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
  • H10F71/00—Manufacture or treatment of devices covered by this subclass
  • H10F71/121—The active layers comprising only Group IV materials
• • 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
  • H10F77/703—Surface textures, e.g. pyramid structures of the semiconductor bodies, e.g. textured active layers
• • 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
  • Y02E10/547—Monocrystalline silicon PV cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• etching can be used on a smooth or polished silicon surface to produce rough surfaces with bumps and pits having typical sizes of several or even ten micrometers, and these rough surfaces exhibit reduced reflectivity due to the reflection and absorption characteristics.
• anisotropic etching of silicon in KOH/C 2 H 5 OH mixtures produces densely packed pyramids that appear black.
• etching has been typically limited to single crystalline silicon with ⁇ 1,0,0,> surface orientation, and solar cell design is made more complex by the large penetration pyramids.
• This texturing also has reflectivity that increases rapidly with the angle of light incidence.
• a fine surface texturing on the nanometer scale may be utilized to control reflectivity of silicon surfaces.
• a textured surface with features smaller than the wavelength of light is an effective medium for controlling reflectivity, and testing with regard to solar cell applications has shown that a fine texture that is only about 300 to 500 nanometers in depth and provides a gradual grading of the silicon density and of the index of refraction from the surface to the bulk that is adequate to suppress reflectivity of a silicon surface in the usable spectral range of photon energies above the band gap.
• Such a textured surface may be thought of as a subwavelength structured surface that behaves itself as an anti-reflective surface, with the gradually tapered density of the anti- reflective surface suppressing reflection over a wide spectral bandwidth and over a large incidence angle of the incoming light.
• One group of researchers has developed a method of nanoscale texturing of silicon surfaces that utilizes wet chemical etching to reduce optical losses due to surface reflection to below 5 percent at all solar wavelengths for crystalline silicon.
• the texturing of the silicon surfaces involves black etching in a three step process.
• a discontinuous gold (Au) layer with a thickness of about 1 to 2 nanometers is deposited by thermal evaporation or other deposition techniques. This initial metal coating is made up of Au clusters or islands that in later steps provide a catalytic action or function.
• a wet chemical etching of the silicon material is performed using an aqueous solution of hydrofluoric acid (HF) and hydrogen peroxide (H 2 O 2 ).
• HF hydrofluoric acid
• H 2 O 2 hydrogen peroxide
• the deposition of gold may be cost prohibitive (e.g., undesirably increase the production cost or price of solar cells or other optoelectronic devices).
• the costs include material costs associated with deposition of the thin layers of pure gold and also include high capital equipment costs associated with the purchase, operation, and maintenance of vacuum deposition and other equipment used in the metallic deposition steps of the process.
• the process also requires two or more steps to provide the etching or texturing, which increases manufacturing complexity and fabrication times.
• inexpensive, less complex e.g., processes with fewer steps and less equipment
• efficient techniques for etching silicon surfaces including ways to facilitate black etching of silicon wafers.
• etching Prior silicon etching research has shown techniques for producing highly non-reflective or "black” silicon surfaces, but these techniques have generally called for evaporating or depositing a thin layer of expensive metals or islands of such metals, such as a 1 to 3 nanometer (nm) layer of gold, upon the silicon surfaces. Then, etching would be performed in a separate step such as by placing the coated silicon surface in an aqueous solution of hydrofluoric acid (HF) and hydrogen peroxide (3 ⁇ 4(3 ⁇ 4) to texture the surface to make a density gradient at the surface with length scales that are less than the wavelength of light.
• HF hydrofluoric acid
• 3 ⁇ 4(3 ⁇ 4) hydrogen peroxide
• the etching process provides molecular or ionic species containing a catalytic metal, such as gold, silver, a transition metal, or the like, in the etching solution along with oxidant-etchant solution components such as an etching agent and an oxidizing agent.
• a catalytic metal such as gold, silver, a transition metal, or the like
• the catalytic metal molecule or ion acts to catalyze the reaction caused in part by the oxidant-etchant solution (e.g., HF and 3 ⁇ 4(3 ⁇ 4), and the resulting etching is very uniform and produces a rapid formation of a non- reflective or a black surface layer on the silicon surface.
• stirring or agitation is also performed to facilitate the texturing, e.g., ultrasonic agitation or sonication is used to stir the etching solution.
• a silicon wafer or a substrate with a silicon surface is placed in the etching solution containing the ionic metal solution and the oxidant-etchant solution, and the etching solution is agitated or stirred for an etch period (e.g., up to about 4 minutes or more using ultrasonic agitation, such as 125 W in a total solution of 10 ml for a 1 square inch wafer).
• the result of such etching is a textured surface with extremely low reflectivity across the broad spectrum of wavelengths useful for solar energy applications.
• the silicon etching may be used on a variety of surface types such as ⁇ 1,0,0>, ⁇ 1,1, 1>, ⁇ 3, 1,1>, and other surfaces of silicon, and on multi-crystalline wafers with grains that may expose silicon surfaces to the etching solution.
• Post etching treatment may be performed with a stripping solution (e.g., I2/KI or the like) to remove residual catalytic metals such as gold from the surface, and this typically has not detrimentally affected reflectivity.
• a stripping solution e.g., I2/KI or the like
• the method continues with etching the silicon surface by agitating the etching solution in the vessel such as with ultrasonic agitation for a relatively short time period such as less than about 4 minutes with 30 to 90 seconds being adequate to achieve a desired surface roughening in some cases.
• the catalytic solution in the presence of the oxidant-etchant solution provides or releases a plurality of metal particles.
• the catalytic solution is a dilute solution of HAuC
• the metal particles are gold particles and/or nanoparticles.
• the catalytic solution comprises a dilute solution of AgF and the metal particles are silver particles and/or nanoparticles.
