PHOTOVOLTAIC JUNCTIONS AND METHODS OF PRODUCTION
20230223485 · 2023-07-13
Inventors
- MATHEW KELLEY (COLUMBIA, SC, US)
- ANDREW B. GREYTAK (COLUMBIA, SC, US)
- MVS CHANDRASHEKHAR (LEXINGTON, SC, US)
- JOSHUA LETTON (COLUMBIA, SC, US)
Cpc classification
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02E10/544
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01L31/022408
ELECTRICITY
H01L31/07
ELECTRICITY
H01L31/0324
ELECTRICITY
H01L31/0336
ELECTRICITY
H10K30/00
ELECTRICITY
Y02E10/542
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01L31/0312
ELECTRICITY
International classification
H01L31/0352
ELECTRICITY
H01L31/0304
ELECTRICITY
H01L31/0312
ELECTRICITY
H01L31/032
ELECTRICITY
H01L31/0336
ELECTRICITY
H01L31/07
ELECTRICITY
Abstract
The present disclosure is directed to methods for producing a photovoltaic junction that can include coating a bare junction with a composition. In one embodiment, the composition includes a plurality of quantum dots to create a film; exposing the film to a ligand to create a first layer; coating the first layer with the composition to form a film on the first layer; and exposing the film on the first layer to the ligand to create a second layer.
Claims
1. A method for producing a photovoltaic junction, the method comprising: coating a bare junction with a composition including a plurality of quantum dots to create a film; exposing the film to a ligand to create a first layer; coating the first layer with the composition including the plurality of quantum dots to form the film on the first layer; and exposing the film on the first layer to the ligand to create a second layer.
2. The method of claim 1, wherein coating the bare junction comprises spin coating.
3. The method of claim 1, wherein coating the bare junction comprises painting.
4. The method of claim 1, wherein the bare junction comprises a semiconductor.
5. The method of claim 4, wherein the semiconductor comprises a nitride or a carbide.
6. The method of claim 4, wherein the semiconductor has a bandgap greater than a bandgap of the first layer.
7. The method of claim 1, wherein the ligand comprises 1,2-ethan dithiol.
8. The method of claim 1, wherein the plurality of quantum dots comprises a plurality of lead sulfide quantum dots.
9. The method of claim 1, wherein the film includes a thickness from about 8 nm to about 400 nm.
10. The method of claim 1, wherein first layer has a thickness of from about 10 nm to about 300 nm.
11. The method of claim 1, wherein the second layer has a thickness that is greater than the thickness of the first layer.
12. The method of claim 1, wherein the second layer has a thickness that is from about 5 micrometers to about 200 micrometers.
13. The method of claim 1, a first surface area of the second layer forms a first physical junction with a first surface area of the first layer, the first physical junction forms a first diode that exhibits Shockley-Read Hall trap-assisted recombination.
14. The method of claim 1, wherein the bare junction comprises graphene.
15. The method of claim 1, further comprising: coating the previous layer with the composition including the plurality of quantum dots to form the film; and exposing the film to the ligand to create a new layer, wherein the method is repeated to create 1-98 new layers.
Description
BRIEF DESCRIPTION OF THE FIGURES
[0010] A full and enabling disclosure of the present invention, including the best mode thereof to one skilled in the art, is set forth more particularly in the remainder of the specification, which includes reference to the accompanying Figures.
[0011]
[0012]
[0013]
[0014]
[0015]
[0016]
[0017] Repeat use of reference characters in the present specification and figures is intended to represent the same or analogous features or elements of the present invention.
DETAILED DESCRIPTION
[0018] Reference now will be made to the embodiments of the invention, one or more examples of which are set forth below. Each example is provided by way of an explanation of the invention, not as a limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as one embodiment can be used on another embodiment to yield still a further embodiment. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the appended claims and their equivalents. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied exemplary constructions.
