Process for producing a transparent layer with low resistivity

• US 5,011,585 A
• Filed: 07/07/1989
• Issued: 04/30/1991
• Est. Priority Date: 07/08/1988
• Status: Expired due to Fees

• Current Assignee: Saint-Gobain Vitrage "LES Miroirs"
• Original Assignee: Saint-Gobain Vitrage
• Inventors: Beaufays, Jean-Pierre, Darmont, Maurice, Pillias, Danielle, Brochot, Jean-Pierre, Wuest, Isabelle
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US07/376,711
• Time in Patent Office: 662 Days
• Field of Search: 204/192.13, 204/192.29
• US Class Current: 204/192.13
• CPC Class Codes: C03C 17/245 by deposition from the vapour phase
• CPC Class Codes: C03C 2217/231 In2O3/SnO2
• CPC Class Codes: C03C 2218/155 by reactive sputtering
• CPC Class Codes: C03C 2218/324 De-oxidation
• CPC Class Codes: C23C 14/086 of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• CPC Class Codes: C23C 14/58 After-treatment
• CPC Class Codes: C23C 14/5806 Thermal treatment
• CPC Class Codes: C23C 14/5846 Reactive treatment

Abstract

A method for depositing on glass, by reactive cathode sputtering, a layer of indium tin oxide with low resistivity and high transparency, where a layer with at least a minimum intrinsic absorption coefficient is deposited and then a heat treatment, including of one reducing phase, is performed.

Claims

1. A process for coating a transparent substrate with a highly conductive, transparent layer having an indium based doped with tin and oxidized and having a resistivity less than 3.5×

10^-4 ohms.cm, comprising the following steps;

depositing a layer of indium tin oxide on glass at substoichiometric conditions by cathode sputtering from a target of an indium alloy comprising at least 2% tin by weight,

controlling said cathode sputtering to produce a layer having an intrinsic absorption coefficient that is equal to or greater than 7,500 cm^-1 at a wavelength of 550 nm, and

heat treating said layer after deposition on said glass using a reducing phase.

2. The process according to claim 1 wherein the intrinsic absorption coefficient of the layer after deposition is greater than 10,000 cm^-1.

3. The process according to claim 1 wherein the layer has a resistivity less than 2.5×

10^-4 ohms.cm and an intrinsic absorption coefficient of approximately 25,000 cm^-1.

4. The process according to claim 1 wherein the reducing phase in the heat treating step is performed in a reducing atmosphere.

5. The process according to claim 4 wherein the reducing atmosphere comprises a neutral gas and a reducing gas in a concentration of at least 1%.

6. The process according to claim 5 wherein the reducing gas is hydrogen.

7. The process according to claim 6 wherein the temperature during the heat treating step is at least 500°

C.

8. The process according to claim 5 wherein the reducing gas is carbon monoxide.

9. The process according to claim 4 wherein the reducing phase of the heat treating step has a duration of about 15 minutes.

10. The process according to claim 1 wherein the reducing phase of the heat treatment is preceded by an oxidizing phase.

11. The process according to claim 10 wherein the oxidizing phase is performed at a minimum of 500°

C.

12. The process according to claim 10 wherein the oxidizing phase has a duration of approximately 15 minutes.

13. A process for coating a transparent substrate with a highly conductive, transparent layer having an indium base doped with tin and oxidized and having a resistivity less than 3.5×

10^-4 ohms.cm, comprising the steps of;

calibrating a cathode sputtering process to determine a relationship between an absorption coefficient of a layer of indium doped with tin and oxidized that is formed by said cathode sputtering process and an intensity of a spectral line in a plasma formed at a cathode during said sputtering;

depositing a layer of indium tin oxide on said transparent substrate at substoichiometric conditions by cathode sputtering from a target of an indium alloy comprising at least 2% tin by weight,

during said sputtering, measuring the intensity of said spectral line in the plasma formed at the cathode during said sputtering;

controlling the cathode sputtering process so that the measured intensity corresponds to an intrinsic absorption coefficient that is equal to or greater than 7,500 cm^-1 at a wavelength of 550 nm as determined during said calibration step; and

heat treating said layer after deposition on said glass using a reducing phase.

14. The method of claim 13 wherein the cathode sputtering process is controlled by varying gas composition.

15. The method of claim 13 wherein the cathode sputtering process is controlled by varying the voltage applied to the cathode.

16. A process for coating a transparent substrate with a highly conductive, transparent layer having an indium base doped with tin and oxidized and having a resistivity less than 3.5×

10^-4 ohms.cm, comprising the steps of;

calibrating the process by forming a plurality of samples by;

depositing a layer of indium tin oxide on a plurality of glass samples at substoichiometric conditions by cathode sputtering from a target of an indium alloy;

measuring the intensities of a spectral line in a plasma formed at the cathode during said sputtering;

measuring the intrinsic absorption coefficient of each glass sample; and

establishing a relationship between the measured intensities and the measured intrinsic absorption coefficients;

depositing a layer of indium tin oxide on a transparent substrate at substoichiometric conditions by cathode sputtering from a target of an indium alloy comprising at least 2% tin by weight, where the layer obtained has an intrinsic absorption coefficient that is equal to or greater than 7,500 cm^-1 at a wavelength of 550 nm;

during said sputtering, measuring the intensity of said spectral line in the plasma formed at the cathode during said sputtering;

controlling said sputtering so that the measured intensity corresponds to the desired intrinsic absorption coefficient as specified in the relationship determined during said calibration step; and

heat treating said layer after deposition on said glass using a reducing phase.

17. The method of claim 16 wherein the cathode sputtering is controlled by varying gas composition.

18. The method of claim 16 wherein the cathode sputtering is controlled by varying the voltage applied to the cathode.