WO2013142585A1 - Procédé de formation d'un module de cellule photovoltaïque - Google Patents

Procédé de formation d'un module de cellule photovoltaïque Download PDF

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Publication number
WO2013142585A1
WO2013142585A1 PCT/US2013/033122 US2013033122W WO2013142585A1 WO 2013142585 A1 WO2013142585 A1 WO 2013142585A1 US 2013033122 W US2013033122 W US 2013033122W WO 2013142585 A1 WO2013142585 A1 WO 2013142585A1
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Prior art keywords
refractive index
photovoltaic cell
polymer layer
graded coating
thickness
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PCT/US2013/033122
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English (en)
Inventor
Pierre Descamps
Christopher Mcmillan
Paul Schalk
Donald Adriaan WOOD
Ludmil Zambov
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Dow Corning Corporation
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Publication of WO2013142585A1 publication Critical patent/WO2013142585A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • Y—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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the disclosure relates to a method of forming a photovoltaic cell module including a compositional graded coating including a gradient of SiC:H and SiOCN:H.
  • Photovoltaic cells and modules are well known in the art. Common photovoltaic cells include photovoltaic (solar) cells and diodes. Photovoltaic cells convert light of many different wavelengths into electricity.
  • This disclosure provides a method of forming a photovoltaic cell module that includes a photovoltaic cell having a refractive index of 3.7 + 2 and polymer layer that is disposed on the photovoltaic cell and that has a refractive index of 1.5 ⁇ 0.1.
  • the photovoltaic cell module also includes a compositional graded coating that is disposed on the photovoltaic cell and sandwiched between the photovoltaic cell and the polymer layer.
  • the compositional graded coating has a thickness and a refractive index varying along the thickness from a first refractive index from (2.2 + 0.4 to 3.2 + 0.4) at a first end to a second refractive index of 1.45 + 0.05 at a second end adjacent to the polymer layer.
  • the compositional graded coating also includes a gradient including SiC:H and SiOCN:H along the thickness.
  • the photovoltaic cell module further includes Si:H disposed between the polymer layer and the photovoltaic cell.
  • the method of forming the photovoltaic cell module includes continuously depositing the compositional graded coating on the photovoltaic cell using chemical vapor deposition and subsequently disposing the polymer layer on the compositional graded coating to form the module.
  • Figure 1 is a side view of one embodiment of the module of this disclosure including a polymer layer disposed on, and spaced apart from, a photovoltaic cell, and a compositional coating disposed on, and in direct contact with, the photovoltaic cell, and sandwiched between the photovoltaic cell and the polymer layer.
  • Figure 2 is a side view of another embodiment of the module including a polymer layer disposed on, and spaced apart from, a photovoltaic cell, a compositional coating disposed on, and also spaced apart from, the photovoltaic cell, an intermediate layer disposed on, and in direct contact with, the photovoltaic cell, wherein the compositional graded coating is sandwiched between the polymer layer and the intermediate layer/photovoltaic cell, and the intermediate layer is sandwiched between the polymer layer/compositional graded coating and the photovoltaic cell.
  • Figure 3 is an FT-IR spectra of an SiC:H coating and an SiOCN:H coating having varying oxygen content.
  • Figure 4 is a graph of a concentration profile of various chemical elements in a graded compositional coating as a function of thickness of the coating.
  • Figure 5 is a graph of refractive index, deposition rate, and absorption coefficient of various coatings as a function of ethylene gas flow rate during PECVD.
  • Figure 6 is a graph of refractive index, deposition rate, and absorption coefficient of various compositional graded coatings as a function of nitrous oxide gas flow rate during PECVD.
  • Figure 7 is a reflectance spectra of an uncoated silicon substrate (RefBareSi), a silicon substrate encapsulated with one embodiment of the polymer layer of this disclosure (RefEncSi), a silicon substrate including a compositional graded coating of this disclosure disposed thereon (CGC1), a silicon substrate including a compositional graded coating of this disclosure and a polymer layer of this disclosure disposed thereon (CGC1ENC), a silicon substrate including a second compositional graded coating of this disclosure disposed thereon (CGC2), a silicon substrate including the second compositional graded coating of this disclosure and a polymer layer of this disclosure disposed thereon (CGC2ENC), and a silicon substrate including a non- gradient antireflective coating of the art disposed thereon.
  • CGC1ENC silicon substrate including a compositional graded coating of this disclosure disposed thereon
  • CGC2ENC silicon substrate including a second compositional graded coating of this disclosure disposed thereon
  • CGC2ENC silicon substrate including
  • Figure 8 is a light transmission spectra of a glass reference (GlassRef), of the CGC1 compositional graded coating disposed on the glass reference (CGC1T), of the CGC2 compositional graded coating disposed on the glass reference (CGC2T), and of a third compositional graded coating disposed on the glass reference (CGC3T).
  • GlassRef GlassRef
  • Figure 9 is a graph of photoluminescence intensity of a compositional graded coating as a function of wavelength and includes a three-component Gaussian model fit.
  • Figure 10 is a graph of refractive index of a compositional graded coating (labeled in this Figures as GRIN) disposed on a silicon substrate as a function of thickness including a second order exponential model fit.
  • GRIN compositional graded coating
  • Figure 11 is an example of a 2-dimensional gradient. DETAILED DESCRIPTION OF THE DISCLOSURE
  • This disclosure provides a photovoltaic cell module (module) and a method of forming the module.
  • the module typically has a light reflection of less than 10, 7, 5, 4, 3, 2, or 1% over a range of wavelengths from about 300 to about 1700 nanometers, see, e.g. Figure 7.
