqueous solution generates the co-precipitation oxyhydroxide of indium and tin; With pure water or ion exchanged water, clean described co-precipitation oxyhydroxide; Remove the supernatant liquor of described co-precipitation oxyhydroxide and prepare the slurry that is dispersed with indium tin hydroxide particle; Dry described slurry; And burn till described dry indium tin hydroxide and obtain indium tin oxide,
The method of described manufacture ito powder is characterised in that,
In the operation of described cleaning, clean the extremely resistivity of described supernatant liquor and at least reach 5000 Ω cm,
In the preparation section of described slurry; the slurry of having removed described supernatant liquor is diluted with water so that the concentration of described hydroxide particles becomes after the scope of 10～30 quality %; when stirring, to adding in described slurry, with respect to described hydroxide particles 100 quality %, be the organic protective agent of the scope of 0.1～5 quality %
In described drying process, the slurry that is added with described organic protective agent and is dispersed with indium tin hydroxide is dried,
In described operation of burning till, in atmosphere, with the microwave of 2.45GHz～28GHz, heat and burn till,
After described operation of burning till, pulverize the aggregate of the ito powder having burnt till, the ito powder of this pulverizing be impregnated in after surface treatment liquid, under nitrogen atmosphere, the scope heating of 200～400 ℃ 0.5～5 hour.
5. manufacture method according to claim 4, wherein,
Described organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl vitriol, polyvinyl alcohol or octyldimethyl ethyl ammonium sulfovinate.
6. a manufacture method for ito powder, its manufacture method that is ito powder claimed in claim 1, it comprises following operation:
In the mixed aqueous solution of 3 valency indium compounds and divalent tin compound, the mixed-alkali aqueous solution generates the co-precipitation oxyhydroxide of indium and tin; With pure water or ion exchanged water, clean described co-precipitation oxyhydroxide; Remove the supernatant liquor of described co-precipitation oxyhydroxide and prepare the slurry that is dispersed with indium tin hydroxide particle; Dry described slurry; And burn till described dry indium tin hydroxide and obtain indium tin oxide,
The method of described manufacture ito powder is characterised in that,
In the operation of described cleaning, clean the extremely resistivity of described supernatant liquor and at least reach 5000 Ω cm,
In the preparation section of described slurry; the slurry of having removed described supernatant liquor is diluted with alcohol so that the concentration of described hydroxide particles becomes after the scope of 1～5 quality %; when stirring, to adding in described slurry, with respect to described hydroxide particles 100 quality %, be the organic protective agent of the scope of 0.1～5 quality %
In described operation of burning till; to the inside of tube furnace that is heated to the scope of 250～800 ℃; under the state that makes nitrogen with the linear velocity circulation of the scope of 0.5～5m/s; to spray with the dilution of described alcohol and the slurry that is added with described organic protective agent and is dispersed with indium tin hydroxide particle, thus thermolysis burn till indium tin hydroxide particle and obtain indium tin oxide particles in described tube furnace.
7. manufacture method according to claim 6, wherein,
Described alcohol is ethanol, methyl alcohol or propyl alcohol, and described organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl vitriol, polyvinyl alcohol or octyldimethyl ethyl ammonium sulfovinate.
8. manufacture a method for dispersion liquid, wherein,
Ito powder claimed in claim 1 or the ito powder that produces by the method described in any one in claim 2～7 are scattered in and in solvent, manufacture dispersion liquid.
9. manufacture a method for ITO film, wherein,
By dispersion liquid claimed in claim 8, manufacture ITO film.
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| EP1967495A1 (en) * | 2007-02-21 | 2008-09-10 | Sumitomo Metal Mining Co., Ltd. | Manufacturing method for antimony-containing tin oxide fine particles for forming solar radiation shielding body, dispersion for forming solar radiation shielding body, solar radiation sheilding body, and solar radiation shielding base material |
| JP2010059040A (en) * | 2008-08-07 | 2010-03-18 | Idemitsu Kosan Co Ltd | Method for producing microparticle and heat-ray-shielding microparticle obtained thereby |
| CN102015538A (en) * | 2008-05-06 | 2011-04-13 | 赢创德固赛有限公司 | Indium tin oxide powder and dispersion thereof |
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| JP3355733B2 (en) * | 1992-12-28 | 2002-12-09 | 三菱マテリアル株式会社 | Low resistance conductive pigment and method for producing the same |
| KR100737657B1 (en) * | 1998-09-06 | 2007-07-09 | 라이브니츠-인스티투트 퓌어 노이에 마테리알리엔 게마인누찌게 게엠베하 | Method for preparing suspensions and powders based on indium tin oxide and the use thereof |
| JP4389368B2 (en) * | 1999-12-02 | 2009-12-24 | 三菱マテリアル株式会社 | Conductive pigment powder and transparent conductive film made using the same |
| JP2004123523A (en) | 2002-09-11 | 2004-04-22 | Sumitomo Chem Co Ltd | Method for producing indium oxide-tin oxide powder |
| GB0411949D0 (en) * | 2004-05-28 | 2004-06-30 | Ici Plc | Mixed metal oxides |
| KR100787635B1 (en) | 2007-01-22 | 2007-12-21 | 삼성코닝 주식회사 | Indium tin oxide target, method of manufacturing the same and transparent electrode manufactured by using the same |
| WO2010131674A1 (en) * | 2009-05-12 | 2010-11-18 | Ｄｏｗａエレクトロニクス株式会社 | Ito powder, ito coating material, and transparent conductive film formed using ito coating material |
| JP2011246305A (en) * | 2010-05-26 | 2011-12-08 | Hiroshima Univ | Method for producing powder by solid phase reaction |
| JP5754580B2 (en) * | 2010-10-26 | 2015-07-29 | 三菱マテリアル電子化成株式会社 | Indium tin oxide powder |
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| EP1967495A1 (en) * | 2007-02-21 | 2008-09-10 | Sumitomo Metal Mining Co., Ltd. | Manufacturing method for antimony-containing tin oxide fine particles for forming solar radiation shielding body, dispersion for forming solar radiation shielding body, solar radiation sheilding body, and solar radiation shielding base material |
| CN102015538A (en) * | 2008-05-06 | 2011-04-13 | 赢创德固赛有限公司 | Indium tin oxide powder and dispersion thereof |
| JP2010059040A (en) * | 2008-08-07 | 2010-03-18 | Idemitsu Kosan Co Ltd | Method for producing microparticle and heat-ray-shielding microparticle obtained thereby |
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