This invention relates to controlling the thickness of films by wafer separation. More particularly, to controlling the thickness of silicon oxide films.
Crystalline silicon solar cells remain one of the most popular product in the photovoltaic industry. While other low cost alternatives have arisen, the alternatives have thus far provided low efficiency products. Industrial trends have increased demand for thinner wafers. Common industrial silicon solar cells suffer from a high rear surface recombination and a poor internal reflection of the full area Al back surface field (BSF). In 1989, Blackers et al. introduced a passivated emitter and rear cell (PERC) solar cell. Combining low surface recombination with a high internal reflection, PERC enables significantly higher conversion efficiencies compared to the Al-BSF technology.
It would be highly desirable to have a low cost but highly effective film coating process for the industrial fabrication of PERC solar cells. For the rear surface, a thick SiOx layer (˜100 nm) is required to obtain good passivation and internal reflection. For the front surface, either of single layer of SiNx or SiOx/SiNx stack (˜10 nm thin SiOx interlayer is inserted between the silicon surface and SiNx layer) is desired for both passivation and anti-reflectance purpose. Improved silicon surface passivation of SiOx/SiNx stacks over a single layer of SiNx has already been reported by a number of papers.
In addition, the recent progress of black silicon solar cell showed that applying 20 nm thermal SiOx passivation layer to a black silicon surface (a chemically etched porous Si surface that could drive the surface reflection down to 2˜3% across the spectrum of sunlight) could potentially replace the PECVD SiNx coated Si surface, resulting in low cost crystalline Si solar cell with minimized efficiency loss. The potential integration of the black silicon surface into PERC solar cell fabrication may increase the need for a coating process allowing the simultaneous growth of a thin film of SiOx on the front surface and a thick film of SiOx on rear surface in a single deposition step.
However, to coat a thin SiOx film on front surface and a thick SiOx film on rear surface of the silicon solar cell respectively in one growth step is difficult for commonly used thermal oxidation system. Alternatively, this is often achieved in two steps of coating process. First, a thin SiOx film (˜10 to 20 nm) is grown on both surfaces with thermal oxidation. Second, a SiOx thick film (˜100 nm) is deposited on the rear surface by the plasma enhanced chemical vapor deposition (PECVD). This two-step growth process increase the cost of production and increases production time significantly. Therefore, a new process that enables SiOx deposition on front and back surfaces with different thickness in a one growth process would be highly desirable.
In an illustrative implementation, a process for coating films of different thicknesses on front and rear surface of a substrate respectively in one growth is provided. The thickness of the film deposition can be controlled by the separation between the substrates during the process. By providing different separation distances between the substrates in the same chemical bath, different film thicknesses may result on the front and rear surfaces of the substrates.
In another illustrative implementation, a process for coating different SiOx thickness on front and rear surface of a silicon wafer respectively in one growth is provided. The thickness of SiOx deposition can be controlled by the separation distance between silicon wafers. By providing different separation distances between the wafers in the same chemical bath, different SiOx film thicknesses may result on the front and rear surfaces of the wafers. In some implementations, the distance may vary along the surface of the wafer. In some implementations, a wafer may be place next to a curtain or the like to provide desired separation distance or distances. The process may facilitate solar cell fabrication where a thin SiOx film on front surface and a thick SiOx film on rear surface are desired. The process can also be utilized to provide films of varying thickness on a single surface. In addition to silicon solar cell applications, the process could be extended to any device in which a film of different thickness on different sides of a substrate is desired.
The foregoing has outlined rather broadly various features of the present disclosure in order that the detailed description that follows may be better understood. Additional features and advantages of the disclosure will be described hereinafter.
For a more complete understanding of the present disclosure, and the advantages thereof, reference is now made to the following descriptions to be taken in conjunction with the accompanying drawings describing specific embodiments of the disclosure, wherein:
Refer now to the drawings wherein depicted elements are not necessarily shown to scale and wherein like or similar elements are designated by the same reference numeral through the several views.
Referring to the drawings in general, it will be understood that the illustrations are for the purpose of describing particular embodiments of the disclosure and are not intended to be limiting thereto. While most of the terms used herein will be recognizable to those of ordinary skill in the art, it should be understood that when not explicitly defined, terms should be interpreted as adopting a meaning presently accepted by those of ordinary skill in the art.
An improved film deposition system and method discussed herein allows the film thicknesses to be controlled by wafer separation. The improved film deposition systems and methods may utilize liquid phase deposition (LPD), chemical bath deposition, or the like to deposit a film on a substrate. For example, it may be desirable to deposit a dielectric film on a silicon substrate in solar cell applications. In the LPD process, the thickness of the film deposited on the substrate may be controlled by the wafer separation.