  • the light reflection is typically measured using a spectrophotometer and/or an ellipsometer such as a Cary 5000 UV-Vis-NIR spectrophotometer commercially available from Agilent Technologies, Inc. (Santa Clara, California).
  • the module includes a photovoltaic cell having a refractive index of (about) 1.7 to 5.7, i.e., 3.7 + 2, 1.5, 1, 0.75, 0.5, 0.25, or 0.1.
  • the photovoltaic cell may include large-area, single-crystal, single layer p-n junction diodes. These photovoltaic cells are typically made using a diffusion process with silicon wafers. Alternatively, the photovoltaic cell may include thin epitaxial deposits of silicon on lattice-matched wafers. Further, the photovoltaic cell may include quantum well devices such as quantum dots, quantum wires, quantum wells, and carbon nanotubes.
  • the photovoltaic cell may include amorphous silicon, monocrystalline silicon, polycrystalline silicon, microcrystalline silicon, nanocrystalline silica, cadmium telluride, copper indium/gallium selenide/sulfide, gallium arsenide, polyphenylene vinylene, copper phthalocyanine, carbon fullerenes, and combinations thereof in ingots, ribbons, thin films, and/or wafers.
  • the photovoltaic cell may also include light absorbing dyes such as ruthenium organometallic dyes. Most typically, the photovoltaic cell includes monocrystalline and polycrystalline silicon.
  • the photovoltaic cell typically has a thickness from 1 to 500, from 1 to 5, from 1 to 20, from 300 to 500, from 50 to 250, from 100 to 225, or from 175 to 225, micrometers.
  • the photovoltaic cell is typically disposed on a substrate via chemical vapor deposition or sputtering. No tie layer may be required between the photovoltaic cell and the substrate in a "thin-film" application.
  • one or more electrical leads may be attached to the photovoltaic cell.
  • the polymer layer described in greater detail below, may then be applied over the electrical leads.
  • the module also includes a polymer layer that is disposed on the photovoltaic cell and that has a refractive index of (about) 1.4 to 1.9, i.e., 1.5 + 0.05, 0.1, or + 0.2, 0.3, or 0.4, as determined using a spectroscopic ellipsometer refractometer.
  • the refractive index of the polymer layer is approximately matched to the refractive index of the compositional graded coating, e.g. +0.1, described in greater detail below.
  • the polymer layer also typically has a light transparency of at least 85, 90, 95, 96, 97, 98, 99, or 99.5, percent, as determined using a spectrophotometer and weighted to the solar spectrum.
  • the polymer layer has a light transparency of about 100 percent (- 10, 5, 2, 1, 0.75, 0.5, 0.25).
  • the terminology "disposed on” includes the polymer layer disposed on and in direct contact with the photovoltaic cell or on and spaced apart from the photovoltaic cell yet still disposed thereon, as set forth in Figures 1 and 2. Typically, the polymer layer is disposed on and spaced apart from the photovoltaic cell.
  • the polymer layer may have a thickness of at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, or 125, ⁇ .
  • the polymer layer may have a thickness from 50 to 150, from 60 to 140, from 70 to 130, from 80 to 120, from 90 to 110, from 50 to 250, from 60 to 350, from 70 to 450, from 80 to 550, or from 100 to 1000, ⁇ .
  • the polymer layer has a thickness of about 100 ⁇ .
  • the polymer layer has a thickness that is about the same or longer than the coherence length of the solar spectrum, whether visible light, UV light, and IR light. This thickness minimizes interference effects due to an optical path length greater than the coherence length of natural light, e.g. sunlight. If the polymer layer is overly thinned, increased interference may occur which may cause coloring and/or spectral effects.
  • the polymer layer may be formed from and/or include an inorganic compound, and organic compound, or a mixture of organic and inorganic compounds. These compounds may or may not require curing.
  • the polymer layer may be formed from and/or include metals, polymers, plastics, silicones, glass, sapphire, and the like so long as the refractive index is as described above.
  • the polymer layer is ethylene vinyl acetate (EVA), glass, a silicone, and/or an acrylate.
  • EVA ethylene vinyl acetate
  • the polymer layer is transparent to light as determined using a spectrophotometer.
  • the polymer layer may be formed from a curable composition including silicon atoms.
  • the curable composition includes a hydro silylation curable PDMS.
  • the polymer layer may be as described in one or more of PCT/US09/01623, PCT/US09/01621, and/or PCT/US09/62513, each of which is expressly incorporated herein by reference.
  • the polymer layer may be an inner layer or an outermost layer of the module.
  • the module may include two, three, or multiple (layers of) transparent semiconductors, each of which may independently be the same or different from those described above.
  • the module includes the polymer layer described above and a second polymer layer. Further, the polymer layer may be transparent to UV and/or visible light and the second (or additional) polymer layers may be transparent to UV and/or visible light.
  • the module also includes a compositional graded coating (CGC) that is disposed on the photovoltaic cell and sandwiched between the photovoltaic cell and the polymer layer, as set forth in Figures 1 and 2.
  • CGC compositional graded coating
  • disposed on describes the CGC disposed on and in direct contact with the photovoltaic cell.
  • This terminology also describes the CGC spaced apart from the photovoltaic cell, yet still disposed thereon.
  • the module may include two or more CGCs that may be the same or different from one another and each of which may be disposed in any location in the module.
  • the CGC has a thickness which is typically from 50 to 1000, from 50 to 950, from 100 to 900, from 150 to 850, from 200 to 800, from 250 to 750, from 300 to 700, from 350 to 650, from 400 to 600, from 450 to 550, from 50 to 750, from 100 to 500, from 150 to 450, from 200 to 300, from 250 to 450, from 350 to 450, about 400, about 450, or about 500, nm.
  • the CGC also has a refractive index varying along the thickness.
