Solar Energy Today I will start out by addressing a couple of (ultimately important) questions What is sunlight? What (exactly) is "'electricity?" I'll will then move on to: Photovoltaics = Direct conversion of sunlight into electricity which requires: The essential difference between photoconductors and photovoltaics And how to create that difference based on material and design Solar Thermal = Capture sunlight's heat => boil something => Indirect Electricity Prompting a short discussion of: Molten Salt Heat Storage Which could give solar thermal an edge over all other renewables An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm What is Sunlight? It's a very BROAD range of wavelengths Resembling Black Body Spectrum (vibrating things randomly sharing energy) Significant portions of which are absorbed in the atmosphere (yellow => red) Source: en.wikipedia.org/wiki/Sunlight How much power can sunlight deliver? Above earth's atmosphere, total power is ~ 1350 Watts / square meter This value is referred to as "AM0" (air mass zero) Atmosphere absorbs ~ 25% of this => ~ 1000 Watts / square meter Referred to as "AM1.5" (air mass 1.5) But this = MAXIMUM solar power intensity on earth's surface Because this is the value when the sun is DIRECTLY overhead Which happens only in certain locations, in certain seasons, once a day AND clouds / haze / fog will further reduce intensities! How do you convert wavelengths to photon energy? Start with fact that light's energy is proportional to its frequency: Elight = h f h = Plank's constant, f = frequency (in Hz = cycles /sec) Add in fact that in one cycle, light travels one wavelength (= "l") So velocity of light = c = l / (cycle time) = l f Plug second relationship into first relationship: Elight = h f = h (c / l) = hc / l Then, agree to express light energies in eV, and wavelengths in microns Yielding relationship: Elight (in eV) = 1.24 / l (light in microns) Where a Joule = (coulomb of charge) (crossing 1 Volt potential) But eV = (electron charge) (crossing 1 Volt potential) = 1.6 x 10-19 Joules Using this to revise scale of earlier sunlight plot: From formula from above (and fact that 1000 nm = 1 micron): Wavelength Energy 5 eV 2 eV 1 eV 0.5 eV And calling out spectral ranges: UV Infrared Now need to know how these colors interact with matter: Because we want to exploit these interactions to CAPTURE the light's energy! 1) INFRARED (IR) LIGHT: Wavelengths > 700 nm (> 0.7 microns) Energy < 1.7 eV If absorbed by matter => heat = atomic & molecular vibrations Symmetric Stretch Asymmetric Stretch Scissoring Rocking Wagging Uniqueness of atom/molecule's vibrational energies => absorption bands => "IR" spectroscopies used by chemists ATMOSPHERIC absorption bands => AM1.5 spectrum: Animated GIFs from: en.wikipedia.org/wiki/Infrared_spectroscopy Twisting IR vibrations may be amusing (and useful elsewhere) HOWEVER, in the context of this lecture, the important conclusion is that: Infrared light lacks the energy necessary to liberate electrons from atoms/bonds So Infrared light cannot DIRECTLY produce electricity But Infrared's heat energy can be transferred (absorbed) by other things And if a liquid captures enough of that heat It will then boil => Huge volume expansion => Pressure Which can propel electrical turbine-generator So Infrared light can INDIRECTLY produce electricity As opposed to light that CAN directly produce electricity: 1) VISIBLE (Vis): 400 nm < Wavelengths < 700 nm (0.4-0.7 micron) 3 eV > Energy > 1.7 eV Visible light CAN knock an electron free from an atom ("ionization") Visible light CAN knock one electron out of a covalent bond Probably why eyes use it: Eye's sensor output = Liberated electrons / ions INSTEAD Infrared would just have caused atoms in eye to vibrate Vibrations CAN be transferred to other atoms (a.k.a. heat flow) But hard to imagine a heat directing "nerve fiber" Instead: Visible light's liberation of electrons can DIRECTLY produce electricity An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm What about ultraviolet light? 