• the molecules or ionic species may directly affect the catalysis.
• the metal particles are transition metal particles, and, in some applications, the etching is performed until the etched silicon surface has a reflectivity of less than about 10 percent in a wavelength range of about 350 to 1000 nanometers.
• etching methods may utilize copper (Cu) nanoparticles to etch or produce nanoporous silicon (Si) that results in anti-reflection, and such etching may be thought of as Cu-assisted etching.
• Cu copper
• Si nanoporous silicon
• the applicants' work with such Cu- assisted etching has been demonstrated to produce a textured or nanoporous surface on a Si substrate with significantly reduced reflection such as about 3% reflectivity of nanoporous Si using Cu as the catalyst.
• a solar cell can be fabricated using such Cu-assisted nanoporous Si to achieve a conversion efficiency of at least about 17%, with other desirable solar cell characteristics such as, but not limited to, a short-circuit current density, J sc , of 36.6 mA/cm 2 , an open-circuit voltage, V oc , of 616 mV, and a fill-factor, FF, of 75.4%.
• Cu-assisted etching with p above about 70 percent, HF volume concentration of 10 percent or higher (in some cases), and high concentrations of HF and 3 ⁇ 4(3 ⁇ 4 with little dilution in water, results in a spectrum-weighted reflection of around 3 percent with p at or above 74 percent.
• an Au-assisted etch may require a p around 36 percent and Ag-assisted etch may require a p around 92 percent.
• Cu-assisted etching is also improved or facilitated by use of concentrated HF and H2O2 to ensure that the etch mixture is not highly diluted in water. Further, it is typically desirable to control the ratio of Cu nanoparticle to spacing (size/spacing) provided on the Si surface prior to the etching step.
• Cu nanoparticle size and spacing determines the configuration of the nanoporous Si structure produced with the Cu-assisted etching and the resulting low reflectivity.
• the Cu nanoparticle size was chosen to be at least about 20 nm, and the spacing was chosen to be at least about 5 nm (e.g., a size to space ratio of at least about 4) to achieve a useful AR coating on a Si substrate.
• a solar cell can readily be fabricated using a Cu-assisted nanoporous black Si etch to prepare the silicon substrate.
• high efficiency solar cells may be obtained through the use of Cu-based nanoporous black silicon that includes a diffused junction emitter.
• Cu is significantly cheaper than Ag and Au. Additionally, Cu is a metal that is already used extensively in commercial Si microfabrication facilities such that its further use in the etching processes described herein is likely compatible with existing industrial technologies. A nitric acid wash may be used to readily dissolve away the copper nanoparticles prior to use of the textured Si substrate in a solar cell.
• Cu impurities within the silicon has proven to be less detrimental to the Si solar cell performance than Au and Ag such that post-etching processing to remove all residual Cu impurities, introduced by etching, from the nanoporous Si surface is not as critical to achieving a desirable Si substrate as is the removal of Au and Ag impurities.
• Some implementations may use HF as the etching agent and one of H2O2, O3, CO2, K 2 Cr 2 0 7 , Cr0 3 , KI0 3 , KBr0 3 , NaN0 3 , HN0 3 , and KMn0 4 .
• the silicon oxidizing agent may be H2O2, and desirable texturing is achieved when the etching solution has a value of rho (p) of at least about 70 percent, with p being defined as a molar concentration of HF divided by a sum of the molar concentrations of HF and 3 ⁇ 4(3 ⁇ 4.
• the etching solution is heated to a temperature in the range of 30 to 50 °C, and the etching may be performed for a time period of a length chosen such that the etching creates a plurality of tunnels in the silicon surface having a depth greater than about 200 nanometers (and typically less than about 500 nanometers).
• FIG. 1 illustrates in schematic and/or functional block form of an etching system for use in texturing silicon surfaces using catalytic solutions, with catalytic metal molecules or ionic species of catalytic material, and a oxidant-etchant solution;
• FIG. 2 illustrates a silicon wafer or substrate after etching with an etching solution including catalytic and oxidant-etchant solutions showing a textured silicon surface with a plurality of etched tunnels or pits;
• FIG. 3 is a flow chart of an exemplary texturing or etching process using catalytic solution combined with a oxidant-etchant solution to texture a silicon surface;
• Fig. 4 is a sectional view of a solar cell fabricated with a silicon layer textured with catalytic metals such as with the system of Fig. 1 and/or the process of Fig. 3;
• Figs. 5-7 are graphs illustrating reduced reflectance levels achieved in experiments or tests performed on silicon surfaces using etching solutions produced from a volume of catalytic solution and a volume of oxidant-etchant solution;
• Fig. 8 is a graph illustrating changes in reflection with increasing HF for a Si-surface etched after deposition of Cu nanoparticles
• Fig. 9 is a graph showing reflection values over a range of p values for an etching solution used in a Cu-assisted etching process described herein;
• etching or texturing silicon surfaces such as to create a surface of tapered density to significantly reduce reflectivity (e.g., to create an anti-reflective surface on a silicon wafer that may be used in a solar cell).
• a source of a catalytic metal to provide gold or silver nanoparticles to assist in the etching or texturing process with reference to Figures 1-7.
• Cu nanoparticles were electrolessly deposited for 1-minute on HF cleaned planar (100) p-type float-zone (FZ) Si substrates (e.g., using a recipe such that shown by J-P. Lee et al, Langmuir Vol. 27, pages 809-814, 201 1).
• the Cu nanoparticle covered samples were then placed in a H 0 2 :HF:H 2 0 solution for 5 minutes at 50 °C with continuous mixing of the solution.
• the spectrum weight reflection, R ave remained in the range of 3 to 4%.
