FORMULATION OF COLLOIDAL TITANIUM-OXIDE SOLUTIONS COMPOSITION FOR COATING AND PRINTING METHODS, AND IMPROVEMENT OF THE OUTPUT AND LIFESPAN OF ORGANIC P-I-N/N-I-P PHOTOVOLTAIC CELLS

• US 20150024539A1
• Filed: 09/12/2012
• Published: 01/22/2015
• Est. Priority Date: 09/16/2011
• Status: Active Grant

• Current Assignee: Ardeje, Centre National De La Recherche Scientifique, Commissariat a L'Energie Atomique (French Alternative Energies and Atomic Energy Commission), Universite De Nantes
• Original Assignee: Ardeje, Centre National De La Recherche Scientifique, Commissariat a L'Energie Atomique (French Alternative Energies and Atomic Energy Commission), Universite De Nantes
• Inventors: Berson, Solenn, Brohan, Luc Ren Roger, Karpinski, Arkadiusz Michal, Richard-Plouet, Mireille, Guillerez, Stphane, Barret, Mickal, Mourao, Jrme
• Granted Patent: US 9,425,344 B2
• Time in Patent Office: Days
• US Class Current: 438/63
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01G 23/053 Producing by wet processes, e.g. hydrolysing titanium salts
• CPC Class Codes: C01G 23/08 Drying; Calcining ; After treatment of titanium oxide
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/22 Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C09D 11/30 Inkjet printing inks
• CPC Class Codes: H01G 9/2031 comprising titanium oxide, e.g. TiO2 H01G9/2036 takes precedence
• CPC Class Codes: H01G 9/2059 comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• CPC Class Codes: H01L 31/032 including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
• CPC Class Codes: H01L 31/18 Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
• CPC Class Codes: Y02E 10/542 Dye sensitized solar cells
• CPC Class Codes: Y02E 10/547 Monocrystalline silicon PV cells
• CPC Class Codes: Y02E 10/548 Amorphous silicon PV cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a method for preparing a colloidal nanoparticle solution, including: (a) dissolving a titanium-oxide precursor, referred to as a precursor, in one or more solvents, referred to as precursor solvents; and (b) chemically converting, preferably by means of hydrolysis, said titanium-oxide precursor and said precursor solvent into a colloidal-solution solvent so as to form titanium-oxide nanoparticles that are dispersed in the colloidal-solution solvent, said colloidal solution having a dynamic viscosity of between 4 and 54 cP at 20° C. and 101,325 Pa.

The invention also relates to a colloidal titanium-oxide nanoparticle solution containing a dispersion of titanium-oxide nanoparticles in a solvent or system of solvents, the viscosity of which is between 4 and 54 cP, said solution being particularly obtainable according to the method of the invention, as well as to the uses thereof, in particular for preparing photovoltaic cells. The invention also relates to a method for generating power using a semiconductor prepared from said solution.

Claims

1-22. -22. (canceled)

23. A method for preparing a colloidal solution of nanoparticles, wherein said method comprises:

(a) dissolving a precursor of titanium-oxide, the precursor, in one or more precursor solvents, the precursor solvent, and (b) chemically converting the precursor to titanium-oxide and the precursor solvent to a colloidal-solution solvent, to form nanoparticles of titanium-oxide dispersed in the colloidal-solution solvent, said colloidal-solution solvent having a dynamic viscosity between 4 and 60 cP at 20°

C. and 101,325 Pa, and (c) forming a colloidal solution of nanoparticles of titanium-oxide having a dynamic viscosity of between 4 and 60 cP at 20°

C. and 101,325 Pa.

24. The method according to claim 23, wherein the dynamic viscosity of the colloidal solution of nanoparticles of titanium-oxide is between 4 and 25 cP at 20°

C. and 101,325 Pa.

25. The method according to claim 23, wherein the dynamic viscosity of the colloidal solution of nanoparticles of titanium-oxide is between 8 and 15 cP at 20°

C. and 101,325 Pa.

26. The method according to claim 23, wherein the precursor solvent comprises at least one first solvent and a second solvent, and in that the first solvent is consumed in full or in part by the chemical conversion of the second solvent, and in that the second solvent is converted in full or in part to a third solvent, said colloidal-solution solvent comprising at least the third solvent and optionally the first and/or second solvent.

