EP3732148A1 - Matériaux conducteurs à base de particules tio dopées nb - Google Patents

Matériaux conducteurs à base de particules tio dopées nb

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Publication number
EP3732148A1
EP3732148A1 EP18814849.8A EP18814849A EP3732148A1 EP 3732148 A1 EP3732148 A1 EP 3732148A1 EP 18814849 A EP18814849 A EP 18814849A EP 3732148 A1 EP3732148 A1 EP 3732148A1
Authority
EP
European Patent Office
Prior art keywords
particles
doped
hydrolyzable
temperature
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18814849.8A
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German (de)
English (en)
Inventor
Peter William De Oliveira
Jana Staudt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH
Original Assignee
Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH filed Critical Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH
Publication of EP3732148A1 publication Critical patent/EP3732148A1/fr
Pending legal-status Critical Current

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    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
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    • C01G33/00—Compounds of niobium
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
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    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • the invention relates to a process for the preparation of conductive materials made of Nb-doped TiCg particles, as well as conductive body produced therewith.
  • Nb-doped TiCg (TNO) is referred to in the literature as a substitute for indium tin oxide (ITO) for transparent conductive layers. This statement is based on the fact that sputtered layers of the material show similar optical and electrical properties as sputtered ITO layers. There are occasional approaches to also wet-chemically apply the material, e.g. in the preparation of a sol of precursor and spin or dip coating. This achieves conductivities that are at least a factor of 1000 worse than sputtered applications.
  • Nb-doped TiO 2 nanoparticles are known, but usually different precursors, solvents or additives (eg acids) are used.
  • Two scientific publications describe the production of Nb-doped nanoparticles and the compression of these particles into pellets. It was after a post-treatment Nitrogen at 600 ° C reaches a resistance of these pellets of up to 4 Qcm (Liu et al., ACS Nano 4, 9 (2010) 5373-5381; Nemec et al., J. Phys. Chem. C, 115 (2011) 6968-6974).
  • the object of the invention is to provide a method which allows the production of conductive bodies of Nb-doped Titandi oxide, and thus produced body and particles for the preparation of these bodies.
  • the object is achieved by a method for producing conductive bodies of Nb-doped TiCg particles comprising the following steps: a) compressing particles comprising Nb-doped TiCg into a body;
  • Nb-doped TiCg particles are pressed into a body.
  • nanoparticles are understood as meaning particles having a particle size of less than 200 nm. This means that with a sample of at least 100 particles none of the particles has a larger diameter (measured with TEM).
  • Be preferred is a particle size of not more than 100 nm, in particular not more than 50 nm, in particular from 1 to 200 nm, preferably from 2 to 100 nm, more preferably from 2 to 50 nm. Particularly preferred are particles having a particle size of 2 to 30 nm, and 2 to 20 nm.
  • the TiCg particles are Nb-doped TiCg particles. Preference is given to particles having an Nb content of up to 30 at%, based on the sum of Nb and Ti atoms, preferably up to 20 at%.
  • the content of Nb is preferably at least 2 at%, preferably at least 5 at%.
  • the particles can usually be prepared in various ways, e.g. by flame pyrolysis, plasma processes, colloid techniques, sol-gel processes, controlled germination and growth processes, MOCVD processes and emulsion processes. These methods are described in detail in the literature.
  • the particles are pressed into a body, preferably with a force of at least 500 kN, in particular over 700 kN, especially above 800 kN, preferably not more than 1500 kN, in particular 1200 kN.
  • a force of 500 kN to 1500 kN in particular from 800 kN to 1200 kN, particularly preferably 900 kN to 1100 kN.
  • the particles can be filled into appropriate forms ge. Preferably, no further adjuvants are added.
  • the pressing time can be 2 seconds to 1 hour. Preference is given to pressing at room temperature.
  • the pressed body is subjected to a temperature treatment in an oxygen-containing atmosphere.
  • the temperature is at least 200 ° C, preferably at least 400 ° C.
  • Particularly good results were obtained in a treatment at 500 ° C to 750 ° C.
  • the temperature treatment is carried out until the organic components have been sufficiently removed. This can lead to a discoloration of the body from blue to white, by the oxidation of the inorganic constituents.
  • the treatment may take between 1 minute and 25 hours depending on the body, preferably 30 minutes to 2 hours, which is the time at which the desired temperature is maintained.
