Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/70—Surface textures, e.g. pyramid structures
  • H10F77/707—Surface textures, e.g. pyramid structures of the substrates or of layers on substrates, e.g. textured ITO layer on a glass substrate
• • 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 present invention relates to etched substrates and processes for making etched substrates.
• the present invention also relates to solar cells incorporating such substrates.
• Solar cells are increasingly becoming a more desirable form of energy production.
• a solar cell operates by converting absorbed photons into electrical current. Therefore, in order to operate at maximum efficiency, a solar cell should absorb as many useful photons as possible.
• more than 35% of the light incident on the cells is reflected from the surface.
• manufacturers have developed various antireflection coatings (ARCs), such as quarter-wavelength silicon nitride (Si 3 N 4 ) thin films deposited by plasma-enhanced chemical vapor deposition.
• Si 3 N 4 ARCs are highly wavelength dependent, and when they are designed to exhibit low reflectivity at wavelengths around 600nm, the reflectivity increases to more than 10% for other relevant wavelengths.
• the present description relates to a method of texturing a substrate.
• the method includes the steps of coating a layer of particles on a top surface of the substrate, modifying the particles, and etching the substrate using the modified particles as an etch mask.
• the present invention relates to a different method of texturing a substrate.
• the method includes the steps of coating a layer of particles on a top surface of the substrate and coating over the layer of particles with a high index layer.
• FIG. 1 is a flow chart representing an exemplary substrate etching process.
• FIG. 2A-C is a schematic diagram of an exemplary substrate etching process.
• FIG. 3A-D is a schematic diagram of exemplary substrate reflow etching processes.
• FIG. 4 is a schematic diagram of an exemplary reflow etching process.
• FIG. 5 is an SEM image of particles coated on an Si substrate by dip-coating.
• FIGs. 6 is a SEM images of etched substrate using melted particles as an etch mask in an etching solution.
• FIGs. 7A-D are SEM images of structures etched using melted particles as an etch mask in an etching solution for various etch times.
• FIG. 8 displays reflection spectra of several structures etched using melted particles as an etch mask for various etch times.
• FIG. 9 is a SEM image of "close-packed” melted particles.
• FIG. lOA-C are SEM images of particles coated with a high-index layer.
• the present description relates to textured substrates and processes for making textured substrates.
• the methods and articles described herein may be particularly useful for preparing roughened surfaces for light absorptive substrates, such as solar cells.
• the methods and articles described herein are useful, however, for any situation in which a roughened surface is desired.
• the present description provides a means of reducing cost and improving both manufacturing and performance efficiency for solar cells.
• the present description relates to a method of texturing a substrate including the steps of coating a layer of particles on a top surface of the substrate, modifying the particles, and etching the substrate using the modified particles as an etch mask.
• Fig. 1 provides a flow chart of an exemplary substrate etching process that includes the above steps as well as other optional steps. It is to be understood that the process may be carried out sequentially, but may also be performed in another sequence.
• Modifying the particles may generally include melting or "reflowing" of the particles. Melting (reflowing) is performed to increase the area of contact between at least some of the particles and the substrate. Furthermore, reflowing improves the adhesion between the two which can reduce or prevent undercutting (of the etch mask) during the etching.
• the first step in the exemplary process is coating a layer of particles 310 on a top surface 315 of a chosen substrate 320.
• the layer of particles 310 may contain any particle materials capable of being melted and serving as an etch mask.
• the particles may be silica, low-melting temperature inorganic glass, metal (such as gold, silver, zinc, indium, tin, lead, bismuth, or cadmium), polystyrene, polymethylmethacrylate) or any thermoplastic polymer, or combinations thereof.
• Polymeric particles may be, for instance, a polystyrene co-polymer comprising amino groups, a polymethylmethacrylate) copolymer comprising hydroxyl groups, an epoxy- type polymer, an aldehyde-type polymer, a methyl chloride-type polymer, or a carboxylic acid and/or amino group containing polymer (e.g., an amino acid-type polymer).
• an appropriate particle may be guided, for instance, by considering the appropriate size and/or size range, adhesive properties, thermal properties, wetting, and etch rates of potential particles.
• the particle size is selected to correspond to the depth of desired etched features.