• This reflectivity result provides a relatively good anti-reflection surface (or Si substrate) and is comparable to what is obtained using Ag or Au catalysts.
• SEM scanning electron microscopy
• the etching methods include positioning a silicon surface in a volume of etching solution that is made up of an oxidant- etchant solution (e.g., an aqueous solution of an etching agent and an oxidizing agent such as HF and H 0 2 ) and a source of a molecule or an ionic species that contains a catalytic metal (e.g., an acid such as chlorauric acid in aqueous solution to provide gold in the etching solution or AgF in aqueous solution to provide silver and so on).
• an oxidant- etchant solution e.g., an aqueous solution of an etching agent and an oxidizing agent such as HF and H 0 2
• a source of a molecule or an ionic species that contains a catalytic metal e.g., an acid such as chlorauric acid in aqueous solution to provide gold in the etching solution or AgF in aqueous solution to provide silver and so on.
• the bath or volume of etching solution is stirred or agitated for a period of time (or an etch time) to achieve a desired amount/depth of texturing of the silicon surface, which may be thought of as forming a non- reflective layer or textured layer on the silicon surface.
• the gold or other metal catalyst is then cleaned or stripped from the silicon surface, and then the silicon surface or a wafer or substrate with such surface may be used to fabricate a device such as a solar cell, a biomedical device, an optoelectrical component, or the like.
• the etching method described herein provides a solution-based approach to etching silicon that may use inexpensive chemicals (e.g., a reaction based on catalytic quantities of ionic or molecular-compound forms of gold, platinum, silver, or other catalytic metals in an oxidant-etchant solution is very inexpensive to create).
• the etching method is "one-step” rather than multi-step in the sense that etching occurs in the presence of the oxidant-etchant solution and the metal ionic or molecular solution as these experience ultrasonic or other agitation.
• the etching method is advantageous in part because of its simplicity and speed, with etch times being relatively short and not requiring deposition/coating pre-etching.
• the etching method is also desirable as it produces textured silicon surfaces with low reflectivity over a broad spectrum, and these non-reflective layers or textured silicon surfaces have a wide acceptance angle of anti-reflection. Further, the etching method(s) is applicable to nearly all surfaces of silicon including multi-crystalline silicon. As will be seen, the resulting silicon surfaces are likely to be highly desirable in the photovoltaic or solar cell industry.
• the etching method has been used on ⁇ 1,0,0> crystal silicon wafers with the reflectivity ranging from about 0.3 % at a wavelength of 400 nm to about 2.5 % at a wavelength of 1000 nm, with most of the usable solar spectrum below 1 % reflectivity.
• the catalytic solution included AgF the etching solution technique was able to obtain reflection of less than about 5 % on 100 crystal silicon wafers.
• catalytic solutions or sources of catalytic metals may be used to practice the etching process.
• One embodiment uses a catalytic solution chosen to provide molecular or ionic species of gold (e.g., chlorauric acid (HAuCl 4 ) in aqueous solution) while another exemplary embodiment uses a catalytic solution (e.g., a solution with AgF) to provide molecular or ionic species of silver.
• a catalytic solution e.g., a solution with AgF
• the molecular or ionic species or a catalytic solution containing such catalysts is mixed with an etchant such as HF or the like and also with an oxidizing agent such as H2O2 or the like.
• the catalytic solution may be chosen to provide molecules and/or ionic species of other metals such as transition and/or noble metals in the etching solution such as platinum or the like, and this may be useful in further reducing the cost of etching and may be desirable as some of these metals may have less deleterious impurities in silicon than gold.
• other metals such as transition and/or noble metals in the etching solution such as platinum or the like
• the silicon surface is a polished surface, but in some cases, the etching techniques may be performed in combination with other anti-reflection techniques.
• the silicon surface may be an anisotropically pyramid-textured Si ⁇ 1,0,0> surface (or other textured Si surface) that is then treated with a one step etching process by placing the Si ⁇ 1,0,0> surface (or a substrate/wafer/device with the Si surface/layer) in an etching solution including a catalytic solution (with a metal-containing molecule or an ionic species of a catalytic metal), an etching agent, and an oxidizing agent. Used independently or with other surfacing processes, the etching solution is stirred or agitated for a period of time (e.g., a predetermined etch time) such as with ultrasonic agitation or sonication.
• a period of time e.g., a predetermined etch time
• exemplary recipes e.g., proportions of and particular types of catalytic solutions and the catalytic metals these solutions may provide, etching agents, oxidizing agents, silicon surfaces, agitation methods, etching times, and the like), processes, and the like to achieve useful results particularly with an eye toward reducing or nearly eliminating reflectance to increase efficiency of a solar cell (e.g., increase photon absorption in photovoltaic devices of silicon).
• Figure 1 illustrates a texturing or etching system 100 of one embodiment.
• the system 100 includes a source of or quantity of wafers, substrates, or devices 110 with silicon surfaces. These may be Si wafers that are to be used in solar cells, optoelectronics, or other products.
• the silicon surface 116 on silicon sample 112 may be mono-crystalline, multi-crystalline, amorphous, or the like, and the type of doping may be varied such as to be n or p-type doping of varying levels (such as from about 0.25 ohm-cm to about 50 ohm-cm or the like).
• the wafer, substrate, or device 110 may have one silicon surface or two or more such surfaces that will be etched during operation of system 100.
• the system 100 does not require a metal deposition station, but, instead, the system 100 includes an etching assembly 120 with a wet etching vessel or container 122. During operation, one or more of the Si wafers 110 or Si layers on substrate 112 are placed into the vessel 122 before or after adding a volume of an etching solution 124. In Figure 1, a single substrate 112 is shown in the vessel with an exposed silicon surface 116 but, of course, a plurality of such surfaces 116 may be etched concurrently. [0043] The assembly 120 includes a mechanism 126 for agitating or stirring the solution 124 initially and/or during etching.
