EP2321373A1 - Particules modifiées et dispersions les contenant - Google Patents

Particules modifiées et dispersions les contenant

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Publication number
EP2321373A1
EP2321373A1 EP09782305A EP09782305A EP2321373A1 EP 2321373 A1 EP2321373 A1 EP 2321373A1 EP 09782305 A EP09782305 A EP 09782305A EP 09782305 A EP09782305 A EP 09782305A EP 2321373 A1 EP2321373 A1 EP 2321373A1
Authority
EP
European Patent Office
Prior art keywords
metal
particles
dispersion
modifiers
modified
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.)
Withdrawn
Application number
EP09782305A
Other languages
German (de)
English (en)
Inventor
Imme Domke
Andrey Karpov
Hartmut Hibst
Radoslav Parashkov
Ingolf Hennig
Marcel Kastler
Friederike Fleischhaker
Lothar Weber
Peter Eckerle
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.)
BASF SE
Original Assignee
BASF SE
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
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09782305A priority Critical patent/EP2321373A1/fr
Publication of EP2321373A1 publication Critical patent/EP2321373A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02601—Nanoparticles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1222—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer
    • H01L27/1225—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating

Definitions

  • the present invention relates to particles modified with a modifier and a dispersant containing the modified particles.
  • Zinc oxide is a promising semiconductor in thin film transistors (TFTs) to produce cheap TFT circuits in large displays or other electronic circuits.
  • MOSFETs metal oxide semiconductor FETs
  • Essential for the deposition is a colloidally stable dispersion to allow the construction of a homogeneous layer of finely divided nanoscale particles.
  • additives modifiers
  • the use of such additives in general has long been known from other applications.
  • WO 2006/138071 and WO 2006/138072 each disclose a method for depositing a semiconducting zinc oxide layer on a substrate from a colloidal dispersion.
  • the dispersion is preferably applied at room temperature and then baked at temperatures below 300 0 C (annealing).
  • the dispersions used are stabilized, but no statements are made about any stabilizers or modifiers.
  • Preferred modifiers are lauryl ether-11-polyethylene glycol acid, capryl ether-6-polyethylene glycol acid, lauryl ether-4 polyethyleneglycolic acid, lauryl ether-6-polyethyleneglycolic acid and / or lauryl ether-8-polyethyleneglycolic acid.
  • DE 10 2005 007 374 A1 discloses nanoparticles which have been modified with a biodegradable polymer, in particular from polyesters, polycyanoacrylates, polyacrylates, polymethyl acrylates, polyepoxides, polyurethanes and polystyrenes.
  • EP 1630136 A1 discloses titanium dioxide particles which have been modified with a hydrophilic polymer, in particular polycarboxylic acids. The carboxyl group of the modifier is bound via an ester bond to the titanium dioxide. Further modifiers are described in DE 10 2005 047 807 A1.
  • modified particles or dispersions used hitherto are those that they significantly impair the performance of the semiconductor components in the deposition of conductive, semiconductive or dielectric layers, or thermal treatment at temperatures at which the substrates are affected is required to improve the performance. This is especially true when using polymer substrates whose thermal stability is generally lower than the inorganic substrates.
  • the object is achieved according to the invention by surface-modified metal, metal halide, metal chalcogenide, metal nitride, metal phosphide, metal boride or metal phosphate particles or mixtures thereof, wherein the particles have an average particle diameter of 1 to 500 nm and whose surface is coated with an o -
  • the plurality of modifiers selected from the formula (I) (II) and
  • X 1 is selected from O, S and Se
  • X 2 is selected from OH, OCH 3 , OC 2 H 5 , CO 2 H, OSi (R 1 ) 3 -x- y (R 2 ) y (R 3 ) xx, y independently of one another equal to 0, 1, 2 or 3 and the sum of x and y is at most 3, R 1 , R 2 , R 3 , R 4 are independently selected from H, C 1 to C 10 alkyl, X 3 is selected from O, S, Se and CH 2 , n, m, p are independently 0, 1, 2 or 3, preferably 0, 1, 2 and more preferably 1
  • R 5 is selected from C 1 to C 4 alkyl
  • X 6 selected from SH, NH 2 , Si (R 1 3 - ⁇ - y ) (R 2 ) y (R 3 ) ⁇
  • X 7 is selected from C 1 to C 10 alkylene, O, S. Se, Te, r is an integer value from 1 to 1000,
  • R 6 is selected from H, C 1 to C 10 alkyl and halogen.
