MXPA00011150A - Micro-lasing beads and structures, and associated methods - Google Patents

Abstract

An elongated structure includes a core (D), one or more gain medium layers disposed about said core for providing a plurality of characteristic emission wavelengths (&lgr;1,&lgr;2,&lgr;3), and a growth matrix of functionalized support suitable for the synthesis therein or thereon of a chemical compound. Other embodiments can be spherical, or planar with a plurality of optical gain medium dots, each providing a different emission wavelength. Also disclosed is a technique for selectively locating micro-laser beads of interest, and then aiming a laser source at the bead(s) of interest in order to interrogate the optically encoded identification information. Also disclosed is a bead that includes a functionalizedsupport, and that further includes a gain medium coupled to a structure that supports the creation of at least one mode for electromagnetic radiation, and/or which has a dimension or length in one or more directions for producing and supporting amplified spontaneous emission (ASE).

Description

SPHERES AND MICRO-LASER FORMER STRUCTURES, AND ASSOCIATED METHODS • PRIORITY CLAIM FROM THE PROVISIONAL, PARTNERS PATENT APPLICATIONS With this document priority is claimed under 35 U.S.C. §119 (e) from the co-pending provisional patent application 60 / 085,286, filed on May 13, 1998, entitled "Cylindrical Micro-Lasing Beads for Combinatorial • 10 Chemistry and Other Applications ", by Nabil M. Lawandy, provisional patent application 60 / 086,126, filed on May 20, 1998, entitled" Cylindrical Micro-Lasing Beads for Combinatorial Chemistry and Other Applications ", by Nabil M. Lawandy Provisional patent application 60 / 127,170, filed on March 30, 1999, entitled "Micro-Lasing Beads and Structures for Combinatorial Chemistry and Other Applications, Including Techniques for Fabricating Same ", by Nabil M. Lawandy, and the provisional patent application" Search, Point and • Shoot Technology for Readout of Assays, by Nabil M. Lawandy The description of each of these four provisional patent applications is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION This invention relates generally to spheres and other • structures typically used in combinatorial chemistry applications, as well as structures that can emit electromagnetic radiation, and optical coding techniques and techniques for reading and detecting coded information.

BACKGROUND OF THE INVENTION • 10 In an article entitled "Plastic microring lasers on fibers and wires", Applied Physics Letters, Vol. 72, No. 15, pp. 1802-1804, April 13, 1998, S.V. Frolov, Z.V. Vardeny, and K. Yoshino demonstrate that narrow, pulsed, photoblown laser emission lines with very low threshold excitation intensities can be obtained using conductive polymer films luminescent (LCP) deposited around optical fibers and thin metal wires. As active material for laser, the authors chose a derivative of poly (p-phenylene-vineylene) (PPV), that is, 2,5-dicetiloxy PPV (DOO-PPV), which has proved to be an active medium for excellent laser in the range of the red / yellow spectrum. The lowest excited states in DOO-PPV are excitons with energy levels similar to those of organic laser dyes, which under optical excitation form a four-level laser system. The polymer laser transition occurs at longer wavelengths compared to the pump wavelength, and therefore, population inversion can be achieved at relatively low excitation densities. In a combinatorial chemistry application, a large • number of the so-called solid supports or spheres so as to have a matrix or a growth matrix phase (also known as a functionalized support) to which various compounds can adhere during the synthesis of various novel compounds, some of the which have, ideally, physiological properties or other useful properties. A problem in the use of such spheres is in the provision of an identification for the spheres that facilitates the subsequent selection and identification of, for example, an oligomer sequence that is synthesized.

OBJECTIVE OF THE INVENTION It is an object of the invention to provide an improved structure useful in combinatorial chemistry and other applications, in which the structure uses one or • more layers or films of optical gain medium deposited around or on a core. It is another object of this invention to provide a manufacturing technique structures suitable for use in combinatorial chemistry and other applications, in which the structures comprise regions of optical gain medium that can provide each of the structures with a characteristic optical emission signature.

