Process for making doped zinc oxide

• US 7,972,898 B2
• Filed: 09/26/2007
• Issued: 07/05/2011
• Est. Priority Date: 09/26/2007
• Status: Active Grant

• Current Assignee: Eastman Kodak Company
• Original Assignee: Eastman Kodak Company
• Inventors: Freeman, Diane C., Pawlik, Thomas D., Cowdery-Corvan, Peter J., Nelson, Shelby F., Levy, David H.
• Primary Examiner(s): Landau; Matthew C
• Assistant Examiner(s): Malek; Maliheh
• Application Number:
  US11/861,455
• Publication Number:
  US 20090081826A1
• Time in Patent Office: 1,378 Days
• Field of Search: 438/104, 438149-153, 438/158, 438/199, 438/384, 438/498, 438/584, 438/695, 438/710, 438/727, 438/758, 438/908, 438478-481, 438/496, 438503-509, 438680-681, 438/765, 438/767, 438769-774, 438778-780, 438783-790, 438/FOR.327, 257/43, 257 66- 71, 257/E21.094, 257/E21.104, 257/E21.121, 257/E21.269, 257/E21.372, 257E21411-E21416, 257/E21.464, 257/E21.479, 257/72, 257/E21.171, 252/519.5, 118/715
• US Class Current: 438/104
• CPC Class Codes: B33Y 80/00 Products made by additive manufacturing
• CPC Class Codes: C23C 16/407 of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• CPC Class Codes: C23C 16/45504 Laminar flow
• CPC Class Codes: C23C 16/45544 characterized by the apparatus
• CPC Class Codes: C23C 16/45551 for relative movement of the substrate and the gas injectors or half-reaction reactor compartments
• CPC Class Codes: C23C 16/45574 Nozzles for more than one gas
• CPC Class Codes: H01L 21/02554 Oxides
• CPC Class Codes: H01L 21/02565 Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
• CPC Class Codes: H01L 21/02576 N-type
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD

Abstract

The present invention relates to a process of making a zinc-oxide-based thin film semiconductor, for use in a transistor, comprising thin film deposition onto a substrate comprising providing a plurality of gaseous materials comprising first, second, and third gaseous materials, wherein the first gaseous material is a zinc-containing volatile material and the second gaseous material is reactive therewith such that when one of the first or second gaseous materials are on the surface of the substrate the other of the first or second gaseous materials will react to deposit a layer of material on the substrate, wherein the third gaseous material is inert and wherein a volatile indium-containing compound is introduced into the first reactive gaseous material or a supplemental gaseous material.

Claims

1. A process of making an n-type zinc-oxide-based thin film semiconductor by depositing a thin film material on a surface area of a substrate, either an entire surface area or a selected portion thereof, wherein deposition is by an atomic layer deposition process that is carried out substantially at or above atmospheric pressure, wherein the temperature of the substrate during deposition is under 300°

C., and wherein the atomic layer deposition process comprises;

simultaneously directing a series of gas flows along elongated substantially parallel channels comprising, in order, at least a first reactive gaseous material containing a zinc-containing compound having a molar flow during deposition, an inert purge gas, and a second reactive gaseous material through a plurality of output openings spaced apart from the substrate, and transporting the substrate in a direction relative to the plurality of output openings, such that any point on the surface area of the substrate experiences a sequence of the first and second gaseous materials and the inert purge gas, whereby the sequence causes a thin film to be formed by atomic layer deposition on the surface area of the substrate,

wherein a volatile indium-containing compound is introduced into the first reactive gaseous material or a supplemental gaseous material such that the indium-containing compound has a molar flow at a level of greater than 20 percent of the molar flow of the zinc-containing compound.

2. The process of claim 1 wherein the zinc-oxide-based thin film semiconductor is used in a thin film transistor.

3. The process of claim 1 wherein crystallinity of the zinc-oxide-based thin film semiconductor is less than 85 percent as measured by x-ray diffraction.

4. The process of claim 1 wherein the volatile indium-containing compound is the trialkylindium compound or cyclopentadienylindium(I), wherein the alkyl has 1 to 4 carbon atoms.

5. The process of claim 1 wherein resistivity of the zinc-oxide-based thin film semiconductor is reduced relative to a resistivity of a similar film not containing indium.

6. The process of claim 5 wherein presence of incorporated Indium dopant derived from the indium-containing compound as a precursor provides a decrease in the resistivity by a factor of at least 10 in the thin film material.

7. The process of claim 1 wherein weight ratio of zinc to indium in the zinc-oxide-based thin film semiconductor is 0.05 to 0.7.

8. The process of claim 1, wherein a volatile acceptor dopant precursor is introduced in the second reactive gaseous material, the inert purge gas, or an additional gas flow of a supplemental gaseous material.

9. The process of claim 8 wherein the volatile acceptor dopant precursor comprises an element selected from the group consisting of N, P, As, Li, Na, K, or mixtures thereof.

10. The process of claim 8 wherein the volatile acceptor dopant precursor is NO, NO₂, or ammonia.

11. The process of claim 1 wherein the zinc-oxide-based thin film semiconductor serves as a channel layer of a thin film transistor.

12. The process of claim 1 wherein the zinc-oxide-based thin film semiconductor serves as one or more conductive electrodes of a thin film transistor.

13. The process of claim 1 wherein the zinc-oxide-based thin film semiconductor serves as an electrical conduit in an electronic circuit.

14. The process of claim 1 wherein the series of gas flows are provided by a deposition device comprising, facing the substrate in plan view, a series of elongated output openings, substantially in parallel, positioned over the substrate in close proximity thereto, in an output face of the deposition device, spaced within 1 mm from the surface of the substrate subject to deposition.

15. The process of claim 14 wherein there are no exhaust channels between the series of elongated output openings for the first reactive gaseous material and the second reactive gaseous material.

16. The process of claim 14 wherein the deposition device further comprises exhaust channels between the substantially parallel elongated output openings for the first and the second reactive gaseous materials.

17. The process of claim 14 wherein the flows of one or more of the gaseous materials to the substrate surface for the thin film deposition provides at least part of a force separating the depositing output face of the deposition device from the surface of the substrate.

18. The process of claim 14 wherein the surface area of the substrate for atomic layer deposition of the thin film semiconductor exceeds total surface area of the output face of the deposition device.

19. The process of claim 1 wherein the substrate or a support for the substrate comprises a moving web.

20. The process of claim 1 wherein the process is in unsealed relationship to ambient atmosphere.

21. The process of claim 1 wherein the process is used to make a multiplicity of thin film transistors in an electronic device, each thin film transistor comprising said n-type zinc-oxide-based thin film semiconductor, wherein the first reactive gaseous material comprises an organo-zinc precursor compound and the second reactive gaseous material comprises a reactive oxygen-containing gaseous material.

22. The process of claim 21, wherein the process further comprises forming, for each of the multiplicity of thin film transistors, a spaced apart source electrode and drain electrode, wherein the source electrode and the drain electrode are separated by, and electrically connected with, the n-type zinc-oxide-based thin film semiconductor;

and forming a gate electrode spaced apart from the n-type zinc-oxide-based thin film semiconductor, wherein the electronic device is selected from a group consisting of an integrated circuit, active-matrix display, solar cell, active-matrix imager, sensor, and rf price, identification, or inventory label.