Low halide lanthanum precursors for vapor deposition

1. A system for purifying a crude lanthanide amidinate material for vapor deposition comprising:

a) the crude lanthanide amidinate material comprising a 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 3 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, and Lu;

b) zone 1 comprising at least one sublimer; wherein the crude lanthanide amidinate material is placed inside the at least one sublimer;

c) zone 2 comprising at least one condenser; wherein the zone 2 is in fluid communication with the zone 1;

d) zone 3 comprising at least one cooler; wherein the zone 3 is in fluid communication with the zone 2; and

e a separation unit selected from the group consisting of a convoluted pathway, glass wool, a 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 of 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), and LnF x (AMD) y (x+y=3), wherein x and y are 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 thereof; and

a purified lanthanide amidinate material is inside the at least one condenser in the zone 2; and the purified lanthanide amidinate material comprises 10.0 ppm or less of each individual halide impurity and 50.0 ppm or less of all halide impurities combined.

2. The system of claim 1 , wherein the purified lanthanide amidinate material comprises 5.0 ppm or less of each individual halide impurity.

3. The system of claim 1 , wherein the lanthanide amidinate compound Ln(AMD) 3 having Formula I, wherein R1 is hydrogen, and R2 and R3 are isopropyl, and 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 .

4. The system of claim 1 , wherein the lanthanide is lanthanum and R 1 is hydrogen.

5. The system of claim 1 , wherein the purified lanthanide amidinate material comprises 2.0 ppm or less of each individual halide impurity.

6. The system of claim 1 , wherein the purified lanthanide amidinate material comprises 1.0 ppm or less of each individual halide impurity.

7. A method for purifying a crude lanthanide amidinate material for vapor deposition comprising:

a) providing the crude lanthanide amidinate material comprising a lanthanide 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 3 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, and Lu; and

further comprising 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), and LnF x (AMD) y (x+y=3), wherein x and y are 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 thereof;

b) providing zone 1 comprising at least one sublimer, zone 2 comprising at least one condenser; and zone 3 condenser, zone 3 comprising at least one cooler, and a separation unit installed between the zone 1 and the zone 2, wherein the separation unit is selected from the group consisting of a convoluted pathway, glass wool, a filter, and combinations thereof; wherein the zone 2 is in fluid communication with the zone 1 via the separation unit, and wherein the zone 3 is in fluid communication with the zone 2;

c) feeding the crude lanthanide amidinate material of step a) into the at least one sublimer of zone 1 of step b) and heating the crude lanthanide amidinate material contained in the at least one sublimer in the zone 1 to generate a crude lanthanide amidinate material vapor;

d) passing the crude lanthanide amidinate material vapor from the zone 1 to the at least one condenser in the zone 2 through the separation unit and condensing a portion of the crude lanthanide amidinate material vapor in the at least one condenser to forma purified lanthanide amidinate material;

wherein the purified lanthanide amidinate material formed in the at least one condenser comprises 10.0 ppm or less of each individual halide impurity and 50.0 ppm or less of all halide impurities combined.

8. The method of claim 7 , wherein the temperature of zone 1 ranges between 60° C. and 200° C., the temperature of zone 2 ranges between 80° C. and 200° C., and the temperature of zone 3 is 30° C. or less.

9. The method of claim 7 , wherein the lanthanide amidinate compound Ln(AMD) 3 having Formula I, wherein R1 is hydrogen, and R2 and R3 are isopropyl, and 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 .

10. The method of claim 7 , wherein the lanthanide is lanthanum and R 1 is hydrogen.

11. The method of claim 7 , wherein the purified lanthanide amidinate material comprises 5.0 ppm or less of each individual halide impurity.

12. The method of claim 7 , wherein the purified lanthanide amidinate material comprises 2.0 ppm or less of each individual halide impurity.

13. The method of claim 7 , wherein the purified lanthanide amidinate material comprises 1.0 ppm or less of each individual halide impurity.