  • the refractive index varies from a first refractive index from (1.8 to 3.6, i.e., 2.2 + 0.4 to 3.2 + 0.4) at a first end to a second refractive index of 1.4 to 1.5, i.e., 1.45 + 0.05 at a second end that is adjacent to the polymer layer.
  • the first refractive index may be alternatively described as from 2.25 to 3.15, from 2.3 to 3.1, from 2.35 to 3.15, from 2.4 to 3.1, from 2.45 to 3.05, from 2.5 to 3, from 2.55 to 2.95, from 2.6 to 2.9, from 2.65 to 2.85, from 2.7 to 2.8, or from 2.75 to 2.8, each + 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, or 0.05.
  • the second refractive index may be alternatively described as 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1.
  • the first end may be further defined as an interface between the CGC and the photovoltaic cell.
  • the first end may be further defined as an interface between the CGC and an intermediate layer, which is described in greater detail below.
  • the second end may be further defined as an interface between the CGC and the polymer layer.
  • the CGC includes a gradient of the refractive indices described above.
  • the CGC includes a gradient of SiC:H and SiOCN:H (and optionally Si:H) along the thickness, for example with varying hydrogen content and/or Si to C and/or O to Si compositional ratios.
  • the CGC includes both a gradient of the refractive indices and of the amounts of SiC:H and SiOCN:H (and optionally the Si:H).
  • the gradients of the refractive indices and of the amounts of SiC:H and SiOCN:H (and optionally the Si:H) may independently be continuous (e.g. uninterrupted and/or consistently changing) or stepped, e.g.
  • the terminology "gradient” typically describes a graded change in the magnitude of the refractive indices and/or the composition expressed by the amounts of SiC:H and SiOCN:H (and optionally the Si:H), e.g. from lower to higher values or vice versa.
  • the gradient may be further defined as a vector field which points in the direction of the greatest rate of increase and whose magnitude is the greatest rate of change.
  • the gradient may be further defined as a series of 2 dimensional vectors at points on the CGC with components given by the derivatives in horizontal and vertical directions. At each point on the CGC, the vector points in the direction of largest possible intensity increase, and the length of the vector corresponds to the rate of change in that direction.
  • An example of a 2-dimensional gradient is set forth in Figure 11.
  • the CGC has a continuous gradient with one extreme of the gradient selected to approximately match the refractive index of the photovoltaic cell or the intermediate layer, described in greater detail below.
  • the index of refraction of the CGC smoothly shifts from approximately matching (e.g. +0.2) the refractive index of the intermediate layer to a refractive index that approximately matches (e.g. +0.2) that of the polymer layer to avoid or minimize significant discontinuity in optical characteristics at interfaces therebetween.
  • the CGC includes hydrogenated silicon (Si:H) at the interface with the photovoltaic cell and then the continuous gradient gradually changes to hydrogenated silicon carbide (SiC:H) and then to hydrogenated silicon oxycarbonitride (SiOCN:H) near the interface with the polymer layer, e.g. in Figure 1.
  • the CGC may include hydrogenated silicon carbide (SiC:H) and then gradually change to hydrogenated silicon oxycarbonitride (SiOCN:H) near the interface with the polymer layer.
  • the module includes the intermediate layer including the Si:H, as described in greater detail below and set forth in Figure 2.
  • the hydrogenated silicon carbide (SiC:H) is typically present near the interface with the intermediate layer (i.e., the Si:H).
  • the composition and/or density of the CGC along with grading the optical impedance of the CGC provides a smooth transition between the photovoltaic cell and the polymer layer approximately matching the optical parameters (e.g. +0.2) of each at the relevant interfaces.
  • the CGC may have a variety of physical properties that benefit performance of the module.
  • the CGC emits light having a wavelength from 375 to 675, from 400 to 650, from 425 to 625, from 450 to 600, from 475 to 575, from 500 to 550, from 525 to 550, from 450 to 700, or from 500 to 600, nm, when excited with light having a wavelength from 300 to 450, from 300 to 400, from 310 to 390, from 320 to 380, from 330 to 370, from 340 to 360, or from 340 to 350, nm.
  • the CGC has a water vapor transmission rate from lE ' lg/m ⁇ /day to lE " 2g/m2/day.
  • the CGC provides good surface passivation when deposited on a silicon surface with minority carrier lifetime values above 300 microseconds at a minimum excitation level of carrier density of 1E15 cm " , corresponding to a surface recombination velocity (SRV) of 30 cm/s and below.
  • SSV surface recombination velocity
  • the module also includes Si:H disposed between the polymer layer and the photovoltaic cell.
  • the Si:H may be included in the intermediate layer disposed between the CGC and the photovoltaic cell, e.g. in Figure 2.
  • the intermediate layer may have a refractive index from 2.8 to 3.5, i.e., 3 to 3.3 + 0.2 or from 2.8 to 3.7, i.e., 3 to 3.5 + 0.2.
  • the CGC has a refractive index varying along the thickness from the first refractive index of 2.2 + 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, or 0.05 at the first end to the second refractive index of 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1 at the second end adjacent to the polymer layer.
  • the Si:H may be present in the compositional graded coating such that the gradient includes Si:H, SiC:H and SiOCN:H.
  • the CGC has a refractive index varying along the thickness from the first refractive index of 3.2 + 0.5, 0.4, 0.3, 0.2, or 0.1 at the first end to the second refractive index of 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1 at the second end adjacent to the polymer layer.
  • the Si:H may also be present both in the gradient and in the intermediate layer.
  • the module may also include a superstrate and/or substrate which may independently include any material known in the art.
  • the superstrate may be utilized with the polymer layer.
  • the substrate provides protection to a rear surface of the module and the superstrate provides protection to a front surface of the module.