1) ULTRAVIOLET (UV): Wavelengths < 400 nm (< 0.4 micron) 3 eV > Energy UV certainly has enough energy to liberate electrons! So we CAN also use UV to directly produce electricity HOWEVER it also has enough energy to BREAK MANY ATOMIC BONDS Distinction: "Liberating" = Removing one of covalent bond's paired electrons Or extracting one electron from unbonded pair (=> "free radical") In both cases, pair can re-form later by capturing an electron Whereas: "Bond breaking" = wiping out bond / changing molecular structure So, over time, UV LIGHT can DESTROY solar cell materials Particular problem for more weakly bonded "organic" solar cell materials Moving on: What (exactly) is electricity? This may sound like a very simple, or even a dumb question – In which case: I've read an incredible number of "dumb" news stories And "dumb" university press releases And even the occasional "dumb" comment from a research scientist That/who imply: "Electricity" = THING that can just ooze out of a lump of material WRONG!! Electricity is not a thing – It is a process: Of electrons being driven in a flow But why CAN'T we just squeeze electrons out (and then USE them)? Revisting James Clerk Maxwell: Maxwell's 1st Equation: Electric Field builds in proportion to net charge "Net charge" = Positive charge density – Negative charge density Electric force is then proportional to the strength of that electric field So just a TINY ACCUMULATION of net charge => HUGE FORCES For a second or two: Then there is a loud snap as charge build-up dissipates On scales much greater than molecular dimensions Nature will not LET you remove or add significant net charge! Photo from : /joyerickson.wordpress.com/2012/08/05/pull-up-something-cool/ So "electricity" is instead about pumping charge PUMP charge in one end of something and out the other end: "Something" = Generator, solar cell, battery, generator, . . . That's WHY it's called electrical current: An analogy to incompressible water: Can pump water THROUGH pipes, but if try to increase water IN pipe => Explosion! Generator, solar cell, battery, capacitor . . . are all CHARGE PUMPS And pumps are judged on basis of the flow and pressure they can generate: Water Power = Flow x Pressure which is analogous to: Electrical Power = "Current" x "Voltage" So what we are NOW looking for is a solar-powered electron pump! An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm Photovoltaics ("solar cells"): Solar-powered electron pumps What happens when light strikes a material? From above: Case 1) Photon energy < Material's bond energy: Photon can't shake anything loose, most just proceed on through That is, material is ~ transparent to these too low energy photons Case 2) Photon Energy = Material's bond energy Photon IS now absorbed and its energy used to kick an electron out of a bond Case 3) Photon Energy > Material's bond energy Photon is absorbed: Part of its energy kicks an electron out of a bond Rest of its energy also goes to that electron in the form of kinetic energy That is, photon kicks it out of the bond, then kicks it in the butt! So when we shine light having bond energy onto a material: (Remembering that I need want power = current x voltage out of a solar cell) This light is (at least eventually) going to be absorbed by a bond in our material: Before: Atom cores (positive nuclei + inner electrons) + bonding electrons In 1D: ~ +2 -2 +2 -2 +2 -2 +2 0 0 0 0 After: One negative electron is liberated, leaving behind a positive region: 0 +1/2 +1/2 -1 0 0 0 0 Electron is drawn BACK to positive region => falling back into bond (or a FEW might wander out the left or right end) This gives me only a "photoconductor" – And NOT a solar cell! Most liberated electrons just wander until pulled back into bonds Or ones that DO exit are equally likely to exit right or left Nothing is pumping (pushing) electrons to flow in one direction! Application? ADD external battery/power supply and use as a light detector: No light: All electrons in bonds, no current through sample (despite battery) Light: Freed electrons. Battery can now suck them out one end and push back into other But where did the light's energy go? Into the atoms Freed electrons later fell back into atoms' clutches Then giving those atoms a kick => atomic vibrations (a.k.a. heat) To produce power we've ALSO got to drive (PUMP) electrons somewhere! Classic Technique: START with fully bonded electrically neutral material, most commonly silicon It sets the bonding rules with its crystal structure: Rule with Si = four bonds ADD atom of almost same size but with one less bonding electron (e.g. boron) Fits into crystal, steals electron from elsewhere, making it an Acceptor (thief?) Bond where electron stolen from now becomes a positive Hole Silicon with added Acceptor atoms => Negative ions + Liberated holes: Silicon atoms = Grey (fixed neutral atoms) Acceptor ions also FIXED in position Holes = MOBILE Why? ANSWER: Hole grabs electron from