Not applicable.
The technology herein relates to optical filters made of porous semiconductor materials, and more specifically to scattering-type optical filters used in the infrared spectral region. Still more particularly, the technology herein relates to infrared long wave pass filters and band pass filters.
Filters of the exemplary non-limiting illustrative implementation can be used to filter light in the near infrared, mid infrared and/or far infrared spectral ranges. Advantages of porous semiconductor filters of the exemplary non-limiting illustrative implementation include improved mechanical stability, manufacturability, and a wide spectral range of transparency.
Generally, optical filters and coatings are passive components whose basic function is to define or improve the performance of optical systems. There are many types of optical filters. They are used for a broad range of different applications. Applications of optical filters and coatings can be diverse as anti-glare computer screens, colored glass, sighting devices, and electrical spark imagers—to name just a few.
Some optical filters are specialized for different wavelength ranges of light because of limitations in available materials that are optically transparent in the range of interest. For example, many applications and instruments require optical filters that can be used to tune the optical behavior of light in the near infrared, mid infrared or far infrared wavelength range (i.e., at frequencies of radiant energy that are generally below the frequencies of visible light). Some example applications for such filters include far- and mid-IR focal-plane arrays for military applications, chemical sensing, astronomy, and space and earth observations to name a few.
Some of these applications (especially those used in mid and far IR) require filters to block the light at short wavelengths (below some “edge” wavelength) and to transmit the light over a broad range of wavelengths above the edge wavelength, while keeping the transmission in this range as high and as “flat” as possible. Such filtering is shown to significantly improve the signal-to-noise ratio of the detection system and is actively used in a large number of applications spanning from Fourier Transform Spectroscopy to astronomy and defense.
One known type of filter serving such applications is the so-called interference filter, consisting of many layers of dissimilar materials (each layer up to several micrometers thick each for far IR filters), which are commonly deposited at or above room temperature conditions. This type of filter is often strongly limited by the width of the flat portion of the transmission band. In addition, such filters can have a number of problems if used at cryogenic temperatures, a quite common environment for far IR filters serving astronomical and military applications. This is because thermal stresses during the cooling of the filters can cause layers to delaminate. This can severely limit the maximum size of the filter, its physical longevity and, through that, the performance and cost-of-use of the optical system incorporating said filters.
Another type of filter serving these applications is scattering-type filters, such as disclosed by K. R. Armstrong and F. J. Low [Appl. Optics., 13(2), p. 425, 1974]. Generally, such filters utilize a layer of diamond particles (or other transparent material) of specific sizes, spread on a surface of a sheet or substrate of a material transparent in the IR region, such as polymer materials (e.g. polyethylene), quartz or sapphire. Light with wavelengths about or below the size of the particles in the applied layer is scattered into a solid angle. If the detection means is sufficiently separated from the filter, such light is effectively blocked. On the other hand, the light with wavelengths above the size of the particles is transmitted with no or little distortion, and reaches the detector even at substantial separation. Hence, a transmission edge is created.
A schematic drawing of an exemplary such filter structure is presented in
From another point of view, porous semiconductor materials have been known for a number of years. Such materials have been proposed for use as filters, either as interference filters or as short-pass filters (see, e.g. [US patent application 20040004779 by V. Kochergin et al., filed Jun. 4, 2003], [US patent application 20050276536 by V. Kochergin et al., filed Oct. 16, 2003], [US patent application 20060027459 by M. Christophersen et al., filed May 27, 2005]).
Information about the manufacture of macroporous silicon (MPSi) arrays can be found in U.S. Pat. No. 5,262,021 issued to V. Lehmann, et al, Nov. 16, 1993 (which claims priority to Fed. Rep. Of Germany Patent # 4202454, issued Jan. 29, 1992), in which a method of the formation of free-standing macropore arrays from an n-doped Si wafer is disclosed.
