Photoelectric conversion material dispersion liquid and producing method thereof, producing method and producing apparatus of photoelectric conversion film, and photoelectric conversion device

Abstract

A photoelectric conversion material dispersion liquid of an embodiment includes: perovskite crystal particles having a composition represented as ABX 3 , where A is a monovalent cation of an amine compound, B is a divalent cation of a metal element, and X is a monovalent anion of a halogen element, and having an average particle diameter of not less than 10 nm nor more than 10000 nm; and a dispersion medium which is composed of a poor solvent to the perovskite crystal particles, and in which the perovskite crystal particles are dispersed.

What is claimed is: 
     
         1 . A photoelectric conversion material dispersion liquid, comprising:
 perovskite crystal particles having a composition represented by a composition formula: ABX 3 , wherein A is a monovalent cation of an amine compound, B is a divalent cation of a metal element, and X is a monovalent anion of a halogen element, and having an average particle diameter of 10 nm or more and 10000 nm or less; and   a dispersion medium which is composed of a poor solvent to the perovskite crystal particles, and in which the perovskite crystal particles are dispersed.   
     
     
         2 . The dispersion liquid of  claim 1 , wherein the amine compound is at least one selected from the group consisting of methylammonium and formamidinium, the metal element is at least one selected from the group consisting of lead and tin, and the halogen element is at least one selected from the group consisting of iodine, bromine, and chlorine. 
     
     
         3 . The dispersion liquid of  claim 1 , wherein the dispersion medium contains at least one selected from the group consisting of a substituted or unsubstituted aliphatic hydrocarbon having six or more carbons, a substituted or unsubstituted alicyclic hydrocarbon having five or more carbons, a halogenated hydrocarbon having four or more carbons, and silicone oil. 
     
     
         4 . The dispersion liquid of  claim 1 , further comprising:
 a charge imparting agent dispersed in the dispersion medium.   
     
     
         5 . A producing method of a photoelectric conversion material dispersion liquid, comprising:
 preparing a material of perovskite crystal particles having a composition represented by a composition formula: ABX 3 , wherein A is a monovalent cation of an amine compound, B is a divalent cation of a metal element, and X is a monovalent anion of a halogen element;   preparing a first liquid composed of a poor solvent to the perovskite crystal particles and a second liquid composed of a solvent which has a solubility of the perovskite crystal particles higher than a solubility of the first liquid and has a vapor pressure higher than a vapor pressure of the first liquid;   dissolving the material in the second liquid to fabricate a first mixed solution;   mixing the first mixed solution and the first liquid together to fabricate a second mixed solution; and   evaporating the second liquid from the second mixed solution and crystallizing the material dissolved in the second liquid to generate the perovskite crystal particles, to obtain a dispersion liquid having the perovskite crystal particles dispersed in the first liquid.   
     
     
         6 . The producing method of  claim 5 , further comprising:
 adding a charge imparting agent into the dispersion liquid.   
     
     
         7 . A producing method of a photoelectric conversion film, comprising:
 forming a photoelectric conversion film containing the perovskite crystal particles on a film forming object by causing the photoelectric conversion material dispersion liquid according to  claim 1  to adhere on the film forming object.   
     
     
         8 . The producing method of  claim 7 , further comprising:
 at least one of exposing the photoelectric conversion film to a good solvent of the perovskite crystal particles, heating the photoelectric conversion film, and pressurizing the photoelectric conversion film.   
     
     
         9 . The producing method of  claim 7 ,
 wherein the film forming includes:
 disposing a coating head above the film forming object; 
 forming a meniscus column of the photoelectric conversion material dispersion liquid between the film forming object and the coating head; and 
 moving at least one of the film forming object and the coating head to apply the photoelectric conversion material dispersion liquid on the film forming object from the meniscus column. 
   
     
     
         10 . The producing method of  claim 7 ,
 wherein the film forming includes:
 supplying the photoelectric conversion material dispersion liquid between the film forming object and a counter electrode for electrodeposition; and 
 applying a voltage to the film forming object and the counter electrode to electrodeposit the perovskite crystal particles in the photoelectric conversion material dispersion liquid onto the film forming object. 
   
     
     
         11 . The producing method of  claim 7 ,
 wherein the film forming includes:
 forming an electrostatic pattern on an electrostatic pattern support body; 
 supplying the photoelectric conversion material dispersion liquid on the electrostatic pattern support body to form a pattern of the perovskite crystal particles according to the electrostatic pattern; and 
 transferring the pattern of the perovskite crystal particles onto the film forming object. 
   
     
     
         12 . A producing apparatus of a photoelectric conversion film, comprising:
 a film forming mechanism which causes the photoelectric conversion material dispersion liquid according to  claim 1  to adhere on a film forming object,   wherein a photoelectric conversion film containing the perovskite crystal particles is formed on the film forming object.   
     
     
         13 . The producing apparatus of  claim 12 , further comprising:
 at least one of a mechanism which exposes the photoelectric conversion film to a good solvent of the perovskite crystal particles, a mechanism which heats the photoelectric conversion film, and a mechanism which pressurizes the photoelectric conversion film.   
     
     
         14 . The producing apparatus of  claim 12 ,
 wherein the film forming mechanism includes:
 a coating head disposed above the film forming object; 
 a supply mechanism which supplies the photoelectric conversion material dispersion liquid between the film forming object and the coating head to form a meniscus column of the photoelectric conversion material dispersion liquid; and 
 a moving mechanism which moves at least one of the coating head and the film forming object to apply the photoelectric conversion material dispersion liquid on the film forming object from the meniscus column. 
   
     
     
         15 . The producing apparatus of  claim 12 ,
 wherein the film forming mechanism includes:
 a counter electrode for electrodeposition disposed to face the film forming object; and 
 a mechanism which applies a voltage to the film forming object and the counter electrode in a state where the photoelectric conversion material dispersion liquid is supplied between the film forming object and the counter electrode, 
   wherein the perovskite crystal particles in the photoelectric conversion material dispersion liquid are electrodeposited onto the film forming object by applying the voltage.   
     
     
         16 . The producing apparatus of  claim 12 ,
 wherein the film forming mechanism includes:
 an electrostatic pattern support body; 
 a mechanism which forms an electrostatic pattern on the electrostatic pattern support body; 
 a mechanism which supplies the photoelectric conversion material dispersion liquid to the electrostatic pattern support body having the electrostatic pattern thereon to form a pattern of the perovskite crystal particles according to the electrostatic pattern; and 
 a mechanism which transfers the pattern of the perovskite crystal particles onto the film forming object. 
   
     
     
         17 . A photoelectric conversion device, comprising:
 a substrate;   a first electrode disposed on the substrate;   a photoelectric conversion film, disposed on the first electrode, containing perovskite crystal having a composition represented by a composition formula: ABX 3 , wherein A is a monovalent cation of an amine compound, B is a divalent cation of a metal element, and X is a monovalent anion of a halogen element, and a charge imparting agent; and   a second electrode disposed on the photoelectric conversion film.   
     
     
         18 . The device of  claim 17 , wherein the amine compound is at least one selected from the group consisting of methylammonium and formamidinium, the metal element is at least one selected from the group consisting of lead and tin, and the halogen element is at least one selected from the group consisting of iodine, bromine, and chlorine.