  • the substrate and/or superstrate may each be soft and flexible or rigid and stiff.
  • the substrate and/or superstrate may include rigid and stiff segments while simultaneously including soft and flexible segments.
  • the substrate may be transparent to light, may be opaque, or may not transmit light. Most typically, the superstrate allows at least some light to penetrate the module.
  • the substrate and/or superstrate may include glass, stainless steel, metal foils, polyimides, ethylene-vinyl acetate copolymers, and/or organic fluoropolymers such as ethylene tetrafluoroethylene (ETFE), Tedlar ® (polyvinylfluoride, available from DuPont), polyester/Tedlar ® , Tedlar ® /polyester/Tedlar ® , polyethylene terephthalate (PET) alone or coated with silicon and oxygen based materials (SiO x ), and combinations thereof.
  • the substrate is selected from the group of polyvinylfluoride and polyethylene.
  • the substrate may alternatively be a PET/SiO x -PET/Al substrate, wherein x is a number having a value from 1 to 4.
  • the substrate and/or superstrate may include silicone, may consist essentially of silicone and not include, or include less than 1 wt , organic monomers or organic polymers, or may consist of silicone.
  • the optional silicone chemistry of the substrate and/or superstrate may include any type known in the art.
  • the substrate and/or superstrate may be load bearing or non-load bearing. Typically, the substrate is load bearing and the superstrate is not load bearing.
  • the substrate When module is oriented towards a light source (e.g. the sun) for a photovoltaic operation, the substrate is typically a bottom and outermost layer of the module. Bottom layers are typically positioned behind the photovoltaic cell and serve as mechanical support.
  • the superstrate is typically a top and outermost layer of the module and may be oriented towards the light source. If both a substrate and superstrate are utilized, the substrate and superstate each typically act as outermost layers and sandwich all other components of the module therebetween.
  • the module may be free of a “backsheet” and/or "front glass.”
  • backsheet typically describes a substrate, as described above.
  • the backsheet includes metal foils, polyimides, ethylene-vinyl acetate copolymers, and/or organic fluoropolymers such as ethylene tetrafluoroethylene (ETFE), Tedlar ® (polyvinylfluoride), polyester/Tedlar ® , Tedlar ® /polyester/Tedlar ® , polyethylene terephthalate (PET) alone or coated with silicon and oxygen based materials (SiOx), and combinations thereof.
  • ETFE ethylene tetrafluoroethylene
  • Tedlar ® polyvinylfluoride
  • polyester/Tedlar ® polyester/Tedlar ®
  • Tedlar ® /polyester/Tedlar ® polyethylene terephthalate
  • SiOx silicon and oxygen based materials
  • the “backsheet” may alternatively be the PET/SiO x -PET/Al substrate.
  • the module may be free of the “backsheet” and still include one or more compounds or components described above as a substrate.
  • the module may still include a substrate and be free of a "backsheet.”
  • the terminology “front glass” typically describes used as a superstate that allows light to pass through.
  • the module may be free of the "front glass” and still include one or more compounds or components described above as a superstate.
  • the module may still include a superstate and be free of "front glass.”
  • the module may also include one or more tie layers which may bind one or more other layers to each other.
  • the one or more tie layers may be disposed on the substrate to bind the photovoltaic cell to the substrate and/or one or more other layers.
  • the module includes multiple tie layers, e.g. first, second, and/or a third tie layer. Any second, third, or additional tie layer may be the same or different from the (first) tie layer. Thus, any second, third or additional tie layer may be formed from the same material or from a different material than the (first) tie layer.
  • the second tie layer may be disposed on the (first) tie layer and/or may be disposed on the photovoltaic cell.
  • the one or more tie layers are each typically transparent to UV and/or visible light. However, one or more of the tie layers may be impermeable to light or opaque. In one embodiment, the tie layer has high transmission across visible wavelengths, long term stability to UV and provides long term protection to the photovoltaic cell.
  • the tie layers typically have a thickness from 1 to 50, more typically from 3 to 30, and most typically from 4 to 15, mils.
  • the tie layers have a thickness from 1 to 30, from 1 to 25, from 1 to 20, from 3 to 17, from 5 to 10, from 5 to 25, from 10 to 15, from 10 to 17, from 12 to 15, from 10 to 30, or from 5 to 20, mils.
  • the tie layer(s) may be as described in PCT/US09/01623, PCT/US09/01621, and/or PCT/US09/62513, each of which is expressly incorporated herein by reference.
  • the method of forming the module includes continuously depositing the CGC on the photovoltaic cell using chemical vapor deposition (CVD) and subsequently disposing the polymer layer on the CGC to form the module.
  • the step of continuously depositing the CGC may be accomplished using plasma-enhanced chemical vapor deposition (PECVD), e.g., in a reactive ion-etching configuration, dual frequency configuration, electron cyclotron resonance configuration or inductively-coupled plasma mode. Any type of CVD known in the art may be utilized.
  • PECVD plasma-enhanced chemical vapor deposition
  • the terminology "continuously depositing” typically describes the CVD operating without interruption or with few interruptions. Continuous processes are very different from, and approximately opposite to, batch processes. The continuous operation of the CVD minimizes or eliminates formation of additional optical interfaces in the CGC which allows a gradient to be formed with minimized reflection, absorption, and interference and also allows the module to be formed with increased durability and flexibility and optimized optical properties.
  • the step of continuously depositing may occur below room temperature (referred to herein as "RT” and is about 21 to 25°C), at RT, or above RT. In various embodiments, the temperature is about 50, 100, 200, 300, or 400, °C.
  • a CVD system such as a PECVD system that mixes precursor gasses in vacuum chambers and excites mixtures of the gases with radio frequency (RF) generators attached to electrodes to create plasmas of ionized gasses.