27. The method according to claim 23, wherein the viscosity is controlled by halting the chemical conversion step of the precursor solvent.

28. The method according to claim 23, wherein said method comprises the contacting of the titanium-oxide precursor with a two-phase solvent, followed by the conversion of the two-phase solvent by hydrolysis to a single-phase solvent comprising titanium-oxide nanoparticles.

29. The method according to claim 26, wherein the first solvent is water.

30. The method according to claim 26, wherein the second solvent is chosen from among propylene carbonate and/or an alcohol having a vicinal diol such as propylene glycol, and/or a vicinal diol derivative such as 2-chloro-propan-1-ol, and/or a triol having a vicinal diol such as glycerol(1,2,3-propanetriol), and/or a glycol ether, or any of the mixtures thereof.

31. The method according to claim 26, wherein the first solvent is water and the second solvent is propylene carbonate (PC).

32. The method according to claim 31, wherein [water]/[PC] molar ratio is of between 0.1 and 1.5.

33. The method according to claim 23, wherein the concentration of the precursor expressed in concentration of titanium is between 0.005 and 0.1 M·

L<sup>−

1</sup>.

34. The method according to claim 23, wherein the conversion of the precursor to titanium-oxide produces hydrochloric acid, and the produced hydrochloric acid is consumed by reaction with at least one compound of said precursor solvent or a compound formed during the chemical conversion of the precursor solvent.

35. The method according to claim 23, wherein colloidal-solution solvent is added to the precursor solvent, or a solvent that is part of the colloidal-solution solvent.

36. The method according to claim 23, wherein the colloidal solution of titanium-oxide nanoparticles is exposed to UV radiation to improve its solar radiation absorption properties.

41. A method for preparing an n-type semiconductor, said method comprising preparing a colloidal solution according to the method of claim 23, and forming an n-type semiconductor.

42. A method for preparing an n-type semiconductor layer, wherein said method comprises the preparation of a colloidal solution according to claim 23, and the depositing of a layer of colloidal solution on a substrate to form an n-type semiconductor layer comprising titanium-oxide nanoparticles, and forming an n-type semiconductor layer.

43. The method according to claim 42, wherein said depositing is performed by printing or coating, spin coating, inkjet printing, screen printing, photo-engraving and/or roll-to-roll optionally using one or more patterns on the substrate (patterning).

44. The method according to claim 42, wherein said method comprises the depositing of the colloidal solution on a substrate, followed by annealing at a temperature of between 50 and 500°

C.

45. A photovoltaic device, wherein said photovoltaic device comprises an n-type semiconductor material obtained according to claim 42.

46. The photovoltaic device according to claim 45, wherein said photovoltaic device forms a photovoltaic cell of p-i-n or n-i-p type, an organic transistor or a light-emitting diode.

47. A method for manufacturing a photovoltaic device, wherein said method comprises the preparation of an n-type semiconductor layer according to claim 42, and forming a photovoltaic device comprising said n-type semiconductor layer.

48. A method for producing power wherein said method comprises producing power from solar radiation with an n-type semiconductor material obtained according to claim 42.

49. A method for producing power wherein said method comprises producing power from solar radiation with a photovoltaic device according to claim 45.

37. A colloidal solution of titanium-oxide nanoparticles, wherein said colloidal solution comprises a dispersion of titanium-oxide nanoparticles in a solvent or solvent system having a viscosity of between 4 and 60 cP at 20°

C. and at 101,325 Pa.

38. The colloidal solution according to claim 37, wherein said colloidal solution comprises titanium-oxide nanoparticles in anatase form.

39. The colloidal solution according to claim 37, wherein said titanium-oxide nanoparticles present a hydrodynamic diameter of between 2 and 50 nm, and any clusters present a hydrodynamic diameter of between 50 and 250 nm.

40. A method for preparing an n-type semiconductor, said method comprising preparing a colloidal solution according to claim 37, and forming an n-type semiconductor.