• the mechanism 126 may be a mechanical or magnetic -based stirring device while in some cases enhanced or more repeatable results are achieved with an ultrasonic agitator for stirring/agitating reactants or solutions such as etching solution 124 by sonication.
• the assembly 120 may include a heater 128 to maintain or raise the temperature of the etching solution 124 within one or more desired temperature ranges to facilitate etching of surface 116.
• a temperature gauge or thermometer 130 may be provided to monitor the temperature of the solution (and, optionally, provide control feedback signals to heater 128), and a timer 134 may be disclosed to provide a visual and/or audio indicator to an operator of the assembly 120 regarding an etching or stripping step.
• the system 100 further includes a catalytic solution 140 that provides a supply or source of a catalytic metal such as a metal containing molecules or ionic species of a catalytic metal.
• a catalytic metal such as a metal containing molecules or ionic species of a catalytic metal.
• This source provides a quantity of catalyst for the etching solution 124 such as a quantity of a transition or noble metal such as gold, silver, platinum, palladium, copper, nickel, cobalt, and the like.
• Good results are typically achieved with solutions containing HAuC , AgF, and the similar acids or materials that release metal-containing molecules or ionic species of such metals when mixed with the oxidant-etchant solution in the etching solution 124 in vessel 122.
• this catalytic solution with a metal catalyst is added to the vessel 122 to make up a portion of the etching solution 124, but, in other cases, the solution (or other source of metal-containing molecules or an ionic species of a catalytic metal) 140 is first added to the oxidant-etchant solution 146 (or to one of its components 142, 144) prior to insertion into the vessel 122 with the Si substrate 112.
• the solution (or other source of metal-containing molecules or an ionic species of a catalytic metal) 140 is first added to the oxidant-etchant solution 146 (or to one of its components 142, 144) prior to insertion into the vessel 122 with the Si substrate 112.
• the system 100 includes a source etching agent 142 and oxidizing agent 144. These are chosen specifically for texturing/etching of silicon, and the etching agent 142 may be HF, N3 ⁇ 4F, or a similar etchant.
• the oxidizing agent may be H2O2 or another agent such as one that has its decomposition catalyzed by the metal provided by catalytic solution 140.
• the oxidizing agent 144 may include H2O2, 0 3 , C0 2 , K 2 Cr 2 0 7 , Cr0 3 , KI0 3 , KBr0 3 , NaN0 3 , HN0 3 , KMn0 4 , or the like or a mixture thereof.
• These agents (or solutions thereof) 142, 144 may be added separately to the vessel 122 to form the etching solution 124 along with the catalytic solution 140 or, as shown, a oxidant-etchant solution 146 may be formed first by combining the etching agent 142 and the oxidizing agent 144 and then putting this solution in the vessel 122.
• the assembly 120 is then operated such as by agitation via mechanism 126 and heating by heater 128 for a time period ("etch time") to texture the surface 116.
• etch time a time period
• the solution 124 is removed (or substrate 112 is moved to another container or vessel for metal stripping), and the remaining metal catalyst is removed as it is likely to present an undesirable impurity in silicon.
• the system 100 includes a source of a metal stripping solution 150 that is added to the vessel 122, and the stripping solution may be stirred or agitated (and, optionally, heated with heater 128) by mechanism 126 until all or substantially all of the metal from solution 140 is removed from surface 116.
• the substrate or wafer 112 may then be used as-is or as a component or layer of a larger device such as a solar cell or photovoltaic device, an optoelectric device, a biomedical device, or the like.
• FIG. 2 illustrates a silicon wafer 200 after treatment of an etching process as described herein.
• the wafer 200 includes an upper surface or Si surface 210 that has been exposed to an etching solution for a period of time or an etch time.
• the Si surface 210 has nanoscale roughening that significantly reduces reflectivity.
• catalytic solutions as described herein is believed to act to produce nanoparticles of gold, silver, or other metal that in situ or in the etching solution (such as 2 to 30 nm gold particles, 2 to 30 nm silver particles, or the like depending on the makeup of the catalytic solution) cause the surface 210 to have a plurality of pits or tunnels 214 where etching has occurred much more rapidly due to the presence of a nanoparticle (not shown in Figure 2).
• Other mechanisms may be fully or partially responsible for the etching results achieved with the use of the catalytic solutions in combination with the oxidant-etchant solution.
• each tunnel 214 includes an opening 216 at the surface 210 with a diameter, Diam Tu nnei, and a depth, D Tu nnei, that is typically less (e.g., up to about 99.91% less) than the thickness, t wa f er , of the wafer 200, about 300 micrometers.
• the tunnel diameters, Diamx unne i may be somewhat larger than the particle size such as about 21 to about 23 nm when 5 to 10 nm nanoparticles are present in the etching solution.
• the tunnel depths, D Tunne i may be selected to provide a desired physical characteristic (e.g., an interference with reflection).
• the tunnel depths, DTunnei may be between about 50 and about 300 nm (e.g., with one test showing tunnels in the 250 to 280 nm depth range being useful).
• a desired depth may be selected or achieved by controlling time and temperature for a particular etching solution.
• the etching processes involving catalytic solutions that provide a source of catalytic metal (and, in some cases, nanoparticles of such metals) are effective in providing a nanoscale roughness or structure with tapered density that is desirable for reducing reflectivity.
• Figure 3 illustrates one embodiment of a solutions-based etching or texturing process 300 for processing a silicon surface to obtain a desired characteristic such as, but not limited to, a tapered surface that reduces reflectance or creates a black surface.
• the process 300 begins at 305 such as with planning or selecting the type of silicon surface to be textured, e.g., a silicon wafer or a substrate or device with a silicon layer and a silicon surface, a particular crystalline surface or makeup, and a particular type of doping.
