The invention relates to anti-reflection coating. More particularly, the invention concerns a device comprising board band anti-reflection coating for photovoltaic devices and other devices.
A photovoltaic device is made of a high index semiconductor material. Therefore, it has strong surface reflections. Although a photovoltaic device is usually encapsulated using an encapsulant, the index contrast between photovoltaic device surface index and encapsulant index is still very high, therefore, the surface reflection is also still very high.
The nature, objectives, and advantages of the invention will become more apparent to those skilled in the art after considering the following detailed description in connection with the accompanying drawings.
A new design and the fabrication method to make broad-band photovoltaic cells with minimized surface reflection at the photovoltaic device surface is disclosed herein. Photovoltaic cells are widely used to convert solar energy to electricity directly. Usually photovoltaic cells suffer from optical surface reflection loss at the photovoltaic device surface due to its high refractive index.
One-layer coating or a two-layer coating, have been developed on the surface of photovoltaic devices to reduce and even eliminate some surface reflections from the photovoltaic device. However, traditional anti-reflection coating technologies can only reduce or eliminate surface reflection within a narrow spectral range and within a narrow incident angle range. These traditional anti-reflection (“AR”) coating technologies cannot work well for broad-band photovoltaic devices, which require an anti-reflection coating with a broad band-width, such as the wavelength range from 300 nm to 1800 nm, and a wide incident angle range, for example, 0° to beyond 45°. Although broad-band, wide incident angle anti-reflection coatings with gradient index profiles have been designed theoretically, there is no practical solution for photovoltaic devices due to the fact that photovoltaic devices have very high refractive index values and there are no optical materials available to achieve such a transparent gradient index profile. “Moth-eye” structures have been demonstrated to mimic the gradient index profile to achieve broad-band anti-reflection. However, moth-eye structures require etching which will damage the photovoltaic device surface. Additionally, its nano-structure generated from the etching process is not mechanically robust enough to survive the encapsulating process. As a result, “moth-eye” structures cannot be used as broad-band anti-reflection coatings on photovoltaic device surfaces.
A manufacturing method and innovative anti-reflection coating solution between photovoltaic device surface and encapsulant is disclosed to achieve broad-band anti-reflection with a wide incident angle range is disclosed herein. Such anti-reflection coating can achieve low reflectivity (<5%) over the wavelength range from 300 nm to 1800 nm and incident angle range from 0° to beyond 45°. The photovoltaic cell structure with such an anti-reflection coating is also disclosed.
The structure and the fabrication method can realize a photovoltaic cell with a broad-band, wide incident angle range anti-reflection coating on the photovoltaic device surface is revealed. The anti-reflection coating on the photovoltaic device can have a surface reflection less than 5% over the wavelength range from 300 nm to 1800 nm and incident angle range from 0° to 45°. The low reflectivity with broad spectral band and wide incident angle range is achieved by combining a gradient index profile and a thin film interference effect in the anti-reflection coating.
Such device can achieve low reflectivity over wide spectral range, e.g., from near UV to near IR; low reflectivity over wide incident angle, e.g., from 0° to over 45°. Such device can be compatible with current PV cell manufacturing process. The AR coating design on photovoltaic can be applied to substrate with high index. The AR performance exceeds other technologies/approaches existing on the market.