[0019] Generally speaking, the present invention is directed to photovoltaic junctions, devices incorporating photovoltaic junctions, and methods for forming the photovoltaic junctions. For instance, a photovoltaic junction as disclosed herein can include a light-absorbing material, an electron acceptor for shuttling electrons, and a metallic contact. In certain implementations, the photovoltaic junction may provide broad-spectrum absorption across a range of wavelengths, from about 200 nm to about 800 nm. As an example, a broad-spectrum photovoltaic junction may include a light-absorbing material that includes one or more quantum dots that are dispersed as a film or coating on the electron acceptor material. The electron acceptor can be manufactured from one or a combination of materials, but in general, the electron acceptor should have a slightly larger bandgap (e.g., greater than 1 eV) with respect to the light-absorber. The electron acceptor and/or the light-absorber can be in contact with a metallic contact for conducting electricity generated by the photovoltaic junction.
[0020] For embodiments of the disclosure, the light-absorbing material can include one or more quantum dots. The quantum dots may include only a single element (e.g., Si, Ge, Te) or multiple elements (e.g., PbS), and the size of the quantum dot may range from about 0.5 nm to about 20 nm. In an example implementation, the light-absorbing material can include a plurality of lead sulfide (PbS) quantum dots distributed as a layer on the photovoltaic junction. In general, the quantum dots can be deposited onto a substrate to create one or more layers that, in combination, comprise the light-absorbing material.
[0021] In some embodiments, the light-absorbing material may include a surface ligand attached to the quantum dots. The surface ligands can include organic molecules that can bind either covalently or non-covalently to the surface of the quantum dots. As an example, the surface ligand can include singly functionalized molecules (e.g., oleic acid) that include a functional group such as a carboxylate (—COO), an amine (—NH.sub.2), or a thiol (—SH) group. In some implementations, the surface ligand can include multi-functional molecules (e.g., 1,2-ethane dithiol) that contain two or more functional groups. By adjusting the functional group and/or an aspect of the organic molecule (e.g., alkyl chain length), properties of the light-absorbing material, including physical properties such as thickness, may be adjusted. For example, longer alkyl chains, such as are present in oleic acid, may decrease efficiency in electron transport. Additionally, the use of multifunctional molecules can produce crosslinking between quantum dots that may improve the mechanical stability of the light-absorbing material. For embodiments disclosed herein, different ligands can be used either alone or in combination to produce photovoltaic junctions, in accordance with the disclosure.
[0022] For embodiments of the disclosure, the light-absorbing material can be described by a film thickness which characterizes the thickness of the light-absorbing material in contact with the electron acceptor. In certain embodiments, the film thickness can be between about 50 nm to about 500 nm, such as about 100 nm to about 400 nm, or about 150 nm to about 300 nm.
[0023] In embodiments of the disclosure, the electron acceptor can include a semiconductor. Generally, the semiconductor may be characterized as having a bandgap greater than the bandgap of the light-absorbing material. According to the disclosure, example electron acceptor materials can include nitrides (e.g., InGaN), carbides (e.g., SiC), or other semiconductor materials.
[0024] In embodiments of the disclosure, the metallic contact can include an electron-conducting material having a resistance (e.g., a sheet resistance) of less than about 1000 ohms (Ω), such as about 5 to about 950, about 10 to about 900, or about 50 to about 800 Ω. Example electron-conducting materials can include, but are not limited to, oxides (e.g., TiO.sub.2), metals (e.g., Cu), and/or 2-dimensional conductors (e.g., graphene).
[0025] One aspect of the photovoltaic junctions produced, according to the disclosure, can include a junction arrangement, which describes the physical contact between the light-absorbing material; the electron acceptor; and/or the metallic contact. In certain embodiments, the light-absorbing material can be in contact with only the electron acceptor or only the metallic contact. Alternatively, for some embodiments, the light-absorbing material can be in contact with both the electron acceptor and the metallic contact. In certain embodiments, the electron acceptor can be in contact with only the metallic contact. Further, in certain embodiments, the electron acceptor can be in contact with the light-absorbing material and the metallic contact; and the light-absorbing material can be in contact with the metallic contact. As an example orientation, a photovoltaic junction, produced according to the disclosure, may be formed in layers, such as a junction having a first layer including the electron acceptor, a second layer including the metallic contact in physical contact with the first layer, and a third layer including the light-absorbing material in physical contact with both the first and the second layer.