  • the body is heated to the target temperature within up to 4 hours. Thereafter, the body is preferably allowed to cool in the oven to a temperature below 100 ° C. This can take 10 to 48 hours.
  • the temperature treatment takes place in an oxygen-containing At atmosphere.
  • the atmosphere should therefore contain a sufficient amount of oxygen. A proportion of at least 5% by volume, preferably of at least 20% by volume, is preferred.
  • the other ingredients preferably comprise unreactive gases such as nitrogen or argon under the conditions. It may also contain up to 0.1 vol.% Other gaseous components.
  • the temperature treatment can also be carried out easily in air.
  • the body is subjected to a further temperature treatment under a reducing atmosphere.
  • the temperature is at least 200 ° C, preferably be at least 400 ° C.
  • Preferred is a temperature of 200 ° C to 900 ° C, preferably 400 ° C to 800 ° C, more preferably 500 ° C to 800 ° C, particularly preferably 500 ° C to 800 ° C.
  • Particularly good results were obtained in a treatment at 500 ° C to 750 ° C.
  • the treatment may take between 1 minute and 25 hours depending on the body, preferably 30 minutes to 2 hours, which is the time at which the desired temperature is maintained.
  • the body is heated to the target temperature within up to 4 hours. Thereafter, the body is preferably allowed to cool in the oven to a temperature of below 100 ° C. This can take 10 to 48 hours.
  • the conditions are preferably chosen such that no reduction of the TiO 2 takes place, ie no formation of lower titanium oxides, titanium suboxides or Magneli phases.
  • the proportion of reducing gas in the gas mixture is in the range of 0.05 to 10 vol.%, Based on the total volume of Gasge mixture.
  • the proportion of reducing gas can be adapted to the selected temperature. The higher the reaction temperature is chosen, the lower the proportion of reducing gas in the gas mixture must be so that it does not come to the formation of Titansuboxi the. At a lower reaction temperature in the aforementioned range, on the other hand, the content of reducing gas in the gas mixture can be selected to be higher.
  • the proportion of reducing gas in the gas mixture at a reac tion temperature of 550 ° C be 3 to 10 vol.%.
  • the X-ray diffractogram of the body only the respec tive crystal modification anatase and / or rutile, preferably only anatase, can be found.
  • the X-ray diffractogram may have a slight shift due to the Nb content.
  • a reducing gas hydrogen, ammonia or hydrocarbon compounds having 1 to 4 carbon atoms (C1-C4) who used the.
  • Suitable carrier gases are in particular nitrogen or argon, which represent the other constituents of the gas mixture.
  • Particularly preferred forming gas (N2 / H2) is used with the above-mentioned small amount of hydrogen.
  • both temperature treatments at temperatures of about 400 ° C, before given at 500 ° C to 800 ° C, in particular at 500 to 750 ° C, performed. It has been found that the conductivity can be significantly improved with the method according to the invention.
  • the temperature treatment in an oxygen-containing atmosphere organic components of the particles can be removed. However, this also reduces the conductivity of the particles. However, this step ensures that the percolation of the particles within the body is improved because their surfaces are no longer covered by organic groups. Also, the porosity of the body is improved. However, the responsible for the blue color Ti 3+ oxi diert. Only treatment in a reducing atmosphere significantly improves conductivity.
  • the particles doped according to the invention are preferably produced by a sol-gel process to form the nanoparticles.
  • a sol-gel process usually hydrolyzable compounds are hydrolyzed with water, optionally with acidic or basic catalysis, and optionally at least partially condensed.
  • the hydrolysis and / or condensation reactions lead to the formation of compounds or condensates with hydroxyl, oxo groups and / or oxo bridges which serve as precursors.
  • the parameters e.g. The degree of condensation, solvent, temperature, water concentration, duration or pH, the sol containing the particles according to the invention can be obtained.
  • the hydrolysis and condensation reaction is preferably carried out in such a way that the hydrolyzable compounds are not completely hydrolyzed and nanoparticles are formed, ie the nanoparticles formed still have hydrolyzable groups on the surface. It is known to a person skilled in the art, whose task it is not to completely hydrolyze the hydrolyzable compounds, how to do this by suitable nete setting of the above parameters reached. Some preferred conditions are explained below. By this method, particles are obtained which are easily re-dispersible by the non-hydrolyzed groups on their surface. In addition, the group can be easily controlled by the choice of compounds and solvents used.
