The invention is related to the field of solar cells, and in particular to the global optimization of thin film photovoltaic cell front coatings.
Front coatings are a critical feature of the highest-efficiency photovoltaic cells, ranging from monocrystalline silicon cells with double-layer anti-reflection (AR) coatings to thin-film CIGS cells with single-layer AR coatings. The most effective front coatings allow light over a broad range of wavelengths to enter the cell and be absorbed. This broad range of wavelengths extends from long-wave ultraviolet (around 300 nm) to the band gap wavelength (for silicon, 1108 nm). While single-layer front coating designs are well known, multiple layers could conceivably allow higher admittance over a broader bandwidth. Thus, the problem of optimizing multilayer coatings for solar cells has been a topic of great interest for some time, but the full range of possible designs had not been explored, especially for thin absorbers and/or multiple coatings.
For the most common type of solar cell, made from silicon wafers, the front-coating design problem mostly reduces to a broad-band anti-reflection problem with dispersion. However, due to the dispersion of silicon and the non-uniformity of the AM1.5 solar spectrum, this problem can only be solved approximately with an analytical approach. More precise solutions require a numerical approach treat the cases of single-layer and double-layer AR coatings, and triple-layer AR coatings. Similar approaches have been taken for other related wide-band absorption problems. Some authors have even expanded this problem to include long wavelengths beyond the bandgap of silicon.
On the other hand, emerging thin-film solar cell technology presents an entirely different challenge for front coating design. First of all, reflections from the front and back interfere over a broad range of wavelengths. Furthermore, unlike a narrow bandwidth problem, where the principles of Q-matching resonant absorption (also known as “impedance-matching”) can be applied, the portion of the solar spectrum considered is broad-bandwidth: e.g., 300 nm to 1100 nm. Moreover the absorption length over the bandwidth is typically greater than the physical optical path length. As a consequence, even light that initially passes through the front coating often reflects back out through the front without being absorbed. Front coatings must not only allow light to enter the silicon cell, but must also trap it to be absorbed. This increases the complexity of the problem while diminishing the accuracy of any analytical approximations. This was examined through ray tracing on a non-systematic basis for thick multicrystalline wafer-based cells. Some recent work on the opposite limit of extremely thin (15 nm) organic cells has demonstrated 40% boosts in relative efficiency with appropriately designed front coatings. Other previous work used metal and dielectric regions in the back in order to maximize fields near the active region of amorphous silicon.
According to one aspect of the invention, there is provided a solar cell. The solar cell includes a thin film photovoltaic material structure used in absorbing light of a selective bandwidth. A multitude of dielectric front coatings are positioned on the thin film photovoltaic material structure so as to maximize admittance over the selected bandwidth. The thicknesses and indices of each of the front coatings are chosen by a global-optimization procedure to maximize the short-circuit current of the solar cell.
According to another aspect of the invention, there is provided a method of forming a solar cell. The method includes providing a thin film photovoltaic material structure used in absorbing light of a selective bandwidth. Also, the method includes positioning a multitude of dielectric front coatings on the thin film photovoltaic material structure so as to maximize admittance over the selected bandwidth. The thicknesses and indices of each of the front coatings are chosen by a global-optimization procedure to maximize the short-circuit current of the solar cell.
The invention provides a front-coating (FC) of a solar cell that controls its efficiency, determining admission of light into the absorbing material and potentially trapping light to enhance thin absorbers. Single-layer FC designs are well known, especially for thick absorbers where their only purpose is to reduce reflections. Multilayer FCs could improve performance, but require global optimization to design. For narrow bandwidths, one can always achieve nearly 100% absorption. For the entire solar bandwidth, however, a second FC layer improves performance by 6.1% for 256 μm wafer-based cells, or by 3.6% for 2 μm thin-film cells, while additional layers yield rapidly diminishing returns.
Emerging thin-film solar cell technology presents an entirely different challenge for front coating design. First of all, reflections from the front and back interfere over a broad range of wavelengths. Furthermore, unlike a narrow bandwidth problem, where the principles of Q-matching resonant absorption (also known as “impedance-matching”) can be applied, the portion of the solar spectrum considered is broad-bandwidth: e.g., 300 nm to 1100 nm. Moreover the absorption length over the bandwidth is typically greater than the physical optical path length. As a consequence, even light that initially passes through the front coating often reflects back out through the front without being absorbed. And front coatings must not only allow light to enter the silicon cell, but must also trap it to be absorbed. This increases the complexity of the problem while diminishing the accuracy of any analytical approximations. This was examined through ray tracing on a non-systematic basis for thick multicrystalline wafer-based cells. Some recent work on the opposite limit of extremely thin (15 nm) organic cells has demonstrated 40% boosts in relative efficiency with appropriately designed front coatings.