[0026] Another example junction arrangement, in accordance with the disclosure, can include a substantially homogeneous composition formed from a mixture containing the light-absorbing material, the electron acceptor, and the metallic contact. The mixture can be in the form of a powder or solution that, upon applying heat or other energy source, produces a substantially homogenous composition where the electron acceptor, the metallic contact, and the light-absorbing material are all in physical contact. Several possible advantages may be derived from this arrangement, such as improving the ease and/or cost of manufacture.
[0027] One aspect of photovoltaic junctions according to the present disclosure can include a physical junction between the light-absorbing material and the metallic contact. This physical junction may be electrically transparent (e.g., an ohmic contact) such that the junction does not necessarily need to act as a photovoltaic junction at all times.
[0028] Another aspect of photovoltaic junctions disclosed herein can include a physical junction between the metallic contact and the electron acceptor. In general, this physical junction may exhibit negligible conductivity during normal modes of use so that the presence of such physical junction does not significantly impact use and/or efficiency of the device.
[0029] Another example embodiment of the disclosure includes a method for producing a photovoltaic junction. Generally, methods for producing a photovoltaic junction can include coating a bare junction with a composition - the composition including a plurality of quantum dots - to create a film and exposing the film to a ligand to create a first layer; coating the first layer with the composition to form a film on the first layer; and exposing the film on the first layer to the ligand to create a second layer.
[0030] Aspects of the bare junction can include materials made from an electron acceptor and a metallic contact, as defined herein. The electron acceptor can be in the form of a single crystal material that may be obtained through a growth-nucleation process or may be purchased commercially. Additionally, the metallic contact may be present on the electron acceptor, may be grown on the electron acceptor as a thin film, or may be combined with the electron acceptor as a mixture (e.g., a powder) that may undergo additional processing to form the bare junction or to directly form the photovoltaic junction.
[0031] Techniques for forming a coating on the bare junction can include spin-coating, painting, or other suitable methods for producing a film of material on a surface.
[0032] In certain implementations, the bare junction may include one or more semiconductors such as the electron acceptor materials disclosed herein. It should be understood that semiconductors can include a wide range of materials, and that embodiments of the disclosure are not solely limited to the semiconductors disclosed herein.
[0033] For some implementations, the method for producing a photovoltaic junction may further include depositing one or more additional (i.e., new) layers. For example, in certain implementations, the method can also include coating the previous layer (e.g., the first layer, second layer, etc.) with a composition, including the quantum dots, to form a film and exposing the film to ligand to produce a new layer (the new layer in contact with the previous layer). In certain embodiments, this can be repeated 1-98 times to produce 1-98 new layers.
[0034] An example advantage of methods and devices disclosed herein includes improved manufacturability due, at least in part, to the different arrangements that can be used with photovoltaic devices of the disclosure. For instance, another example method for producing a photovoltaic junction can include obtaining a mixture of a light-absorbing material, an electron acceptor, and a metallic contact. Example mixtures can include powdered forms of the light-absorbing material, the electron acceptor, and the metallic contact. The mixture can then be activated by applying an energy source to heat the electron acceptor and/or the metallic contact above the metaling temperature of the material. In this manner, methods for forming the bare junction or photovoltaic junctions, as disclosed herein, may be combined with manufacturing technology, such as 3D printers, to design thin-film photovoltaic junctions or photovoltaic junctions having a complex structure for use in applications such as light emitting diodes or solar panels.
