Various aspects of this disclosure may pertain to economical manufacturing processes of visible light rectenna arrays for the conversion of solar energy to electricity.
Rectifiers for AC to DC conversion of high frequency signals have been well known for decades. A particular type of diode rectifier when coupled to an antenna, called a rectenna, has also been known for decades. More specifically, over 20 years ago, Logan described using an array of rectennas to capture and convert microwaves into electrical energy in U.S. Pat. No. 5,043,739 granted Aug. 27, 1991. However, the dimensions of the antenna limited the frequency until recently, when Gritz, in U.S. Pat. No. 7,679,957 granted Mar. 16, 2010, described using a similar structure for converting infrared light into electricity, and Pietro Siciliano suggested that such a structure may be used for sunlight in “Nano-Rectenna For High Efficiency Direct Conversion of Sunlight to Electricity,” by Pietro Siciliano of The Institute for Microelectronics and Microsystems IMM-CNR, Lecce (Italy).
Still, the minimum dimensions required for such visible light rectennas are generally in the tens of nanometers. While these dimensions may be accomplished by today's deep submicron masking technology, such processing is typically far more expensive than the current solar cell processes, which require much larger dimensions.
Still, as Logan pointed out in U.S. Pat. No. 5,043,739, the efficiency of microwave rectennas can be as high as 40%, more than double that of typical single-junction poly-silicon solar cell arrays, and when using metal-oxide-metal (MOM) rectifying diodes, as Pietro suggests, no semiconductor transistors are needed in the array core.
As such, it may be advantageous to be able to utilize the existing fine geometry processing capability of current semiconductor fabrication without incurring the cost of such manufacturing.
Also, recently, Rice University reported that their researchers created a carbon nanotube (CNT) thread with metallic-like electrical and thermal properties. Furthermore, carbon nanotube structures are becoming more manufacturable, as described by Rosenberger et al. in U.S. Pat. No. 7,354,977 granted Apr. 8, 2008. Various forms of continuous CNT growth may have also been contemplated, such as Lemaire et.al. repeatedly harvesting a CNT “forest’ while it is growing in U.S. Pat. No. 7,744,793 granted Jun. 29, 2010, and/or put into practice using techniques described by Predtechensky et al. in U.S. Pat. No. 8,137,653 granted Mar. 20, 2012. Grigorian et al. describes continuously pushing a carbon gas through a catalyst backed porous membrane to grow CNTs in U.S. Pat. No. 7,431,985 granted Oct. 7, 2008.
Furthermore, others have contemplated using CNTs for various structures such as Rice University's CNT thread as described in “Rice's carbon nanotube fibers outperform copper,” by Mike Williams, posted on Feb. 13, 2014 at: news.rice.edu/2014/02/13/rices-carbon-nanotube-fibers-outperform-copper-2; magnetic data storage as described by Tyson Winarski in U.S. Pat. No. 7,687,160 granted Mar. 30, 2010; and in particular, antenna-based solar cells, as described by Tadashi Ito et al. in US Patent Publication 2010/0244656 published Sep. 30, 2010. Still, Ito et al. did not describe methods to inexpensively construct carbon nanotube solar antennas for efficient conversion of solar energy.
Various aspects of the present disclosure may relate to ways to manufacture structures of CNT rectenna arrays for converting sunlight into electricity, which may utilize a stamp made using current IC manufacturing techniques and self-aligning process steps, and which may be used to achieve the dimensions required for the antenna arrays.
The structure of the rectenna array may include an array of CNT antennas connecting a ground line to a voltage line through geometric diodes, formed by the tip of the carbon nanotube touching the metal on the voltage line. The antennas may be of varying lengths and orientations, distributed for maximum reception of the full spectrum of ambient sunlight, e.g., having ¼ wavelengths or harmonic multiples of ¼ wavelengths. Two ¼-wavelength antenna diode combinations may be coupled with low resistance carbon nanotube fuzz to full-wave rectify the received light. An array of such double diode-antenna structures may be connected both in rows and columns such that the ground line of one row of double-diode antenna structures is connected to the voltage line of the next row of double-diode antenna structures. The number of rows may determine the voltage generated by the array, and the number of columns may determine the current generated by the array. Multiple arrays may be connected in parallel to form a die. Multiple die may be connected together to form a module. Switches may be used to vary the number of rows and columns of the double-diode antenna structures in an array. Such switches may be constructed from geometric diodes, which may change from conducting electrons to conducting holes in the presence of an electric field.