It is another object of this invention to provide an optical-based technique for exciting optical gain means disposed on the structures, and for detecting the signature of optical emission characteristic of those different from • the structures.

BRIEF DESCRIPTION OF THE INVENTION A structure in accordance with one aspect of this invention may include a core or other substrate, at least one and preferably one • plurality of optical gain medium films arranged around said core to provide a plurality of characteristic emission wavelengths. The structure may also include a functionalized support suitable for the synthesis therein, or on it, of a chemical compound. Various structural geometries are described, such as discs and spheres, as well as several pumping sources and appropriate detectors. A technique for manufacturing planar structures is also described, in which a micro-laser forming sphere structure contains a plurality of areas or points of optical gain material and is contained between the protective substrates using, for example, a base adhesive of cross-linked polymer solvent resistant. At least one of the protective substrates is substantially transparent (at the excitation and emission wavelengths of interest) and is positioned between a substrate surface that carries the micro-laser forming spots and the environment.

In one embodiment a method uses a head with one or more holes to selectively stamp the optical gain material in the areas, and the mechanism to cause relative movement between the head and the head. • substrate. The deposition step can deposit a total complement of optical gain material in each of the area pluralities. In this case, a method includes a removal step in a selective manner (for example, mechanical removal or laser wear or photo-wear) or deactivation (for example photobleaching in optical form) of the optical gain material within those selected areas. . The substrate may be large in size to fabricate many micro-laser forming sphere structures, which are then physically separated by sawing or dice slicing, in a manner similar to that used in the fragmentation of integrated circuits. It also describes a sphere of a type that includes a support functionalized (an appropriate growth matrix to be used in at least one combinatorial chemistry application), and that also includes a medium • of gain coupled to a structure that supports the creation of at least one mode for electromagnetic radiation, and / or that has a dimension or length in one or more directions to produce and support spontaneous emission amplified (ASE). The structure may have limits that impart a general geometry to the structure which, in combination with at least one property of the material of the structure, supports an increase of electromagnetic radiation emitted from the gain medium favoring the creation of at least one so as to increase an emission of electromagnetic radiation within a narrow band of wavelengths. The information is encoded in the sphere using only wavelength coding, or using both wavelength coding and signal level coding. The information can be encoded using one of an individual level coding or multi-level coding.

BRIEF DESCRIPTION OF THE DRAWINGS The features indicated above and other features of the invention become more apparent from the following detailed description of the invention when read together with the accompanying drawings, in which: Figure 1A is an enlarged elevation view of a structure of a cylindrical sphere to produce micro-laser. Figure 1B is an enlarged cross-sectional view of the cylindrical sphere structure for producing micro-lasers. Figure 2 is a graph showing an example laser production emission from the cylindrical sphere-forming structure of the micro-laser. Figure 3 is an enlarged cross-sectional view of a cylindrical sphere-forming structure of micro-laser that can emit three different wavelengths and includes a functionalized support.

Figure 4 is an enlarged cross-sectional view of a micro-laser forming structure with spherical geometry, in accordance with one embodiment, or a top view of a micro-laser forming structure • disk-shaped, in accordance with another modality. Figures 5-9 show each embodiment of a laser-based optical system that uses Raman scattering to generate all or some of the multiple pump wavelengths. Figure 10 is a schematic diagram of a Raman laser module using a pumping Nd: YLF laser. • Figure 11 is a graph illustrating a typical emission spectrum of the Raman laser module of Figure 10. Figure 12 is a graph in which the energy output is plotted against the energy input, and thus Lustrates a slope of the efficiency curve for the Raman laser module of Fig. 10. Fig. 13 is a block diagram of a pump source / reader system mode. Figure 14 is a block diagram of a stamping step for the manufacture of a laser-forming sphere structure. Fig. 15 is an enlarged cross-sectional view of a laminated material of the laser-forming sphere structure with a crosslinked solvent-resistant polymer. Figure 16 shows additional manufacturing steps of the laser forming sphere structure, in which Figure 16A shows an integrated solid support, Figure 16B shows the bonding of the resins, such as the Dynospheres LLCs, commercially available by flexographic processes , of engraving or a procedure with inverse analox rollers, and Figure 16C shows the action of directly grafting the functionalized support. Figure 16D shows a further embodiment in which resin spheres are placed in cavities and fixed in place with a mesh-like structure, while Figure 16E shows a structure of mixed material of multiple fragments. Figure 17 is a top view of a wafer containing a • 10 plurality of laser-forming spheres structures, and a wavelength calibration and fragmentation in thin sheets of the wafer as individual laser-forming sphere structures. Figure 18 shows an example Lawn test reading technique in accordance with an aspect of this invention. Figure 19 illustrates a substrate having embedded fibers or filaments that emit light in narrow band, when excited by a • optical source such as a laser, which contain one or more characteristic wavelengths. Figure 20A illustrates a planchette mode of a sphere suitable for use in a combinatorial chemistry application or other application, in accordance with the teachings of this invention.

