Method for manufacturing a compound film

• US 9,666,745 B2
• Filed: 07/26/2013
• Issued: 05/30/2017
• Est. Priority Date: 09/12/2007
• Status: Active Grant

• Current Assignee: Flisom AG
• Original Assignee: Flisom AG
• Inventors: Kaelin, Marc, Studer, Thomas, Budde, Felix, Rudmann, Dominik
• Primary Examiner(s): Baldwin, Gordon R
• Assistant Examiner(s): LEE, AIDEN Y
• Application Number:
  US13/952,420
• Publication Number:
  US 20130312664A1
• Time in Patent Office: 1,404 Days
• CPC Class Codes: C23C 14/0623 Sulfides, selenides or tellurides
• CPC Class Codes: C23C 14/545 using measurement on deposited material
• CPC Class Codes: C23C 14/548 Controlling the composition
• CPC Class Codes: H01L 31/0322 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
• CPC Class Codes: H01L 31/18 Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
• CPC Class Codes: H01L 31/1844 comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P
• CPC Class Codes: Y02E 10/541 CuInSe2 material PV cells
• CPC Class Codes: Y02E 10/544 Solar cells from Group III-V materials
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

A method for manufacturing a compound film comprising a substrate and at least one additional layer is disclosed. The method comprising the steps of depositing at least two chemical elements on the substrate and/or on the at least one additional layer using depositions sources, maintaining depositing of the at least two chemical elements while the substrate and the deposition sources are being moved relative to each other, measuring the compound film properties, particularly being compound film thickness, compound-film overall composition, and compound-film composition in one or several positions of the compound film, comparing the predefined values for the compound film properties to the measured compound film properties, and adjusting the deposition of the at least two chemical elements in case the measured compound film properties do not match the predefined compound film properties.

Claims

1. An apparatus for forming a compound film layer that comprises a CIGS material, comprising:

a deposition chamber comprising a deposition zone;

a flexible substrate having a deposition surface and a non-deposition surface, wherein the flexible substrate comprises a metal-containing layer that has a surface that forms at least part of the deposition surface;

a substrate transport device that is configured to transfer the flexible substrate in a first direction through the deposition zone of the deposition chamber when forming the compound film layer;

a deposition source block disposed in the deposition zone, comprising;

a first deposition source that is configured to deliver a flux of a first material to the deposition surface of the flexible substrate as the flexible substrate is transferred through the deposition zone, wherein a heated region of the first deposition source contains the first material which consists essentially of gallium (Ga); and

a second deposition source that is configured to deliver a flux of a second material to the deposition surface of the flexible substrate as the flexible substrate is transferred through the deposition zone, wherein the first and second deposition sources are disposed a distance apart along the first direction, and a heated region of the second deposition source contains the second material which consists essentially of indium (In);

a measurement device having an x-ray detector and either an x-ray source or an electron source that are positioned over the non-deposition surface of the flexible substrate and directly over the deposition source block within the deposition zone, wherein the non-deposition surface is opposed to the deposition surface of the flexible substrate, and the flexible substrate is disposed between the measurement device and the deposition source block; and

a controller that is configured to;

determine a ratio of the first material to the second material deposited on the deposition surface of the flexible substrate based on information received from the x-ray detector of the measurement device, wherein the x-ray detector is configured to detect K-line fluorescence radiation only or K-line and L-line fluorescence radiation, and the determined ratio is generated by analyzing the detected fluorescent radiation wavelengths, and

adjust an amount of the first material provided by the first deposition source or an amount of the second material provided by the second deposition source to the deposition surface-based on the determined ratio.

2. The apparatus of claim 1, wherein

the first deposition source further comprises a heating element that is configured to heat an amount of the first material disposed within the first deposition source, and

the second deposition source further comprises a heating element that is configured to heat an amount of the second material disposed within the second deposition source.

3. The apparatus of claim 2,

wherein the heating elements in the first and the second deposition sources each further comprise a plurality of deposition source units that are disposed along a second direction that is perpendicular to the first direction, wherein each of the deposition source units in the first deposition source are configured to evaporate a portion of the first material disposed in the heated region and each of the deposition source units in the second deposition source are configured to evaporate a portion of the second material disposed in the heated region.

4. The apparatus of claim 1, wherein

the deposition source block further comprises:

a third deposition source that is configured to deliver a flux of a third material to the deposition surface of the flexible substrate, and having an amount of a third material disposed within a heated region of the third deposition source, wherein the third material consists essentially of copper (Cu); and

a fourth deposition source that is configured to deliver a flux of the first material to the deposition surface of the flexible substrate, wherein a heated region of the fourth deposition source contains the first material which consists essentially of gallium (Ga),

wherein the first, second, third and fourth deposition sources are sequentially disposed along the first direction.

5. The apparatus of claim 1, wherein the measurement device further comprises:

the x-ray source; and

a housing in which the x-ray detector and the x-ray source are disposed.

6. The apparatus of claim 1, wherein the measurement device further comprises the x-ray source and a housing in which the x-ray detector and the x-ray source are disposed, wherein the housing is in contact with the non-deposition surface of the flexible substrate.

7. The apparatus of claim 1, wherein the measurement device further comprises a housing in which the x-ray detector and either the x-ray source or the electron source are disposed, and the apparatus further comprises a cooling device configured to cool the measurement device.

8. The apparatus of claim 1, wherein the flexible substrate further comprises a polymer material, the measurement device further comprises the x-ray source and a housing in which the x-ray detector and the x-ray source are disposed, and the housing is in contact with the non-deposition surface of the flexible substrate.

9. The apparatus of claim 1, further comprising a cooling device configured to cool the measurement device.

10. The apparatus of claim 1, wherein the controller is further configured to adjust the amount of the first material provided by the first deposition source or the amount of the second material provided by the second deposition source based on a comparison of the determined ratio and a stored compositional profile that is accessible to the controller.