  • the modifiers have a decomposition temperature at which deformation, warpage, decomposition or other thermal changes of the substrate are not observed, especially when the modified particles are applied to the polymer substrate. This allows the modifiers to be removed from the layer applied to a polymer substrate without affecting the structure of the substrate.
  • the decomposition temperature of the modifier (s) used is preferably below 250 ° C.
  • the decomposition temperature should furthermore be above 50 ° C., preferably above 75 ° C., more preferably above 100 ° C., in order to avoid premature decomposition.
  • the decomposition temperature is preferably below 200 ° C., more preferably below 150 ° C.
  • the decomposition temperature is the temperature at which the organic modifier loses its original structure and is decomposed into smaller molecules (eg CO 2 ).
  • X 2 is preferably selected from OH, OCH 3 , COOH, OSi (R 1 ) 3 -x- y (R 2 ) y (R 3 ) ⁇ , particularly preferably selected from OH or OSi (R 1 ) 3-x- y (R 2 ) y (R 3 ) ⁇ .
  • X 3 is selected from O, S, CH 2, in particular selected from O and CH 2. Particularly preferably, X 3 is CH 2.
  • x and y are independently of one another equal to 0, 1 or 2, particularly preferably 0 or 1.
  • R 1 , R 2 , R 3 and R 4 are independently selected from H and Ci to C 4 alkyl, more preferably H, methyl and ethyl.
  • n, m, p are each independently equal to O, 1, 2, more preferably 0 or 1. Furthermore, it is particularly preferred if at least one of m, n or p is 0.
  • X 5 is selected from H, OH, OSi (R 1) (3 -x- y) (R 2) x (R 3) y, CO 2 R 5, OCO 2 R 5, more preferably from CO 2 R 5 .
  • R 5 is preferably selected from methyl, ethyl or tert-butyl, very particularly preferably from ethyl or tert-butyl.
  • Halogens for the purposes of the present invention are F, Cl, Br and I.
  • X 6 is preferably selected from SH, OSi (R 1 3 -x- y ) (R 2 ) y (R 3 ) x, particularly preferably OSi (R 1 3 - x - y ) (R 2 ) y (R 3 ) x
  • X 7 is selected from C 1 to C 4 alkylene, more preferably selected from -CH 2 - and -C 2 H 4 -.
  • r is an integer value of 1 to 100, more preferably from 1 to 10.
  • R 6 is preferably selected from H and C 1 to C 4 alkyl, particularly preferably selected from methyl or ethyl.
  • Preferred modifiers are furthermore those of the formulas Ia to Ih.
  • n, p, X 1 , X 2 , X 4 and X 5 have the abovementioned meanings and R 1 , R 2 , R 3 are selected from C 1 --dAlkyl, more preferably methyl, ethyl or t-butyl.
  • -HC CH-, CH 2 .
  • X 5 is selected from OCH 3 , OC 2 H 5 , CO 2 R 5 and OCO 2 R 5 .
  • Particularly preferred modifiers are compounds of the following structures IV to IX:
  • the particles may be metal, metal chalcogenide, metal phosphide, metal boride, metal nitride or metal phosphate particles or mixtures thereof.
  • the metal chalcogenide, metal phosphide, metal boride, metal phosphate and / or metal nitride particles, in particular metal oxide particles, may here be doped or undoped.
  • Suitable metal halides in the context of the present invention are metal fluorides, metal chlorides, metal bromides and metal iodides, preferably fluorides and chlorides. Particularly preferred are metal chlorides.
  • Suitable metal chalcogenides in the context of the present invention are oxides, sulfides, selenides and tellurides, preferably oxides and sulfides.
  • Suitable metal chalcogenide compounds for depositing semiconductive layers are, in addition to the oxides, for example CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, Cu-In-Ga-Se. Particularly preferred are metal oxide particles.
  • Preferred metal nitrides are AIN, GaN, InN, Al-Ga-N, In-Ga-N, Al-Ga-In-N.
  • Preferred metal phosphides are GaP, InP, Al-Ga-P, Ga-As-P, Al-Ga-In-P.