It is important to consider the behavior of the cell designs depicted in
The key factor that enables the use of global optimization to exhaustively search the parameter space of possible front-coating films is the availability of extremely efficient algorithms to model the optical properties of multilayer films. In particular, the light-trapping properties of the structures discussed in this paper are studied using a transfer-matrix approach known as the S-matrix method. The structure is broken up into homogeneous slabs of chosen thicknesses, boundary conditions are imposed at the interfaces, and fields are propagated throughout the structure.
The boundary conditions employed correspond to light normally incident from above the solar cell. Light absorption is calculated by modeling the c-Si regions with a complex refractive index that depends on wavelength. The c-Si region is treated as if it is only intrinsic, i.e., the doping of the p- and n-doped regions can be considered to have a negligible impact on the optical properties of the device. Since most dielectric materials have very large band gaps, the dispersion and absorption of the front- and back-coatings is assumed to be negligible over the range of wavelengths considered.
The metal region (back-reflector) is modeled as a frequency independent, negative permittivity (lossless) medium, as shown later, the exact details of the back-reflector have almost no impact on the optimal front coating design for the full solar bandwidth problem. In principle, the calculation of the model's optical properties is exact apart from these approximations. Verification has been performed for several structures using the finite-difference time-domain method with perfectly-matched boundary layers. The results are in good agreement, but the FDTD method is much slower for the same level of accuracy, so it is not used for most calculations.
In order to calculate the efficiency of the light capture of the model one can assume that each absorbed photon with energy greater than the band gap energy generates an electron-hole pair, and both carriers reach the electrical contacts. This corresponds to the statement that the diffusion length LD is much greater than the distance traveled by each carrier (i.e., LD>>d), a reasonable assumption for thin Si films with high mobilities.
The optimized quantity is the generated short-circuit current JSC, given by:
where represents the light intensity experienced by the solar cell per unit wavelength (given by the ASTM AM1.5 solar spectrum), and A(λ) is the absorption calculated above. (The integration was carried out by a 1000-point trapezoidal rule.) The coefficients w(λ) capture the relative importance of absorption at each wavelength, and will be referred to as “current weights” for short. This allows us to define a figure of merit (FOM) by:
which is proportional to the objective function used to maximize. It gives us a measure of the absorbing efficiency of the structure weighted for the solar-cell application; perfect absorption at all wavelengths within the range of silicon's absorption (300 nm to 1108 nm) yields FOM=1.
Important spectra factoring into the JSC calculation are displayed in
For the calculations, the front coating thicknesses were bounded by 0 and 700 nm and the indices by 1 and 5. The range of thicknesses includes the largest quarter-wave thickness in the lowest index material; the range of indices includes most materials that can be easily fabricated as a front coating. However, restricting the range of indices to a narrower range, or even fixing the indices entirely to the values for selected materials and optimizing only over the thicknesses, yields a FOM only slightly worse than when a wide range of indices is explored.
In general, this problem may have many local optima, especially as the range and number of parameters is increased. This is illustrated in
The MLSL algorithm is distinguished by clustering techniques to avoid repeatedly searching the same local optimum, and is guaranteed to find all local optima in a finite number of local searches. Also, the MLSL is compared to several other global-optimization techniques, such as the DIRECT-L algorithm, via a free-software package implementing many optimization algorithms, and found MLSL to find the same optimum in a shorter time. Because the BFGS algorithm requires the gradient of the objective function (the FOM), a computationally efficient method for calculating the gradient based on the adjoint method was used. Adjoint methods allow the gradient to be computed in a time comparable to the time required in calculating the objective function and independent of the number of parameters (here, the front coating indices and thicknesses).
In order to understand the physically-relevant problem of maximizing short-circuit current in a solar cell subject to the AM1.5 solar spectrum, it is instructive to start at the simpler, opposite limit of zero bandwidth. In this zero-bandwidth limit, it is well known that 100% absorption can be achieved when the rate of radiative escape from a resonant cavity is equal to its rate of absorption; this is referred to as the Q-matching condition.
