Method for forming doped metal oxide films on a substrate by cyclical deposition and related semiconductor device structures

• US 10,529,563 B2
• Filed: 03/09/2018
• Issued: 01/07/2020
• Est. Priority Date: 03/29/2017
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holdings B.V.
• Inventors: Blomberg, Tom, Zhu, Chiyu
• Primary Examiner(s): Yushina, Galina G
• Application Number:
  US15/917,262
• Publication Number:
  US 20180286675A1
• Time in Patent Office: 669 Days
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/407 of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• CPC Class Codes: C23C 16/45523 Pulsed gas flow or change of composition over time
• CPC Class Codes: C23C 16/45527 characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/02565 Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
• CPC Class Codes: H01L 21/0257 Doping during depositing
• CPC Class Codes: H01L 21/02592 amorphous
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 21/28194 by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence

Abstract

Methods for forming a doped metal oxide film on a substrate by cyclical deposition are provided. In some embodiments, methods may include contacting the substrate with a first reactant comprising a metal halide source, contacting the substrate with a second reactant comprising a hydrogenated source and contacting the substrate with a third reactant comprising an oxide source. In some embodiments, related semiconductor device structures may include a doped metal oxide film formed by cyclical deposition processes.

Claims

1. A method for forming a doped metal oxide film on a substrate by cyclical deposition, the method comprising:

contacting the substrate with a first reactant comprising a metal halide source;

contacting the substrate with a second reactant comprising a hydrogenated source, wherein the hydrogenated source is a dopant precursor for the doped metal oxide film; and

contacting the substrate with a third reactant comprising an oxide source;

wherein the doped metal oxide film comprises between 2 atomic percent and 15 atomic percent of dopant.

2. The method of claim 1, wherein the cyclical deposition comprises atomic layer deposition.

3. The method of claim 1, further comprising selecting the metal halide source to comprise at least one of titanium tetrachloride (TiCl₄) and zirconium tetrachloride (ZrCl₄).

4. The method of claim 1, further comprising selecting the hydrogenated source to comprise at least one of a hydrogenated silicon source, or a hydrogenated germanium source.

5. The method of claim 4, further comprising selecting the hydrogenated silicon source to comprise at least one of silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), or tetrasilane (Si₄H₁₀).

6. The method of claim 5, further comprising selecting the hydrogenated silicon source to comprise disilane (Si₂H₆).

7. The method of claim 4, further comprising selecting the hydrogenated germanium source to comprise at least one of germane (GeH₄), digermane (Ge₂H₆), trigermane (Ge₃H₈), or tetragermane (Ge₄H₁₀).

8. The method of claim 1, further comprising selecting the oxide source to comprise at least one of ozone (O₃), an oxygen (O) radical, atomic oxygen (O), molecular oxygen (O₂), an oxygen plasma, water (H₂O), or hydrogen peroxide (H₂O₂).

9. The method of claim 8, further comprising selecting the oxide source to comprise water vapor (H₂O).

10. The method of claim 1, wherein the method comprises at least one deposition cycle in which the substrate is alternately and sequentially contacted with the first reactant, the third reactant and the second reactant.

11. The method of claim 10, wherein the deposition cycle is repeated two or more times.

12. The method of claim 10, further comprising forming the doped metal oxide film to have an electrical resistivity of greater than 1000 me-cm.

13. The method of claim 10, further comprising forming the doped metal oxide metal film to have a substantially amorphous structure.

14. The method of claim 1, further comprising heating the substrate to a temperature of less than about 350°

C.

15. The method of claim 1, further comprising selecting the doped metal oxide film to comprise at least one of silicon doped titanium oxide (Ti₁₋

xSi_xO₂), germanium doped titanium oxide (Ti<sub>1−

x</sub>Ge_xO₂), silicon doped zirconium oxide (Zr<sub>1−

x</sub>Si_xO₂), germanium doped zirconium oxide (Zr<sub>1−

x</sub>Ge_xO₂), silicon doped hafnium oxide (Hf<sub>1−

x</sub>Si_xO₂), or germanium doped hafnium oxide (Hf<sub>1−

x</sub>Ge_xO₂).