  • Preferred metal phosphates are rare earth phosphates (lanthanum, cerium, terbium).
  • the particles in particular metal oxide particles, may be dielectric, semiconductive or conductive compounds.
  • binary systems are metal oxides of group 2 (eg MgO), group 3 (eg Y 2 O 3 ), group 4 (eg TiO 2 , ZrO 2 , HfO 2 ), 5 (eg V 2 O 5 , Nb 2 O 5 , Ta 2 O 5 ), Group 6 (e.g., Cr 2 O 3 , MoO 3 , WO 3 ), Group 7 (e.g., MnO 2 ), Group 8 (e.g. B.
  • group 2 eg MgO
  • group 3 eg Y 2 O 3
  • group 4 eg TiO 2 , ZrO 2 , HfO 2
  • 5 eg V 2 O 5 , Nb 2 O 5 , Ta 2 O 5
  • Group 6 e.g., Cr 2 O 3 , MoO 3 , WO 3
  • Group 7 e.g., MnO 2
  • Group 8 e.
  • Group 9 e.g., CoO, Co 3 O 4
  • Group 10 e.g., NiO
  • Group 11 e.g., CuO , Cu 2 O
  • group 12 eg ZnO, CdO
  • group 13 B 2 O 3 , Al 2 O 3 , Ga 2 O 3 , In 2 O 3
  • group 14 SiO 2 , GeO 2 , SnO 2 ,, PbO, Pb 3 O 4
  • group 15 eg Sb 2 O 3 , Bi 2 O 3 , Bi 2 O 3 * Bi 2 O 5 ) of the lanthanides (La 2 O 3 , CeO 2 )
  • oxides may contain additional doping elements (eg Sn, Ge, Mo, F, Ti, Zr, Hf, Nb, Ta, W Te-doped In 2 O 3 , Sb, F, As, Nb, Ta doped
  • mixtures of metal oxides or ternary systems eg Zn 2 SnO 4 , ZnSnO 3 , Zn 2 In 2 O 5 , Zn 3 In 2 O 6 , In 4 Sn 3 O 2 , CdIn 2 O 4 , MgIn 2 O 4 , GaInO 3 , CaTiO 3 , BaTiO 3 , MnFe 2 O 4
  • quaternary systems eg Zn-In-Sn-O, Zn-In-Li-O, In-Ga-Zn-O
  • Preferred metal oxides for depositing semiconducting layers are, for example, ZnO, Ga 2 O 3 , GeO 2 , CdO, In 2 O 3 , SnO 2 , their mixtures or reaction products (ternary - Zn-Sn-O, Zn-In-O, quaternary systems). Ga-In-Zn-O, Zn-In-Sn-O).
  • Particularly preferred metal oxides for depositing semiconducting layers are ZnO and In 2 O 3 .
  • n-type mobility In the case of semiconducting compounds, increasing the n-type mobility frequently involves In, Al, Ga, OH, H doping or intrinsic defects (O vacancies or Zn atoms).
  • Intercalation at interstitial sites used.
  • the increase of the p-type mobility takes place, for example, by doping with Li, N.
  • metal oxides for depositing semiconductive layers are Al- or Mg-doped ZnO, Ga-doped ZnO, Al-doped MgO, Sn-doped ZnO, Bidoped ZnO, and Sn-doped In 2 O 3
  • metallic particles can be used.
  • Suitable metal particles are selected from Ag, Cu, Au and their alloys with other metals.
  • the mean diameter of the particles used is 1 to 500 nm, preferably 2 to 200 nm, more preferably 5 to 100 nm, particularly preferably 10 to 50 nm.
  • the particle size distribution may be unimodal, bimodal or multimodal.
  • the particles can be spherical or also have a platelet-shaped or rod-shaped morphology. Particularly preferred is the rod-shaped morphology.
  • Another object of the present invention are dispersions containing
  • a dispersant in principle, all fluids are suitable in which the particles can be dispersed under the processing conditions.
  • an organic compound is used which is liquid at room temperature and normal pressure.
  • aprotic polar organic liquids Preference is given to using aprotic polar organic liquids.
  • the dipole moment of the dispersant is preferably 3 to 10 m 10 30 C 10 "C 30 m.
