Multi-layer thin-film, flexible silicon alloy photovoltaic cell

• US 4,479,027 A
• Filed: 09/24/1982
• Issued: 10/23/1984
• Est. Priority Date: 09/24/1982
• Status: Expired due to Fees

• Current Assignee: William J. Todorof
• Original Assignee: William J. Todorof
• Inventors: Todorof, William J.
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US06/422,944
• Time in Patent Office: 760 Days
• Field of Search: 136/256, 136/257, 136/259, 136/255, 136/249 TJ, 136/258 PC, 136/258 AM, 136/261, 136/245, 357/30, 252/62.3 R, 252/62.3 BT, 252/501.1
• US Class Current: 136/249
• CPC Class Codes: H01L 31/02168 the coatings being antireflective or having enhancing optical properties for the solar cells
• CPC Class Codes: H01L 31/022425 for solar cells
• CPC Class Codes: H01L 31/0682 back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
• CPC Class Codes: H01L 31/076 Multiple junction or tandem solar cells
• CPC Class Codes: H01L 31/206 Particular processes or apparatus for continuous treatment of the devices, e.g. roll-to roll processes, multi-chamber deposition
• CPC Class Codes: Y02E 10/547 Monocrystalline silicon PV cells
• CPC Class Codes: Y02E 10/548 Amorphous silicon PV cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

The flexible photovoltaic cell includes thin front and rear junction regions electrically in series each formed of ceramic metallic glass semi-conductor alloys of silicon of approximately zero thermal expansion/contraction coefficient laminated with an intervening semi-conducting layer less than 60 Angstroms thick or an insulating layer less than 20 Angstroms thick. The respective spectral sensitivities of front and rear junction regions are tailored to different frequency ranges. In front are six layers described in sequence rear to front. The lowermost (sixth) is a green/blue semi-insulating cobalt and tin passivating and filter layer less than 10 Angstroms thick. The fifth is a semi-conductive, degradation-protective "window" and one-way mirror for returning back-reflected light. The fourth is an insulating tunneling layer less than 15 Angstroms thick for coupling a front collection grid to the "window". Covering the fourth layer is a triple-layer, anti-reflection coating (ARC) whose middle layer bonds the outer ARC layers and secondarily protects the cell from atmospheric degradation. An internally refelective rear ARC layer cooperates with the "window" for returning back-reflected light. The frontmost ARC layer is mainly comprised of Al₂ O₃ /S_i O₂ in the range of 200 to 650 Angstroms thickness. The cell backside is shown having undulations for randomizing reflected light rays. The six front layers effectively adapt the cell for receptivity to solar radiation from about 4,000 to about 12,000 Angstroms, excluding radiation outside thereof, thus accepting 68 percent of solar energy vertically reaching the earth'"'"'s surface.

Claims

1. In a photovoltaic cell an anti-reflective coating (ARC) covering the front surface of the cell adapted to receive incident radiation, the improvement comprising said ARC coating comprising upper and lower layers bonded together by an intervening layer being formed from a semi-vitreous glass alloy composition comprising:

about 67 to about 82 percent silicon dioxide, about 5 to about 14 percent aluminum trioxide, about 6 to 18 percent boron trioxide, about 4 to about 20 percent sodium oxide and about 0.01 to about 5 percent phosphorous pentoxide, wherein the percentages are expressed as percents by weight based upon the total weight of the alloy composition.

2. In a photovoltaic cell, an intervening layer as defined in claim 1, wherein said intervening layer is bonded to the surface of an underlying layer by heating said intervening layer to a temperature of from about 750°

C. to a temperature of less than about 850°

C.

3. In a photovoltaic cell, an intervening layer as defined in claim 1 or 2, wherein said intervening layer has a thickness in the range from about 50 Angstroms to about 400 Angstroms.