• the particles and/or the substrate are selected by the ease of modifying the particles. For instance, in the case where the modification of the particles consists of melting them, the time and temperature required to reflow the particles must be compared to time and temperature exposure that would damage the substrate. The particles should reflow at a temperature that preferably does not lead to melting or distorting the substrate. Further, the particles should reflow at a temperature that avoids heating the substrate above any temperature that would damage any device structures that have previously been fabricated on the substrate. These temperature considerations tend to drive the particle materials choice towards thermoplastic polymers, low-melting-temperature glass, or low melting point metals.
• Exemplary metals include gold, silver, zinc, indium, tin, lead, bismuth, or cadmium.
• Thermoplastic polymers may also be used, as they allow for reflow without damaging many substrate materials, which cannot tolerate temperatures higher than a 200-300°C.
• Dispersions of masking particles may optionally also have smaller inorganic particles added; these can be used to control the dispersion of the larger particles, wetting, or the etch rate.
• Also to be considered when selecting a particle-substrate combination is the wetting of the substrate by the melted particle.
• the particles to make good mask layers for wet etching processes they must adhere well to the substrate. This may be influenced by the relative surface energies of the particle and substrate.
• etch rate of a particle relative to that of the substrate, during the etching step, via whatever process is being used (that is, etching selectivity). In order to etch sufficiently deep features, it may be desirable for the reflowed particles to etch much more slowly than the substrate.
• Non-uniform features can be obtained by using a distribution of particle sizes, by relying on natural statistical variations in particle spacing (for sparse layers) or by relying on the fact that sparsely-coated (e.g., sub-monolayer) layers tend to show clumping which, after melting, would produce islands of variable size.
• sparsely-coated (e.g., sub-monolayer) layers tend to show clumping which, after melting, would produce islands of variable size.
• Using different materials with different etch rates may also produce variable etching profiles, which may or may not be desirable.
• the particles may be any size appropriate, taking into account, for instance, dispersion capabilities, surface identity, particle identity, the size of features desired, the etch method to be used, and the like. Particle sizes may range, for instance, from 50nm to 10 ⁇ .
• the particles may be dispersed in a solvent capable of providing a relatively uniform coating of the particles on a substrate (unless non-uniform features are desired, in which case a different solvent system should be considered).
• the solvent may be selected from water or an appropriately solvating organic solution.
• the particles when the particles are polystyrene, the solvent may be selected from an aliphatic alcohol, water, or a combination thereof.
• the particles are polymethylmethacrylate
• the solvent may be selected from an aliphatic alcohol, water, or a combination thereof.
• optical properties of the particles may be taken into account.
• particles may not be etched completely away and may remain adhered to the substrate. In some cases a separate layer may also be coated over the remaining particles. This will be discussed further below.
• the transparency or opaqueness of the particles may be taken into account. Further the index of refraction and any absorptive or reflective properties may be taken into account such that the particle serves a suitable purpose.
• the substrate described herein may be any substrate capable of being etched.
• the substrate is light absorbing.
• the substrate may be used for the purpose of a semiconductor solar cell.
• the substrate may be a semiconducting material forming the solar cell, or a transparent optical glass such as silica or borosilicate, that will form a window above the semiconductor solar cells.
• a transparent optical glass such as silica or borosilicate
• the substrate may be particularly useful for the substrate to be formed from a crystalline material. Examples of especially desirable crystalline materials include silicon, gallium arsenide, copper indium diselenide, or cadmium telluride. Any other suitable solar cell materials are also contemplated for use as a substrate.
• the particles described herein may be coated by any method capable of applying a layer of particles on the surface of the substrate.
• such coating methods provide a substantially mono-layer of particles, that is, a layer which is essentially free of regions having more than one layer of particles.
• the mono-layer may be close-packed, where the space between the particles is minimized.
• the projection of close packed particles onto the substrate surface covers - 91% of the surface.
• the percentage coverage will vary.
• the layer may cover at least 50% of the substrate surface. In other embodiments the layer may cover at least 60% of the substrate surface.
• the layer may cover at least 70%, 80% or 90% of the substrate surface.
• a "close-packed" monolayer may be understood as a layer that covers at least 70% of the substrate surface.
• a better understanding a "close- packed" monolayer is defined as may be achieved by reference to Fig. 9. This figure displays an SEM image of one contemplated embodiment of a layer of particles in the present description.
• Suitable methods of coating the particles onto the substrate include, but are not limited to, dip coating, spin coating, bar coating, roll coating, knife coating, spray coating, vertical evaporation, convective assembly/deposition, Langmuir-Blodgett assembly, chemical or electrochemical coating, or electrostatically driven coating.