  • organic liquids as dispersants, their mixtures with water can be used.
  • the modifier serves to nanoscale stabilize the particles, preferably metal oxide particles. Since one application is the preparation of thin films from these dispersions (e.g., via spin coating, printing, etc.), it makes sense to use as little modifier as possible because the modifier usually needs to be removed after application of the coatings. On the other hand, sufficient stabilizer must be used to permanently stabilize the dispersions.
  • the molar ratio of modifier to metal oxide can vary between 2: 1 and 1:60. Preference is given to a molar ratio of from 1: 1 to 1: 30, more preferably from 1: 5 to 1:25.
  • the content of particles in the dispersion may be from 0.01 to 30% by weight, preferably from 0.1 to 10% by weight, in particular from 1 to 5% by weight.
  • Substrates for the purposes of the present invention may be any conductive, semiconductive or non-conductive substance. The choice of the electrical, mechanical and chemical properties of the substrate depend essentially on the application. Suitable substrates for depositing conductive, semiconductive or non-conductive layers are well known to those skilled in the art.
  • the dispersions according to the invention are particularly suitable for applying layers to polymer substrates, which in turn may be conductive, semiconductive or non-conductive
  • Particularly suitable polymeric substrates are polyimides (PI, available, for example, under the trade name KAPTON), polyester naphthalate (PEN, available, for example, under the trade name TEONEX Q 51) and polyethylene terephthalate (PET, available, for example, under the trade name Hostaphan ).
  • PI polyimides
  • PEN polyester naphthalate
  • PET polyethylene terephthalate
  • the modified particles can be prepared by
  • the dispersions thus obtained may be used directly or may be concentrated to dryness to recover the modified particles. These can be sold directly or subsequently redispersed in another dispersant.
  • a Zn salt e.g. zinc chloride or Zn (CH 3 COO) 2 -2H 2 O
  • a base e.g, KOH or NaOH
  • a dispersing agent e.g. in an alcohol such as methanol, ethanol, isopropanol
  • Doped ZnO particles are obtained, for example, by reacting a mixture of a Zn salt and a corresponding metal salt (eg AICb, Al (OiPr) 3, Al acetylacetonate in the case of an Al doping) with a base in a dispersion medium implemented.
  • the separation of the precipitated particles from by-products can be carried out in a manner known per se, for example by filtration or centrifugation. If necessary, the ZnO dispers ion may be concentrated prior to isolation of the precipitated particles by a membrane technique such as nano, ultra, micro or crossflow filtration. After the fall and before the functionalization, it is also possible to carry out a solvent exchange (for example by means of crossflow filtration).
  • the corresponding modifier is added in the predetermined ratio, so that a transparent dispersion of metal oxide particles is formed.
  • the functionalization takes place at temperatures from room temperature to boiling points of the dispersants used.
  • the pressure is usually from 1 mbar to 50 bar, preferably atmospheric pressure (about 1, 013 bar).
  • the stable dispersion obtained in this way can be applied to the substrate by means of all common, liquid-based deposition methods. Suitable methods for deposition are, in particular, dip coating or spin coating or a printing process (screen printing, flexographic printing, gravure printing, inkjet printing), without being limited thereto.
  • the deposited layer thicknesses are usually between 10 nm and 10 .mu.m, preferably 10 nm to 2 .mu.m, particularly preferably 20 nm to 200 nm.)
  • the layer is at a temperature of between about 50 0 C and 500 0 C, preferably between 75 0 C and 300 0 C, more preferably between 100 0 C and 200 0 C thermally treated.
  • the maximum temperature and duration of treatment depend on the thermal stability of the substrate, the decomposition temperature of the modifier and the purity of the layer to be deposited.
  • the modifier is decomposed and stored in the form of volatile substances, i. Substances that are gaseous in the treatment, removed from the deposited layer.
  • the decomposition into volatile substances should be as complete as possible, but at least 60% by weight, preferably 75% by weight, more preferably 85% by weight, particularly preferably 90% by weight.
  • the thermal treatment can be carried out in air, in oxygen, nitrogen, argon, hydrogen, in steam, or mixtures, etc.
  • the duration of the thermal treatment is usually from about 1 minute to about 30 hours, preferably 30 minutes to 12 hours. Treatment in several steps with different gases is also possible.
