Apparatus for plasma assisted evaporation of thin films and corresponding method of deposition

• US 4,514,437 A
• Filed: 05/02/1984
• Issued: 04/30/1985
• Est. Priority Date: 05/02/1984
• Status: Expired due to Term

• Current Assignee: United Solar Systems Corp.
• Original Assignee: Energy Conversion Devices
• Inventors: Nath, Prem
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US06/606,014
• Time in Patent Office: 363 Days
• Field of Search: 427/38, 427/39, 427/42, 118/50.1, 118/723, 118/718
• US Class Current: 427/566
• CPC Class Codes: C23C 14/32 by explosion; by evaporation and subsequent ionisation of the vapours , e.g. ion-platingC23C14/34 - C23C14/48 take precedence
• CPC Class Codes: H01J 37/3053 for evaporating or etching
• CPC Class Codes: H01J 37/32422 Arrangement for selecting ions or species in the plasma
• CPC Class Codes: H01L 31/1884 Manufacture of transparent electrodes, e.g. TCO, ITO
• CPC Class Codes: Y02E 10/50 Photovoltaic [PV] energy

Abstract

An improved method of and apparatus for depositing thin films, such as indium tin oxide, onto substrates, which deposition comprises one step in the fabrication of electronic, semiconductor and photovoltaic devices. The method includes the novel steps of combining the use of (1) an electron beam to vaporize a source of solid material, and (2) electromagnetic energy to provide an ionizable plasma from reactant gases. By passing the vaporized solid material through the plasma, it is activated prior to the deposition thereof onto the substrate. In this manner, the solid material and the reactant gases are excited to facilitate their interaction prior to the deposition of the newly formed compound onto the substrate.

Claims

1. An improved method of depositing a thin film onto a substrate, said method including the steps of:

vacuumizing a chamber;

providing an electrically unbiased substrate in the chamber;

providing a supply of solid vaporizable material in the chamber;

heating the solid material with electron beam means so as to vaporize said material in a vapor zone formed between the substrate and the supply of solid material;

disposing electrode means in the vapor zone, said electrode means operatively disposed in electrical communication with a source of alternating current;

providing an ionizable gas; and

,

activating the source of alternating current so as to energize the electrode means and develop an ionized plasma from at least the ionized gas, said ionized plasma developed in a plasma region formed proximate the electrode means;

whereby the vaporized solid material is activated by the plasma and deposited as a thin film onto the substrate.

2. A method as in claim 1, including the further steps of:

introducing a reactive gas proximate the plasma region; and

activating the reactive gas in the plasma region, whereby the activated gas and the reactive vapor of the solid material react for the deposition thereof as a thin film.

3. A method as in claim 1, including the further step of:

maintaining the substrate at a temperature of about room temperature to 300°

C. during the deposition of the thin film thereonto.

4. A method as in claim 1, including the further step of:

selecting the solid material from the group consisting essentially of;

In, Sn, Cd, Zn, Ti, Si, Ge and mixtures thereof.

5. A method as in claim 2, including the further step of:

selecting the reactive gas from the group consisting essentially of;

O₂, N₂, NH₃, CH₄, H₂ S N₂ O, CF₄ and mixtures thereof.

6. A method as in claim 1, wherein the step of energizing the electrode means with alternating current comprises:

energizing the electrode means with radio frequency energy.

7. A method as in claim 1, wherein the step of energizing the electrode means with alternating current comprises:

energizing the electrode means with microwave energy.

8. A method as in claim 1, including the further step of:

maintaining the pressure within the chamber in the range of 10^-2 -10^-4 torr.

9. A method as in claim 1, including the further step of:

continuously advancing the substrate through the chamber, whereby a thin film is continuously deposited upon the advancing substrate.

10. A method as in claim 2, wherein:

the step of heating the solid vaporizable material with electron beam means comprises the heating of an indium;

tin alloy;

the step of introducing a reactive gas comprises the introduction of oxygen; and

the method includes the further step of maintaining the substrate at a temperature from about room temperature to 300°

C.