  • the hydrolysis and condensation may be carried out in a solvent, but they may also be carried out without a solvent, whereby hydrolysis may produce solvents or other liquid constituents, e.g. in the hydrolysis of alcoholates.
  • the removal of the solvent may include the removal of existing liquid constituents.
  • the removal of the solvent may e.g. by filtration, centrifuging and / or drying, e.g. Evaporation, done.
  • the hydrolysis is carried out in a solvent Runaway.
  • an organic solvent is used, in which the hydrolyzable titanium compound, as well as the preferably also hydrolyzable niobium compound, preferably before soluble.
  • the solvent is also preference, with water miscible.
  • suitable organic solvents include alcohols, ketones, ethers, amides and mixtures thereof.
  • Alcohols are preferably used, preferably lower aliphatic alcohols (C 1 -C 6 -alcohols), such as ethanol, 1-propanol, isopropanol, sec. Butanol, tert.
  • the hydrolysis is preferably carried out with a substoichiometric amount of water, ie the molar ratio of water to hydrolyzable groups of the hydrolyzable compounds is less than 1, preferably not more than 0.8, more preferably not more than 0.6 and more preferably not more than 0 , 5, in particular less than 0.5.
  • the molar ratio is greater than 0.05 and more preferably greater than 0.1.
  • a preferred molar ratio is, for example, 0.1 to 0.5.
  • the hydrolysis can be catalysed acidic or basic, with acid catalysis being preferred.
  • Anor ganic or organic acids can be used.
  • Particularly preferred are inorganic acids, with organic acids such as acetic acid, the reaction may be incomplete.
  • the use of nitric acid or sulfuric acid may lead to additional doping with N or S atoms.
  • hydrochloric acid (HCl) in particular with a concentra tion of at least 2 molar, preferably at least 10 molar, in particular concentrated hydrochloric acid.
  • Concentrated hydrochloric acid is a solution of at least 10 mol / l, in particular at least 12 mol / l.
  • the acid which in the case of hydrochloric acid is an aqueous solution of HCl, is the only addition of water for the production of the particles.
  • the hydrolysis can be carried out at room temperature (about 23 ° C), but preferably under heating, for example to at least 60 ° C, preferably at least 100 ° C or at least 200 ° C.
  • the hydrolysis is carried out under heating and pressure (hydrothermal reaction), FITS preferred by heating in a sealed container (auto generous pressure).
  • the hydrolysis is carried out in a sealed container at autogenous pressure and a temperature of 200 to 300 ° C, preferably 220 to 260 ° C.
  • the hydrolysis is carried out until particles according to the invention are obtained. Preference is given to a duration of 30 minutes to 48 hours, preferably 12 hours to 36 hours, in particular 20 to 36 hours.
  • reaction conditions naturally depend on the starting compounds used, so that e.g. Depending on the Sta stability of the starting compound, a wide range of appro priate conditions may be appropriate. The skilled person can easily select suitable conditions depending on the selected compounds.
  • alkoxides can be used, but also other compounds which are capable of hydrolysis, e.g. acyl group-containing precursors or complex-formed precursors, e.g. ß-diketone complexes.
  • Organyls with metal carbon compounds can also be used.
  • the hydrolyzable compound is a titanium compound of the general formula MX n ( I), wherein M is Ti above and X is a hydrolyzable group which may be the same or different, where two groups X are represented by a biennial hydrolysable group or a Oxo group can be replaced or three groups X can be replaced by a tridentate hydrolyzable group, and n corresponds to the valence of the element M and in the case of Ti is 4.
  • M stands for Nb
  • n is usually 5.
  • the group X is a low mass group.
  • halogen F, Ci, Br or I, in particular C and Br
  • alkoxy preferably Ci- 6 -alkoxy, in particular CH 1-4 alkoxy, such as methoxy, ethoxy, n-propoxy , i-propoxy, butoxy, i-butoxy, sec-butoxy and tert-butoxy
  • aryloxy preferably C 6-i o _ aryloxy, such as phenoxy
  • acyloxy preferably Ci- 6 acyloxy, such as Acetoxy or propionyloxy
  • alkylcarbonyl preferably C 2-7 alkylcarbonyl such as acetyl
  • the hydrolyzable metal or semimetal compounds may also have complexing groups, e.g. ß-diketone and (meth) acrylic radicals.
  • suitable complexing agents are unsaturated carboxylic acids and ⁇ -dicarbonyl compounds, e.g. Methacrylic acid, acetylacetone and ethyl acetoacetate.
  • the Nb compound added for doping is also a compound of the formula (I), where M is then Nb. This allows it to be better incorporated into the particles.
  • All compounds of the formula (I) used are preferably alkoxides or complexes comprising alkoxides. Preferably, they only comprise groups of carbon, hydrogen and oxygen. Examples of preferred compounds are: Ti (OCH3) 4 ,
  • the composition preferably has no further metal compounds.
  • the Ti and Nb compounds are used according to the desired degree of doping.
  • the produced bodies can still be contacted with electrodes. This can be done for example by the sputtering of me-metallic layers.