[0035] Alternatively, certain embodiments can be manufactured as separate layers having one or more contact regions between different components of the photovoltaic junction. For instance,
[0036] Additionally, in contact with both the electron acceptor and the metallic contacts is a light-absorbing material (e.g., a quantum dot film). The quantum dot film can substantially cover the entirety of the electron conductor surface, such that any incident light must pass through the light-absorbing material before reaching the electron acceptor. Further, the photovoltaic junction may be manufactured as a sheet, having one or more dimensions that are substantially greater than a third dimension. For instance, the thickness of the light-absorbing material can be at least an order of magnitude (about ten-fold) smaller than the length and/or the width of the layer, creating a rectangular prism. This structure can provide a larger surface area for light capture, while limiting loss due to scattering or other inefficiencies as electromagnetic radiation contacts the photovoltaic junction. For instance, while exemplified in
[0037] Another aspect of example photovoltaic junction can include a thickness of the electron acceptor. As illustrated, the electron acceptor thickness is generally greater than the thickness of the light-absorbing materials. For instance, while exemplified in
EXAMPLES
Methods
Diode Formation
[0038] The epitaxial graphene (EG) and silicon carbide (SiC) Schottky diodes were created by first growing a homoepitaxial layer of n-type 4H-SiC, unintentionally doped N.sub.d=1.6×10.sup.14 cm-.sup.3 on a -n.sup.+-SiC substrate by chemical vapor deposition (CVD) in a hot wall reactor using SiF.sub.4 and propane precursors in a hydrogen ambient, as described elsewhere. The doping of the active layer was determined from a mercury probe capacitance-voltage measurement and the thickness of the 26 nm n-type active SiC layer was determined from Fourier transform infrared reflectance (FTIR). The EG Schottky contacts were then grown natively on this previous homoepitaxial layer, also using SiF.sub.4 in an Ar ambient, preventing the etching of carbon that would occur in a hydrogen ambient. All growths were carried out at 1600° C. EG showed the key Raman peaks: the intrinsic G-peak at ~1580 cm.sup.-1, the disorder induced D-peak at ~1350 cm.sup.-1, and the second order 2D peak at ~2650 cm.sup.-1. The D/G ratio was ~0.1, indicating good quality. The thickness was determined from X-ray photoelectron spectroscopy to be ~15 ML. Individual device mesas were fabricated using standard photolithography with O.sub.2-plasma reactive ion etching to pattern the EG.
Quantum Dot Formation
[0039] PbS QDs were synthesized following the method outlined by Zhang et al. (“Synthetic conditions for high-accuracy size control of PbS quantum dots” J. Phys. Chem. Lett. 6 (2015) pp. 1830-1833). The QDs were found to have a diameter of 4.5 nm based on the lowest energy exciton peak position found to be at 1280 nm from UV-vis absorption spectroscopy. Following synthesis, the QDs were initially protected by alkyl carboxylate surface coating (ligand) and were then purified by gel permeation chromatography. A thin film was formed on the bare Schottky device by spin-coating followed by in situ ligand-exchange with ethanedithiol. The resulting film had a thickness of about 34 nm, based on the absorbance of a comparable film. The QD film could be removed using hydrofluoric acid and restoring the EG/SiC Schottky diode to its original state. Notably, it was found that re-spinning a new QD film produced the same results. The cleaning and re-spinning process was tested four times with reproducible results.
Current-Voltage Measurement Quantum Dot Formation
[0040] Current-voltage (I-V) measurements were conducted with the device configured as shown in
Scanning Photocurrent Microscopy
[0041] Current scanning photocurrent microscopy (SPCM) was used to spatially map the photocurrent and charge collection in the device. This was done with a 444 nm laser chopped at 113 Hz to illuminate the sample. The resultant photocurrent was recorded with a lock-in amplifier referenced to the chopper and mapped across the device surface with an estimated spot size and spatial resolution ~2 .Math.m. Further details on the SPCM setup can be found in previous work.
Results
[0042] Results provided in the figures and described herein are meant to be exemplary and are not intended to limit the methods and compositions to modifications or alternatives, as would be understood by a person of ordinary skill in the field of endeavor.
[0043] The bare EG/SiC Schottky diodes were rectifying (
giving a Schottky barrier height ϕ.sub.b ~0.9 eV and an ideality n~1.1.