Macroporous silicon layers with modulated pore diameters throughout the pore depth is disclosed in, for example, [U.S. Pat. No. 5,987,208 issued to U. Gruning and V. Lehmann et al. Nov. 16, 1999] or [J. Schilling et al., Appl. Phys. Lett. V 78, N.9, February 2001].
There are also several disclosures relating to methods of manufacturing macroporous structures with controlled positions of the pores. One such disclosure is U.S. Pat. No. 4,874,484 issued to H. Föll and V. Lehmann issued Oct. 17, 1989 (which claims priority to Fed. Rep. Of Germany Patent # 3717851 dated May 27, 1987). This patent describes a method of generating MPSi arrays from n-doped (100)-oriented silicon wafers in HF-based aqueous electrolytes (i.e., electrolytes based on HF diluted with water) under the presence of backside illumination. It also describes a method of controlling the position of macropores through formation of etch-pits. Etch pits are typically, but not exclusively, pyramid-shaped openings formed on the silicon or other semiconductor surface that can be formed through mask openings upon exposure to anisotropic chemical etchants. In addition, the use of wetting agents (such as formaldehyde) and controlling the pore profile through chronologically-varying applied electrical potentials also were disclosed.
A method of MPSi layer formation in non-aqueous electrolytes is disclosed in U.S. Pat. No. 5,348,627 issued Sep. 20, 1994 and U.S. Pat. No. 5,431,766 issued Jul. 11, 1995, both to E. K. Propst and P. A. Kohl. Organic solvent-based electrolytes were used for forming porous layers in n-doped silicon under the influence of front-side illumination. Example solvent based electrolytes are acetonitrile (MeCN), diemethyl formamide (DMF), propylene carbonate (C3O3H6) and methylene chloride (CH2Cl2))-containing organic supporting electrolytes, such as the examples of tetrabutilammonium perchlorate (C16H36NClO4), tetramethylammonium perchlorate (C4H12NClO4) and anhydrous sources of fluoride, HF, fluoroborate (BF4−), tetrabutylammonium tetrafluoroborate (TBAFB), aluminum hexafluorate (AlF63−) and hydrogen difluoride (HF2−).
A method of manufacturing ordered, free-standing MPSi arrays, including pore walls coated by a semiconducting layer with follow-on oxidizing or nitriding through a CVD process was disclosed in U.S. Pat. No. 5,544,772 issued Aug. 13, 1996 to R. J. Soave, et al., in relation to the production of microchannel plate electron multipliers. N-doped silicon wafers, photoelectrochemically etched in an HF-based aqueous electrolyte, were disclosed. Another method of manufacturing MPSi-based microchannel plate electron multipliers is disclosed in U.S. Pat. No. 5,997,713 issued Dec. 7, 1999 to C. P. Beetz, et al. This patent describes an ordered, freestanding MPSi array made by the electrochemical etching of a p-doped silicon wafer. Both aqueous and non-aqueous (e.g., acetonitrile, tetrabuthylsulfoxide, propylene carbonate or metholene chloride-based) electrolytes, based on both HF and fluoride salts, were disclosed for MPSi layer manufacturing. The use of mechanical grinding, polishing, plasma etching or chemical back-thinning to remove the remaining part of the silicon wafer in line with the pores were disclosed. The use of a surfactant to improve pore quality was also taught.
The use of a conductivity-promoting agent in organic-based electrolytes (e.g., DMF) during the photoelectrochemical etching of n-doped silicon was disclosed in S. Izuo et al., Sensors and Actuators A 97-98 (2002), pp. 720-724. The use of isopropanol ((CH3)2CHOH) as a basis for an organic electrolyte for electrochemical etching of p-doped silicon was disclosed in, for example, A. Vyatkin et al., J. of the Electrochem. Soc., 149 (1), 2002, pp. G70-G76. The use of ethanol (C2H5OH) to reduce hydrogen bubble formation during electrochemical etching of silicon as an addition to aqueous HF-based electrolytes was disclosed in, for example, K. Barla et al. J. Cryst. Growth, 68, p. 721 (1984). A detailed review of the various aspects of MPSi formation can be found in H. Föll et al, Mat. Sci. Eng. R 39 (2002), pp. 93-141.