  • the energy supply for the decomposition of the modifier by entry by means of a lamp or a laser of a certain wavelength can be carried out.
  • the possible wavelength range is between UV and IR (150nm to 2500nm).
  • a lamp eg. As a mercury lamp or an excimer lamp is either continuously for a period of 1 s to 24 h, preferably 1 min to 1 h and an effective power density of 1 mW / cm 2 to 300 kW / cm 2 or pulsating with one Radiation flash duration of 10 ns to 10 s and an effective power density of 0.02 KW / cm 2 to 300 kW / cm 2 irradiated.
  • a laser When using a laser is preferably irradiated with a duration of the radiation flash of 10 ns to 10 s and an effective power density of 0.02 kW / cm 2 to 300 kW / cm 2 .
  • Another optional alternative is to steam the layer with an acidic, basic or pH neutral chemical (e.g., SO 2, N 2 O, N 2 H 4, NH 3, H 2 O) in addition to a certain energy input to completely remove the corresponding metal oxide surface modification.
  • an acidic, basic or pH neutral chemical e.g., SO 2, N 2 O, N 2 H 4, NH 3, H 2 O
  • the decomposition products were investigated using the example of Malonkladoethylesters.
  • the decomposition of the preferred molecules are temperatures of max. 200 0 C necessary; the decomposition can be carried out under an inert atmosphere (Ar, N2) or under air.
  • Another object of the present invention is the use of the dispersion according to the invention for the production of conductive layers, dielectric layers and / or semiconducting layers.
  • conductive layers a dispersion of electrically conductive particles, in particular metals, prepared and applied to a suitable substrate.
  • Dielectric layers use metal oxide particles, semiconducting layers doped or undoped metal oxide, metal chalcogenide, metal nitride, metal phosphide, metal halide, metal boride or metal phosphate particles.
  • Another object of the present invention is a method for producing a semiconductor device, for. B. a TFTs:
  • Doped or undoped metal oxide particles are used as the semiconductor layer of a TFT.
  • the particles can be made of dispersion z. B. by dip coating, spin coating or printing process to build the TFTs and (if necessary) baked (annealed).
  • TFT architectures such as bottom gate, top gate, top contact, bottom contact, etc.
  • Dielectrics may be any possible organic, inorganic or organic-inorganic hybrid materials gate, source and drain contact materials are conductive materials (eg Al, Au, Ag, Ti / Au, Cr / Au, ITO, Si, PEDOT / PSS etc.).
  • Suitable substrates are in particular also polymeric and flexible materials with low decomposition temperature, as well as other temperature-labile substrates, without being limited thereto.
  • Substrate, gate, source and drain contact materials as well as dielectrics are not subject to any primary restrictions and may vary according to the chemical / physical compatibility, the processing process as well as the desired application.
  • the metal, metal oxide, metal nitride, metal phosphide, metal halide, metal boride or metal phosphate particles and dispersions of the invention are also suitable for these TFT components.
  • the particles and dispersions according to the invention can be used for the deposition of transparent conductive layers, which can be used in a large number of electronic components and can replace the layers used hitherto.
  • Transparent in the sense of the present application meant a transmission of electromagnetic radiation in the range of 400 nm to 800 nm of more than 80%.
  • Moist zinc oxide from example 1 was filled up with 1 l of chloroform. 200 g of a ZnO suspension in chloroform having a ZnO content of 1.6 g (19.66 mmol) were admixed at room temperature with 3.93 mmol of ethyltrimethylsilylmalonate (from Fluka). A few seconds after the addition, the solution cleared. The mixture was stirred for a further 15 minutes at room temperature and then the proportion of ZnO in the dispersion to 4 wt .-% concentrated.
  • FIG. 1 particle size distribution
  • FIG. 2 TEM analysis
  • Example 4 Modification of ZnO with the 3-oxoglutaric acid monoethyl ester (molar ratio of ZnO to modifier equal to 3: 1)
  • Moist zinc oxide from Example 1 was made up with 1 l of methylene chloride. 200 g of a ZnO suspension in methylene chloride with a ZnO content of 1.6 g (19.66 mmol) at room temperature with 1.14 g of 3-Oxoglutar Acidethyl mono-ethyl ester (6.55 mmol) from Example 3 were added; the dispersion cleared up immediately. Subsequently, methylene chloride was distilled off on a rotary evaporator at 40 0 C and the residue dried for a further 4 hours under vacuum.