4. In a photovoltaic cell, an intervening layer as defined in claim 1 or 2, wherein the ratio by weight of silicon dioxide to aluminum trioxide is in the range from 16.4 to 1 to 4.8 to 1.

5. In a photovoltaic cell, an intervening layer as defined in claim 1 or 2, including a flux in an amount less than about 20 percent by weight of the total composition, said flux being a compound selected from the group of compounds consisting of tin dioxide, antimony dioxide and antimony trioxide, and wherein the balance of said total composition is trace elements in an amount less than about 2 percent by weight of the total composition.

6. In a photovoltaic cell, an intervening layer having semi-vitreous glass alloy composition as defined in claim 1 or 2, including about 73 percent silicon dioxide, about 7 percent aluminum trioxide, about 10 percent boron trioxide, about 8.7 percent sodium oxide and about 1.3 percent phosphorous pentoxide.

7. In a photovoltaic cell, an intervening layer having semi-vitrous glass alloy composition as defined in claim 1 or 2, including about 68 percent silicon dioxide, about 5 percent aluminum trioxide, about 15 percent boron trioxide, about 11.2 percent sodium oxide and about 9.8 percent phosphorous pentoxide.

8. In a photovoltaic cell having a silicon-containing semiconductor body in which the silicon comprises more than 50% by weight of the semiconductor body and wherein silver contact members are used to collect the charge carriers from the semiconductor body, strike barriers positioned between said semiconductor body and said contact members, each such strike barrier having a width at least as wide as the associated contact member and comprising a layer formed of titanium nitride and cobalt nitride containing at least 90% titanium nitride and at least 1% cobalt nitride by weight percent of the total composition of the strike barrier layer for preventing migration of silver atoms from the contact members into the semiconductor body and for reducing the contact resistance of the silver contact members with respect to the semiconductor body.

9. In a photovoltaic cell, strike barriers as defined in claim 8, having a thickness of approximately 100 Angstroms.

10. A photovoltaic cell having a first plurality of elongated, spaced parallel contact members on the front thereof and a second plurality of elongated, spaced, parallel contact members on the rear thereof, said contact members of the first plurality being in a first chevron pattern, said contact members of the second plurality on the rear of the cell being in a second chevron pattern of the same configuration as the first chevron pattern and reversed with respect to the first pattern for minimizing likelihood of short circuit between front and rear contact member, said rear of the cell being optically reflective and having an undulating configuration between each of the rear contact members for reflecting light rays within the cell along various paths with respect to the respective chevron patterns.

11. A photovoltaic cell having at least one photoactive region formed of a ceramic metallic glass semi-conductor alloy of silicon characterized by the indicated weight percent of the following elements:

space="preserve" listing-type="tabular">______________________________________ Range in Weight Percent Ingredient of Total Composition ______________________________________ Silicon 51-88% Lithium 3-30% Aluminum 0.5-29% Fluorine 0.5-8% Hydrogen 1-12% Vanadium 0-5% Trace Elements, Less than 0.1% Including Oxygen ______________________________________

12. A photovoltaic cell having at least one photoactive region formed of a ceramic metallic glass semi-conductor alloy of silicon characterized by the indicated weight percent of the following elements:

space="preserve" listing-type="tabular">______________________________________ Range in Weight Percent Ingredient of Total Composition ______________________________________ Silicon 51-88% Lithium 3-30% Aluminum 0.5-29% Fluorine 0.5-8% Hydrogen 0.5-12% Antimony 0.01-20% Cobalt 0.01-6% Trace Elements, Less than 0.1% Including Oxygen ______________________________________

13. In a photovoltaic cell having a photoactive region, internally reflective rear mirror means applied to said photoactive region comprising a layer of tin, a layer of chromium applied to said tin layer and being located behind said tin layer, said tin layer preventing migration of chromium atoms into said photoactive region.

14. In a photovoltaic cell, internally reflective rear mirror means as claimed in claim 13, in which:

said tin layer is at least 50 Angstroms thick.