• Step 305 may also include choosing a recipe or step-by-step design for the texturing or etching of the silicon surface, and this may include choosing a catalytic metal and sources of molecules or ionic species of such a metal, an etching agent for the silicon surface (e.g., HF or the like) and an oxidizing agent (e.g., H2O2, O3, CO2, K 2 Cr 2 0 7 , or the like), the ratio of each of these to provide in the oxidant-etchant solution that includes these two ingredients, the type and amount of agitation/stirring, the desired depth of surface penetration to provide with the etching, and the time and temperature for etching (which, of course, will vary based on the prior decisions/parameters).
• a catalytic metal and sources of molecules or ionic species of such a metal e.g., HF or the like
• an oxidizing agent e.g., H2O2, O3, CO2, K 2 Cr 2 0 7 , or the
• the texturing/etching method 300 continues at 310 with the wafer(s) (or substrates/devices) with the silicon surface being chosen and then positioned into a reaction or etching vessel.
• an oxidant-etchant solution is formed by combining or mixing the chosen etching and oxidizing agents (or solutions thereof), but, in some embodiments, this step is not performed and these two agents are simply added to the vessel concurrently or nearly so.
• the method 300 continues with the performance of steps 330 and 340, which may be performed concurrently or nearly so such as within a preset time period (e.g., less than about 5 minutes or more typically less than about 2 minutes between performance of each step) with either being performed first.
• the oxidant-etchant solution is added or input into the vessel with the silicon surface, and at 340, a catalytic solution is added to the vessel (such as an acid or an aqueous solution of an acid that acts as a source of molecules containing (or ionic species of) gold, silver, platinum, palladium, copper, cobalt, nickel, another noble or transition metal, or another catalytic metal/material).
• a catalytic solution is added to the vessel (such as an acid or an aqueous solution of an acid that acts as a source of molecules containing (or ionic species of) gold, silver, platinum, palladium, copper, cobalt, nickel, another noble or transition metal, or another catalytic metal/material).
• the particles are provided "dry” or in similar form while in other cases metal-containing molecules (or materials that provide such molecules or ionic species in the presence of the oxidant-etchant solution) are contained in deionized water or aqueous solution and a volume of such solution is added to the
• the method 300 includes mixing or agitating the etching solution in the vessel such as with mechanical mixing devices or, more typically, with ultrasonic mixing technologies or sonication.
• the method 300 may optionally include heating the solution in the vessel to a predetermined temperature range (or adding heat to maintain the initial temperatures of the oxidant-etchant solution in a desired temperature range) chosen to hasten etching processes.
• the method 300 may include illuminating the etching solution and/or the wafer or silicon surface with light to facilitate or drive the etching reactions/processes.
• the method 300 involves determining whether a preset etch time has elapsed (e.g., a time determined previously through testing to provide a desired depth or amount of etching based on the silicon surface type, the catalytic metal, and the oxidant-etchant solution composition). If not, the method 300 continues at 350.
• a preset etch time elapsed (e.g., a time determined previously through testing to provide a desired depth or amount of etching based on the silicon surface type, the catalytic metal, and the oxidant-etchant solution composition). If not, the method 300 continues at 350.
• the method 300 includes removing the etch solution from the vessel or removing the Si wafer(s) from the vessel at 376.
• the catalytic metal is removed from the now textured silicon surface such as with use of a stripping solution selected based on the composition of the catalytic solution (e.g., a differing stripping solution may be used for gold, for silver, for platinum, and the like).
• the method 300 may include further processing of the textured wafer to fabricate a device that makes use of the textured/etched silicon surface such as a solar cell, a biomedical device, an optoelectrical device, a consumer electronic device, or the like.
• the method 300 is ended (or repeated by returning to step 305 where the same method may be repeated or changed such as to use one of the differing "recipes" described herein).
• etch a silicon surface As discussed above, one reason it may be desirable to etch a silicon surface according to the processes described herein is to form a silicon substrate for use in forming a silicon- based solar cell with little or no total reflectance (e.g., without the need for application of an
• FIG 4 illustrates a relatively simple solar cell 400.
• the exemplary solar cell 400 includes a silicon substrate 410 with at least an upper surface that has been textured or roughened with a catalytic nanomaterial-based etching process (such as using the system 100 of Figure 1 or the method 300 of Figure 3) as described herein.
• the reflectance of substrate may be controlled to be under about 20 percent, more typically less than about 10 percent, and in many cases in the range of about 0.3 to 2.5 percent or up to about 5 percent or more by such techniques.
• the substrate 410 may be, for example, a Boron-doped, p-type silicon surface or nearly any other silicon surface useful in solar cells.
• the silicon substrate 410 with an etched surface may take many forms such as an edge-defined film fed grown (EFG) silicon wafer, string ribbon silicon, float zone (FZ) silicon, Czochralski (CZ) grown silicon, cast multi-crystalline silicon (mc-Si), a monocrystalline silicon, epitaxially grown silicon layer, or another silicon structure or type.
• EFG edge-defined film fed grown
• FZ float zone
• CZ Czochralski
• mc-Si cast multi-crystalline silicon
• a monocrystalline silicon epitaxially grown silicon layer, or another silicon structure or type.
• formation of a solar cell from a textured/etched silicon wafer may involve the following or other processes known to those skilled in the art.
• Formation of an emitter may involve the diffusion of phosphorus or similar material through the etched surface (e.g., from a spin-on dopant).
• the doping source may be removed by further etching in concentrated HF or the like, and the result of the diffusion may be the formation of w-type regions.