Macropores have been obtained in types of semiconductor and ceramic materials other than silicon. For example, macropores obtained in n-type GaAs by electrochemical etching in acidic electrolytes (aqueous HCl-based) were reported by, for example, D. J. Lockwood et al, Physica E, 4, p. 102 (1999) and S. Langa et al, Appl. Phys. Lett. 78(8), pp. 1074-1076, (2001) Macropores obtained in n-type GaP by electrochemical etching were reported by B. H. Erne et al., Adv. Mater., 7, p. 739 (1995). Macropore formation during the electrochemical etching of n-type InP (in aqueous and organic solutions of HCl and mixtures of HCl and H2SO4) was reported by P. A. Kohl et al., J. Electrochem. Soc., 130, p. 228 (1983) and more recently by Schmuki P et al., Physica Status Solidi A, 182 (1), pp. 51-61, (2000); S. Langa et al., J. Electrochem. Soc. Lett., 3 (11), p. 514, (2000). Macroporous GaN formation during electrochemical etching was reported by J. v. d. Lagemaat, Utrecht (1998). Macropore formation during electrochemical etching of Ge was reported by S. Langa et al., Phys. Stat. Sol. (A), 195 (3), R4-R6 (2003). Reviews of macropore formation in III-V semiconductors can be found in H. Föll et al., Phys. Stat. Sol. A, 197 (1), p. 64, (2003); M. Christophersen et al., Phys. Stat. Sol. A, 197 (1), p. 197, (2003), and H. Föll et al., Adv. Materials, Review, 2003, 15, pp. 183-198, (2003).
The exemplary illustrative non-limiting technology herein provides a mechanically stable infrared long-wave pass or band-pass filter utilizing the scattering in at least one layer of porous semiconductor material. The exemplary illustrative non-limiting technology herein also provides practical methods of fabricating such filters.
An exemplary illustrative non-limiting infrared filter implementation comprises a semiconductor substrate having first and second surfaces. The semiconductor material of the substrate can be silicon, germanium, III-V compound semiconductor or any other semiconductor material known to form porous semiconductor layer under the electrochemical etching process in suitable electrolyte. The array of holes (pores) is formed on a first surface of said semiconductor substrate in an infrared filter of the presently preferred exemplary non-limiting illustrative implementation such that the holes have some specific arrangement, specific distribution of sizes and specific distribution of spacings with respect to each other. Such holes form the porous layer on the first surface of the semiconductor wafer.
There can be more than one porous layer on the surface of the wafer with either different pore topology (orientation of pores with respect to each other and with respect to the surface of the wafer) or with different pore parameters (such as pore size distribution and pore spacing distribution). Said porous surface of the exemplary illustrative non-limiting semiconductor wafer in an infrared filter implementation can be coated by a layer of transparent material to serve as an antireflection layer or for the mechanical and environmental protection of the filter, or both together, or for other reasons.
The second surface of the semiconductor wafer can be left flat and uncoated to provide “flat” uniform transmission through the wide range of wavelengths across the infrared spectral region. Alternatively, said second surface of the semiconductor wafer can be coated, e.g., by one or more layers of materials that are transparent in the infrared range in order to serve as an antireflection layer. This will also enhance transmission through the exemplary illustrative non-limiting filter in the desired spectral ranges or will modify the transmission in some wavelength range through the thin film interference effect. Alternatively, said second surface of the semiconductor wafer can be geometrically structured to form an antireflection coating (similar to the “motheye” structure well-known to those skilled in the art). The nonporous portion of the semiconductor wafer can be also completely removed so the porous semiconductor membrane can be formed to act as a filter. Such a design will provide higher transmission in the pass band of the filter, but will offer less mechanical stability. Alternatively, the porous layer can be formed on the second surface of the semiconductor wafer with the same or different pore structure to enhance optical characteristics of the filter (e.g., by enhancing transmission within the pass band, sharpening the rejection edge or increasing the rejection level).