  • the produced body has a resistivity of less than 10 ⁇ cm, preferably less than 1 ⁇ cm.
  • the invention also relates to bodies produced by the method according to the invention.
  • the invention also relates to a method for producing Nb-doped TiCy nanoparticles according to a preferred embodiment of the method described above.
  • a mixture comprising at least one hydrolyzable bare titanium compound, preferably of the formula (I), and at least one hydrolyzable niobium compound, preferably of the formula (I), in an organic solvent and water in a stoichiometric amount, based on all existing hydroly sierbaren groups used.
  • This mixture is treated at autogenous pressure at 200 to 300 ° C to form Nb-doped TiCy nanoparticles.
  • the treatment can be done for 12 to 36 hours.
  • a powder of Nb-doped TiCy nanoparticles can be obtained.
  • the resulting particles are crystalline and have an anatase structure.
  • the hydrolyzable compounds are alkoxide compounds having 1 to 3 carbon atoms.
  • area information always includes all - not mentioned - intermediate values and all imaginable subintervals.
  • the embodiments are shown in the figures schematically Darge.
  • the same reference numerals in the individual figures denote NEN same or functionally identical or with respect to their functions corresponding elements. In detail shows:
  • Fig. 1 TEM image of TN05 nanoparticles. The particles
  • Fig. 2 XRD of the prepared nanoparticle powders. From undoped Ti0 2 as a reference up to 20at% Nb anatase remains as a modification. The order of measurements from top to bottom: TNO20, TNO10, TN08,
  • Air and forming gas at 550 ° C for each hour.
  • the organics are first burned and the material turns from blue to white.
  • the sintering of forming gas reduces the material again and bring it back to its original blue state. As a result, the resistance drops by 4 orders of magnitude;
  • Fig. 7 SSA specific surface area and particle size as a function of Nb content determined by BET measurements.
  • the particles have then on average a size between 9 and 11 nm, whereby this decreases slightly with increasing Nb content.
  • FIG. 1 shows a TEM image of TN05 nanoparticles.
  • the narrow size distribution of the particles is easy to recognize.
  • Figures 2 and 3 show XRD measurements of various particles. It turns out that the reflections are easily shifted to smaller angles. Nevertheless, all samples show an anatase structure.
  • the order of the lines in the measurement from top to bottom corresponds to the order in the legend (TN08, TN05, TN02.5 and Ti02).
  • a commercial ITO nanoparticle powder was also used.
  • the pellets were removed by means of a cold isostatic press at 1000 kN and 30 s
  • the resistances were determined with a 2-point multimeter to GOhm range. From the thickness h and the diameter d of the pellets, a specific resistance p was determined from this, which should represent a temperature-dependent material constant in the case of a bulk body. Of course, it must be taken into account that the pellets have a certain porosity.
  • the pellets were heated at various temperatures (550 to 750 ° C.) in air and then at 550 ° C. in forming gas (N 2 / H 2, 95: 5). sinters.
  • Heating in air should serve to increase the crystallinity and burn off organic residues on the surface. From each doping, three pellets were prepared from different synthetic approaches. From this, the mean value and the standard deviation were calculated in each case.
  • the blue pellets (before the temperature treatment) have the highest resistance of the TNO pellets. As the Nb content increases, the resistance decreases slightly. Aftertreatment of the pel lets to air and forming gas, however, reduces the resistance by several orders of magnitude. The lowest resistance achieved is only a factor of 40 from the value of a comparable ITO pellet.
  • the results of the resistance measurement are shown in FIG. 5. The results show that TNO treated according to the invention can be a possible alternative to ITO.

Abstract

L'invention concerne un procédé de fabrication de matériaux conducteurs à base de particules TiO<sb /> dopées Nb ainsi que des corps conducteurs réalisés avec lesdits matériaux. A cet effet, les particules TiO<sb /> dopées Nb sont comprimées de manière à former des corps et lesdits corps sont traités sous atmosphère contenant de l'oxygène et sous atmosphère réductrice. L'invention concerne en outre un procédé de fabrication de particules TiO<sb /> dopées Nb.
EP18814849.8A 2017-12-27 2018-12-03 Matériaux conducteurs à base de particules tio dopées nb Pending EP3732148A1 (fr)

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DE102017131349.4A DE102017131349A1 (de) 2017-12-27 2017-12-27 Leitfähige Materialien aus Nb-dotierten TiO2-Partikeln
PCT/EP2018/083323 WO2019129463A1 (fr) 2017-12-27 2018-12-03 MATÉRIAUX CONDUCTEURS À BASE DE PARTICULES TIO<sb /> DOPÉES NB

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US20210078872A1 (en) 2021-03-18
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