• Surface passivation may be provided by oxidizing (e.g., with (3 ⁇ 4) and annealing (e.g., with N 2 ), which may provide a dry oxide layer with an annealed interface to the silicon to reduce the surface recombination at the heavily doped emitters.
• a back contact may then be formed by removing the passivating oxide from the back surface of the silicon wafer or substrate and then applying a layer of aluminum or other similar metal and a silver or similar metal onto these back surfaces such as by vacuum evaporation or the like.
• a front contract grid may be formed such as by opening an array of slits in the passivating oxide on the front or textured surface side of the wafer/substrate and then covering these slits with Ti or the like such as by vacuum evaporation and lift-off of photoresist.
• the solar cell may be further processed or be assembled with other cells to make solar modules, which in turn may be linked to form photovoltaic arrays.
• the processes described herein are believed useful with many silicon substrates such as single-crystal p-type Czochralski, ⁇ 1,0,0,> and ⁇ 1,1, 1,> ⁇ , n and -type Float Zone, intrinsic, n and -doped amorphous, and -doped multi- crystalline as well as other silicon surfaces.
• the catalytic solution was a dilute (e.g., less than about 2 mM or, in some cases, less than about 1 mM) solution of gold, silver, platinum, and other ions that may be presented in the form of HAuC , AgF, and the like.
• This catalytic solution is added to the oxidant-etchant solution and these solutions combine under agitation to form an etch solution that etches a silicon surface.
• the etch time was significantly reduced relative to prior etching techniques such as less than about 4 minutes (e.g., 2 to 4 minutes or a similar time frame) to obtain a minimum achievable reflectivity (e.g., less than about 3% such as 1 to 2% or even as low as 0.2 to 0.4% in some cases such as those using gold as the catalyst) and also to achieve a relatively uniform surface texture.
• amorphous silicon layers approximately 1 micrometer thick required only about 90 seconds to achieve minimum achievable reflectance.
• both magnetic stirring and ultrasonication were utilized for solution mixing during the etching reactions.
• Magnetic stirring generally was found to yield wafers with a flatter reflectivity profile over the 350 to 1000 nm wavelength range.
• magnetic stirring may not yield wafers or silicon surfaces with the minimum achievable reflectivity in the middle of this wavelength range and may be ineffective for initiation of certain black etch procedures depending upon the catalytic nanomaterial utilized.
• Ultrasonication or ultrasonic agitation hence, may be more useful in some applications.
• polytetrafluoroethylene (PTFE) or Teflon® labware was used for the investigations, and the chemicals/solutions used were clean room/reagent grade.
• the oxidant-etchant solution generally includes an etching agent chosen for silicon and a silicon oxidizing agent whose decomposition can be catalyzed by the chosen catalytic metal.
• HF is used as the etching agent while H 0 2 is the oxidizing agent with the balance of the etching solution volume being deionized water.
• the specific make up of the oxidant-etchant solution may vary widely to practice the described etching such as 5 to 15% w/w HF, 15 to 30% H 0 2 with the balance being DI H 0.
• an oxidant-etchant solution (sometimes referred herein to as a 2x strength oxidant-etchant solution) was formed with 6.25% w/w HF, 18.75% w/w H 0 2 , and balance DI H 2 0 while in another case an oxidant- etchant solution with 26.25% H 2 0 2 and 6.25% HF was used and found effective when the wafers are deeply doped (e.g., w-doping may require longer etch times such as up to 8 minutes or more and/or higher etching solution temperatures such as up to about 45 °C or more).
• the final etching solution is somewhat more diluted due to the combination with the solution provided with the catalytic nanomaterial.
• the etching solution may include equal volumes of the oxidant-etchant solution and the catalytic nanomaterial solution (e.g., a metal colloid solution), and in the above specific example, this would yield an etching solution of 3.125% w/w HF, 9.375% w/w H 2 0 2 and DI H 2 0 to provide a volume ratio of 1 :5:2 of HF:H 2 0 2 :DI H 2 0.
• the etching solution may include equal volumes of the oxidant-etchant solution and the catalytic nanomaterial solution (e.g., a metal colloid solution), and in the above specific example, this would yield an etching solution of 3.125% w/w HF, 9.375% w/w H 2 0 2 and DI H 2 0 to provide a volume ratio of 1 :5:2 of HF:H 2 0 2 :DI H 2 0.
• a wide variety of silicon wafers may be etched as described herein with some testing being performed on 1 square inch Czochralski wafers that were polished on one side.
• the wafers may be n-type or p-type with a wide range of doping (e.g., 0.25 ohm-cm to about 50 ohm-cm or the like).
• the resistivities of p-doped CZ, FZ, and multi-crystalline wafers were between about 1 and about 3 ohm-cm.
• p-doped CZ ⁇ 3, 1, 1> wafers were tested that had a resistivity of about 0.5 ohm-cm. Further, tests were performed using p-doped CZ ⁇ 1, 1,1> wafers with a resistivity in the range of about 0.2 to about 0.25 ohm-cm.
• the volume of the etching solution used was typically about 5 ml to about 15 ml per square inch of silicon wafer or silicon surface with 10 ml reactant per square inch of wafer being used in some cases, but, of course, the volume may be optimized or selected to suit the size/shape of the reactant vessel and size and number of the silicon wafers processed in each batch and based on other variables.
• the stripping solution used to remove remaining nanoparticles after etch is complete may also vary to practice the process and is typically selected based on a number of factors such as to provide a chemistry suitable for the catalytic nanomaterial.
• the stripping solution may be 25 g I 2 /100 g KI per liter of DI H 2 0 or aqua regia or the like, and the stripping or metal removal time, agitation technique, and volume of stripping solution may be similar or even the same as used in the etching process.
• Reflectance measurements after etching and stripping may be performed in a number of ways such as with a Cary-5G UV-vis spectrometer that is equipped with a calibrated spherical reflectance or similar device.