• a coating method one of skill in the art will consider such factors as the size of the substrate (e.g., the surface area); whether the article is a flexible web, in particular if it is to be processed in a roll-to-roll continuous format; the coating uniformity required; and the nature of the solvent used to suspend the particles.
• the coating solution may include a surfactant for purposes of dispersion.
• the particles are part of a solution that is ultimately coated onto the substrate, and a surfactant may be added to properly disperse the particles.
• Surfactants may be selected based upon their dispersing ability in the solvent, the surface properties of the particles, the temperatures to which they will be exposed, the ability of a surfactant to be removed from a surface (by rinsing, etching, or some other method), and the chemical and thermal stability of the surfactant.
• surfactants of each type include (a) ionic (i) anionic
• PFOA perfluorooctanoate
• PFOS perfluorooctanesulfonate
• SDS sodium dodecyl sulfate
• sodium laureth sulfate also known as sodium lauryl ether sulfate (SLES)
• alkyl benzene sulfonate and, generally, soaps or fatty acid salts
• cationic e.g., based on quaternary ammonium cations
• cetyl trimethylammonium bromide cetyl trimethylammonium bromide
• cetylpyridinium chloride (so-called CPC), polyethoxylated tallow amine (so-called POEA), benzalkonium chloride (so-called BAC), and benzethonium chloride (so-called BZT); and (iii) Zwitterionic (also known as amphoteric): dodecyl betaine, cocamidopropyl betaine, and Coco ampho glycinate
• nonionic alkyl poly(ethylene oxide), alkylphenol poly(ethylene oxide), copolymers of poly(ethylene oxide) and poly(propylene oxide) (commercially known as poloxamers or poloxamines), alkyl polyglucosides (including, for instance, octyl glucoside and decyl maltoside), fatty alcohols (including, for instance, cetyl alcohol and o
• the next step is to modify the particles 310 resulting in particles 312.
• the modification of the particles may include the steps of melting the particles (or "reflowing" the particles), shrinking the particles, or both.
• a better understanding of this step is shown in Fig. 2A and 2B.
• the step from Fig. 2A to 2B illustrates melting the particles 210 onto the substrate 220 such that some of the melted particles coalesce, and coating elements 212 are created with increased contact area and improved adhesion.
• the particles When melting the particles, one of skill in the art will understand that the particles should be heated, for instance, above their melting point, or sufficiently above their glass transition temperature (i.e., Tg) such that they reflow during the allotted process time, but without undesirable decomposition, evaporation, or reaction with the substrate.
• Tg glass transition temperature
• Tg glass transition temperature
• Techniques potentially useful for melting the particles while imparting a minimum heating to the substrate include infrared radiant heating, flash heating, or exposure to optical radiation (e.g., from a laser) of a wavelength strongly absorbed by the particles but not the substrate.
• the particles may be modified by being "shrunk" either instead of, before, after, or contemporaneously with melting the particles.
• the shrinking step can involve reactive-ion-etching or oxygen plasma etching the particle layer.
• Oxygen plasma etching produces energized radicals and ions at the surface of the substrate capable of etching equally from all angles (isotropically).
• the process generally can be employed at fairly high pressures (e.g. from 0.1 Torr to 1.0 Torr).
• the process of reactive-ion-etching is a comparable process to oxygen plasma etching except that the etching occurs at lower pressures (e.g.
• the particles are reduced in size from different angles. In other words, the height of the particles (from the substrate to the top of the particle) not only decreases, the side-to-side distance (or width) also decreases. The result is that the shrunken particles do not cover as much surface area of the substrate.
• the reactive-ion-etching or oxygen plasma etching step may also be performed under such conditions that the particles contemporaneously melt to the substrate top surface while being shrunk.
• the particles may be first modified by being shrunk, followed by a second modification of melting. Conversely, the particles may be melted before being shrunk.
• shrinking step alone more surface area of the substrate top surface will be left uncovered (or unmasked). This may be desirable in certain applications.
• a shrinking step followed by a melting step may leave more surface area unmasked than a melting step alone, depending on how much the particles spread and wet the substrate surface during the melt. It is also important to note that if the particles of uniform size form a close-packed pattern on the substrate, and then the particles are shrunk so they no longer are in contact, the periodicity and fill factor (ratio of feature size to spacing) of the pattern may be controlled independently.
• the next step is etching the substrate using the modified particles as an etch mask resulting in depressions between the masked regions.