neighboring bond, leaving a hole in a NEW place . . . Can also add things that will shed electrons Donor = Similar to Si in size, but with one additional bonding electron (e.g. P, As) Fits into crystal but final electron has nothing to pair with and bond. Thus: It easily loses that electron (ionizes), becoming a positive Donor: With that last, now liberated, electron free to wander: Silicon with added Donor impurity atoms => Positive ions + Liberated electrons: Here only liberated electrons are MOBILE And, as in other material, net charge is still zero! So James Clerk Maxwell is still happy And if mobile electrons return home, heat will eventually kick them back out! NOTE: Acceptor and Donor impurities are called "DOPANTS" Payoff comes when you put two such "doped" regions side by side: Acceptor ions + Mobile Holes: Donor ions + Mobile Electrons: At intersection ("junction”) mobile electrons are going to rush across to FILL mobile holes!! (Because holes ARE just bonds that have lost one of the normal paired electrons!) Mobile electrons filling the holes (in the bonds) is called "recombination" Central junction thus becomes depleted of ALL mobile charges (liberated electrons or holes): But this leaves uncompensated FIXED acceptor ions (-) / donor ions (+) at the junction Which produces a growing Electric field at that junction Migration / recombination continues UNTIL field is strong enough to block further migration Because Electric field pushes positive charges left and negative charges right Electric field thus locks remaining mobile holes and electrons on their respective sides NOW add light to knock electrons out of background silicon: Light photon knocks an electron out of a bond, creating a wandering electron + hole (traveling together ="exciton") New electron and hole can both wander, but if reach "junction:" "Built-in" electric field traps new electron on right, but propels hole to left If instead created on left, hole trapped on left, but electron swept to right = A CHARGE PUMP (BTW this is also a DIODE: Can only force current through it in ONE direction) More general way of creating boundary charge-separating electric field: ABOVE: ONE MATERIAL but divided it in TWO DIFFERENTLY BEHAVING REGIONS Made two regions different by adding acceptor OR donor impurity atoms ALTERNATIVE: Just put two DIFFERENT MATERIALS side by side Electrons at higher energies on one side may try to cross over to other side NET RESULT (again) = Build up of electric field at boundary It's analogous to diatomic bonding in molecules: Atoms of two different materials: Possibility 1) Covalent Bond = Equal sharing of electrons in bond: Possibility 2) Polar Covalent Bond = Unequal sharing of electrons in bond: Slight Electric Field Possibility 3) Ionic Bond = Transfer of electron from one atom to other: Big Electric Field! + - Solar cell materials MUST allow some electron movement, thus: At junction of two different materials, interfacial bonding can be polar or ionic: OR: Both => Interfacial Electric field + - UNLESS the electron energy levels of the two materials are too similar Then electron in one material may not find a lower energy state in the other And the interfacial bonding will remain covalent (and E =>0) If layers are of same material there's no reason for electrons to shift (and E =>0) But we can then, instead, add different impurities to layers (as in Si cells): Impurities => Interfacial Electric field But remember, charge only shifts near the interfaces: Materials are composed of atoms which are intrinsically charge neutral So natural state of any single layer is ALSO neutral: And junction between two materials also "starts out" neutral But if energy levels in materials are different enough, charge can cross interface: However, charge shift builds electric field eventually blocking further charge transfer So charge DEEPER in layers will not get chance to cross! Leading to common rules for almost all photovoltaics (solar cells): Must have at least one set of paired materials: Be it two distinctly different materials OR One basic material (e.g., silicon) modified into two differently acting layers In that pair, one layer/material must cling onto electrons more tightly So that electrons will flow into it from second material Until shift of charge across boundary builds up ELECTRIC FIELD at interface Which will tend to counter further shifting of charge That "interfacial" electric field will then provide the critical push Light energy => breaks electron