• Real-time UV-visible reflectance spectrometry assays may be performed to obtain information about the progress of etching using devices such as an Ocean Optics' fiber- optic pixel array UV-visible spectrometer.
• the stability of the pre-mixed etching solution formed with HAuCl 4 solution may be relatively short such as about 2 minutes at room temperature, and after this time, gold nanoparticles may form such as by the in-situ reduction of Au 3+ by H2O2, rendering the pre-mixed etching solution inactive or less active with respect to achieving black etching.
• One useful procedure entails placing the Si wafer in the HAuCl 4 solution prior to the addition of the 2x strength oxidant-etchant solution and then performing concurrent or subsequent ultrasonication such as for about 3 to 4 minutes or longer.
• the size of the resultant "Purple of Cassius" gold particles from catalytic solutions of 0.4 mM HAuCl 4 :2x strength black etch after 4-minute etching was determined by TEM to be less than about 10 nm.
• XPS spectroscopy revealed that the gold particles did not contain Au(I) ions , (e.g., from AuF) but only or mainly Au°.
• One useful catalytic concentration of HAuCl 4 has been determined via iterative experiments to be about 0.0775 mM for p-CZ ⁇ l,0,0> wafers while about 0.155 mM was useful for p-doped CZ ⁇ 1, 1,1> and ⁇ 3, 1, 1> wafers and about 0.31 mM was found desirable for / multi-crystalline wafers.
• p-VZ wafers and un-doped p-CZ ⁇ , ⁇ , ⁇ >, ⁇ *R 75 ⁇ -cm ⁇ silicon surface were better etched with a catalytic solution containing a minimum HAuC of about 0.04 mM.
• wafers containing excess positive carriers and, in some cases, having a lower sheet resistance may be better or completely black etched or textured with a higher HAuCl 4 concentration or amount provided in the etching solution.
• etching was performed for about 30 to 60 seconds and texturing reached about the same degree of black-etch at 45° C etching temperature compared with about 180 to 240 seconds or more provided for etching time with etching solutions maintained at room temperature (e.g., about 25°C).
• an etch solution of about 5.0 ml/0.5 in 2 was used to etch a p-CZ ⁇ 1,0,0> silicon wafer with sonication for about 4 minutes.
• the catalytic solution was 0.29 mM AgF to provide silver as the catalytic metal during etching.
• the etching solution also included an equal volume of 2x oxidant-etchant solution with HF and H 2 0 2 .
• Figure 5 illustrates a graph 500 illustrating the results with line 510, while line 520 shows similar results after etching and removal of the remaining silver.
• the increase in reflectivity for wavelengths above about 1100 nm is caused by a reflective background behind the silicon wafer during measurement.
• Figure 6 illustrates a graph 600 with the results of etching of a single crystal silicon surface shown with line 610.
• the increase in reflectivity for wavelengths above about 1100 nm is caused by a reflective background behind the silicon wafer during measurement.
• the etching solution included equal volumes of 0.39 mM HAuCl 4 and of oxidant-etchant solution with 6.25% HF and 26.25% H2O2 and etching proceeded for 4 minutes in this strong solution, followed by an aggressive surface oxide strip with 5% HF under sonication for 5 minutes.
• This strong black etching solution was often beneficial in texturing surfaces that were free of oxide.
• the results show, that reflectance of the surface was lowered to less than about 5% and down to about 1 or 2% in some portions of the 350 to 1000 nm spectrum.
• Etching has also been completed on other silicon surfaces with catalytic solutions such as 0.31 mM HAuCl 4 or the like.
• a black etch was performed for 3.5 minutes on a 0.67 micrometer w-doped amorphous silicon layer on a stainless steel substrate using the 0.31 mM HAuCl 4 catalytic solution combined equally with lx strength oxidant-etchant solution of HF and 3 ⁇ 4(3 ⁇ 4.
• the reflectance was generally 5 to 10% less over the 350 to 1000 nm wavelength range, but reflectance still averaged about 40%. Better results were seen when a black etch was performed on a 1.0 micrometer non-doped amorphous silicon layer on a stainless steel substrate.
• etching was performed for 90 seconds with a 1: 1 volumetric ratio of 0.31 mM HAuCl 4 and 2x strength oxidant-etchant solution.
• the reflectance was reduced about 15 to 25% across the 350 to 1000 nm spectrum to values ranging from about 18 to about 60%.
• Reasonable results were also achieved when a 2.45- minute black etch was performed on 1.0 micrometer non-doped amorphous silicon on a glass substrate with an etch solution having equal volumes of 0.31 mM HAuCl 4 and 2x strength oxidant-etchant solution.
• the etching solution included equal volumes of 0.4 mM HAuCl 4 and oxidant-etchant solution (with 26.25% 3 ⁇ 4(3 ⁇ 4).
• line 710 when the etching was performed without adding light or illuminating the silicon surface and etching solution with high intensity light reflectance was only lowered to about 15% to about 27% in the useful 350 to 1000 nm spectrum.
• the etching method further included providing light sources at about 50 mm above the wafer, the etching results were much more desirable for using the silicon surface in a solar cell or similar application in which low reflectance is desired.
• the reflectance in the 350 to 1000 nm range is lowered to below about 5% (e.g., in the 2.5 to 4% range).
• the light source is a 3 W, 12 V LED the reflectance as shown with line 730 is reduced below 5% to the range of about 2 to about 4% over the 350 to 1000 nm wavelength range.
• light sources may be used to provide light (e.g., relatively high-intensity and/or directed light with a significant component of blue light that is considered to be useful) that can be directed onto the etched surface to act as a further driver of the etching process, and anti-reflection surfaces are better obtained by adding illumination when etching a silicon surface such as that found in a solar cell with a diffuse junction of n-emitter on a p-base wafer.