In various applications, it may be desirable to provide films of different thicknesses on different surfaces of a substrate. For example, in a solar cell, it may be desirable to have film coatings of different thicknesses on the front surface and rear surface. For the front surface, a thin dielectric layer may be desired for both passivation and anti-reflectance purpose. For the rear surface, a thick dielectric layer is required to obtain good passivation and internal reflection. However, achieving different film thicknesses in a single growth process is extremely difficult. The coating process may be split up into two steps to provide the desired film thicknesses. For example, both surfaces may be coated with a thin SiOx film using thermal oxidation in a first step. Next, a plasma enhanced chemical vapor deposition (PECVD) process may be utilized to further deposit a thicker SiOx film on the rear surface in a second step. In contrast, LPD provides a single growth process in which film thickness can be controlled by wafer separation. LPD is a low cost process to deposit a dielectric film, such as SiOx, on silicon at nearly room temperature. Further, LPD does not require the use of a high temperature furnace or large vacuum deposition chamber, as with thermal oxidation and PECVD. LPD of SiOx has been demonstrated to provide good passivation to both n-type and p-type silicon surface in U.S. Provisional Application 61/442,461, filed on Feb. 14, 2011, to Yuanchang Zhang.
Additional Deposition Methods:
Additional deposition methods may utilize variations in variations in wafer separation. In contrast to wafer separations arranging the wafers parallel to each other, other implementations may include different wafer arrangements.
The film deposition systems and methods discussed may also be applicable in areas other than PERC, such as multiple colored solar cells. The light receiving surface of a solar cell is preferably as black as possible to get more sunlight absorption. It is possible, however, to produce solar cells in other colors, or even to print images or text on the solar cell so that it serves as a decorative element. For example, color charts indicating a color corresponding to different thicknesses for SiO2 films are known in the art, see Ghandhi, S. K., VLSI Fabrication Principles, Table 7.4, 1982.
In addition to silicon solar cell applications, the wafer separation methods and systems could be extended to any LPD process in need of coating a film of different thickness on different sides of the substrate. The methods discussed are suitable for, but not limited to, LPD SiOx deposition process. The methods can be adapted to any solution based thin film fabrications where it is desirable to control the film thickness in order to get different film thickness on front and rear surfaces, a thickness gradient across a surface, a patterned film on a surface, different film thicknesses in various regions of a surface, or the like. The methods discussed provide a one step deposition process that is suitable for depositing a variety of different materials. Current solution based thin film fabrication processes could be divided into different types, such as sol-gel deposition process, electrodeposition, hydrothermal reaction, chemical bath deposition (CBD), Successive ion layer adsorption and reaction (SILAR), Electroless deposition (ED) with catalyst, Liquid phase deposition (LPD), or the like. Most of these processes focus on deposition of metal oxides with a formulation as MxOy or LxMyOz (where L and M are metal elements, O is oxygen element), metal sulfides with a formulation as MxSy (M is metal elements, S is sulfur element), and metal selenides with a formulation MxSey (M is metal elements, Se is selenium element). Solution based thin film fabrications have been widely used due to its flexibility of depositing a broad spectrum of materials. For example, electrodeposition allows deposition of pure metals, alloys, semiconductors, ceramics, and polymers on a variety of substrates. Similarly, the above-mentioned deposition methods may be utilized with a broad spectrum of materials to control a film thickness deposited on a substrate. Materials that may be utilized include, but are not limited to, TiO2, ZrO2, In2O3, SnO2, BaTiO3, ZnS, Bi2Se3, and/or the like. For example, TiO2 and ZrO2 are alternative materials for silicon solar cell anti-reflection coating. In2O3 and SnO2 are essential materials to make indium tin oxide (ITO), one of the most widely used transparent conducting oxides in solar cell fabrication.
For example, various suitable methods and solutions for thin film fabrications are known in the art (See Masuda, Yoshitake “Patterning of TiO2 Thin Films and Particles using Self-assembled Monolayers,” Doctoral Dessertation, Nagoya University, Japan, 2003). Any of the methods discussed herein for controlling film thickness may be utilized with known LPD processes.
LPD process used here could be performed at ambient temperature or above the ambient temperature. The growth rate typically increases with the reaction temperature. However, larger particles or serious precipitation may occurs earlier using higher temperature that makes the solution blur and unsuitable for the film quality. For typically used concentration H2SiF6:H2O=1:2, the deposition time for 100 nm SiOx will take a minimum time of 1.5 hour at 45° C. and up to 7 hours at 18° C.
For the purposes of illustration, the growth process is discussed in relation to silicon solar cell applications. However, it will be recognized by one of ordinary skill in the art that the growth process could be applied to any LPD process of coating a film of different thickness on different sides of a substrate including, but not limited to, coating nanostructures on a substrate, photovoltaics, semiconductors, lens coatings, and the like.
