Low Halide Lanthanum Precursors For Vapor Deposition

Abstract

Lanthanide compounds for vapor deposition having ≤50.0 ppm, ≤30.0 ppm, or ≤10.0 ppm of all halide impurity combined is provided. The purification systems and methods are also provided.

1 . A composition comprising lanthanide amidinate compound Ln(AMD) 3  having Formula I 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from the group consisting of hydrogen, and C 1  to C 5  linear or branched alkyl; and R 2  and R 2  each is independently selected from the group consisting of C 1  to C 5  linear or branched alkyl; Ln is a lanthanide selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; 
         wherein the composition comprises at least one halide impurity and each of halide impurity ranges from 10.0 ppm or less; and all halide impurities combined ranges 50.0 ppm or less. 
       
     
     
         2 . The composition of  claim 1 , wherein the at least one halide impurity is selected from the group consisting of chloride, bromide, iodide, fluoride and combinations thereof; and each of halide impurity ranges from 5.0 ppm or less. 
     
     
         3 . The composition of  claim 1 , wherein the composition comprising ≤1.0 ppm chloride, ≤1.0 ppm bromide, ≤1.0 ppm iodide, and ≤1.0 ppm fluoride. 
     
     
         4 . The composition of  claim 1 , wherein R 1  is hydrogen and the lanthanide amidinate compound is selected from the group consisting of La(FAMD) 3 , Ce(FAMD) 3 , Pr(FAMD) 3 , Nd(FAMD) 3 , Pm(FAMD) 3 , Sm(FAMD) 3 , Eu(FAMD) 3 , Gd(FAMD) 3 , Tb(FAMD) 3 , Dy(FAMD) 3 , Ho(FAMD) 3 , Er(FAMD) 3 , Tm(FAMD) 3 , Yb(FAMD) 3 , and Lu(FAMD) 3 . 
     
     
         5 . The composition of  claim 1 , wherein the lanthanide is lanthanum and R 1  is hydrogen. 
     
     
         6 . A system for purifying a crude lanthanide amidinate material for vapor deposition comprising
 f) the crude lanthanide amidinate material comprises lanthanide amidinate compound having Formula I   
       
         
           
           
               
               
           
         
         
           wherein R 1  is selected from the group consisting of hydrogen, and C 1  to C 5  linear or branched alkyl; and R 2  and R 2  each is independently selected from the group consisting of C 1  to C 5  linear or branched alkyl; Ln is a lanthanide selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; 
         
         g) zone 1 comprising at least one sublimer; wherein the crude lanthanide amidinate material is placed inside the at least one sublimer; 
         h) zone 2 comprising at least one condenser; wherein the zone 2 is in fluid communication with the zone 1; 
         i) zone 3 comprising at least one cooler; wherein the zone 3 is in fluid communication with the zone 2; and optionally 
         j) a separation unit selected from the group consisting of convoluted pathway, glass wool, filter, and combinations thereof; wherein the separation unit is installed between the zone 1 and the zone 2;
 wherein 
 the crude lanthanide amidinate material comprises 50 ppm or more at least one impurity selected from the group consisting of (i) halide impurities selected from the group consisting of LnCl x (AMD) y  (x+y=3), LnBr x (AMD) y  (x+y=3), LnI x (AMD) y (x+y=3), LnF x (AMD) y  (x+y=3), wherein x or y is selected from 1 or 2, and combinations thereof; (ii) light impurities LnO(AMD) 2 , (iii) trace metals, and (iv) trace amounts of non-volatile impurities Ln 2 O 3 , Ln(OH) 3 , or combinations; 
 and 
 purified lanthanide amidinate material is inside the at least one condenser in the zone 2; and the purified lanthanide amidinate material comprises each of halide impurity ranging from 10.0 ppm or less and all halide impurities combined ranging from 50.0 ppm or less. 
 
       
     
     
         7 . The system of  claim 6 , wherein the purified lanthanide amidinate material comprises each of halide impurity ranging from 5.0 ppm or less. 
     
     
         8 . The system of  claim 6 , wherein the lanthanide amidinate compound is selected from the group consisting of La(FAMD) 3 , Ce(FAMD) 3 , Pr(FAMD) 3 , Nd(FAMD) 3 , Pm(FAMD) 3 , Sm(FAMD) 3 , Eu(FAMD) 3 , Gd(FAMD) 3 , Tb(FAMD) 3 , Dy(FAMD) 3 , Ho(FAMD) 3 , Er(FAMD) 3 , Tm(FAMD) 3 , Yb(FAMD) 3 , and Lu(FAMD) 3 . 
     
     
         9 . The system of  claim 6 , wherein the lanthanide is lanthanum and R 1  is hydrogen. 
     
     
         10 . The system of  claim 6 , wherein the system comprises the separation unit and the purified lanthanide amidinate material comprises each of halide impurity ranging from 2.0 ppm or less. 
     
     
         11 . The system of  claim 6 , wherein the system comprises the separation unit and the purified lanthanide amidinate material comprises each of halide impurity ranging from 1.0 ppm or less. 
     