In one aspect, the rectenna arrays may be constructed by a series of depositions from a glass base up to a plastic back such that the antennas collect light through the glass base. Bus bars, composed of some combination of aluminum, copper, silver, or some other suitable conducting, reflecting metal may further reflect the received or retransmitted light to be re-collected by the antennas. In one such series of depositions, silicon nitride, or some other non-adhesive oxide that the catalyst will not adhere to, and aluminum, or some other suitable non-magnetic metal, may be deposited, stamped and etched, leaving the non-adhesive oxide between metal lines of varying heights. Another oxide may be deposited on the top of the metal, and nickel, or some other magnetic metal such as cobalt or iron, may be deposited to form a thin layer of catalyst for growing the CNT antennas. Subsequently, the catalyst may be polished off the high spots of the metal across the entire top of the voltage lines and half of the ground lines leaving “beads” of catalyst between the non-magnetic metal, after which the residual catalyst on the non-adhesive oxide may be washed off. Optionally, the non-adhesive oxide may then be selectively etched. Later, the catalyst may be annealed to prepare the layer of catalyst for growing the CNT antennas.
In another aspect, a stamp may be constructed to pattern metals for selectively etching the structures necessary to create the CNT antenna array. Alternatively, the stamp may be used to directly pattern metal, or may be further used to pattern a drum for high volume continuous CNT antenna array manufacturing.
In yet another aspect, oxide may be grown subsequent to the growth of the CNTs anchoring the CNTs to the aluminum lines. Furthermore, a clear plastic sheet may separate metal bus bars from the CNT antennas. A laser may be used to form vias in the plastic sheet. The plastic sheet may be a polycarbonate sheet. Resist may be exposed by shining light through the glass, forming a self aligned separation for the blade spread power and ground bus bars. The bus bars may be comprised of aluminum and copper. A cover layer of plastic may also be deposited on the bus bars, thereby forming a fully encapsulated continuous roll of flexible solar cells.
Various aspects of the present disclosure will now be described in connection with the attached drawings, in which:
Various aspects of the present disclosure are now described with reference to
An electrical diagram 10 of a double-diode antenna structure according to an aspect of the present disclosure is shown in
Reference is now made to
Reference is now made to
In order to efficiently rectify visible light, the diodes may need to have a cutoff frequency above 700 THz, with forward bias voltages as close to zero volts as possible. This may require geometric diodes 46 with sufficiently small diameters connected to the voltage lines from sufficiently large enough diameter carbon nanotubes to maintain at least a 4:1 ratio of the carbon nanotube diameter to the diameter of the contact with the voltage line. Furthermore, the antennas' lengths and directions may vary to cover substantially the entire spectrum of un-polarized sunlight. This may be accomplished by varying the distance the carbon nanotubes 43 must cover from the ground 41 line to the voltage line 40, such that the difference of the shortest to the longest carbon nanotube may be greater than the difference between a ¼ wavelength of ultraviolet light (˜80 nanometers) and ¼ wavelength of infrared light (˜640 nanometers). This may ensure that at least one harmonic of substantially all frequencies of sunlight may be covered by the range of CNT lengths.
Such small structures may require the combination of complex semiconductor processing coordinated with controlled growth of carbon nanotube antennas. It may, therefore, be desirable to leverage as much of existing semiconductor processing as possible, and to modify the process to reduce cost and increase volume by eliminating all (or as many as possible) wafer handling and photolithographic operations, the most expensive aspects of semiconductor processing. Secondly, it may also be desirable to eliminate the need to align any structure formed in the process with any other structure subsequently formed later in the process. This may be accomplished, e.g., by only performing one stamping step.
Reference is now made to
Reference is now made to
Reference is now made to
A “pump up” may then be performed to process the rest of the vacuum steps in a low vacuum. In addition, the anneal may be a combination of a reduction step using hydrogen or ammonia to reduce oxide from the layer of nickel 112, and a rapid thermal anneal (RTA) to convert the nickel layer into suitable nickel balls for carbon nanotube growth.