  • Example 5 Modification of ZnO with the 3-oxoglutaric acid ethyl monoester (molar ratio of ZnO to modifier equal to 5: 1)
  • Example 6 Modification of ZnO with the 3-oxoglutaric acid monoethyl ester (molar ratio of ZnO to modifier equal to 29: 1)
  • Moist zinc oxide from Example 1 was made up with 1 l of methylene chloride. 200 g of a ZnO suspension in methylene chloride with a ZnO content of 1.6 g (19.66 mmol) were added at room temperature with 0.12 g of the 3-Oxoglutar Tarklamono- ethylester (0.67 mmol); the dispersion cleared up immediately. Subsequently, methylene chloride was distilled off on a rotary evaporator at 40 ° C. and the residue was dried under vacuum for a further 4 hours.
  • Moist zinc oxide from Example 1 was made up with 1 l of THF. To this suspension is added 3.5 g of 2- [2- (2-methoxyethoxy) -ethoxy] -acetic acid (Fluka). The resulting mixture was heated to boiling with stirring and held at this temperature for 30 minutes. The suspension cleared. Subsequently, THF was distilled off on a rotary evaporator at 60 0 C and the residue dried for a further 4 hours under vacuum.
  • Moist zinc oxide from Example 1 was made up with 1 l of THF. To this suspension was added 5 g of ethoxyacetic acid (Fluka). The resulting mixture was heated to boiling with stirring and held at this temperature for 30 minutes. The suspension cleared. Subsequently, THF was distilled off on a rotary evaporator at 60 0 C and the residue dried for a further 4 hours under vacuum. According to the TG analysis of the resultant functionalized ZnO powder (. Heating rate 5 ° C / min to 200 0 C, 60 min at 200 0 C, then 5 ° C / min to 500 0 C;..
  • top contact source / drain structures were created by thermal vapor deposition of aluminum.
  • Representative output curves (AK) and transfer curves (TK) of a corresponding transistor are shown in FIGS. 7 and 8 (VD: voltage between source and drain, VG: voltage between source and gate, ID: current between source and drain).
  • Mobility ⁇ 3 * 10 " 3 cm 2 / (V * s), on / off ratio: 10 5 , Vthreshold voltage: 12 V.

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Abstract

L'invention concerne des particules qui sont modifiées au moyen d'un modificateur et un agent de dispersion contenant les particules modifiées. Les particules de métal, halogénure de métal, chalcogénure de métal, nitrure de métal, phosphure de métal, borure de métal ou phosphate de métal ou de mélanges correspondants, qui sont modifiées en surface, présentent un diamètre moyen compris entre 1 et 500 nm et leur surface est modifiée au moyen d'un ou de plusieurs modificateurs de formule (I), (II), et (III).
EP09782305A 2008-09-04 2009-08-28 Particules modifiées et dispersions les contenant Withdrawn EP2321373A1 (fr)

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PE20120730A1 (es) 2009-03-04 2012-06-15 Basf Se Separacion magnetica de minerales metalicos no ferrosos por acondicionamiento en multiples etapas
WO2011061132A1 (fr) * 2009-11-20 2011-05-26 Basf Se Catalyseur multicouche utilisé pour la production d'acides carboxyliques et/ou d'anhydrides d'acide carboxylique, à l'antimoniate de vanadium dans au moins une couche de catalyseur, et procédé de production d'anhydride d'acide phtalique à basse température en zone de surchauffe maximale
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JP2013525250A (ja) 2010-04-28 2013-06-20 ビーエーエスエフ ソシエタス・ヨーロピア 溶液中で亜鉛錯体を調製する方法
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US8859459B2 (en) 2010-06-30 2014-10-14 Basf Se Multilayer catalyst for preparing phthalic anhydride and process for preparing phthalic anhydride
US9212157B2 (en) 2010-07-30 2015-12-15 Basf Se Catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride
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WO2010026102A1 (fr) 2010-03-11
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US8734899B2 (en) 2014-05-27
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US20110163278A1 (en) 2011-07-07
TWI488815B (zh) 2015-06-21

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