METHODS OF MANUFACTURING NANOCRYSTAL THIN FILMS AND ELECTROCHROMIC DEVICES CONTAINING NANOCRYSTAL THIN FILMS

1 . A method of forming a nanocrystal thin film (NTF), the method comprising:

depositing a precursor solution on a substrate to form a precursor layer, the precursor solution comprising:

metal oxide nanoparticles;

a solvent; and

C8 or lower capping ligands bound to the metal oxide nanoparticles; and

annealing the precursor layer to form the NTF on the substrate.

2 . The method of claim 1 , further comprising forming the precursor solution by exchanging C12 or higher capping ligands bound to the metal oxide nanoparticles for the C8 or lower capping ligands.

3 . The method of claim 2 , wherein the C8 or lower capping ligands comprise a C8 or lower phosphonic acid, a C8 or lower carboxylic acid, or a C8 or lower amine.

4 . The method of claim 2 , wherein the exchanging comprises:

providing a solution comprising the metal oxide nanoparticles having the C12 or higher capping ligands bound thereto, a solvent, and C8 or lower capping ligands; and

exchanging the C12 or higher capping ligands with the C8 or lower capping ligands.

5 . The method of claim 4 , further comprising:

sonicating the solution to exchange the C12 or higher capping ligands with the C8 or lower capping ligands;

extracting the metal oxide nanoparticles from the sonicated solution; and

dispersing the extracted metal oxide nanoparticles in a solvent to form the precursor solution.

6 . The method of claim 4 , wherein the C8 or lower capping ligands comprise a phosphonic acid.

7 . The method of claim 2 , wherein the exchanging comprises:

preparing a first solution comprising the metal oxide nanoparticles having the C12 or higher capping ligands bound thereto and a solvent;

sonicating the first solution to remove the C12 or higher capping ligands from the metal oxide nanoparticles;

extracting the metal oxide nanoparticles from the sonicated first solution;

preparing a second solution comprising the metal oxide nanoparticles, a solvent, and C8 or lower capping ligands; and

sonicating the second solution to bind the C8 or lower capping ligands to the metal oxide nanoparticles.

8 . The method of claim 7 , further comprising:

extracting the metal oxide nanoparticles from the sonicated second solution; and

dispersing the extracted metal oxide nanoparticles in a solvent to form the precursor solution.

9 . The method of claim 7 , wherein the C8 or lower capping ligands comprise C8 or lower carboxylic acid ligands, C8 or lower amine ligands, or a combination thereof.

10 . The method of claim 1 , wherein:

the depositing a precursor solution comprises forming the precursor layer using a single coating step or a printing step; and

the NTF has a thickness of at least 500 nm.

11 . The method of claim 10 , wherein the NTF comprises less than 1 discontinuity per cm 2 of surface area.

12 . The method of claim 1 , wherein the NTF comprises a working electrode of an electrochromic device and the nanoparticles comprise electrochromic metal oxide nanoparticles.

13 . The method of claim 12 , further comprising forming an electrolyte between the working electrode and a counter electrode of the electrochromic device.

14 . The method of claim 1 , wherein:

the precursor solution further comprises a structural component;

annealing the precursor layer removes the C8 or lower capping ligands to form the NTF on the substrate; and

the structural component reduces shrinkage of the precursor layer during the annealing to prevent or reduce formation of discontinuities during the annealing.

15 . The method of claim 14 , wherein:

the nanoparticles comprise metal oxide nanoparticles having an average particle size ranging from about 1 nm to about 10 nm; and

the structural component has an average size that is at least two times greater than an average particle size of the nanoparticles, or the structural component has an average aspect ratio that is at least two times greater than the average aspect ratio of the nanoparticles.

16 . The method of claim 15 , wherein the structural component comprises:

a scaffolding agent comprising elongated nanoparticles having an average aspect ratio of at least 1:5, having the average aspect ratio that is at least two times greater than an average aspect ratio of the nanoparticles, and having an average length ranging from about 10 nm to about 100 nm;

oversized nanoparticles comprising a metal oxide having an average particle size ranging from about 20 nm to about 50 nm;

an interconnected supporting matrix around the metal oxide nanoparticles; or any combination of the scaffolding agent, the oversized nanoparticles, and the matrix.

17 . The method of claim 16 , wherein the structural component comprises the scaffolding agent selected from carbon nanotubes, metal nanowires, crystalline metal oxide or metal nitride nano-rods, or any combinations thereof.

18 . The method of claim 16 , wherein the structural component comprises the oversized nanoparticles, which comprise an electrically conductive an optically transparent material.

19 . The method of claim 16 , wherein the structural component comprises the matrix selected from at least one of a lithium metal oxide material or a Li-rich anti-perovskite (LiRAP) material having the formula Li 3 OX, where X may be a halogen or a combination of halogens.

20 . A method, comprising:

providing a precursor solution comprising a solvent and metal oxide nanoparticles having C12 or higher capping ligands bound thereto; and

exchanging C12 or higher capping ligands bound to the metal oxide nanoparticles for the C8 or lower capping ligands bound to the metal oxide nanoparticles.

21 . The method of claim 20 , further comprising

depositing a precursor solution on a substrate to form a precursor layer; and

annealing the precursor layer to form a nanocrystal thin film on the substrate.