The following experimental examples are provided for illustrative purposes only. The various aspects described in the examples merely represent exemplary implementations. It will be recognized by one of ordinary skill in the art that various changes can be made in the implementations described without departing from the spirit and scope of the present disclosure. In silicon solar cell applications, it may be desirable to provide SiOx films on the front and back surfaces of a silicon wafer. For illustrative purposes, an experimental example of an LPD SiOx process is discussed herein for coating the front surface with thin SiOx film while simultaneously coating the rear surface with a thick SiOx film in one step of growth.
Experimental Results:
The reagent solution for the LPD growth of SiOx was prepared by saturating a ratio of 1 liter of 3 M hexafluorosilicic acid (H2SiF6) with 60 g 0.007 μm fumed silica powder at room temperature. After overnight saturation, the solution was filtered, first with a course VWR Grade 315 fluted filter for 25 μm particle retention, then with the Millipore Stericap system using 0.22 μm filters. The solution was then diluted to 1 M by adding 18 MOhm DI water.
The addition of water initiated the reaction and precipitated the silica according to:
H2SiF6+2H2OSiO2↓6 HF
525 μm 4″ single side polished silicon wafers were used. The wafers cleaned by standard procedures were immersed in the solution at a temperature of 18° C. The wafers were aligned vertically and the separations between the adjacent wafers were set to d1=0.2, d2=0.5, and d3=1.0 mm respectively, as shown in
According to the above experimental results, the SiOx film thickness is determined by the gap between the wafer surfaces. This provides an approach to coat the different sides of wafers with SiOx films of different thicknesses in one step of growth. In this growth process to achieve different film thicknesses, all the wafers may be aligned with the surfaces facing front to front and rear to rear. In addition, the wafers may be separated by different gaps for the front surfaces (gap a) and rear surfaces (gap b). With using solution of standard concentration (H2SiF6:H2O=1:2), the SiOx film deposited on the front surface will consequently have different thickness compared to that deposited on the rear surface, and the thickness ratio can be adjusted as requested with varying the ratio of gap a to gap b.
The methods can be adapted to any solution based thin film fabrications where it is desirable to control the film thickness in order to get different film thickness on front and rear surfaces, a thickness gradient across a surface, a patterned film on a surface, different film thicknesses in various regions of a surface, or the like. The methods discussed provide a one step deposition process that is suitable for depositing a variety of different materials. For example, the process may be utilized to deposit of metal oxides with a formulation as MxOy or LxMyOz (where L and M are metal elements, 0 is oxygen element), metal sulfides with a formulation as MxSy (M is metal elements, S is sulfur element), and metal selenides with a formulation MxSey (M is metal elements, Se is selenium element). Further materials that may be utilized include, but are not limited to, TiO2, ZrO2, In2O3, SnO2, BaTiO3, ZnS, Bi2Se3, and/or the like.
Unlike the thermal oxidation, LPD deposited silicon oxide is a low temperature process to achieve dielectric thin film on Si substrate, potentially reducing the energy consumption and the wafer thickness used in the fabrication of crystalline Si solar cells. Additionally, the LPD process discussed provides a novel method of controlling the film thickness of the LPD deposited silicon oxide. Compared to the multiple steps of process usually taken for coating different surfaces of the cell with different thicknesses, the LPD process allows for one step growth to accomplish the goal, which features a simple and low-cost method. Further, by controlling the separation distances between the wafers, the LPD process creates a way of minimizing the chemical solution consumption providing a significant cost reduction.
While the abovementioned wafer separation methods and systems discuss may discuss specific temperatures, concentrations, and deposition periods, the wafer separation methods and systems discussed can be performed at different temperatures, different solution concentrations, different deposition periods, and/or the like. It will be recognized by one of ordinary skill in the art that temperatures, concentration, deposition periods, and/or the like can be modified as desired.
The process deposits a thin film to a group of specially aligned wafers in a chemical bath. The process may includes the steps of the operation, such as solution preparation, wafer loading to wafer carrier, immersing the wafers in the solution for a certain period of time, or the like. One of ordinary skill in the art will recognize that the type of wafers, gap between wafers, type of solution, solution concentration, and/or any other parameters in the process may be varied as desired.
Implementations described herein are included to demonstrate particular aspects of the present disclosure. It should be appreciated by those of skill in the art that the implementations described herein merely represent exemplary implementation of the disclosure. Those of ordinary skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific implementations described and still obtain a like or similar result without departing from the spirit and scope of the present disclosure. From the foregoing description, one of ordinary skill in the art can easily ascertain the essential characteristics of this disclosure, and without departing from the spirit and scope thereof, can make various changes and modifications to adapt the disclosure to various usages and conditions. The implementations described hereinabove are meant to be illustrative only and should not be taken as limiting of the scope of the disclosure.
This application claims the benefit of U.S. Provisional Patent Application No. 61/468,696 to Yuanchang Zhang, filed on Mar. 29, 2011, which is incorporated herein by reference.
Number | Date | Country | |
---|---|---|---|
61468696 | Mar 2011 | US |