Step coverage using an inhibitor molecule for high aspect ratio structures
View Patent ↗Disclosed is a method for improving step coverage of a film deposited on high aspect ratio (HAR) apertures in a substrate. The method comprises i) sequentially or simultaneously exposing the substrate to a vapor of an inhibitor, a vapor of a precursor and a vapor of a co-reactant; and ii) allowing the film with a desired step coverage being deposited on the surface of the HAR apertures through a vapor deposition process, wherein the inhibitor contains O, N, S, P, B, C, F, Cl, Br, or I.
1. A method for improving step coverage of a film deposited on high aspect ratio (HAR) apertures in a substrate, the method comprising:
i) sequentially or simultaneously exposing the substrate to a vapor of an inhibitor, a vapor of a precursor ZrCp(NMe 2 ) 3 and a vapor of a co-reactant; and
ii) allowing the film with a desired step coverage being deposited on the surface of the HAR apertures through a vapor deposition process,
wherein the inhibitor is selected from one or more of
a) phosphorus based aliphatic and aromatic inhibitors;
b) boron based aliphatic and aromatic inhibitors;
c) H 2 O vapor, H 2 gas, CO gas, CS gas and nitrogen oxide (NO x ) gases; and
d) combinations of a)-c).
2. The method of claim 1 , further comprising maintaining a temperature of the substrate in a range of from room temperature to 650° C.
3. The method of claim 1 , wherein the inhibitor is selected from one or more of
a. diols, ethers, epoxides, aldehydes, ketones, carboxylic acids, enols, esters, anhydrides, phenols, substituted phenols;
b. amines, imines, imides, azides, cyanates, nitrile, nitrate, nitrite, nitrogen containing heterocycles;
c. thiols, sulfides, disulfide, sulfonxide, thiocyanates, isothiocyanates, thioesters;
d. phosphines, phosphonic acid, phosphodiesters;
e. boronic acid, boronic ester, borinic esters; carbon based aliphatic inhibitors including alkanes, alkenes, alkynes and benzene derivatives;
f. I 2 ;
g. or combinations of a)-f).
4. The method of claim 3 , wherein the inhibitor is a radical form of a vapor or gas of the inhibitor at a temperature ranging from room temperature to approximately 650° C. generated with or without plasma.
5. The method of claim 1 , wherein the co-reactant is O 3 , O 2 , H 2 O, H 2 O 2 , D 2 O, alcohols, NH 3 , N 2 , N 2 H 2 , H 2 , or radicals thereof generated by plasma.
6. The method of claim 1 , wherein the co-reactant is O 3 or O 3 radicals generated by plasma.
7. The method of claim 1 , wherein the desired step coverage is ≥100%.
8. The method of claim 1 , wherein the desired step coverage is larger than the step coverage with the absence of the inhibitor.
9. The method of claim 1 , wherein the HAR ranges from 25:1 to 200:1.
10. The method of claim 1 , wherein the substrate is a patterned or 3D structure.
11. The method of claim 1 , wherein the aperture is a hole, a via, a trench, a gap or an opening formed in the substrate from a previous manufacturing step.
12. The method of claim 1 , wherein the vapor deposition process is ALD, CVD or combination thereof.
13. The method of claim 1 , wherein the vapor deposition process is a plasma enhanced CVD selected from a spatial ALD, a thermal ALD, or a plasma enhanced ALD.
14. The method of claim 1 , wherein an order of exposing the substrate to the inhibitor, the precursor and the co-reactant includes
i) the inhibitor, the precursor and the co-reactant sequentially;
ii) the precursor, the inhibitor and the co-reactant sequentially;
iii) the precursor, the co-reactant and the inhibitor sequentially; or
iv) the inhibitor and the precursor simultaneously and then the co-reactant.
15. The method of claim 14 , further comprising
purging and removing one or more of an excess inhibitor, an excess precursor and an excess co-reactant after each exposure using a purge gas,
wherein the purge gas is an inert gas selected from N 2 , Ar, Kr or combinations thereof.