Figure 20B illustrates a filament or fiber embodiment of a sphere in accordance with the teachings of this invention and which is suitable for modalizing the filaments shown in Figure 19. Figure 20C illustrates a distributed feedback mode (DFB) of a sphere in accordance with the teachings of this invention. Figure 20D illustrates a top view of a planchette, such as in Figure 20A, or an end view of the fiber, in which the planchette or fiber is divided into sectors and is capable of emitting multiple wavelengths. Figure 20E illustrates a top view of a planchette, such as in Figure 20A, or an end view of the fiber, in which the planchette or fiber is structured radially so as to be capable of emitting wavelengths multiple Figure 21 is an enlarged cross-sectional view of one embodiment of a sphere that is also suitable for modalizing the filaments shown in Figure 19. Figure 22 is an enlarged cross-sectional view of another embodiment of the sphere of Figure 21 Figure 23 shows the emission peak of a dye selected in any of the modalities of Figures 20A-20E, before (B) and after (A) of a spectral collapse. Figure 24 shows the characteristic emission peaks for a filament constituted by a plurality of constituent polymer fibers, each of which emits a characteristic wavelength.

Figure 25 is a graph illustrating a number of appropriate dyes that can be used to form the gain medium in accordance with this invention. Figure 26 is a simplified block diagram of one embodiment of a sphere identification system which is an aspect of this invention. Fig. 27 is a simplified block diagram of a further embodiment of a sphere identification system which is an aspect of this invention; and Fig. 28 shows the amplitude of the emission wavelength signal and is useful to explain an embodiment of this invention in which both the wavelength and the amplitude of the encoded signal level are used.