bonds But ELECTRIC FIELD then pushes freed electrons all in one direction But what is the amount of POWER (= current x voltage) PRODUCED? Current comes from the number of electrons liberated by light / second - Function of how strongly that material absorbs photons of that color - AND of how much material is doing the absorbing (e.g. its layer thickness) Voltage comes from charge driving/separating junction ELECTRIC FIELD Which was created by process of bond filling/liberating. Leading to fact that: Photo-electrons/holes are driven out of cell by ~ 60-70% of liberation energy => Solar cell voltage ~ (0.65) (liberation energy) / (electron charge = "e") For Si solar cell, "Voc" ~ (0.65) (Si electron liberation energy = 1.1 eV) / e ~ 0.7 Volt Larger the liberation-energy (a.k.a. bandgap) => More VOLTAGE But Less current: Why? (Answer => motivation for using quantum dots) So to optimize power capture, must go back to solar spectrum In particular, the "AM1.5" solar spectrum below the earth's atmosphere: Energy Wavelength If this strikes a solar cell made of a material having Small liberation energy => MOST colors liberate electrons, but are driven out of cell by small voltages If this strikes a solar cell made of a material having Large liberation energy => Only HIGH ENERGY light liberates electrons But fewer electrons that ARE liberated will be driven by higher voltages! Maximum possible power out with ~ 1.3 eV bonds => ~ 35% power conversion Diagrams on how that optimum is worked out (for simpler AM0 case): 100% PERCENTAGE of light's energy captured as electricity by different bandgap materials: 50% 0% 5 eV 2 1.5 1.25 1 eV 0.75 eV 0.5 eV Sun's AM0 Power Spectrum Sun's Energy Spectrum and parts captured by different bandgap materials: Difference between yellow and other lines = lost "butt kicking" E 250 500 750 1000 1500 2000 Wavelength in nm (or above, equivalent energy in eV) 2500 Larger the area under the bottom curve => More solar energy captured BIGGEST area comes between 1 eV and 1.5 eV curves, for ~ 1.3 eV material Material of this bandgap would capture & convert ~ 35% of Sun's energy Called Shockley-Queisser Limit after William Shockley & Hans Queisser. Thus: Fact that single-material solar cells efficiencies top out at 35% is NOT because we are doing a poor job of engineering! It is instead because: We ONLY CAPTURE part of light energy liberating electron from bond, REST of light energy is wasted giving liberated electron kick in the butt Applies whenever one photon liberates only one electron (and cell material contains bonds of only one energy) (Suggesting possible work-arounds) Another way of visualizing what's behind the Shockley-Quiesser Limit: VERY energetic photon is absorbed by bonding electron: Electron is freed and, with extra energy, crashes around semiconductor crystal: Crashed into atoms absorb energy => atomic vibrations (= heat) + now slowed down electron Shockley-Quiesser: With energy spread of of solar photons 2/3 of solar power => atomic vibration Si has ALMOST perfect bandgap to reach S-Q Limit! So it can approach ~ 30% efficiency. But silicon is also fragile and expensive Fragility: It's tougher than OTHER semiconductors, but it is still brittle/breakable Expense: In solar cell want light-liberated electrons/holes to wander a long time So have good chance of wandering into electric field at junction (essential!) But wandering electrons/holes tend to STOP at impurities If both stop there, likely that electrons will fill holes (effectively vanishing) So solar cell grade Si must be about 1000X more pure than electronic grade About 1 part in 1012 pure! => Much more expensive than normal Si So we'd really like some sort of breakthrough! To beat the Shockley-Quiesser Limit, minimize the electron butt kicking: How? By stacking solar cells of DIFFERENT materials atop one another Choosing materials with different bond energies/"bandgaps" Top: Material with large bond energies ~ purple/blue light: High energy photons liberate electrons from these bonds Less energetic photons will pass right through . . . Middle: Material with medium bond energies ~ green light: Medium energy photons liberate electrons from these bonds Less energetic photons will pass right through . . . Bottom: Material with low bond energies ~ red light: Low energy photons liberate electrons from these bonds ~ ALL photon energy => electron liberation => ~ 100% energy capture!! These are called "Multi-Junction Solar Cells" or "Tandem Solar Cells" BIG REMAINING PROBLEM: Shockley-Quiesser Limit was ~ 33% energy capture efficiency Multi-junction cell can approach ~ 3X (= 100%) energy capture efficiency but requires the combination of ~ 3 different cells to get there So it likely costs (at least) 3X times as much!!!! (!