• an appropriate etching technique one should consider the etch rate ratio between the particles and the substrate, the degree of etching anisotropy required (that is, the aspect ratio of the desired structure), and the potential for damage to the substrate during the process.
• appropriate etching techniques may include dry etching, wet etching, or a combination of the two. Wet etching techniques may be most appropriate for etching structures into solar cell substrates given the cost and simplicity of such processes in manufacturing.
• Wet etching may be accomplished, for instance, by immersion in well- known acidic or basic etchants, or solvents. Dry etching and wet etching may be used in combination with one another in certain embodiments. Appropriate dry etching methods may include sputter etching, reactive ion etching or ion beam etching, amongst others. This may be particularly desirable where the goal is to create structures in the substrate with high aspect ratios.
• modifying the particles include both a greater adherence to the substrate, as well as the ability to cover more surface of the substrate (without as many gaps), or to independently set the size and spacing of the masking elements. Without the modification of the particles, wet etchants typically penetrate under the particles and degrade the ability of the particles to mask the substrate effectively. This may be understood by reference to Figs. 3 A and 3B. As a general comment, it should be understood that Fig. 3A-3D shows the process as accomplished in two manners. The first involves the steps in Fig. 3A, 3B and then 3C. The second involves the steps in Fig. 3A, 3B and then 3D. The final step in both processes will be explained further below.
• Fig 3A illustrates the particles 210 before any melting/reflow. It is noted that there exists a good deal of surface area on the substrate 220 that is under the particles, but is not in contact with the particles 210. This surface area may be easily penetrated by etchant, which is undesirable in many circumstances. For example, while the substrate area immediately below the contact points with particles 210 would be masked, a great deal of etchant would freely contact the substrate and etch most of the surface. In contrast, Fig. 3B illustrates the effect that melting the particles into melted particles 212 has. It is easily seen that a great deal more of the surface area is "masked" resulting in more effective masking for the etching process. This is the greatest benefit of the melting process.
• surface features are provided. Such surface features can be any appropriate shape for a roughened surface.
• an anisotropic etchant generally, the etching will occur in the substrate according to the material structure of the substrate. For instance, in a crystalline material, such as silicon, an anisotropic wet etchant will generally etch at a greater rate along one of the crystalline planes. This generally results in the formation of prism structures. This effect may be better understood by reference to Figs. 3B and 3D. In this case, despite the fact that the melted particles have a rounded shape, the etchant etches through substrate 220 according to the crystalline structure. Therefore, prismatic surface features 217 are created.
• etched substrate structures Any number of etched substrate structures are contemplated.
• surface structures or features may be conical, pyramidal, prismatic, hemispheric, cylindrical, truncated versions of the above, and also any other sort of randomly shaped
• the etching may occur such that the main structures created are actually large holes into the substrate with micropeaks dispersed throughout the substrate between the holes.
• Figs. 2A-2C, 3A,B&C and 3A,B&D show the process as performed in three different manners.
• Fig. 2A-2C displays a schematic flow chart of a first process.
• the monolayer of particles 210 is layered onto the substrate 220 such that the particles are spaced apart.
• the distribution of the particles results in various sized and distributed melted particles 212.
• the melted particles widen at the base such that more surface area of the substrate 220 is covered.
• wet etching is performed with the different shaped melted particles 212 used as a mask.
• the result is a variety of differently shaped structures 214. These shapes may be described as random and based upon how the particles disperse on the substrate 220.
• the layer of particles 210 may be closely packed as shown in the schematic diagram for Figs. 3A-3D.
• melting the particles results in a tightly packed distribution of melted particles 212, such that there is very little surface area of the substrate 220 that is not covered by the particles 212.
• the manner of etching may then determine the sort of structures created on the substrate 220.
• the substrate is isotropically etched resulting in rounded concave depressions 216. Between the depressions are microstructures 218.
• Fig. 3D illustrates the result of an anisotropic etch, such that the structures 217 are formed according to the crystalline structure of substrate 220.
• FIG. 4 A process that utilizes reactive-ion-etching or oxygen plasma etching to shrink the particles is illustrated in the schematic diagram of Fig. 4.
• the particles 310 are distributed in a closely packed manner in the layer on the substrate 320 (much as in Fig. 2(B-C)).
• the particles are both melted and etched. This results in the particles 312 being shrunk such that there is more distance between neighboring melted particles.
• the substrate etching step is performed, a great deal more etchant is in contact with the substrate 320 and recessions 316 are formed into the substrate.