[0044] Upon addition of the QD-film, the QD/EG/SiC diodes demonstrated significantly higher reverse leakage ~10.sup.2 more than without QDs, suggesting the presence of trap states increasing leakage. Such traps are responsible for “soft-breakdown” in diodes, where the increasing leakage with voltage indicates a field-activated transport mechanism, indicating the presence of a second parallel barrier interface through which <0.2 V current is flowing. This observation was associated with the QD-film interface at the diode periphery (
[0045] To obtain the effective I-V of the parallel current, the bare EG/SiC current was subtracted from the QD/EG/SiC current (
[0046] Upon illumination of the bare EG/SiC diodes with monochromatic light, above 4H-SiC bandgap (3.2 eV, λ <380 nm) photocurrent is seen (
at these low short circuit currents Isc~1-2 nA depending on wavelength. With the addition of the QD-film, Voc and Isc both decrease, indicating the reduction of above bandgap light intensity by the QD-film, preventing the same of intensity light from creating electron-hole pairs in the SiC. While Isc is similar, Voc is reduced significantly to <0.1 V. The emergence of R.sub.sh,.sub.QD/SiC at the device edge (
[0047] Eq. (3) produces a value in reasonable agreement with the measured Voc ~0.1 V, at Isc =1 nA. Upon reverse-biasing, the QD/EG/SiC dark current, I.sub.dark, as well as photocurrent (I.sub.ph = I(λ) - I.sub.dark), increase monotonically with voltage. The increasing I.sub.ph with voltage in QD/EG/SiC indicates the presence of carrier traps, leading to photoconductive gain, increasing photocurrent. This effect is physically accounted for in
[0048] Illumination with sub-bandgap light from a monochromator 380 nm < λ < 700 nm showed similar I-V behavior compared to above-bandgap light but with a much smaller I.sub.ph due to the weak absorption in the thin QD-film compared to what is essentially complete absorption in the thick SiC epitaxial layer for above-bandgap light. R.sub.sh,.sub.QD/SiC decreased under illumination at all wavelengths, indicating that photo absorption is occurring in the QD-film.
[0049] To test the applicability of this model beyond the visible, 700 nm < λ < 1280 nm (absorption edge of PbS QDs) 3 LEDs were used with λ = 655 nm, 843 nm, and 1550 nm adjusted so ~180 nW of incident power falls within the EG mesa.
[0050] Removal of the QD-film with HF eliminates the sub-bandgap photovoltaic effect. The possibility of a second-order artifact from the UV tail in the monochromated light source was precluded by performing measurements with a 550 nm long-pass filter. Dividing I.sub.ph (V.sub.a = -1 V) by the measured power incident on the device, the responsivity, R(λ), was extracted as a function of wavelength (
[0051] The assertion that photoconductive gain occurs at the QD/SiC diode around the EG mesa periphery is clearly seen in the SPCM maps of
where t.sub.QD is the thickness of the QD film, P.sub.s,QD is the (3D) resistivity of the QD film, and P.sub.sh,.sub.QD/SiC is a specific interface resistance at the QD/SiC interface, defined such that R.sub.sh,.sub.QD/SiC = R.sub.sh,.sub.QD/SiC / A.sub.sh,.sub.QD/SiC, with A.sub.QD/SiC the effective interface area. The SPCM maps give L.sub.T ~115 .Math.m near Vα = 0 V. To approximate the effective interface area, we consider a ring of width L.sub.T surrounding the mesa of radius r so that A.sub.QD/SiC = 2πr L.sub.T + π L.sub.T2. Using R.sub.sh,.sub.QD/SiC = 200 MΩ as seen in
[0052] The increase in I.sub.ph with larger reverse voltage shown in
[0053] Referring now to
[0054] Referring now to
[0055] Referring now to
[0056] Referring now to
[0057] The addition of multiple layers of quantum dots can be used to adjust certain properties of the photovoltaic junctions. For example, referring now to
TABLE-US-00001 Carrier lifetime Device Data Layers of PBS Quantum Dots Bare 1 Layer 2 Layer 3 Layer Carrier Lifetime of Base SiC Chip 6.5 ms 9 ms 16 ms 82 ms