DETAILED DESCRIPTION OF THE INVENTION Referring to Figures 1A and 1B, the cylindrical dielectric sheet structures are equivalent to a closed two-dimensional slab waveguide and support a resonant mode. Modes with Q values greater than 106 with active layer thicknesses of 1-2 μm and D ~ 5 μm - 50 μm are possible. The structure can be constructed in a manner similar to that described by Frolov et al. such that it includes a layer or film of LCP. Referring to Figure 2, the presence of the amplifying means in the guide region results in a laser oscillation with narrower emission spectra of about 1 Angstrom. Unlike fluorescence, the laser emission signature of the micro-laser forming sphere is not saturable and leads to detection with signal ratios at • high noise. With reference to Figure 3, the cylindrical geometry is ideal for producing laser emission with multiple wavelengths (e.g.,? I? 2? 3) from the micro-laser forming spheres. The core region can be metallic, polymeric or dispersing. Cylindrical geometry allows the use of economical extrusion and coating techniques in manufacturing • 10 of each of the micro-laser forming sphere codes. It should be noted that the sphere includes a functionalized support layer or region in the solid state, making it suitable for use in combinatorial chemistry applications such as those described above. The typical amplification coefficients required are in the range of 100 cm "1 resulting in optical pump absorption depressions of 50 μm - 100 μm This allows as many as N = 30 different laser forming layers in a single micro-laser forming sphere. transverse dimension of 50 μm together with a region of waveguide isolation (~ 1 μm), leads to N ~ 6 possible wavelengths from a single sphere. The number of optical bits for forming laser (M) for the micro-laser forming spheres is adjusted by the excitation sources, the detection range and the required wave separation (<1 nm). For example, for an excitation of 532 nm on the short wavelength side and a silicon detector response on the long wavelength side (900 nm), we have M-350. A binary coding scheme with up to N bits of a total of M possibilities leads to a coding capability r. The reading systems that have direct applicability in combinatorial chemistry and in HTS applications allow the reading of the wavelength signatures of the spheres. The wavelength range and the coding capacity of the cylindrical micro-laser producing spheres can be extended using compact and intense nanosecond sources that extend through the range of the silicon detector. The excitation source can preferably be located spatially and the laser excites the individual micro-laser producing spheres in a wide field of view. Although the description has been made up to now in the context of LCP material as a gain material, other gain materials can be used in the same way. Other suitable gain media materials include, but are not limited to, semiconductor polymers, PPV, methyl-PPV, etc.; dye-doped polymers, sol-gel glasses and many other glass, such as glass impurified with semiconductor, and stimulated Raman medium. In general, any means of gain having a refractive index greater than that of the core and that of the surrounding insulation layers can be used. The teachings of this invention are not limited solely to elongated cylindrical structures, for example, and with reference to Figure 4, a generally spherical geometry can be provided, in an "onion skin" mode with one or more layers of material of gain and layers of insulation. Each of the micro-laser forming spheres can be used in a combinatorial chemistry application or in some other application. In addition, the structure could be fabricated in the form of an elongated fiber and then cut into disk-shaped structures. In this case, a minimum disk thickness would be in the order of a half of the wavelength. Any suitable pump source can be used. For the case of multiple wavelength emission, one or more pumping sources may be required, or a single pumping source that is capable of emitting a plurality of wavelengths. A dye laser is one such example. Further, in accordance with this invention, other appropriate wavelength pumping sources utilize Raman scattering stimulated in a narrow line width, salts with high Raman cross section, such as Ba (N? 3) 2, Ca (CO3) ) and NaNO3 (in general Rx (M03) y). Such a source can be used to create a low maintenance, low cost, compact pumping source in a totally solid state to excite spherical structures. Preferred crystals have Raman gains of the order of 10-50 cm / GWatt and exhibit excellent transparencies with typical shifts in the range of 1000-1100 cm "1 (for example, Ba (NO3) 2 gives 1047 cm" 1). In addition, the Raman procedure does not match the phase so that the source is extremely insensitive to the vibrations, translations and rotations of the crystal. The typical costs for such crystals can be $ 1000 dollars or less, and simple single step gain designs or resonant cavity designs are suitable for most if not all applications. In addition, the use in some embodiments of a robust NdrYAG laser to drive all the required wavelengths results in a much improved life and improved service requirements. Figure 5 shows a first mode of an optical source in a totally solid state 10 which is capable of providing wavelengths of red-green-blue (RGB) pumping. The source 10 uses a Nd: YAG laser with individual Q switches that emits 1.06 micron light, an external frequency duplicator, such as a KTP crystal to produce 532 nm light, an additional non-linear crystal to generate 355 nm light, and two Raman scattering structures with resonant cavity each using a selected crystal of R? (MO) and to generate red light and blue light. The green light is generated directly from the emission of Nd: YAG with a duplicate frequency of 532 nm. Figure 6 shows a second embodiment of an optical source in a fully solid state using an Nd: YAG laser with duplicated Q switches inside the cavity and a Nd: YAG laser with separate Q switches. The two lasers are electrically and delayed synchronized so that the combined pulses are applied to a non-linear crystal in the Raman channel of blue light. The red light is generated by a second resonant cavity structure of Raman scattering from the 532 nm light, while the green light is obtained directly from the light at 532 nm. This method can provide higher energies than the modality of Figure 5. • Mode 30 and Figure 7 use only light at 532 nm and 5 coherent Raman dispersion Anti-Stokes (CARS) to produce blue color emission. The red and green emissions are generated in the manner shown in Figure 6. Mode 40 of Figure 8 uses Raman shift for both red and blue emissions. • 10 Mode 50 of Figure 9 uses the Anti-Stokes which are emitted as a ring or as a "donut" from the resonator. This ring is then converted by an optical diffraction element into a solid spot, thus providing the RGB source in solid state with a single laser source. It is worth mentioning that the inventor observed up to the fourth Stokes (? O - 4? R) and up to the third Anti-Stokes without using the resonator. Figure 10 illustrates a Raman laser module 60 using a pump laser Nd: YLF. The mirrors in the Raman cavity are as follows. The output coupler is highly reflective at 527-590 nm, and has R = 70% at 630 nm. The input coupler is highly transmissive at 527 nm and highly reflecting at 557-630 nm. The input coupler has a concave curvature radius of 10 cm, and the output coupler is flat. This configuration is, of course, only as an example for the 5 cm barium nitrate crystal that was used in the cavity.