15. In a photovoltaic cell, internally reflective rear mirror means as claimed in claim 13, in which:

said photoactive region has a multiplicity of interdigitated n+ and p+ stripes alternating in position immediately adjacent one to another, said n+ and p+ stripes being adjacent to said tin layer.

16. In a photovoltaic cell having a photosensitive region, charge carrier collection means on the rear of said region comprising a plurality of interdigitated p+ and n+ doped stripes alternating in position and each having a thickness in the range from 0.5 to 1.5 microns, said interdigitated stripes being immediately adjacent one to another.

17. In a photovoltaic cell, charge carrier collection means as defined in claim 16, in which:

a first plurality of said immediately adjacent interdigitated p+ and n+ stripes are located on a first sloping rear surface of said photosensitive region, and

a second plurality of said immediately adjacent interdigitated p+ and n+ stripes are located on a second sloping rear surface of said photosensitive region which slopes in the opposite direction from said first sloping rear surface.

18. In a photovoltaic cell, charge carrier collection means as defined in claim 17, in which:

a first internally reflective mirror is positioned adjacent to and slopes at the same angle as said first plurality of interdigitated stripes, and

a second internally reflective mirror is positioned adjacent to and slopes at the same angle as said second plurality of interdigitated stripes.

19. In a photovoltaic cell having a photosensitive region with a front surface and having contact members extending in front of said front surface, combined spectral filter and passivating means comprising:

a spectral filter layer on the front surface of said photosensitive region, said spectral filter layer extending continuously across said front surface and extending beneath said contact members and consisting mainly of cobalt nitride together with tin oxide having a bright green-to-blue color, said spectral filter layer also acting as a passivating layer on the front surface of said photosensitive region.

20. In a photovoltaic cell, a spectral filter layer as defined in claim 19, in which:

said spectral filter layer contains cobalt nitride and tin oxide in a weight ratio of about 58% to 42%.

21. In a photovoltaic cell, a spectral filter layer as claimed in claim 19, in which:

said green-to-blue colored filter excludes wavelengths longer than approximately 12,000 Angstroms.

22. A multiple junction photovoltaic cell comprising a front and a rear cell, said cells being formed of ceramic metallic glass alloys of silicon having different band gaps and being positioned one in front of the other with a thin optically transparent lattice matching layer optically and electrically coupling them in series, and with electrical contact members on the front of the front cell and on the rear of the rear cell for operating the two cells in series.

23. A multiple junction photovoltaic cell as claimed in claim 22, in which:

one of said cells has a band gap in the range of 1.55 to 1.65 electron volts and the other has a band gap in the range from 0.9 to 1.1 electron volts.

24. A multiple junction photovoltaic cell as claimed in claim 22, in which:

one of said cells has a glassy silicon alloy composition characterized by the following weight percent of the following elements;

space="preserve" listing-type="tabular">______________________________________ Range in Weight Percent Ingredient of Total Composition ______________________________________ Silicon 51-88% Lithium 3-30% Aluminum 0.5-29% Fluorine 0.5-8% Hydrogen 1-12% Vanadium 0-5% Trace Elements, Less than 0.1% Including Oxygen ______________________________________

25. A multiple junction photovoltaic cell as claimed in claim 22, in which:

one of said cells has a glassy silicon alloy composition characterized by the following weight percent of the following elements;

space="preserve" listing-type="tabular">______________________________________ Range in Weight Inqredient of Total Composition ______________________________________ Silicon 51-88% Lithium 3-30% Aluminum 0.5-29% Fluorine 0.5-8% Hydrogen 0.5-12% Antimony 0.01-20% Cobalt 0.01-6% Trace Elements, Less than 0.1% Including Oxygen ______________________________________

26. A multiple junction photovoltaic cell as claimed in claim 22, in which:

the band gap of the glassy silicon alloy in the front cell is higher than the band gap of the glassy silicon alloy in the rear cell.