     
         12 . A method for purifying a crude lanthanide amidinate material for vapor deposition comprising
 a. providing the crude lanthanide amidinate material comprises lanthanide compound having Formula I   
       
         
           
           
               
               
           
         
         
           wherein R 1  is selected from the group consisting of hydrogen, and C 1  to C 5  linear or branched alkyl; and R 2  and R 2  each is independently selected from the group consisting of C 1  to C 5  linear or branched alkyl; Ln is a lanthanide selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; 
           and 
           the crude lanthanide amidinate material comprises at least one impurity selected from the group consisting of (i) halide impurities selected from the group consisting of LnCl x (AMD) y  (x+y=3), LnBr x (AMD) y  (x+y=3), LnI x (AMD) y  (x+y=3), LnF x (AMD) y  (x+y=3), wherein x or y is selected from 1 or 2, and combinations thereof; (ii) light impurity LnO(AMD) 2 , and (iii) trace amounts of non-volatile impurities Ln 2 O 3 , Ln(OH) 3 , or combinations; 
         
         b. providing zone 1 comprising at least one sublimer, zone 2 comprising at least one condenser; and zone 3 comprising at least one cooler; optionally a separation unit installed between the zone 1 and the zone 2 and the separation unit is selected from the group consisting of convoluted pathway, glass wool, filter, and combinations thereof; wherein the zone 2 is in fluid communication with the zone 1 and the zone 3 is in fluid communication with the zone 2; 
         c. heating the crude lanthanide amidinate material contained in the at least one sublimer in the zone 1 to get crude lanthanide amidinate material vapor separated from the halide impurities and the trace amounts of non-volatile impurities; 
         d. passing the crude lanthanide amidinate material vapor from the zone 1 to the at least one condenser in the zone 2 and condensing the crude lanthanide amidinate material vapor to form purified lanthanide amidinate material in the at least one condenser; 
         e. passing the non-condensed light impurity LnO(AMD) 2  from the zone 2 into the at least one cooler in the zone 3 to form solid light impurity; 
         wherein the purified lanthanide amidinate material comprises each of halide impurity ranging from 10.0 ppm or less and all halide impurities combined ranging from 50.0 ppm or less. 
       
     
     
         13 . The method of  claim 12 , wherein temperatures are set between 60° C. to 200° C. in zone 1; between 100° C. to 180° C. in zone 1; and below 30° C. in zone 3. 
     
     
         14 . The method of  claim 12 , wherein the lanthanide amidinate compound is selected from the group consisting of La(FAMD) 3 , Ce(FAMD) 3 , Pr(FAMD) 3 , Nd(FAMD) 3 , Pm(FAMD) 3 , Sm(FAMD) 3 , Eu(FAMD) 3 , Gd(FAMD) 3 , Tb(FAMD) 3 , Dy(FAMD) 3 , Ho(FAMD) 3 , Er(FAMD) 3 , Tm(FAMD) 3 , Yb(FAMD) 3 , and Lu(FAMD) 3 . 
     
     
         15 . The method of  claim 12 , wherein the lanthanide is lanthanum and R 1  is hydrogen. 
     
     
         16 . The method of  claim 12 , wherein the purified lanthanide amidinate material comprises each of halide impurity ranging from 5.0 ppm or less. 
     
     
         17 . The method of  claim 12 , wherein the separation unit is used and the purified lanthanide amidinate material comprises each of halide impurity ranging from 2.0 ppm or less. 
     
     
         18 . The method of  claim 12 , wherein the separation unit is used and the purified lanthanide amidinate material comprises each of halide impurity ranging from 1.0 ppm or less. 
     
     
         19 . A vessel containing a composition comprising lanthanide amidinate compound Ln(AMD) 3  having Formula I 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from the group consisting of hydrogen, and C 1  to C 5  linear or branched alkyl; and R 2  and R 2  each is independently selected from the group consisting of C 1  to C 5  linear or branched alkyl; Ln is a lanthanide metal selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; 
         wherein the composition comprises at least one halide impurity and each of halide impurity ranges from 10.0 ppm or less; and all halide impurities combined ranges 50.0 ppm or less. 
       
     
     
         20 . The vessel of  claim 19 , wherein the at least one halide impurity is selected from the group consisting of chloride, bromide, iodide, fluoride and combinations thereof; and each of halide impurity ranges from 5.0 ppm or less. 
     
     
         21 . The vessel of  claim 19 , wherein the lanthanide amidinate compound is selected from the group consisting of La(FAMD) 3 , Ce(FAMD) 3 , Pr(FAMD) 3 , Nd(FAMD) 3 , Pm(FAMD) 3 , Sm(FAMD) 3 , Eu(FAMD) 3 , Gd(FAMD) 3 , Tb(FAMD) 3 , Dy(FAMD) 3 , Ho(FAMD) 3 , Er(FAMD) 3 , Tm(FAMD) 3 , Yb(FAMD) 3 , and Lu(FAMD) 3 . 
     
     
         22 . The vessel of  claim 19 , wherein the lanthanide is lanthanum and R 1  is hydrogen. 
     
     
         23 . The vessel of  claim 19 , wherein the composition comprising ≤1.0 ppm chloride, ≤1.0 ppm bromide, ≤1.0 ppm iodide, and ≤1.0 ppm fluoride.