The semiconductor wafer can be bonded at the first side to another wafer that is transparent in the IR range. Fusion bonding, anodic bonding or any other type of bonding known to those skilled in the art can be used. Alternatively, said semiconductor wafer can be made of two semiconductor wafers with different doping densities bonded together before etching. The exemplary illustrative non-limiting infrared filter can be used as a long wave pass filter. Alternatively, the exemplary illustrative non-limiting filter can be used as a band pass type of filter.
These and other features and advantages will be better and more completely understood by referring to the following detailed description of exemplary non-limiting illustrative implementations in conjunction with the drawings of which:
According to an exemplary non-limiting illustrative implementation, an infrared filter is made of a single-crystal semiconductor wafer having a porous layer etched at least part way through the wafer. Said pores in porous layer are essentially straight and parallel to each other such as illustrated in
According to a further presently preferred exemplary non-limiting illustrative implementation, the infrared filter is made of a single-crystal semiconductor wafer having a porous layer etched at least part way through the wafer. Said pores in the porous layer are essentially parallel to each other, such as illustrated in
According to a further exemplary illustrative non-limiting implementation, the infrared filter is made of the single-crystal semiconductor wafer having a porous layer etched at least part way tough the wafer. Said pores in the porous layer grow along a number of orientations as illustrated in
In a further presently preferred exemplary non-limiting illustrative implementation, the infrared filter is made of a single-crystal semiconductor wafer having a porous layer etched at least part way through the wafer. Said pores in the porous layer can be divided into two groups according to the direction of growth: 1) main pores 6.2 which are commonly grown in a direction perpendicular to the wafer surface (i.e., in the [100] crystallographic direction) and 2) secondary pores that grow along a number of orientations, typically at some angle with respect to the direction of growth of the main pores. Such a porous layer can be electrochemically etched into an n-type doped silicon wafer with a (100) crystallographic orientation with resistivity in the range of 0.1 to 100 Ωcm, in HF-containing electrolytes under constant current (galvanostatic) or constant voltage (potentiostatic) anodic etching conditions, with no illumination or small back side illumination during the electrochemical etching process. Due to the morphology of the porous layer, the scattering of light is effective throughout the layer depth so the rejection level within the rejection band is as high as in the filters described above.
As an illustrative example,
The exemplary illustrative non-limiting infrared filters described herein are mechanically stable and tolerate well the pressure differentials and temperature cycling. Such filters can be used at both cryogenic temperatures and at room temperature. Optically, such filters exhibit sufficiently sharp rejection edge combined with flat and high level of transmission within the pass band, and a good and uniform rejection within the rejection band at a proper filter-to-detector separation. Such filters also show reasonably good stability at high power laser illumination and exhibit low or no polarization effect on the light transmitted within the pass band. The size of the filter is limited by the size of the semiconductor wafer, thus permitting the fabrication of filters up to 200 mm in diameter and above. The technology of fabrication of such filters is sufficiently inexpensive for filters to have competitive pricing.
While the technology herein has been described in connection with exemplary illustrative non-limiting implementations, the invention is not to be limited by the disclosure. The invention is intended to be defined by the claims and to cover all corresponding and equivalent arrangements whether or not specifically disclosed herein.
This application claims the benefit of U.S. Provisional Application No. 60/681,155 filed May 16, 2005, entitled “LONG WAVE PASS INFRARED FILTER BASED ON POROUS SEMICONDUCTOR MATERIAL AND THE METHOD OF MANUFACTURING THE SAME” (Attorney Docket 340-99), incorporated herein by reference. This application is also related to commonly assigned copending application Ser. No. 10/686,520 filed 16 Oct. 2003 of Kochergin et al. entitled “SPECTRAL FILTER FOR GREEN AND LONGER WAVELENGTHS” (attorney docket 340-80)
Number | Date | Country | |
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60681155 | May 2005 | US |