A photovoltaic cell with low optical reflection loss can use a broad-band anti-reflection coating on the photovoltaic device surface. Surface reflection (Fresnel reflection) is caused by the refractive index contrast at the interface between two materials. Its reflectivity at normal incidence can be calculated by Eq. 1
where namb and nsub is the refractive index of the ambient and substrate, respectively. Eq. 1 shows that large refractive index contrasts result in high reflectivities. The photovoltaic device is a semiconductor device made of semiconductor materials, such as but not limited to, GaP, GaInP, AlInP, GaAs, Si, Ge, CdS, etc. It has a high refractive index at the top surface. For example, broad-band inverted metamorphic multi-junction (IMM) photovoltaic devices usually have AlInP as the top layer, which has a refractive index >3. The encapsulant, such as, but not limited to, silicone encapsulant, usually has refractive index value of about 1.5 to 1.4. Therefore, there is a huge index contrast between the photovoltaic device surface and the encapsulant. As a result, the photovoltaic device surface reflection has high reflectivity. An anti-reflection coating is usually coated on the surface of the photovoltaic devices to eliminate or reduce its surface reflection. A schematic structure of a photovoltaic cell is shown in
Following Eq. 1, a coating with a gradual or gradient refractive index change from substrate's index, nsub, to ambient index, namb can eliminate the index contract and the surface reflection. Such an anti-reflection coating can eliminate the surface reflection over a broad spectral range and over a wide incident angle range, which is desired by broad-band photovoltaic devices. However, photovoltaic devices usually have such a high index that no transparent optical material is available to form a coating with a gradient or gradual index change. For example, the current broad-band IMM photovoltaic devices have a GaInP sub-cell and a AlInP window layer on top, both of which have refractive index >3.0. At near ultra-violet spectrum, both GaInP sub-cell and AlInP window layer have index value >4.0, which is much larger than conventional transparent optical material index values. As a result, there are no conventional transparent optical materials available to smoothly eliminate the index contrast between GaInP or AlInP and their ambient, the silicone adhesive with a cover glass. Note, the material selected for an anti-reflection coating should be transparent or have low absorption in the interested spectral range to avoid absorption loss
A thin-film based anti-reflection coating design placed between the top surface of the photovoltaic device and the encapsulant can achieve low reflectivity, over a broad spectral range, such as the 300 nm to 1800 nm wavelength range. The anti-reflection coating 200 consists of two components as shown in
A gradient-index layer with a quintic profile, such as a ZrO2—SiO2 composite layer, can be deposited on top of the high-index layer to reduce the surface reflection between photovoltaic device and the encapsulant adhesive. The gradient layer must be thick enough to achieve a broad band-width (preferably 500 nm or larger to reduce reflectivity over the broad spectral range from 300 nm to 1800 nm), therefore, only highly transparent materials throughout the solar spectrum can be used. The gradient layer is graded from ZrO2 down to SiO2 to index match the index of encapsulant, such as Dow Corning's 93-500 silicone adhesive, and the cerium doped cover glass.
ZrO2 has the highest refractive index among the viable optical thin film materials that are transparent from 300 nm to 1800 nm. Therefore, a gradient-index ZrO2—SiO2 composite layer can be used to eliminate index contrast between ZrO2 (n≈2.2 and encapsulant/cover glass (n≈1.5). The quintic profile is theoretical the ideal gradient refractive index profile for eliminating surface reflections. The gradient layer will effectively reduce surface reflection at long wavelengths (450 nm to beyond 1800 nm). However, at near UV, there is still a huge index gap between ZrO2 and GaInP/AlInP, which can cause significant surface reflection at the near UV. To reduce the reflection loss at the near UV, a thin high-index layer can be inserted between the ZrO2—SiO2 composite layer and the PV cell to minimize the reflection at the near UV using an interference effect. TiO2 has the highest refractive index among the transparent optical thin film. But it is not chosen for the gradient-index composite layer fabrication because it is absorbing below 400 nm. However, TiO2 can be used for this thin high-index layer between the gradient-index ZrO2—SiO2 layer and the PV cell. The thin high-refractive index layer will reduce spectral reflectance for short wavelengths (between 300 nm to 450 nm). Due to TiO2's small thickness, the absorption losses for wavelengths below 400 nm will be minimized, therefore, TiO2 is still acceptable as the high-index layer.
The selection criteria for the thin high-index layer on PV cell as shown in
n
high-n=√{square root over (nsubnamb)} (2)
where nhigh-n, nsub, and namp are the refractive index value of the high-index layer, substrate, and surrounding ambient material, respectively. To minimize reflections at 350 nm for a material between a GaInP substrate (ns≈4.2 @ 350 nm) and a ZrO—SiO2 gradient (ambient of ZrO2, nambient≈2.35 @ 350 nm), the perfect material would be nhigh-n=3.14 @ 350 nm. TiO2 (nTiO2≈2.8 @ 350 nm) (measured and deposited by inventor) and ZnS (nZnS≈2.8 @ 350 nm) have refractive index values close to this ideal nhigh-n. Therefore, they can be chosen for this high index layer. The ideal quarter-wave thickness for TiO2 and ZnS is 31.5 nm. Therefore, a TiO2 or ZnS with a thickness close to 30 nm can be used in this anti-reflection coating. Ideally, a high-index thin film with no or low absorption over the whole interested spectrum, from 300 nm to 1800 nm, is preferred. Other candidates include SiC or AlP. In practice, optical material with low absorption or absorption in the near ultra-violet spectrum, such as TiO2 or ZnS, can also be used as high index layer 210.