$#!$@$%) We must, instead, produce stack of three cells for ~ cost of single cell To radically cut cost, need materials that are so similar that they can be grown by one continuous processes An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm How to select those candidate semiconductor materials: Bandgap (electron liberation energy) of semiconductors vs. their "lattice constant" Shockley-Quiesser optimum bandgap for single material cell Strained Layer Epitaxy of Germanium-Silicon Alloys, John C. Bean, Invited Review, Science Magazine 230, p127 (1985) "Lattice constant" = Size of fundamental atomic grouping => Spacing of atoms Connecting lines => "Alloy" mixtures of one semiconductor with another With connecting line giving the bandgap of the resultant material mixture To grow atop one another, materials must be along vertical line: Shockley-Quiesser optimum bandgap for single material cell Strained Layer Epitaxy of Germanium-Silicon Alloys, John C. Bean, Invited Review, Science Magazine 230, p127 (1985) Why? So lattices match well enough that bonds between layers are not interrupted: That is, so that this is possible: Layers of cell #1 Layers of cell #2 (and so on) Because if bonds between cells materials do NOT match up . . . You'll end up with something like this: Many/most bonds at interface are incomplete: Incomplete bonds will try to grab ("trap") passing electrons or holes INCLUDING our photo-generated electrons or holes BEFORE they get out of cell And if they don't make it out, we don't get photovoltaic power out! Broke bonds can also be a problem in single thin film cells: Because "thin film" = They are not made from one big monolithic crystal Instead consist of a lot of micro-crystals packed together = "polycrystal" OR from something that is not crystalline at all = "amorphous" Thus, while still only one material, there are LOTS of screwed up interfacial bonds: And those screwed up bonds can also trap photo-carriers! Trying to take ALL of this into account: HAVE solar cells (of ANY type) broken through the S-Q limit? Following figure: Compilation by U.S. National Renewable Energy Lab (NREL) of latest, greatest, one of a kind, possibly never reproduced (or horrendously expensive), solar cell efficiency records: Best RESEARCH solar cells (1976 – 2015): At lower resolution but with some guidance as to cell types: Multi-junction / Tandem Single crystal GaAs Single crystal Si Polycrystal thin film Si Other thin films "Hero" (best in lab / single shot) efficiencies, top to bottom: Multi-junction solar cells: Highest at almost 45% So have beat, but not shattered, Shockley-Quiesser Limit Crystalline GaAs solar cells (more exotic/$ crystal than Si): Hair over 34% Crystalline silicon solar cells: Highest at 27.6% Thin-film cells (e.g. polycrystalline/amorphous Si and CdTe): Highest at 23% Perovskite cells: Highest just over 20% Dye-sensitized, organic . . . cells: Highest at 12% Quantum Dot solar cells: Highest at 9.2% I will explain the differences between all of these cell types in my upcoming Next Generation Solar Power lecture Solar Thermal Power: How to use all of that infrared sunlight! Wavelength Energy 5 eV UV 2 eV 1 eV 0.5 eV Infrared (IR) Solar Photovoltics: Ignored IR because infrared couldn't knock electrons loose Solar Thermal: Exploits fact that IR CAN still excite vibrations (a.k.a "heat") An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm Concentrate infrared light with mirrors – then boil something: One way of doing this is to build from small single mirror / liquid pipe units: http://www.esolar.com/business/w here-esolar-fits-in-the-industry/ And to then combine large numbers of these into solar thermal "farms:" www.treehugger.com/renewableenergy/us-army-goes-solar-500-mwsolar-thermal-power-plant-to-bebuilt-at-fort-irwin.html Or use mirrors (only) to send COMBINED IR to central tower: Big: http://blog.zintro.com/cleantech-alt-energy/page/2/ Or "supersized" - California's recently completed "Ivanpah" Mojave Desert farm: "Tower of Power" Time Magazine June 24, 2013 1600 Hectares (4000 acres)! But goal is to "boil something" and drive turbine–generator Which leads to advantages and disadvantages for each alternative DISADVANTAGE of small units: They don't incorporate