Tin compound and resist solution using the same, pattern forming method, thin film, patterned thin film, and method for producing tin compound

1 . A tin compound, comprising:

a tin atom;

at least one organic group R bonded to the tin atom; and

at least one of an oxo-ligand and a hydroxo-ligand bonded to the tin atom, wherein the tin compound has a diffraction angle 2θ (*) of a peak with a strongest intensity between 5.00 to 15.00° in an X-ray diffraction measurement,

wherein the strongest intensity peak has a half-value width of 1.00 to 4.00°, and

wherein the organic group R has 1 to 30 carbon atoms.

2 . The tin compound according to claim 1 , wherein the tin compound is represented by a formula RSnO (3/2-X/2) (OH) X , wherein 0≤x≤3.

3 . The tin compound according to claim 1 , wherein the tin compound is a compound comprising a cation represented by a formula (RSn) 12 O 14 (OH) 6 +2 .

4 . The tin compound according to claim 1 ,

wherein the tin compound has a ratio [(k1+k2)/(k3)] of not less than 0.9,

wherein the ratio is a total value (k1+k2) in 119 Sn-NMR of a total (k1) of peak integration values of a pentavalent Sn (−250 to −350 ppm) and a total (k2) of peak integration values of a hexavalent Sn (−450 to −600 ppm) relative to a total value (k3) of all peak integration values (including k1 and k2) within a range of 1000 to −1000 ppm detected from the 119 Sn-NMR.

5 . The tin compound according to claim 4 , wherein the value of [(k1+k2)/(k3)] is not less than 0.95.

6 . The tin compound according to claim 1 , wherein the tin compound has a ratio (k1/k2) of 0.5 to 2.5, wherein the ratio is a total (k1) of peak integration values of a pentavalent Sn (−250 to −350 ppm) relative to a total (k2) of peak integration values of a hexavalent Sn (−450 to −600 ppm) in 119 Sn-NMR.

7 . The tin compound according to claim 1 , wherein the half-value width of the strongest intensity peak is 1.43 to 4.00°.

8 . The tin compound according to claim 1 , wherein the organic group R has 3 to 10 carbon atoms.

9 . The tin compound according to claim 1 , wherein the organic group R is a hydrocarbon group.

10 . The tin compound according to claim 1 , wherein the organic group R is a hydrocarbon group, and not less than 50 mol % of substituents constituting the hydrocarbon group is a secondary hydrocarbon group R 2 .

11 . A resist solution, comprising:

the tin compound according to claim 1 ; and

an organic solvent.

12 . A patterning method, comprising:

a step of applying the resist solution of claim 11 onto a substrate;

a step of exposing a thin film comprising the tin compound to radiation; and

a step of developing the thin film by using a developer liquid.

13 . A thin film on a substrate, the thin film comprising the tin compound according to claim 1 .

14 . A patterned thin film on a substrate, the patterned thin film comprising the tin compound according to claim 1 .

15 . A method for producing the tin compound according to claim 1 ,

the method comprising step 1 and step 2,

<step 1> using a monoalkyl tin composition as a raw material;

wherein the monoalkyltin composition comprises:

a monoalkyltin compound RSnX 3 (A1) at 50 mol % to 99.99 mol %; and

a monoalkyltin compound RSnX 2 Y (B1) at not less than 0.01 mol % and less than 50 mol %,

wherein X and Y each represent a hydrolysable group with different chemical formulae,

X is selected from OR′, NR′ 2 , and C≡CR′,

Y is selected from OR′ Y ,

N

⁢

R

′

⁢

Y

2

,

and

⁢

C

≡

C

⁢

R

′

⁢

Y

,

 and C≡CR′ Y ,

R′ and R′ Y each represent an organic group having 1 to 10 carbon atoms,

in at least one of a case when X is NR′ 2 and a case when Y is the

N

⁢

R

′

⁢

Y

2

,

R

′

⁢

and

⁢

R

′

⁢

Y

 R′ and R′ Y may be independently same as or different from each other, and

when a plurality of R′ and R′ Y are present in a molecule, the plurality of R′ and R′ Y may have a structure different from each other and may be bonded to each other to form a cyclic structure, and ≤step 2> contacting the raw material with at least one of water and water vapor.

16 . The method for producing a tin compound according to claim 15 , wherein, in the step 2, a blend of the raw material and an organic solvent is contacted with liquid water.

17 . The method for producing a tin compound according to claim 15 , wherein, in the step 2, not less than 100 parts by mass of an organic solvent is blended relative to 100 parts by mass of the raw material to prepare a composition.

18 . The method for producing a tin compound according to claim 15 , wherein the half-value width of the strongest intensity peak is 1.43 to 4.00°.

19 . The tin compound according to claim 1 , wherein in the diffraction angle 2θ (°), a number of peak tops detected within a range of 5.00° to 15.00° is not greater than two.

20 . The tin compound according to claim 1 , wherein in the diffraction angle 2θ (°), a number of peak tops detected within a range of 5.00° to 15.00° is one.