Solution for fabrication of electron-emitting devices, manufacture method of electron-emitting devices, and manufacture method of image-forming apparatus

Abstract

In a solution for forming electron-emitting regions of electron-emitting devices, the solution contains a metal carboxylate expressed by the following general formula (I), an organic solvent <DEL-S DATE="20021029" ID="DEL-S-00001"/>and/or<DEL-E ID="DEL-S-00001"/> <INS-S DATE="20021029" ID="INS-S-00001"/>, and <INS-E ID="INS-S-00001"/>water;where k=<DEL-S DATE="20021029" ID="DEL-S-00002"/>numeral from<DEL-E ID="DEL-S-00002"/> 1 <DEL-S DATE="20021029" ID="DEL-S-00003"/>to 4<DEL-E ID="DEL-S-00003"/> , m=<INS-S DATE="20021029" ID="INS-S-00002"/>a <INS-E ID="INS-S-00002"/>numeral from 1 to 4, and <DEL-S DATE="20021029" ID="DEL-S-00004"/>R=CnX2n+1-k<DEL-E ID="DEL-S-00004"/> <INS-S DATE="20021029" ID="INS-S-00003"/>R=CnX2n+2-k <INS-E ID="INS-S-00003"/>where X=<INS-S DATE="20021029" ID="INS-S-00004"/>a <INS-E ID="INS-S-00004"/>hydrogen or halogen <DEL-S DATE="20021029" ID="DEL-S-00005"/>(total number of hydrogen and halogen atoms is 2n+1)<DEL-E ID="DEL-S-00005"/> , n=<INS-S DATE="20021029" ID="INS-S-00005"/>an <INS-E ID="INS-S-00005"/>integer from 0 to 30, and M=<INS-S DATE="20021029" ID="INS-S-00006"/>a <INS-E ID="INS-S-00006"/>metal<INS-S DATE="20021029" ID="INS-S-00007"/>, wherein the organic solvent is a carboxylic ester having the same carboxylic group as R(COO)k expressed in the general formula (I)<INS-E ID="INS-S-00007"/>. In a manufacture method of electron-emitting devices each provided between electrodes with a conductive film including an electron-emitting region, a process of forming the conductive film includes a step of coating and calcining the above solution. An image-forming apparatus is manufactured by using the electron-emitting devices. Variations in sheet resistance values of electron-emitting region-forming thin films and characteristics of the electron-emitting devices are reduced.

What is claimed is:  
     
       1. A solution (for fabrication of electron-emitting devices) and for forming electron-emitting regions of electron-emitting devices, wherein said solution contains a metal carboxylate expressed by the following formula (I), and a carboxylic ester; 
       
         
           (R(COO) k ) m M  (I)  
         
       
       where k=numeral from 1 to 4, m=numeral from 1 to 4, and 
       R=C n X 2n+1−k  where X=hydrogen or halogen (total number of hydrogen and halogen atoms is 2n+1),  
       n=integer from 0 to 30, and M=metal.  
     
     
       2. A solution according to  claim 1 , wherein said carboxylic ester has the same carboxylic group as R(COO) k  expressed in said general formula (I). 
     
     
       3. A solution according to  claim 1 , wherein said carboxylic ester has a carboxylic group different in R from R(COO) k  expressed in said general formula (I). 
     
     
       4. A solution according to  claim 1 , wherein the content of said metal carboxylate expressed by said general formula (I) is in the range of 0.1 wt % to 10 wt %. 
     
     
       5. A solution according to any of claims  1 ,  2 ,  3  and  4  further containing a carboxylic acid. 
     
     
       6. A solution according to  claim 5 , wherein said carboxylic acid has the same carboxylic group as R(COO) k  expressed in said general formula (I). 
     
     
       7. A solution according to  claim 6 , wherein said carboxylic acid has the carboxylic group in 1 to 1/100 equivalent with respect to said metal carboxylate expressed in said general formula (I). 
     
     
       8. A solution according to  claim 5 , wherein said carboxylic acid has a carboxylic group different in R from R(COO) k  expressed in said general formula (I). 
     
     
       9. A solution according to  claim 8 , wherein said carboxylic acid has the carboxylic group in 1 to 1/100 equivalent with respect to said metal carboxylate expressed in said general formula (I). 
     