  • RF radio frequency
  • Vacuum pressure, electrode power, temperature, and gas flow can be customized, see, e.g. Figures 3-10.
  • the PECVD system includes a powered parallel electrode reactor with electrodes powered with two generators.
  • One generator is typically a standard RF generator (also called a high frequency power supply (e.g.
  • the PECVD system may operate in a dual frequency configuration (e.g. mode). Operation in the dual frequency configuration typically includes the operation of PECVD at a first and a second frequency simultaneously.
  • the first frequency is typically between 50 and 400 kHz and can range from 60 to 390, from 70 to 380, from 80 to 370, from 90 to 360, from 100 to 350, from 110 to 340, from 120 to 330, from 130 to 320, from 140 to 310, from 150 to 300, from 200 to 290, from 210 to 280, from 220 to 270, from 230 to 260, or from 240 to 250, KHz.
  • the first frequency ranges between 70 and 400 KHz.
  • the first frequency is about 380 KHz.
  • the second frequency is typically between 15 MHz and 1, or more than 1, GHz. In various embodiments, the second frequency ranges from 10 to 50, from 10 to 40, from 12 to 30, from 13 to 20, from 13 to 15, or from 13 to 14, MHz. In one embodiment, the second frequency is about 13.56 MHz.
  • the power of the electrodes used in the CVD system can be varied. In various embodiments, two electrodes are utilized wherein the power to each electrode may be varied independently.
  • the power to a first electrode typically ranges from 10 to 1000, from 10 to 600, from 50 to 200, from 80 to 160, from 90 to 150, from 100 to 140, from 110 to 130, or about 120, Watts.
  • the first electrode is typically associated with the first frequency described above.
  • the power to a second electrode typically ranges from 10 to 1000, from 10 to 600, from 200 to 400, from 210 to 390, from 220 to 380, from 230 to 370, from 240 to 360, from 250 to 350, from 260 to 340, from 270 to 330, from 280 to 320, from 290 to 310, or about 300, Watts.
  • the second electrode is typically associated with the second frequency described above.
  • the second (e.g. high) frequency may influence plasma density due to more efficient displacement current and sheath heating mechanisms.
  • the first (e.g. low) frequency may influence peak ion bombardment energy. Accordingly, separate adjustment and customization of ion bombardment energy and plasma density may be utilized to influence control of deposition stress and optical properties. In addition, greater control of lattice spacing of the CGC as well as stacking faults in crystal structure, control of pin holes and location of interstitial atoms, and minimization of deposition tension and stress may be customized.
  • the step of continuously depositing the CGC may include one or more sub- steps.
  • the step of continuously depositing includes introducing a source of silicon, such as monosilane (SiH 4 ), to the photovoltaic cell, introducing a hydrocarbon gas (e.g. methane, ethylene, acetylene, or any known in the art) to the photovoltaic cell, and introducing at least one of nitrous oxide, oxygen, and carbon dioxide to the photovoltaic cell.
  • a source of silicon such as monosilane (SiH 4 )
  • a hydrocarbon gas e.g. methane, ethylene, acetylene, or any known in the art
  • the step of introducing "to the photovoltaic cell” may be alternatively defined as introducing "into the plasma” or "into a CVD chamber” wherein the photovoltaic cell is exposed to the plasma and/or the source of the silicon, the hydrocarbon gas, or the other gases, in the CVD chamber.
  • the introduction of the source of silicon allows the CVD process to produce the Si:H of the module and/or gradient.
  • the introduction of the hydrocarbon gas allows the CVD process to produce the SiC:H of the gradient.
  • the introduction of at least one of the nitrous oxide, oxygen, and carbon dioxide allows the CVD process to produce the SiOCN:H of the gradient.
  • the method may alternatively include the step of introducing a source of nitrogen (e.g. nitrous oxide) and/or the step of introducing a source of oxygen (e.g. nitrous oxide and/or oxygen), to the photovoltaic cell (e.g. into the plasma).
  • the source of silicon is introduced at a high power (e.g. above 300 Watts).
  • This step typically forms a first portion of the gradient with a high refractive index (e.g. ⁇ 2.7 to 3.6).
  • the method includes the step of increasing pressure (e.g. increasing from 50 to 500 mTorr). Typically, increasing the pressure deceases the refractive index of the gradient that is being formed (e.g. from 2.4 to 1.4).
  • the method includes the step of decreasing power and increasing pressure to continue to form the CGC.
  • the total gas flow can range from 200 to 3,000, from 400 to 2,000, or from 450 to 850, standard cubic centimeters per minutes (seem).
  • the temperature can range from 20 to 400, from 30 to 250, or from 30 to 80°C.
  • the pressure can range from 20 to 2000, from 20 to 1000, from 80 to 800, from 50 to 500, or from 90 to 200, mTorr.
  • the method also includes the step of disposing the polymer layer on the CGC.
  • the step of disposing the polymer layer may be further defined as disposing a curable composition on the CGC and then either partially or completely curing the curable composition to form the polymer layer.
  • the polymer layer may be disposed on the CGC without any additional curing.
  • the polymer layer and/or curable composition may be applied using any suitable application (dispensing) method known in the art including spray coating, flow coating, curtain coating, dip coating, extrusion coating, knife coating, screen coating, laminating, melting, pouring, and combinations thereof.
  • the polymer layer is formed from a liquid and the step of disposing the polymer layer is further defined as disposing a liquid on the CGC and curing the liquid on the CGC to form the polymer layer.
  • the curable composition is supplied to a user as a multi-part system, e.g. including first and second parts. The first and second parts may be mixed immediately prior to use. Alternatively, each component and/or a mixture of components may be applied individually.
