Atomic layer deposition method of metal (II), (0), or (IV) containing film layer

1 . An atomic layer deposition (ALD) method of a metal (M) containing film layer on a substrate, the method comprising:

forming a chemisorbed, surface-bound metal-ligand species using a metal (M) (II) primary precursor of formula (I):

wherein:

M is Sn (II), such that the metal (M) containing film layer is an M (II) containing film layer;

L is a ligand displaying ALD reactivity for a secondary precursor;

R 1 , R 2 , and R 3 are each independently selected from: H or a linear or branched alkyl groups, and wherein at least one of R 1 , R 2 and R 3 is a linear or branched alkyl group.

2 . The atomic layer deposition method as claimed in claim 1 , in which the Sn (II) containing film layer is an Sn (II) oxide film layer.

3 . The atomic layer deposition method as claimed in claim 2 , in which the Sn (II) oxide film layer is a crystalline Sn (II) oxide containing film layer.

4 . The atomic layer deposition method as claimed in claim 1 , in which the metal (M) containing film layer is a multicomponent metal (M) containing film layer comprising at least one additional metal (M′).

5 . The atomic layer deposition method as claimed in claim 4 , in which the at least one additional metal (M′) is selected from one or more of: Ti, In, Ga, Zn, Cu, Sr, Ba, Mg, W, Pb, Se, S, Te, Bi, Fe, Ni, Co, Al, Si, Sb, K, Na, Ca, Sr, Ba, Li, V and La, or any combination thereof.

6 . The atomic layer deposition method as claimed in claim 1 , in the atomic layer deposition (ALD) of a metal (M) and F containing film layer.

7 . The atomic layer deposition method as claimed in claim 1 , in which L is an amide, alkoxide, aminoalcohol, aminoamide, alkoxyether, cyclopenadienyl (Cp), or Cp derivative, or halide.

8 . The atomic layer deposition method as claimed in claim 7 , in which L is an amide ligand or an alkoxide ligand.

9 . The atomic layer deposition method as claimed in claim 8 , in which L is an alkoxide ligand of formula (OCR 1′ R 2′ R 3′ ), wherein R 1′ , R 2′ , and R 3′ are each independently selected from: H or a linear or a branched alkyl group, and wherein at least one of R 1′ , R 2′ and R 3′ is a linear or branched alkyl group.

10 . The atomic layer deposition method as claimed in claim 9 , in which L is an alkoxide ligand of formula (OCR 1′ R 2′ R 3′ ), in which (OCR 1′ R 2′ R 3′ ) is the same as (OCR 1 R 2 R 3 ) group of the metal (M) (II) containing primary precursor of formula (I).

11 . An atomic layer deposition (ALD) method for forming a film layer of a metal (M) containing film layer on a surface of a substrate, the method comprising:

heating a substrate in a processing chamber;

introducing an M (II) primary precursor of formula (I):

wherein:

M is Sn (II);

L is a ligand displaying ALD reactivity for a secondary precursor;

R 1 , R 2 , and R 3 are each independently selected from: H or a linear or branched alkyl groups, and

wherein at least one of R 1 , R 2 and R 3 is a linear or branched alkyl group, to the processing chamber in a first dose stage for a predetermined first dose time;

subsequently purging the processing chamber in a first purge stage to remove remaining M (II) primary precursor;

introducing a secondary precursor to the processing chamber in a second dose stage for a predetermined second dose time; and

subsequently purging the processing chamber in a second purge stage to remove the secondary precursor; optionally repeating one or more of: the first dose stage, first purge stage, second dose stage and second purge stage;

to produce an M (II) containing film layer on the surface of the substrate.

12 . The atomic layer deposition method as claimed in claim 11 , in which R 1 , R 2 , and R 3 are each independently selected from: H or linear or branched C 1-4 alkyl groups, and wherein at least one of R 1 , R 2 and R 3 is a linear or branched C 1-4 alkyl group.

13 . The atomic layer deposition method as claimed in claim 12 , in which the film layer is a crystallized film layer.

14 . The atomic layer deposition method as claimed in claim 12 , in which the M (II) primary precursor is selected from: Sn(O i Pr) 2 , Sn(O t Bu) 2 , Sn(OC(H)MeEt) 2 , Sn(OC(H)Me i Pr) 2 , and Sn(OCMe 2 Et) 2 .

15 . The atomic layer deposition method as claimed in claim 14 , in which the M (II) primary precursor is selected from: Sn(O t Bu) 2 , Sn(OC(H)MeEt) 2 and Sn(OCMe 2 Et) 2 .

16 . The atomic layer deposition method as claimed in claim 11 , in which the processing chamber is heated to a temperature within a range of between 70° C. and 250° C.

17 . The atomic layer deposition method as claimed in claim 16 , in which the processing chamber is heated to a temperature within a range of between 130° C. and 210° C.

18 . An atomic layer deposition (ALD) method for forming a film layer of a metal (M) containing film layer on a surface of a substrate, the method comprising:

heating a substrate in a processing chamber;

contacting a surface of the substrate with an M (II) primary precursor of formula (I):

wherein:

M is Sn (II);

L is a ligand displaying ALD reactivity for a secondary precursor;

R 1 , R 2 , and R 3 are each independently selected from: H or a linear or branched alkyl groups, and wherein at least one of R 1 , R 2 and R 3 is a linear or branched alkyl group, in the processing chamber in a first dose stage for a predetermined first dose time;

either optionally purging the processing chamber in a first optional purge stage to remove remaining M (II) primary precursor, or optionally moving the substrate relative to a precursor source in a first optional movement stage;

contacting the surface of the substrate with a secondary precursor in a second dose stage for a predetermined second dose time; and

either optionally subsequently purging the processing chamber in a second optional purge stage to remove the secondary precursor, or optionally moving the substrate relative to a secondary precursor source in a second optional movement stage;

optionally repeating one or more of: the first dose stage, first optional purge stage, first optional movement stage, second dose stage and second optional purge stage, and second optional movement stage;

to produce an M (II) containing film layer on the surface of the substrate.

19 . An atomic layer deposition (ALD) method for forming a film layer of a metal (M) containing film layer on a surface of a substrate, the method comprising:

heating a substrate in a processing chamber;

introducing an M (II) primary precursor of formula (I) to the processing chamber in a first dose stage for a predetermined first dose time:

wherein:

M is Sn (II);

L is a ligand displaying ALD reactivity for a secondary precursor;

R 1 , R 2 , and R 3 are each independently selected from: H or a linear or branched alkyl groups, and

wherein at least one of R 1 , R 2 and R 3 is a linear or branched alkyl group;

subsequently purging the processing chamber in a first purge stage to remove remaining M (II) primary precursor;

introducing a secondary precursor to the processing chamber in a second dose stage for a predetermined second dose time; wherein the secondary precursor is selected from H 2 O, H 2 O 2 , plasma, carboxylic acids, nitrous oxide, hydrogen, oxygen, ozone, ammonia, hydrogen sulfide, NH 3 , PR 3 , H 2 Se, E(NR 2 ), SiR′ 3 , OP(OR) 3 , HOP(O)(OR) 2 , PR 3 or PH 3 ;

wherein E is Se or Te, and

R and R′ are independently selected from H, alkyl or aryl; and

subsequently purging the processing chamber in a second purge stage to remove the secondary precursor;

to produce an M (II) containing film layer on the surface of the substrate.

20 . The method of claim 19 , further comprising repeating one or more of: the first dose stage, the first purge stage, the second dose stage, and the second purge stage.