11. A method as in claim 2, wherein:

the step of heating the solid vaporizable material comprises heating indium with electron beam means;

the step of introducing a reactive gas comprises the introduction of oxygen; and

the method includes the further step of maintaining the substrate at a temperature of up to 300°

C.

12. A method as in claim 1, wherein the substrate in the chamber includes a body of semiconductor material thereupon.

13. A method as in claim 1, wherein the substrate in the chamber includes having a plurality of amorphous semiconductor layers thereupon.

14. Apparatus for depositing a thin film onto a substrate, said apparatus including:

a vacuum chamber;

means for vacuumizing the chamber;

means for supporting an electrically unbiased substrate;

a source of solid vaporizable material operatively disposed in the vacuum chamber;

electron beam means adapted to vaporize the solid material in a vapor zone formed between the substrate and the supply of solid material;

a source of ionizable gas;

electrode means operatively disposed proximate the source of solid material in the vapor zone;

said electrode means adapted to develop an ionized plasma from at least the ionizable gas, said plasma developed in a plasma region formed proximate the electrode means; and

a source of alternating current operatively disposed in electrical communication with the electrode means, whereby activating the source develops the plasma and the plasma activates the vaporized solid material for the deposition thereof as a thin film onto the substrate.

15. Apparatus as in claim 14, further including:

gas inlet means adapted to introduce a reactive gas proximate the plasma region, whereby the reactive gas and activated vapor of the solid material react to deposit the thin film onto the substrate.

16. Apparatus as in claim 14, further including:

means for heating the substrate to a temperature from about room temperature to 300°

C. during the deposition of the thin film thereonto.

17. Apparatus as in claim 14, further including:

means adapted to continuously move the substrate through the chamber at a preselected rate of speed, whereby a thin film of preselected thickness may be continuously deposited onto the substrate.

18. Apparatus as in claim 14, further including:

thickness monitoring means for measuring the thickness of the thin film as it is deposited.

19. Apparatus as in claim 14, further including:

a first crucible in which the source of solid material is disposed; and

control means adapted to (1) control the energy and intensity of the electron beam means, and (2) direct the electron beam means to impinge upon the solid material in the crucible for the vaporization thereof.

20. Apparatus as in claim 19, further including:

at least two crucibles in each of which the source of solid material is disposed; and

said control means is further adapted to direct the electron beam means to sequentially impinge upon the material in each of the crucibles.

21. Apparatus as in claim 14, wherein the electrode means comprises:

a first generally planar metallic plate having an aperture formed therein;

a second generally planar metallic plate disposed in spaced relation to a first surface of said first plate and having an aperture formed therein; and

a third generally planar metallic plate disposed in spaced relation to the second surface of the first generally planar plate, said third plate having an aperture formed therein, the apertures in the first, second and third plates being generally aligned.

22. Apparatus as in claim 21, wherein the first plate is in electrical communication with the source of alternating current, and the second and third plates are electrically grounded.

23. Apparatus as in claim 21, wherein the apertures in the first, second and third plates are generally circular and the aperture in the first plate has a diameter less than the diameter of the apertures in the second and third plates.

24. Apparatus as in claim 21, wherein the first metallic plate further includes a relatively thin, electrically conductive member in electrical communication therewith and extending at least partially across the aperture thereof.

25. Apparatus as in claim 21, wherein the first metallic plate further includes an electrically conductive metallic mesh extending at least partially across the aperture thereof and in electrical communication therewith.

26. Apparatus as in claim 14, wherein the source of alternating current is adapted to provide radio frequency energy.

27. Apparatus as in claim 14, wherein the source of alternating current is adapted to provide microwave energy.

28. Apparatus as in claim 14, wherein the source of solid material is adapted to provide a material selected from the group consisting essentially of:

In, Sn, Cd, Zn, Ti, Si, Ge and mixtures thereof.

29. Apparatus as in claim 15, wherein the gas inlet means is adapted to provide a reactive gas selected from the group consisting essentially of:

O₂, N₂, NH₃, CH₄, H₂ S, N₂ O, CF₄ and mixtures thereof.