Reference is now made to
Reference is now made to
The carbon nanotube growth may be performed by applying an electrical field between the ground lines 134 and the voltage lines 13.3. Furthermore, the current may be clamped and monitored to minimize the disconnection of the carbon nanotubes 130, which may bridge the gap between the ground lines 134 and the voltage lines 133.
To manufacture the geometric diodes, the carbon nanotubes 130 may be grown to aluminum on the voltage lines 133, which may not have aluminum oxide 135 on them. This step may be followed by an optional step to grow oxide 47 over all the aluminum lines, which may grow around the tips of the carbon nanotubes 46, as shown in
Reference is now made to
Reference is now made to
Reference is now made to
Reference is now made to
Reference is now made to
Reference is now made to
Reference is now made to
It will be appreciated by persons skilled in the art that the present invention is not limited by what has been particularly shown and described hereinabove. Rather the scope of the present invention includes both combinations and sub-combinations of various features described hereinabove as well as modifications and variations which would occur to persons skilled in the art upon reading the foregoing description and which are not in the prior art.
This application is a continuation-in-part of U.S. patent application Ser. No. 15/411,396, filed on Jan. 20, 2017, which is a continuation-in-part of U.S. patent application Ser. No. 15/249,953, filed on Aug. 29, 2016, which is a continuation-in-part of U.S. patent application Ser. No. 15/133,807, filed on Apr. 20, 2016, all of which are incorporated herein by reference.
Number | Name | Date | Kind |
---|---|---|---|
5043739 | Logan et al. | Aug 1991 | A |
7354877 | Rosenberger et al. | Apr 2008 | B2 |
7354977 | Woods et al. | Apr 2008 | B1 |
7431965 | Grigorian et al. | Oct 2008 | B2 |
7431985 | Iwama | Oct 2008 | B2 |
7679057 | Gritz et al. | Mar 2010 | B2 |
7679957 | Ma et al. | Mar 2010 | B2 |
7687160 | Winarski | Mar 2010 | B2 |
7744793 | Lemaire et al. | Jun 2010 | B2 |
8137653 | Predtechensky et al. | Mar 2012 | B1 |
20040085247 | Mickle et al. | May 2004 | A1 |
20050112049 | Hofmeister | May 2005 | A1 |
20050214198 | Park et al. | Sep 2005 | A1 |
20070240757 | Ren et al. | Oct 2007 | A1 |
20090128893 | McCarthy et al. | May 2009 | A1 |
20100084475 | Hata et al. | Apr 2010 | A1 |
20100244656 | Ito | Sep 2010 | A1 |
20100263709 | Norman | Oct 2010 | A1 |
20100284086 | Novack et al. | Nov 2010 | A1 |
20110121258 | Hanein et al. | May 2011 | A1 |
20110163920 | Cutler | Jul 2011 | A1 |
20120186635 | Eastman et al. | Jul 2012 | A1 |
20120206085 | Stevens | Aug 2012 | A1 |
20120211063 | Lee et al. | Aug 2012 | A1 |
20130249771 | Kotter | Sep 2013 | A1 |
20130276861 | Cooke | Oct 2013 | A1 |
20150130692 | Cooke | May 2015 | A1 |
20150155396 | Cooke et al. | Jun 2015 | A1 |
20150243817 | Cooke et al. | Aug 2015 | A1 |
20160027949 | Cooke et al. | Jan 2016 | A1 |
Number | Date | Country |
---|---|---|
102171811 | Aug 2011 | CN |
2996681 | Apr 2014 | FR |
2996681 | Apr 2014 | FR |
201110272 | Mar 2011 | TW |
2007120175 | Oct 2007 | WO |
2014063149 | Apr 2014 | WO |
Entry |
---|
Machine translation of FR-2996681-A1, Costel-Sorin. (Year: 2014). |
Extended European Search Report dated Sep. 7, 2018 in EP Application No. 15873906.0. |
Extended European Search Report dated Oct. 15, 2018 in EP Application No. 16789760.2. |
Office Action dated Sep. 18, 2018 in CN Application No. 201680025443.3. |
Office Action dated Sep. 22, 2017 in U.S. Appl. No. 13/454,155, by Cooke. |