• light e.g., relatively high-intensity and/or directed light with a significant component of blue light that is considered to be useful
• the described etching process provides excellent control over silicon characteristics such as reduction of reflectance to facilitate use of textured silicon in solar cells with numerous tunnels being bored or formed fairly uniformly across the silicon surface (e.g., a single nanoparticle may act to catalyze a hole of about the diameter being created in the surface and then etching a very high aspect ratio tunnel or pit in the surface such as a hole diameter of 2 to 30 nm and a tunnel depth in the 200 to 300 nm range).
• a solar cell such as cell 400 shown in Figure 4 may be produced with a silicon substrate, e.g., substrate 410, with an AR coating or nanoporous or textured surface with reflectance of less than about 5 percent as tests have shown a R ave of about 3 percent using the Cu-assisted etching processes described herein.
• the system 100 may be modified such that the Si wafer, substrate, or device 110 that is provided into the wet etching vessel is first coated with copper nanoparticles (which eliminates the need for catalytic solution 140). Further, the chemistry of the black etch solution 146 may be modified as discussed below. Additionally, the temperature (measured by sensor 130) may be controlled (such as by operation of heater 128) to obtain a desirably low R ave , and the use of copper alters the metal stripping solution 150 and/or post-etching steps
• Cu nanoparticles may be deposited upon a silicon surface (e.g., a Si substrate, wafer, or device) to prepare it for a later wet etching step.
• the Si wafer or substrate undergoes electroless copper deposition (e.g., 1 minute Cu electroless deposition).
• Table 1 shows results of this study with regard to varying HF volume while holding H2O2 and H2O volumes constant in the etching solution. It can be seen that p varies with the changing HF volume. The changes in p leads to changes in the achieved etching of the Si surface and corresponding reflectivity (as can be seen further with reference to Figures 8-11).
• Figure 8 illustrates a graph 800 showing the solar spectrum-weighted average reflection, R ave , compared with HF volume for these seven etched Si samples with Cu- assisted AR surfaces.
• increasing HF volume with constant volumes of H 2 0 2 (e.g., 5 ml) and H 2 0 (e.g., 50 ml) results in a decreasing R ave from over 35 percent down to below 5 percent (e.g., R ave of about 3%).
• Figure 9 illustrates a graph 900 showing for the seven samples of this study the relationship of R ave to p being that an increasing p provides a decreasing R ave .
• the graph 900 indicates that if a goal R ave for a silicon device (such as for a solar cell) is less than about 5 percent it may be desirable to use an etching solution with a p value of at least about 70 percent (such as at least about 74 percent to achieve R ave of about 3 percent).
• SEMS analysis and inspection of these samples shows an increasing density of etched holes/tunnels and increased roughness/depth of tunnels with increasing p values, which supports and/or explains in part the low values of R ave obtained with higher p values.
• Figure 10 illustrates a graph 1000 illustrating the four samples with the lowest reflection versus wavelength.
• line 1010 provides data for a Si surface etched with an etching solution with a p value of 69 percent
• line 1020 provides data for a Si surface etched with an etching solution with a p value of 74 percent
• line 1030 provides data for a Si surface etched with an etching solution with a p value of 80 percent
• line 1040 provides data for a Si surface etched with an etching solution with a p value of 90 percent.
• the graph 1000 is useful for showing that the etched Si surfaces provided by Cu-assisted etching with a p value of at least about 74 percent are useful in providing low reflection, e.g., less than 3 percent, for many wavelengths (ranges of most interest in many solar cell applications). This means the HF concentration should be maintained at least 3 times that of the H2O2 concentration in the solution.
• An additional test was performed in which p was maintained at about 80 percent (i.e., 7 ml HF and 5 ml H 0 2 ), but the volume of H 0 in the etching solution was increased. The results of 10 minute etch with four differing H2O volumes relative to reflectivity is shown in the graph 1100 of Figure 11.
• reducing the concentration of the etching and oxidizing agents causes the reflectivity to increase well above 5 percent, which often is undesirable. In other words, it may be desirable to achieve less than 5 percent reflectivity to maintain the concentration of HF at about 10 percent (or higher) and concentration of H 2 0 2 at about 10 percent (or higher).
• the black etching solution recipe in this study was 50 ml H 2 0, 5 ml HF, and 5 ml H 2 0 2 (so HF concentration of about 8 percent (i.e., more dilute than the above example) and an H 0 2 concentration of about 8 percent (again more dilute than the above study indicating that at least about 8 percent concentrations may be adequate)).
• solution mixing and/or agitation was used to obtain a desired result (see agitation, such as sonication, as discussed above with regard to performance of etching steps). Further, the study was used to show that heating (particular temperature ranges) was useful during etching to obtain low R ave .
• post-etching was used to remove the copper, and the Cu removal was performed using concentrated HNO 3 at RT for 3 minutes with sonication (mixing/agitation).
• Table 2 illustrates the photovoltaic illuminated current-voltage properties of the eight Si samples after completion of Cu-assisted etching and post-etching processing to remove the
• the temperature and time may both have to be controlled and may have to be set based on the type of Si surface being etched (planar versus pyramid). For example, a R ave value of 3% was achieved with a pyramid Si sample with this etching solution/recipe with a 5 minute etch at 30 °C, but the value of R ave actually increased with increased temperature of the etching solution.
• the method 300 may be modified to implement the Cu-assisted etching particularly to replace the addition of a catalytic solution with electroless or other deposition of Cu nanoparticles upon a silicon surface.
• the modifications also may involve use of differing recipes for the etching solution, control of etching with regard to time and temperatures, and post-etching to remove the copper prior to formation of a solar cell or other device with the etched Si element.

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