The combination of high index layer 210 and gradient index layer 250 can achieve low reflectivity over the whole spectral range from the ultra-violet to near infrared spectra. The gradient-index layer 250 can also be other material systems as long as it can provide high index value at the side next to the high index layer 210, and index match to the ambient at the side next to the ambient, such as encapsulant. For example, a Si3N4—SiO2 or SiON gradient index layer can be used as gradient index layer 210 in this anti-reflection coating design due to the fact that Si3N4's refractive index is also high (n≈2).
The gradient index layer 250 can be deposited using a co-sputtering process or other deposition processes that can deposition two or multiple materials together to engineer the index profile of the coating. For example, ZrO2—SiO2 composite layer can be deposited using co-sputtering process. This co-sputtering process is the simultaneous deposition of ZrO2 and SiO2 that generates a composite or “mixed” material with a refractive index value between the index of ZrO2 and SiO2. By adjusting the deposition rate of ZrO2 and SiO2 independently during the co-sputtering process, ZrO2—SiO2 composite layers with any refractive index between ZrO2 and SiO2 can be achieved. For example, assuming a linear relationship, the refractive index of ZrO2—SiO2 composite material, nZrO2-SiO2, can be calculated using the following formula
n
ZrO2-SiO2
=n
ZrO2
x+n
SiO2(1−x) (3)
x is the ZrO2 compositional fraction with nZrO2≈2.35 and nSiO2≈1.45. In the sputtering process, the deposition rate of ZrO2 and SiO2 is controlled properly so that a final gradient index ZrO2—SiO2 composite layer with desired index profile can be achieved. Other deposition processes can also be used to deposit gradient index layer, as long as it can mix multiple material together or has the tunability to adjust the composition or index profile of the gradient index layer. Other deposition processes are, but not limited to, thermal evaporation that thermally evaporate two or multiple material simultaneously, electron beam evaporation that evaporate two or multiple material simultaneously using e-beam evaporator, molecular beam epitaxy, chemical vapor deposition, etc. The gradient index layer can also be a composite layer consisting of more than two materials.
For example, two method may be used for gradient index deposition. The first is the co-deposition process, which can be co-sputtering, co-evaporation, and any other co-deposition process. The second is to use a stack of engineered multiple layers with each layer having very small thickness, such as <50 nm. The effective refractive index of the stacked multiple layers can form a gradient index profile as designed.
nh is the index at the end with higher index value, which should be nZrO2. nl is the index at the end with lower index value, which is nSiO2. H is the total thickness of the gradient index layer. x is the location of the index, n(x), to be calculated, with x=0, n(0)=nh=nZrO2, and x=H, n(H)=nl=nSiO2. The simulation shows average reflectivity is below 5% over the spectral range from 330 nm to 1800 nm at normal incident. At 45° incident angle, its average reflectivity is almost the same and below 5% over the whole spectra from 330 nm to 1800 nm.
The gradient index layer 250 in
Also, the high index layer in the anti-reflection layer can consist of multiple layers. For example,
The graded index layer can also be achieved using a stack of multiple discrete layers with large index difference. For example,
After the anti-reflection coating deposition, the photovoltaic device will be encapsulated using an encapsulant, and a cover glass can be attached to the photovoltaic device using an encapsulant, such as shown in
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Furthermore, although elements of the invention may be described or claimed in the singular, reference to an element in the singular is not intended to mean “one and only one” unless explicitly so stated, but shall mean “one or more”. Additionally, ordinarily skilled artisans will recognize that operational sequences must be set forth in some specific order for the purpose of explanation and claiming, but the present invention contemplates various changes beyond such specific order.
This claims priority to provisional U.S. patent application Ser. No. 61/737,101, filed Dec. 14, 2012, the entirety of which is incorporated herein by this reference thereto.
This invention was made with government support contract number FA9453-12-M-0355 awarded by Air Force Research Laboratory. The Government has certain rights in the invention.
Number | Date | Country | |
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61737101 | Dec 2012 | US |