     
       10. A manufacture method of electron-emitting devices each provided between electrodes with a conductive film including an electron-emitting region, said electron- emitting devices being capable of emitting electrons from the electron - emitting region to the outside thereof,  wherein the method comprises: 
       ( a ) a process of forming  creating the conductive film in which the electron-emitting region is to be formed that includes a step of coating and calcining a solution which contains  0 . 1  wt %  to  10  wt  %  of  a metal carboxylate expressed by the following general formula (I), an organic solvent and/or, and water;  
       
         
           (R(COO) k ) m M  (I)  
         
       
        where k=numeral from  1 to 4 , m=a numeral from 1 to 4, and R=C n X 2n+1−k X 2n+2−k  where X=a hydrogen or halogen (total number of hydrogen and halogen atoms is 2n+1) , n=an integer from 0 to 30, and M=a metal, wherein said organic solvent is a carboxylic ester having the same carboxylic group as R( COO ) k    expressed in the general formula  ( I ) , at least  90   %  of the metal carboxylate being decomposed during the calcining step; and    
       ( b )  a process of forming the electron - emitting region in said created conductive film .  
     
     
       11. A manufacture method of electron-emitting devices according to  claim 10 , wherein said organic solvent is carboxylic ester. 
     
     
       12. A manufacture method of electron-emitting devices according to  claim 11 , wherein said carboxylic ester has the same carboxylic group as R(COO) k  expressed in said general formula (I). 
     
     
       13. A manufacture method of electron-emitting devices according to  claim 11 , wherein said carboxylic ester has a carboxylic group different in R from R(COO) k  expressed in said general formula (I). 
     
     
       14. A manufacture method of electron-emitting devices according to  claim 10 , wherein said organic solvent is hydrocarbon halide. 
     
     
       15. A manufacture method of electron-emitting devices according to  claim 10 , wherein the content of said metal carboxylate expressed by said general formula (I) is in the range of 0.1 wt % to 10 wt %. 
     
     
       16. A manufacture method of electron-emitting devices according to  claim 10 , wherein the solution used in process ( a ) further containing  contains a carboxylic acid. 
     
     
       17. A manufacture method of electron-emitting devices according to  claim 16 , wherein said carboxylic acid has the same carboxylic group as R(COO) k  expressed in said general formula (I). 
     
     
       18. A manufacture method of electron-emitting devices according to  claim 17 , wherein said carboxylic acid has the carboxylic group in 1 to 1/100 equivalent with respect to said metal carboxylate expressed in said general formula (I). 
     
     
       19. A manufacture method of electron-emitting devices according to  claim 16 , wherein said carboxylic acid has a carboxylic group different in R from R(COO) k  expressed in said general formula (I). 
     
     
       20. A manufacture method of electron-emitting devices according to  claim 19 , wherein said carboxylic acid has the carboxylic group in 1 to 1/100 equivalent with respect to said metal carboxylate expressed in said general formula (I). 
     
     
       21. A manufacture method of electron-emitting devices according to any one of claims  10 toor  16 - 20 , further including a step of applying a voltage to the conductive film formed by said film forming step  wherein said process of forming the electron- emitting region includes a step of applying a voltage to the conductive film created by said film - creating process . 
     
     
       22. A manufacture method of an electron source comprising a plurality of electron-emitting devices, wherein said electron-emitting devices are produced by the manufacture method according to  claim 10 . 
     
     
       23. A manufacture method of an image-forming apparatus comprising electron-emitting devices and an image-forming member, wherein said electron-emitting devices are produced by the manufacture method according to  claim 10 . 
     
     
       24. A manufacture method of electron- emitting devices each provided between electrodes with a conductive film including an electron - emitting region, said electron - emitting devices being capable of emitting electrons from the electron - emitting region to the outside thereof, wherein the method comprises:    
       ( a )  a process of creating the conductive film in which the electron - emitting region is to be formed that includes a step of coating and calcining a solution which contains  0 . 1  wt  %  to  10  wt  %  of a metal carboxylate expressed by the following general formula  ( I ) , an organic solvent, and water:    
       
         
           ( R ( COO ) k ) m   M   ( I )  
         
       
         where k= 2 ,  3 , or  4 , m=a numeral from  1  to  4 , and R=C   n   X   2n+2−k    or C   6   H   4    where X=hydrogen or halogen, n=an integer from  0  to  30 , and M=a metal, provided that when n= 0 , k= 2 , and when R=C   6   H   4   , k= 2 , and wherein said organic solvent is a carboxylic ester having the same carboxylic group as R ( COO ) k    expressed in the general formula  ( I ) , at least  90   %  of the metal carboxylate being decomposed during the calcining step; and    
       ( b )  a process of forming the electron - emitting region, in said created conductive film.