As an example, an Nd: YLF laser from Photonics Industry is operated at a PRR of 300 Hz and a PW of 200 nsec. The curve efficiency at 630/527 nm is approximately 17.5% with the maximum energy at 630 nm = • 330 mW at a green output of 2.4 W. FIG. 11 is a graph illustrating a typical emission spectrum of the Raman laser module of FIG. 10; and Figure 12 is a graph in which the energy input against the energy output is shown, and thus an efficiency curve slope is illustrated for the Raman laser module of Figure 10. • 10 Referring to 13, a device 70 for reading the emission wavelengths can be constituted of a spectrometer, preferably with monolithic spectrometer 72. A device as such can comprise an optical fiber 74 and a diffraction grating 76 to allow the individual wavelengths emitted by a structure forming The individual laser or sphere is resolved and identified through the use of a multi-pixel detector 78, such as a CCD array. A color search table (LUT) 80 can be used to issue a code or sphere identification (sphere ID) corresponding to the detected wavelength or lengths. The laser source 82 for the reading device can be any of the various sources referred to above. An appropriate spectrometer is one known as an S2000 miniature fiber optic spectrometer that can be obtained from Ocean Optics, Inc.

The teachings of this invention also cover the use of a reader device with a search phase, a target selection phase, or a targeting phase, and a laser excitation phase (i.e., search, • pointing and firing (or SPS), such as that based on or similar to those described in patent application E.U.A. Commonly assigned serial number 09 / 197,650, filed on November 23, 1998, entitled "Self Targeting Reader System for Remote Identification" by William Goltsos, the disclosure of which is incorporated herein by reference in its entirety. This type of reading system can be used to quickly read the results of ^ BP 10 any "reporter" essay in a one-dimensional, two-dimensional or three-dimensional field. In one example, the Lawn test using E-coli (or other bacteria) and a reporter gene (for example, a test for green fluorescent protein or a chemiluminescent protein) can be used to provide an optical fiber correlated with a specific target, when a solid support containing the compound is placed on it. The optically encoded spheres with synthesized material are randomly deposited on the medium (e.g., agar), resulting in an area of approximately 6 mm to 8 mm in activity that arises from the successful test. This activity gives as The result is also a fluorescence that is detected by the search phase (for example a camera for digitizing the intensities with a defined range and / or parameters of the affected area (for example, radio, etc.)). The SPS device then points to or selects the sphere as white and then illuminates (shoots) it with a sufficient laser pulse to read its optical code. The optical code can arise from a laser-forming material or fluorescent material on the sphere, such as those described above and / or subsequently described in the flat device mode. The SPS system can then read the Lawn test at a rate of approximately 20 msec / sphere, a time that is several orders of magnitude faster than what is possible with currently available millimeter or submillimeter scale elements or support spheres solid. In addition, no manipulation is required to read the code, such as manipulation for chemical deconvolution or mass spectroscopy. The method can use the creation of threshold values to establish the level of activity of the test, which allows the selection of different levels of activity. This allows users to refine their understanding of which molecular parameters (eg, ring position) generates the activity for a specific target (drug). For other tests, such as direct bonding or fluid based testing, the search phase can be replaced by any coordinate source. For the liquid systems in the tests, the spheres located in the plate of the sample and other types of cavities can be read by means of coordinates which are supplied to the pointing and firing stages. For radioactive tests with x-rays and gamma rays, the coordinates can be obtained from CCD arrays (for example, those made of amorphous silica) or from flash plates to create a signal for the optical pointing phase. Other tests that could create changes in the temperature can also be used with calorimetric, piezoelectric or thermoelectric sensors with a pattern to create a coordinate location for