  • the polymer layer is formed from the curable composition and the method further includes the step of partially curing, e.g. "pre-curing," the curable composition to form the polymer layer.
  • the method further includes the steps of applying the curable composition to the CGC and curing the curable composition to form the polymer layer.
  • the curable composition is cured prior to the step of disposing the polymer layer on the substrate.
  • the curable composition may be cured at any temperature, e.g. from 25 to 200 °C.
  • the curable composition may also be cured for any time, e.g. from 1 to 600 seconds. Alternatively, the curable composition may be cured in a time of greater than 600 seconds, as determined by one of skill in the art.
  • curable silicone compositions include hydro silylation- curable silicone compositions, condensation-curable silicone compositions, radiation- curable silicone compositions, and peroxide-curable silicone compositions.
  • a hydrosilylation-curable silicone composition typically includes an organopolysiloxane having an average of at least two silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms per molecule; an organosilicon compound in an amount sufficient to cure the organopolysiloxane, wherein the organosilicon compound has an average of at least two silicon-bonded hydrogen atoms or silicon- bonded alkenyl groups per molecule capable of reacting with the silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the organopolysiloxane; and a catalytic amount of a hydrosilylation catalyst.
  • a condensation-curable silicone composition typically includes an organopolysiloxane having an average of at least two silicon-bonded hydrogen atoms, hydroxy groups, or hydrolysable groups per molecule and, optionally, a cross-linking agent having silicon-bonded hydrolysable groups and/or a condensation catalyst.
  • a radiation-curable silicone composition typically includes an organopolysiloxane having an average of at least two silicon-bonded radiation- sensitive groups per molecule and, optionally, a cationic or free-radical photoinitiator depending on the nature of the radiation- sensitive groups in the organopolysiloxane.
  • a peroxide-curable silicone composition typically includes an organopolysiloxane having silicon-bonded unsaturated aliphatic hydrocarbon groups and an organic peroxide.
  • the silicone composition can be cured by exposing the composition to ambient temperature, elevated temperature, moisture, or radiation, depending on the type of curable silicone composition.
  • the silicone composition can be cured by exposing the composition to a temperature from RT to 250 °C, alternatively from RT to 150 °C, alternatively from RT to 115 °C, at atmospheric pressure.
  • the silicone composition is generally heated for a length of time sufficient to cure (cross-link) the organopolysiloxane.
  • the film is typically heated at a temperature from 100 to 150 °C for a time from 0.1 to 3 h.
  • the conditions for curing the composition depend on the nature of the silicon-bonded groups in the organopolysiloxane.
  • the composition can be cured (i.e., cross-linked) by heating the composition.
  • the composition can typically be cured by heating it at a temperature from 50 to 250 °C, for a period from 1 to 50 h.
  • the condensation-curable silicone composition includes a condensation catalyst, the composition can typically be cured at a lower temperature, e.g., from RT to 150 °C.
  • the curable silicone composition is a condensation-curable silicone composition including an organopolysiloxane having silicon-bonded hydrogen atoms
  • the composition can be cured by exposing the composition to moisture or oxygen at a temperature from 100 to 450 °C for a period from 0.1 to 20 h.
  • the condensation-curable silicone composition contains a condensation catalyst
  • the composition can typically be cured at a lower temperature, e.g., from RT to 400°C.
  • the curable silicone composition is a condensation-curable silicone composition including an organopolysiloxane having silicon-bonded hydrolysable groups
  • the composition can be cured by exposing the composition to moisture at a temperature from RT to 250°C, alternatively from 100 to 200°C, for a period from 1 to 100 h.
  • the silicone composition can typically be cured by exposing it to a relative humidity of 30% at a temperature from about RT to 150 °C, for a period from 0.5 to 72 h. Cure can be accelerated by application of heat, exposure to high humidity, and/or addition of a condensation catalyst to the composition.
  • the composition can be cured by exposing the composition to an electron beam.
  • the accelerating voltage is from about 0.1 to 100 keV
  • the vacuum is from about 10 to 10 ⁇ 3 Pa
  • the electron current is from about 0.0001 to 1 ampere
  • the power varies from about 0.1 watt to 1 kilowatt.
  • the dose is typically from about 100 microcoulomb/cm ⁇ to 100 coulomb/cm ⁇ , alternatively from about 1 to 10 coulombs/cm ⁇ .
  • the time of exposure is typically from about 10 seconds to 1 hour.
  • the radiation-curable silicone composition when the radiation-curable silicone composition further includes a cationic or free radical photoinitiator, the composition can be cured by exposing it to radiation having a wavelength from 150 to 800 nm, alternatively from 200 to 400 nm, at a dosage sufficient to cure (cross-link) the organopolysiloxane.
  • the light source is typically a medium pressure mercury-arc lamp.
  • the dose of radiation is typically from
  • the silicone composition can be externally heated during or after exposure to radiation to enhance the rate and/or extent of cure.
  • the curable silicone composition is a peroxide-curable silicone composition
  • the composition can be cured by exposing it to a temperature from RT to 180 °C, for a period from 0.05 to 1 h.
  • the method may also include the step(s) of disposing the photovoltaic cell on the polymer layer, the tie layer and/or the substrate.
  • the photovoltaic cell may also include the CGC disposed thereon such that this step may be a part of, or a further definition of, the step of disposing the polymer layer on the CGC.
  • the photovoltaic cell can be disposed (e.g. applied) by any suitable mechanisms known in the art but is typically applied using an applicator in a continuous mode. Other suitable mechanisms of application include applying a force to the photovoltaic cell to more completely contact the photovoltaic cell and the polymer layer, the CGC, the tie layer and/or the substrate, either directly or indirectly.