27. A multi-junction cell comprising:

front and rear juction regions positioned in tandem one in front of the other, each of said junction regions being formed of a glassy silicon alloy, the spectral sensivity of the rear junction region being different from the spectral sensitivity of the front junction region said front and rear junction regions being optically and electrically coupled together in series by an intervening thin, optically transparent lattice matching layer, first electrical contact means associated with the front of the cell and second electrical contact means associated with the rear of the cell for operating the two junction regions in series.

28. A multi-junction cell as claimed in claim 27, having back surface reflector means for internally reflecting light rays forwardly, and having over the front of said cell a semi-conductive one-way window layer transparent to incoming light rays but acting as an optical mirror for internally reflecting light rays rearwardly which have previously been reflected forwardly from the back for preventing escape of these internal light rays.

29. A multi-junction cell as claimed in claim 28, having a non-planar rear surface configuration including a plurality of sloping reflecting regions in said back surface reflector means for internally reflecting light rays along various paths.

30. A multi-junction cell as claimed in claim 29, in which:

said sloping regions slope at an angle in the range from approximately 10°

to 15°

to the plane of the cell.

31. A multi-junction cell as claimed in claim 27, having a green-to-blue spectral filter in front of the front junction region for excluding wavelengths longer than the middle of the near infra-red range at approximately 12,000 Angstroms for keeping the cell operating relatively cool and also for excluding ultra violet radiation shorter than about 4,000 Angstroms for preventing ultraviolet degradation.

32. A multi-junction cell as claimed in claim 27, in which:

the front junction region includes a highly doped zone immediately adjacent to the front of said intervening matching layer, and

the rear junction region includes a highly doped zone of opposite polarity type immediately adjacent to the rear of said intervening matching layer.

33. A photovoltaic cell including a contact structure comprising:

a plurality of elongated contact members formed of silver positioned on the cell for providing electrical connection with the cell,

a plurality of intermediate buses connected to said silver contact members,

said intermediate buses including lower portions formed of silver integral with said contact members and formed at the same time as said silver contact members, and

said intermediate buses each including an upper portion of larger cross-sectional area than said lower portion, and

said upper portion being formed of copper and being positioned directly on top of and contiguous with said lower silver portion.

34. A photovoltaic cell including contact structure as claimed in claim 33, in which:

a plurality of main buses are connected to said intermediate buses,

said main buses include first, second and third portions,

said second portion has a larger cross-sectional area than said first portion and is positioned directly on top of said first portion and is contiguous therewith,

said third portion has a larger cross-sectional area than said second portion and is positioned directly on top of said second portion and is contiguous therewith,

said first portion is formed of silver integral with said silver lower portion of each intermediate bus and is formed at the same time as said lower portion,

said second portion is formed of copper integral with said copper upper portion of each intermediate bus and is formed at the same time as said upper portion, and

said third portion is formed of solder.

35. A photovoltaic cell including a contact structure as claimed in claim 34, in which:

said second portion of each main bus has a copper thickness equal to the thickness of the upper copper portion of each intermediate bus, and

said third portion of each main bus has a solder thickness many times greater than the thickness of the second portion.

36. A photovoltaic cell including a contact structure as claimed in claim 33, in which:

said upper copper portion of each intermediate bus has a vertical thickness many times greater than the thickness of the lower silver portion.

37. A photovoltaic cell including a contact structure as claimed in claim 33, in which:

said elongated contact members extend at an angle approximately 60°

to said intermediate buses.

38. In a photovoltaic cell having a photoresponsive region, charge carrier collection means on the rear of said region comprising a plurality of interdigitated p+ and n+ doped stripes alternating in position, said interdigitated stripes being immediately adjacent one another, and an electrically conductive metal layer immediately adjacent to the rear of said interdigitated stripes, said stripes having a width in the direction parallel to said metal layer greater than their thickness in the direction perpendicular to said metal layer.