It is predicted that the optimal design of
This prediction is tested numerically using the simulation framework discussed in the previous section; the results are shown in
where layer −1 is air, layer 0 is the front coating, and layer 1 is the silicon; nj is the real part of the refractive index of layer j, κj is the imaginary part, tj is the thickness, λ the vacuum wavelength. At normal incidence, φj=4π(nj+iκj)tj/λ and rj=(nj+iκj−nj-1−iκj-1)/(nj+iκj+nj-1+iκj-1) are the phases and Fresnel reflection coefficients.
The reflectance can be divided into three regimes, depending on the fractional absorptance of the silicon layer: The case where |eiφ1|<<r1: virtually no light reaches the back reflector. Thus, the problem reduces to that of creating an anti-reflection coating between two semi-infinite regions. The reflection is now written as r≈−(r1eiφ0+r0)/(r0r1eiφ0+1). With the proper choice of front-coating layer index and thickness, 100% transmission (and thus, 100% absorption), can be achieved at a single λ. This is exhibited by the results up to a wavelength of 675 nm in
The case where |eiφ1|≈r1: partial absorption after one pass through the cell means that interference between reflections from the front and back surfaces is possible. Furthermore, it is impossible to fully optimize this system by controlling a single, uniform dielectric layer. Mathematically, solving for the root of the numerator of Eq. (3) requires three independent variables because it has four linearly independent terms. If only two independent variables are present, a constant value is added to a term which rotates in the complex plane. This results in Fabry-Perot-type oscillations, which are seen in
However, these Fabry-Perot oscillations can be suppressed with an additional single back layer, illustrated in
The case where |eiφ1|→1: the absorption strength is virtually nil, and Q-matching cannot be achieved without a number of front layers proportional to log(1−|eiφi|), since the maximum reflectivity goes exponentially with the number of layers. Mathematically, the amplitude of the reflection coefficient |r| will approach unity. This limit is approached on the right-hand side of
Next, consider what happens to the FOM as the window of absorption wavelengths expands from zero up to the width of the usable solar spectrum for silicon-based solar cells (300-1108 nm). The results for optimized structures with 0-3 front layers are plotted in
Now let us consider the problem of absorption over the whole solar spectrum in more detail. The absorption spectra of optimized thin-film crystalline silicon solar cells (t=2 μm) are plotted in
The values of the front coating indices, thicknesses and figure of merit for the optimized structures of
Moreover, as one might expect, each of the optimized front coatings generates destructive interference between reflections from their front and back at the central frequency (corresponding to a phase shift≈π). In addition, the optimized structure for the 1 front-coating and 1 back-coating structure was found to be d=60.0 nm, n=2.070 and d=20.7 nm, n=1, respectively; the corresponding figure of merit was 0.440, which is nearly the same as the 1 front-layer structure. While it appears that the back layer is not much use in a broad bandwidth problem, for a lossy metal backing the back layer can help to reduce unwanted absorption loss.
Let us consider the effects of thickness over a broad range of silicon thicknesses, from thin-film values of 1 μm to effectively semi-infinite values of 1.6 cm. For the case of 2 μm-thick thin films, increasing the number of front coatings from zero to one yields a relative increase of 39.8% to the FOM (from 0.314 to 0.439); adding a second front coating yields a relative increase of 3.6% to the FOM (to 0.455), and adding a third coating yields another relative increase of 0.6% (to 0.458). For wafer-based cell thicknesses, e.g., 256 μm, increasing the number of front coatings from zero to one yields a 42.3% relative increase in the FOM (from 0.614 to 0.874); adding a second coating yields a relative increase of 6.1% (to 0.927); adding a third coating yields a relative increase of 1.3%. For effectively semi-infinite cells, e.g., 1.6 cm, increasing the number of front coatings from zero to one yields a 42.0% relative increase to the FOM (from 0.645 to 0.916); adding a second coating yields a 6.6% relative increase (to 0.976); and adding a third coating yields a relative increase of 1.5% (to 0.991).