11. The apparatus of claim 10, wherein the determined ratio is generated from fluorescent radiation detected by the x-ray detector, wherein the detected florescent radiation has a wavelength of the K-line fluorescent radiation.

12. An apparatus for forming a compound film layer that comprises a CIGS material, comprising:

a deposition chamber comprising a deposition zone;

a first deposition source block disposed in the deposition zone of the deposition chamber, the first deposition source block comprising;

a first deposition source comprising a heating element and a heated region that contains an amount of a first material, wherein the heating element is positioned to heat an amount of the first material disposed within the heated region of the first deposition source and the first material consists essentially of gallium (Ga);

a second deposition source comprising a heating element and a heated region that contains an amount of a second material;

wherein the heating element is positioned to heat an amount of the second material disposed within the heated region of the second deposition source, and the second material consists essentially of indium (In); and

a third deposition source comprising a heating element and a heated region that contains an amount of the first material;

wherein the heating element is positioned to heat an amount of the first material disposed within the heated region of the third deposition source, and the first, second and third deposition sources are serially disposed a distance apart along a first direction;

a flexible substrate that extends from an input roll to an output roll and through the deposition zone of the deposition chamber, wherein the flexible substrate comprises a flexible body and a metal-containing layer, and a surface of the metal-containing layer forms at least part of a deposition surface of the flexible substrate;

a substrate transport device that is configured to transfer the flexible substrate, relative to the first deposition source block, in the first direction from the input roll to the output roll, wherein the first, second and third deposition sources are positioned to deliver a flux of either of the first or the second material to the surface of the metal-containing layer disposed over the flexible substrate during processing;

a measurement device that is fixedly positioned within the deposition zone of the deposition chamber and having an x-ray detector and an x-ray source that are positioned over a non-deposition surface of the flexible substrate and directly over the first deposition source block, wherein the non-deposition surface is opposed to the deposition surface of the flexible substrate, and the flexible substrate is disposed between the measurement device and the first deposition source block; and

a controller that is configured to;

determine a ratio of the first material to the second material deposited on the deposition surface of the flexible substrate based on information received from the x-ray detector of the measurement device, wherein the x-ray detector is configured to detect K-line fluorescence radiation only or K-line and L-line fluorescence radiation, and the determined ratio is generated by analyzing the detected fluorescent radiation wavelengths, and

adjust an amount of energy generated by the heating element in the first, second or third deposition sources based on the determined ratio.

13. The apparatus of claim 12, wherein the heating elements in the first, second and third deposition sources each further comprise a plurality of deposition source units that are disposed along a second direction that is perpendicular to the first direction, wherein

the first deposition source block further comprises:

a fourth deposition source that is configured to deliver a flux of a third material to the metal-containing layer disposed over the deposition surface of the flexible substrate, and containing an amount of a third material that comprises copper (Cu) disposed within a heated region of the fourth deposition source, wherein the fourth deposition source is disposed between the second and third deposition sources along the first direction, and

wherein the first, second, fourth and third deposition sources are sequentially disposed along the first direction.

14. The apparatus of claim 12, wherein the measurement device further comprises a housing in which the x-ray detector and the x-ray source are disposed.

15. The apparatus of claim 12, wherein the measurement device further comprises a housing in which the x-ray detector is disposed, wherein the housing is in direct contact with the non-deposition surface of the flexible substrate.

16. The apparatus of claim 12, wherein

the measurement device further comprises:

a housing in which the x-ray detector and the x-ray source are disposed, wherein the housing is in contact with the non-deposition surface of the flexible substrate, and

the apparatus further comprises a cooling device configured to cool the measurement device.

17. The apparatus of claim 12, wherein the measurement device further comprises a housing in which the x-ray detector and x-ray source are disposed, and the housing is fixedly disposed over a portion of a second region of the flexible substrate, wherein the second region is opposite to a first region of the flexible substrate which receives the flux of the first material from the first deposition source, the flux of the second material from the second deposition source and the flux of the first material from the third deposition source.

18. The apparatus of claim 12, further comprising a second deposition source block that is disposed in the deposition chamber, and a distance in the first direction from the first deposition source block, and the second deposition source block comprises:

a fourth deposition source configured to deliver a flux of the first material to the deposition surface of the flexible substrate during the formation of the compound film layer; and

a fifth deposition source configured to deliver a flux of the second material to the deposition surface of the flexible substrate during the formation of the compound film layer,

wherein the apparatus further comprises;

an additional measurement device that is fixedly positioned over a non-deposition surface of the flexible substrate and over a gap formed between the first deposition source block and the second deposition source block, and the additional measurement device comprises an x-ray detector and an x-ray source, and

the controller is further configured to adjust an amount of energy generated by the heating element in the first, second or third deposition sources based on information received from the additional measurement device.

19. The apparatus of claim 18, wherein

the measurement device further comprises a first housing in which the x-ray detector and the x-ray source of the measurement device are disposed,

the additional measurement device further comprises a second housing in which the x-ray detector and the x-ray source of the additional measurement device are disposed, and

the first housing and the second housing are both in contact with the non-deposition surface of the flexible substrate.

20. The apparatus of claim 12, further comprising a cooling device configured to cool the measurement device.

21. The apparatus of claim 12, wherein the controller is further configured to adjust the amount of energy generated by the heating element in the first, second or third deposition sources based on a comparison of the determined ratio and a stored compositional profile that is accessible to the controller.

22. The apparatus of claim 21, wherein the determined ratio is generated from fluorescent radiation detected by the x-ray detector, wherein the detected florescent radiation has a wavelength of the K-line fluorescent radiation.