• the major structure formed is the recession 316 with micropeaks 318 located between the recessions at the position where the most particle etch mask 312 was present.
• the final product of the process in Fig. 4 may be noted as being similar to that in Fig. 3C.
• Any of the processes from Fig. 2A through Fig. 4 may be effective at reducing reflection at the light absorbing substrate surface.
• the modified particles may optionally be removed.
• the etching will generally result in at least some, if not all, of the particle layer being removed through the etching process. However, some of the particle layer may remain.
• the particle layer may have anti-reflective properties or other desirable properties that would create a desire to leave the particle layer adhered to the substrate for its ultimate use. However, in many embodiments, it will be desirable that remaining particles are removed. Removal of the particles may occur through any number of known processes in the art. For example, the particles may be removed mechanically, by solvent, by further etching, by physical vibration, or any other number of methods.
• one alternative manner of lowering the reflectivity of the light absorbing substrate involves depositing the layer of particles onto the substrate, and potentially modifying the particles, but not etching.
• the layer is covered by another high-index of refraction layer of material.
• the high-index material used for coating may be any number of suitable materials. Particularly useful materials include Si3N4, ZnS, ZnSe, Ti02, Zr02, A1203, Hf02, Ta205, and SiON.
• Fig. lOA-C illustrates one example of such an embodiment. In this figure, 440 nm Si0 2 nanoparticles are coated onto the substrate. No melting occurs.
• the entire surface (of both the substrate and nanoparticles) is coated with a 400nm layer of ZnS by vacuum evaporation from a baffled boat.
• the layer may be of any appropriate thickness, but may be chosen according to the most suitable thickness for heightened light absorption.
• the high-index of refraction layer may be deposited by an appropriate method, such as e-beam evaporation, sputtering, physical vapor deposition, plasma enhanced chemical vapor deposition, chemical vapor deposition, spin- on coating, or any other number of methods. If modification of the particles is desired in this particular process, it again may occur through melting, reactive -ion etching or oxygen plasma etching, or both the melting and etching processes.
• a powder of spherical polymethylmethacrylate) (PMMA) particles with nominal diameter of 0.8 ⁇ (available from Soken Chemical & Engineering Co., Ltd) was dispersed in water to produce suspensions have 12 wt.% by solids content.
• PMMA polymethylmethacrylate
• 0.01% tomadol 25-9 nonionic surfactant (available from Air Product and Chemicals, Inc.) was added to the solution.
• the particle solution was coated on a (100 oriented) silicon wafer substrate by dip coating with a coating speed of 65mm/min. The coated substrate was then heated at 130°C for 1 minute on a hotplate to reflow the particles.
• Fig. 5 provides SEM images of the melted particles coated on the Si showing increased contact area.
• the Si wafer was next isotropically wet-etched. This was performed by immersing the coated Si wafer with the PMMA mask into ⁇ 0 3 :12 ⁇ 2 0: ⁇ 4 ⁇ (25: 12: 1) solution for 3 hours at room temperature without agitation.
• Fig. 6 shows SEM images of the etched Si with the melted PMMA still in place. The etching depth into the Si was approximately 300 nm.
• Example 1 A similar process was used as in Example 1 , except that a number of different samples were immersed into the HN0 3 :12H 2 0:NH 4 F (25:4: 1) wet etchant for different times. Further, after the wet etching, the samples were sonicated in an isopropanol solution for 5 minutes in order to remove the residual PMMA particles. Figs. 7A-D displays the results for etch times of 5 minutes (Fig. 7A), 8 minutes (Fig. 7B), 10 minutes (Fig. 7C), and 13 minutes (Fig. 7D). Pyramidal structures were achieved in spite of the isotropic nature of the wet etchant. Hence, use of an isotropic etchant can result in asymmetric structures, indicating that the process described herein is not limited to single-crystalline silicon, but may also be applied to amorphous silicon, polycrystalline silicon, and potentially other solar cells.
• Fig. 8 displays the results.
• the graph provides the reflection spectra of the structures etched for the designated times using melted 0.8 ⁇ PMMA particles as etch masks. An etching time of 8 minutes showed the best
• the diffuse reflectance of the 8-minute etched sample ranged from 24% at 400nm wavelength, to 18% at 800nm.
• the silicon wafer with no etching performed had very high reflectivity, ranging from approximately 48% to approximately 33% over the same wavelength range.

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• 2010
  • 2010-11-08 JP JP2012538866A patent/JP5690348B2/ja not_active Expired - Fee Related
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