individual mini-turbines Instead, tubes are all plumbed together then eventually all routed to turbine-generator(s) => Lot of piping and lot of pumping => Lot of heat loss (before reaching turbine)? http://en.wikipedia.org/wiki/Solar _thermal_energy ADVANTAGE of small units: Stationary with little (or possibly no!) need to tilt or steer Because, even as sun moves, IR stills hits somewhere on tube An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm Versus central tower design: DISADVANTAGE of central tower farms: For IR from ALL mirrors to hit top of tower EVERY mirror MUST CONINUOUSLY steer! And tilt of EVERY mirror is DIFFERENT => Large investment in 2-Axis steering gear for each mirror + control! ADVANTAGE of central tower farms: No distributed (mirror to mirror) plumbing No heat loss in that plumbing Instead ALL IR goes directly (as light) to top of central tower An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm Which solar thermal design is better? Both sides (naturally) claim their design is better So I usually turn to (nominally?) objective government studies In particular, to data gathered by U.S. Energy Information Agency (EIA) However, EIA data (to date) do not differentiate between two alternatives But their "levelized cost" 1 data for solar thermal power (all types) IS currently 2X cost of solar photovoltaic power (all types) However, I DO note that over last ~ half dozen years: I've read more worldwide reports on central tower solar thermal farms To which one might cynically respond: "But Mega-projects => Mega PR!" 1) I'll explain "Levelized costs" in the Economic Analysis lecture Frequent problem with both types of current solar thermal: WATER Many (most?) projects to date have used water as the liquid Which boils at 100°C => Expands => Turns turbine => Generates electricity But what happens next? Get more water? Not in deserts where these plants are built! Not in California! Not in Spain! (locations of some of biggest solar thermal farms) Reuse water? Fine, but must first cool and re-condense it Even 50°C desert air can eventually cool pipes/water But to be expedite: Use FORCED air cooling (using up some of your power) OR use new COOL WATER to cool old water (but cool water from where?) An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm Better answer: Replace water with an oil Choosing an oil that, instead of boiling at 100°C, might boil at say 400°C Get the top of that tower REALLY HOT (in order to boil that oil!) But then, by contrast, desert air is so cool that: Even passive (non-forced) air suffices to cool / re-condense oil This alternative IS now used in some solar thermal designs And could become the STANDARD in solar thermal! An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm But there may be a better coolant: Molten salt Keep water or oil as fluid to be eventually boiled, powering generator But in the solar tower itself, have molten salt absorb IR heat AND add big reservoir to store large amounts of heated salt Tower Hot salt reservoir Salt loop to reservoir Salt to H2O/Oil heat exchanger Salt loop from reservoir Boiling H2O/Oil loop to generator An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm But why add in another layer of complexity? Because with enough molten salt (heated in the middle of the day) That molten salt can be used to boil water/oil all night Producing around the clock solar energy Why use molten salt reservoirs? - Non-toxic / Non-flammable - Melts at a low temperature (~130 °C for sodium/potassium/calcium salt mixture) - Mass => Its heating sucks in a huge amount of energy (= high "heat capacity" ) Our only other, non-nuclear, sustainable 24/7 power source is Hydroelectric Power Which also operates 24/7 based on its use of big storage reservoirs! Credits / Acknowledgements Some materials used in this class were developed under a National Science Foundation "Research Initiation Grant in Engineering Education" (RIGEE). Other materials, including the "UVA Virtual Lab" science education website, were developed under even earlier NSF "Course, Curriculum and Laboratory Improvement" (CCLI) and "Nanoscience Undergraduate Education" (NUE) awards. This set of notes was authored by John C. Bean who also created all figures not explicitly credited above. Copyright John C. Bean (2016) (However, permission is granted for use by individual instructors in non-profit academic institutions) An Introduction to Sustainable Energy Systems: www.virlab.virginia.edu/Energy_class/Energy_class.htm