  • the method includes the step of compressing the photovoltaic cell and the polymer layer, the CGC, the tie layer and/or the substrate. Compressing the photovoltaic cell and the polymer layer, the CGC, the tie layer and/or the substrate is believed to maximize contact and maximize encapsulation, if desired.
  • the step of compressing may be further defined as applying a vacuum to the photovoltaic cell and the polymer layer, the CGC, the tie layer and/or the substrate.
  • a mechanical weight, press, or roller e.g. a pinch roller
  • the step of compressing may be further defined as laminating.
  • the method may include the step of applying heat to the module or any or all of the substrate, the CGC, the photovoltaic cell, polymer layer, and/or the tie layer. Heat may be applied in combination with any other step or may be applied in a discrete step.
  • the entire method may be continuous or batch or may include a combination of continuous and batch steps.
  • the step of disposing the polymer layer may be further defined as encapsulating at least part of the photovoltaic cell and/or the CGC with the polymer layer. More specifically, the polymer layer may partially or totally encapsulate the photovoltaic cell and/or CGC. Alternatively, the polymer layer may not encapsulate the photovoltaic cell and/or CGC. Partial encapsulation encourages more efficient manufacturing and better utilization of the solar spectrum, thereby resulting in greater efficiency.
  • the polymer layer allows for production of a module with the optical and chemical advantages of silicone. Additionally, use of silicone allows for formation of UV transparent tie layers and/or polymer layers and may increase cell efficiency by at least 1 to 5 relative %. Use of peroxide catalysts, as described above, may also provide increased transparency and increased cure speeds. Sheets of the curable composition including silicone may be used for assembly of the module.
  • the polymer layer and/or the tie layer may be further defined as a film and the step of disposing may be further defined as applying the film, e.g. applying the film to the CGC.
  • the step of applying the film may be further defined as melting the film.
  • the film may be laminated on the CGC.
  • the method includes the step of laminating to melt the tie layer and/or the polymer layer. After the step of laminating, the method may include applying a protective seal and/or the frame to the module. In an alternative embodiment, the method includes the step of applying the photovoltaic cell to a substrate by chemical vapor deposition. This step may be performed by any mechanisms known in the art. The method may also include the step of applying the additional tie layer, substrate, and/or superstrate.
  • the module includes the photovoltaic cell, the polymer layer, and the CGC disposed on the photovoltaic cell and sandwiched between the photovoltaic cell and the polymer layer.
  • the CGC relative to the module itself, may be formed by any method or process known in the art or the method described above.
  • the CGC is formed using electrical heating, hot filament processes, UV irradiation, IR irradiation, microwave irradiation, X-ray irradiation, electronic beams, laser beams, plasma, RF, radio frequency plasma enhanced chemical vapor deposition (RF-PECVD), electron-cyclotron-resonance plasma-enhanced chemical vapor deposition (ECR-PECVD), inductively coupled plasma enhanced chemical vapor deposition (ICP-ECVD), plasma beam source plasma enhanced chemical vapor deposition (PBS- PECVD), and/or combinations thereof.
  • RF-PECVD radio frequency plasma enhanced chemical vapor deposition
  • ECR-PECVD electron-cyclotron-resonance plasma-enhanced chemical vapor deposition
  • ICP-ECVD inductively coupled plasma enhanced chemical vapor deposition
  • PBS- PECVD plasma beam source plasma enhanced chemical vapor deposition
  • a first example evaluates continuously graded CGCs of this disclosure that are deposited on monocrystalline silicon wafers (i.e., examples of photovoltaic cells) and glass slides in a parallel-plate capacitive type plasma reactor operating in reactive ion- etching (RIE) configuration.
  • the deposition process includes introducing a reactive gas mixture in a deposition chamber. More specifically, monosilane (SiH 4 ), hydrogen (H 2 ) and argon (Ar) are introduced into the deposition chamber to deposit amorphous hydrogenated silicon. Subsequently, ethylene (C 2 H 4 ) is introduced for depositing amorphous hydrogenated silicon carbide.
  • Oxidizers such as nitrous oxide (N 2 0) and oxygen (0 2 ) are also added to the reactor chamber for depositing amorphous hydrogenated silicon oxycarbonitride.
  • the CGC is gradually-changed from hydrogenated oxygen and nitrogen rich SiOCN at the interface with air or the polymer layer to hydrogenated oxygen and nitrogen deficient SiOCN in the direction away from the polymer layer and further to highly hydrogenated SiC and still further to less hydrogenated SiC and yet further to amorphous hydrogenated Si at the opposite interface with the monocrystalline silicon substrate (see, e.g., Figures 3 and 4).
  • composition and optical properties of the CGC are changed within a single process run and without interrupting the plasma process.
  • the composition, density and optical characteristics of the CGC are changed by varying the flow rate of the C 2 H 4 .
  • Increased flow rates of C 2 H 4 increases carbon incorporation in the CGC resulting in lower absorption coefficients and refractive indices.
  • Figure 5 shows that increased flow rates of C 2 H 4 lower the refractive index of the CGC and increase deposition rate.
  • Figure 6 shows that increased N 2 0 flow rates result in lower deposition rates, absorption coefficients and refractive index values. Typically, this is due to gradual transition from hydrogenated SiC to hydrogenated SiOCN expressed by changes in the FTIR Si-C, Si-N and Si-0 stretching oscillations as can be seen from the spectra set forth in Figure 7.