These numbers illustrate the diminishing returns associated with adding more front layers for the broad-bandwidth problem. Thus, it comes as no surprise that increasing the number of layers to 10 provides no more than a 0.5% relative improvement over 3 layers, for a 2 μm-thick thin film. This result contrasts strongly with the zero-bandwidth results shown in
Furthermore, it is intriguing to note that both the relative and absolute gains are greater for the thicker, wafer-based cells than for thin films. This can be explained by noting that the long wavelengths that are poorly absorbed by thin cells with a single front coating layer can be absorbed well by thick cells. Thin-film cells are simply too thin to ever strongly absorb longer wavelengths without compromising their shorter-wavelength absorption, whereas wafer-based cells are free from this limitation. This assertion is also supported by the absorption spectra of
For thin films exposed to the full solar bandwidth, the FOM and the optimal front-coating design are insensitive to the type of back-reflector. Considering only lossless planar back-reflectors, limiting to 100% specular reflection, different back-reflector schemes (different materials, Bragg mirrors, etc.) are distinguished only by the phase θ of the reflected wave. However, one can show here that the FOM is essentially independent of the back-reflector phase. Of course, the phase generally varies with wavelength, but it is sufficient to demonstrate this independence using a constant phase (employing n=3.5 for silicon and a constant imaginary index for the back-reflector, as explained previously). The FOM relative difference, which measures the influence of the back-reflector on the absorption, versus θ is shown in
This robust behavior is enabled by the large bandwidth of the incident flux that averages out the change at each λ; while the location of the absorption peaks can shift, the total absorbed flux will show almost no change as illustrated in
Though the refractive index bounds exceed those of common materials, one can find that optimization with a smaller range of indices, 1 to 3, does not significantly change the FOM. In fact with a restricted refractive index range, the 3 front-coating structure FOM decreases by less than 0.5% (0.458 to 0.456). (The thicknesses and indices of each layer of the optimal structure changes, even those in the original structure with an index less than 3.) Moreover, if the indices of the front coatings were fixed to values corresponding to experimentally accessible materials and allow only the thicknesses to vary, one can find the FOM changes very little, less than a 0.2% relative change in all three cases. If the front coatings were chosen to be MgF2, ZrO2, and TiO2 with indices 1.38, 2.39, and 3.9 yields a FOM of 0.457, a relative decrease of just 0.2% compared to the optimal 3 front-coating structure in Table 22 of
The designs presented in this work are also robust against small fabrication errors. For example, vertical LPCVD systems can routinely achieve uniformities of better than 2% in the deposition of silicon nitride. For the designs, that corresponds to an error of ±2 nm or less. However, it's clear that this corresponds to a variation in the objective function of less than 0.001, which shows that the designs can tolerate typical experimental errors.
The proper design and optimization of front coatings of crystalline silicon solar cells has a critical impact on their overall efficiency. For narrow bandwidths in optically thin absorbing media, it is best to employ the Q-matching condition. The benefit of additional layers is large until this criterion is achieved. When the bandwidth is equal to the portion of the solar spectrum that can be absorbed by crystalline silicon, it is necessary to take a different approach. It is found that just two optimized layers (going from low to high index) suffice to realize most of the benefits of a multilayer front coating design. The relative improvement associated with going from one to two front layers is 6.1% for 256 micron-thick wafer-based cells, and only 3.6% for 2 micron-thick thin-film cells. This result comes about because weak absorption of near-IR by planar thin films limits the utility of broadening the bandwidth of strong transmission through the front coating. Adding a third layer yields relative improvements of 1.3% and 0.6% for wafers and thin films, respectively; the results for four or more layers show even smaller additional improvements. Finally the broad bandwidth results achieved do not depend on the type of back-reflector used.
Furthermore, the weak absorption of near-IR by thin-film cells can be improved by introducing optimized 2D or 3D patterns in the front or back coatings, whose purpose is to convert incoming normal incidence radiation to transversely propagating, waveguided modes that achieve a longer optical path within the absorbing layer. It has been demonstrated how photonic crystals can improve reflection off of a realistic, lossy metal (such as aluminum) while also redirecting light in the near-IR into guided modes. They should also enable front coatings to improve absorption over a broader wavelength range than would be possible in a planar structure. This combined approach may result in efficiency gains equal to the sum of their contributions. The method presented in this patent can also be extended to include the effect of non-normally incident radiation, so as to maximize the performance over a range of incident angles. The results outlined in this work also provide a clear baseline to which more complex, non-planar photonic structures ought to be compared.
Although the present invention has been shown and described with respect to several preferred embodiments thereof, various changes, omissions and additions to the form and detail thereof, may be made therein, without departing from the spirit and scope of the invention.
This invention was made with Government support under Grant No. DMR 0819762, awarded by the National Science Foundation and also under Grant No. DAAD-19-02-D002, awarded by the Army Research Office. The Government has certain rights in the invention.