Office Action dated Jan. 11, 2018 in U.S. Appl. No. 15/249,953, by Cooke. |
Int'l Preliminary Report on Patentability dated Nov. 16, 2017 in Int'l Application No. PCT/US2016/029336. |
Office Action dated May 29, 2018 in CN Application No. 2015800712314. |
Office Action dated Feb. 27, 2018 in U.S. Appl. No. 15/411,396, by Cooke. |
Office Action dated Mar. 9, 2018 in U.S. Appl. No. 15/133,807, by Cooke. |
Collinear—Definition and More from the Free Merriam-Webster Dictionary, “http://www.merriam-webster.com/dictionary/collinear”, 2014. |
Rows—Definition and More from the Free Merriam-Webster Dictionary, “http://www.merriam-webster.com/dictionary/rows,” 2014. |
Siciliano et al., “Nano-Rectenna for High Efficiency Direct Conversion of Sunlight to Electricity,” presented at 17th World Micromachine Summit, Apr. 26-29, 2011. |
Williams, “Rice's carbon nanotube fibers outperform copper,” at “http://news.rice.edu/2014/02/13/rices-carbon-nanotube-fibers-outperform-copper-2,” posted Feb. 13, 2014. |
Hata, “From Super Growth to DWNT forests, CNT solids, Flexible Transparent CNT films, and Super-Capacitors and Much More,” Jun. 19, 2006. |
Ma et al., “The production of horizontally aligned single-walled carbon nanotubes,” Carbon, 49, pp. 4098-4110, 2011. |
Kumar, “Chemical Vapor Deposition of Carbon Nanotubes: A Review on Growth Mechanism and Mass Production,” Journal of Nanoscience and Nanotechnology, vol. 10, pp. 3739-3758, 2010. |
Office Action dated Feb. 11, 2014 in U.S. Appl. No. 13/454,155. |
Office Action dated Jun. 27, 2014 in U.S. Appl. No. 13/454,155. |
Office Action dated Sep. 26, 2014 in U.S. Appl. No. 13/454,155. |
Office Action dated Jan. 13, 2015 in U.S. Appl. No. 13/454,155. |
Type—definition of type by The Free Dictionary, downloaded from web page: http://www.thefreedictionary.com/type, Download date: Mar. 9, 2015, original posting date: unknown, 1 page. |
Office Action dated Mar. 17, 2015 in U.S. Appl. No. 13/454,155. |
Int'l Search Report and Written Opinion dated Apr. 8, 2016 in Int'l Application No. PCT/US15/59852. |
Int'l Search Report and Written Opinion dated Aug. 11, 2016 in Int'l Application No. PCT/US16/29336. |
Office Action dated Nov. 14, 2016 in U.S. Appl. No. 14/582,747, by Cooke. |
Office Action dated Dec. 29, 2016 in U.S. Appl. No. 15/133,807, by Gonzalez Ramos. |
Office Action dated Apr. 5, 2017 in U.S. Appl. No. 14/582,747 by Cooke. |
Office Action dated May 4, 2017 in U.S. Appl. No. 15/249,953, by Cooke. |
Office Action dated Apr. 20, 2017 in U.S. Appl. No. 14/871,958, by Cooke. |
Office Action dated Mar. 7, 2017 in U.S. Appl. No. 14/701,765, by Cooke. |
Int'l Search Report and Written Opinion dated Jun. 20, 2017 in Int'l Application No. PCT/US2017/026130. |
Office Action dated Jun. 8, 2017 in U.S. Appl. No. 14/701,765, by Cooke. |
Int'l Preliminary Report dated Jul. 6, 2017 in PCT Application No. PCT/US2015/059852. |
Office Action dated Jul. 3, 2017 in U.S. Appl. No. 15/133,807, by Cooke. |
Office Action dated Jul. 27, 2017 in U.S. Appl. No. 15/411,396, by Cooke. |
Office Action dated May 5, 2019 in CN Application No. 2015800712314. |
Search Report dated Jul. 8, 2019 in TW Application No. 104137565. |
Office Action dated Apr. 4, 2019 in U.S. Appl. No. 15/411,396. |
Number | Date | Country | |
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20180026149 A1 | Jan 2018 | US |
Number | Date | Country | |
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Parent | 15411396 | Jan 2017 | US |
Child | 15661854 | US | |
Parent | 15249953 | Aug 2016 | US |
Child | 15411396 | US | |
Parent | 15133807 | Apr 2016 | US |
Child | 15249953 | US |