  • the range of refractive index change realized in the aforementioned CGC is from 1.45 to 3.2
  • Figure 7 is a reflectance spectra of an uncoated silicon substrate (RefBareSi), a silicon substrate encapsulated with one embodiment of the polymer layer of this disclosure (RefEncSi), a silicon substrate including a compositional graded coating of this disclosure disposed thereon (CGC1), a silicon substrate including a compositional graded coating of this disclosure and a polymer layer of this disclosure disposed thereon (CGC1ENC), a silicon substrate including a second compositional graded coating of this disclosure disposed thereon (CGC2), a silicon substrate including the second compositional graded coating of this disclosure and a polymer layer of this disclosure disposed thereon (CGC2ENC), and a silicon substrate including a non- gradient antireflective coating of the art disposed thereon. It is seen from Figure 7 the superior reduction in light reflection provided by CGCs over large wavelength ranges (e.g. from 250 to 1700 nm) compared to a single antireflective coating.
  • CGC1ENC silicon substrate including
  • Figure 8 is a light transmission spectra of a glass reference (GlassRef), of the CGC1 compositional graded coating disposed on the glass reference (CGC IT), of the CGC2 compositional graded coating disposed on the glass reference (CGC2T), and of a third compositional graded coating disposed on the glass reference (CGC3T).
  • GlassRef GlassRef
  • CGC1 compositional graded coating disposed on the glass reference
  • CGC2T CGC2T
  • CGC3T third compositional graded coating disposed on the glass reference
  • a portion of the light absorption causes luminescence with a broad emission band from 375 to 675 nm, as it is seen from the spectrum set forth in Figure 9.
  • the broad emission band originates mainly from defects in the Si-O-C-N-H amorphous complex.
  • Example 3 describes an additional embodiment of this disclosure.
  • This embodiment includes a photovoltaic cell that has a refractive index from 3.2-3.6.
  • An intermediate layer including Si:H is deposited thereon by a PECVD method using a parallel-plate capacitive type reactor operating in a reactive ion-etching (RIE) mode (bottom electrode coupled) from a SiH 4 -H 2 -Ar gas mixture.
  • RIE reactive ion-etching
  • the particular set of process parameters provides a deposition rate of 6-10 nm/min.
  • the thickness of 3.5 to 15 nm of the first layer is selected to minimize light absorption and provide excellent surface passivation.
  • the CGC is disposed on the photovoltaic cell and, in this embodiment, on the intermediate layer, by the same PECVD method described above utilizing the same parallel-plate capacitive type reactor and components described in Example 2.
  • the polymer layer is then disposed on the CGC.
  • the polymer layer of this embodiment is a crosslinked silicone elastomer formed by dispensing and spreading a poly(dimethylsiloxane) composition on the CGC. This composition is subsequently cured to form the polymer layer having a refractive index of 1.41 and a thickness of 0.5 mm.
  • Figure 7 shows the minimized reflectance for normal incident light achieved by CGC compared to the reflectance from PDMS coated silicon wafers.
  • Figure 7 also shows superior reduction in light reflection loss provided by the CGC of this disclosure compared with Si wafers and single ARCs.
  • Figure 10 is a graph of refractive index of a compositional graded coating disposed on a silicon substrate as a function of thickness including a second order exponential model fit.
  • One or more of the values described above may vary by ⁇ 5%, ⁇ 10%, ⁇ 15%, ⁇ 20%, ⁇ 25%, etc. so long as the variance remains within the scope of the disclosure. Unexpected results may be obtained from each member of a Markush group independent from all other members. Each member may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims.

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Abstract

L'invention concerne un module de cellule photovoltaïque comprenant une cellule photovoltaïque ayant un indice de réfraction de 3,7 ± 2 et une couche polymère disposée sur la cellule et ayant un indice de réfraction de 1,5 ± 0,1. Le module comprend également un revêtement à gradient de composition disposé sur la cellule et pris en sandwich entre la cellule et la couche polymère. Le revêtement à gradient de composition a une épaisseur et un indice de réfraction variant le long de l'épaisseur d'un premier indice de réfraction à une première extrémité à un second indice de réfraction à une seconde extrémité adjacente à la couche polymère. Le revêtement à gradient de composition comprend un gradient incluant du SiC:H et du SiOCN:H le long de l'épaisseur. Le module comprend en outre du Si:H disposé entre la couche polymère et la cellule. Le module est formé en utilisant un procédé qui comprend le dépôt en continu du revêtement à gradient de composition sur la cellule en utilisant le dépôt chimique en phase vapeur, et le dépôt de la couche polymère sur le revêtement à gradient de composition.
PCT/US2013/033122 2012-03-21 2013-03-20 Procédé de formation d'un module de cellule photovoltaïque WO2013142585A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111152452A (zh) * 2020-01-14 2020-05-15 青岛理工大学 一种PDMS/SiC功能梯度衬底及其制备方法与应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100129994A1 (en) * 2007-02-27 2010-05-27 Yousef Awad Method for forming a film on a substrate
WO2011032272A1 (fr) * 2009-09-18 2011-03-24 Sixtron Advanced Materials, Inc. Cellule solaire à performance améliorée
US20110146787A1 (en) * 2008-05-28 2011-06-23 Sebastien Allen Silicon carbide-based antireflective coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100129994A1 (en) * 2007-02-27 2010-05-27 Yousef Awad Method for forming a film on a substrate
US20110146787A1 (en) * 2008-05-28 2011-06-23 Sebastien Allen Silicon carbide-based antireflective coating
WO2011032272A1 (fr) * 2009-09-18 2011-03-24 Sixtron Advanced Materials, Inc. Cellule solaire à performance améliorée

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111152452A (zh) * 2020-01-14 2020-05-15 青岛理工大学 一种PDMS/SiC功能梯度衬底及其制备方法与应用
CN111152452B (zh) * 2020-01-14 2023-04-18 青岛理工大学 一种PDMS/SiC功能梯度衬底及其制备方法与应用

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