the pointing and firing phases of the optical code reading. Referring to Figure 18, an example Lawn test is shown in which the example fluorescent GFP rings (R) result in sites of spheres with test activity. A UV source 92 is used to illuminate the micro-laser forming spheres in accordance with the embodiments of this invention. GFP or UV-irradiated chemiluminescent tests irradiate and provide power to an appropriate sensor 94 (possibly with threshold values) for the search phase of the SPS system. Then the coordinates of the sphere are provided to a laser 96 (L) having a ray that can be directed, and the laser 96 then selects as target the specific spheres (for example 9, 11, 22) with the ray of interrogation that can be addressed 96a. A detector (D) 98 that can discriminate the various possible emission wavelengths (? S) resulting from the laser excitation, such as the monolithic spectrometer 72 of FIG. 13, sends a list of the wavelengths detected towards an associated processor (P) 100. The processor 100, which may include the color search table (LUT) 80 of FIG. 13, emits the identification of the sphere (ID) based on the wavelengths of detected emission codes for the sphere ID, which identifies the areas of interest. As mentioned above, the search phase can be calibrated to detect activity levels by multiple threshold value levels, and is not limited to a single threshold value (binary, yes / no) needed to handle the slow deconvolution speeds of the sphere. The search phase may be sensitive to the presence of a particular fluorescent or chemiluminescent emission region or ring, as well as to the size of the region (or the diameter of the ring). This aspect of the invention thus provides a system and method for identifying a particular sphere in a combinatorial chemistry application or similar application. The method includes a first step of providing a population of spheres, wherein each of the spheres includes a functionalized support and means for optically encoding the identification information of the sphere. A second step uses the sensor 94 that responds to a desired sphere activity to identify a location of one or more spheres of interest within the population of spheres. A third step uses the identified location to direct an interrogation beam 96a to a particular sphere, and another step determines, using the detector 98, the processor 100 and LUT 80, an identification of the particular sphere from a plurality of wavelengths emitted by the particular sphere in response to the interrogation beam 97a. The sensor 94 can be constituted by at least one of an optical energy detector, an ionizing radiation detector or a thermal energy detector. The sensor 94 may be capable of operating with more than one sensitivity threshold value. It is worth mentioning that the sensor 94, particularly when it detects ionizing radiation energy (eg alpha, beta, gamma) or thermal energy, can be integrated into or placed below the plate, plate or other type of container containing the spheres, as indicated generally by the sensor 94 '. The sensor 94 'may be, for example, a flash type imager or a CCD for ionizing radiation, or a bolometer or other type of thermal energy detector. Preferably, the sensor 94 'differs in particular by patterns or differs in some other way so as to provide a desired degree of spatial resolution when it detects a location of a sphere or spheres of interest. For the optical power detector 94, the detector could be sensitive to fluorescent emission or a chemiluminescent emission from the spheres of interest, or in some embodiments to a lack of an optical emission (e.g., the spheres normally fluoresce, and the Fluorescence is deactivated by a desired sphere test activity). In the latter case, the system 90 can instead search for "dark spots" on a fluorescent background, and can then direct the interrogation laser to the dark spots. Although it has been described mainly in the context of a combinatorial chemistry application, it should be appreciated from the foregoing that these teachings apply equally in high-throughput screening applications, including products that work against a goal, such as the test of Lawn described above, as well as genomic applications, including genomic products, targets and / or polymorphisms. Figures 14-17 show various steps related to the manufacture of micro-laser producing spheres, also known as laser sphere structures, in accordance with additional embodiments of the teachings of this invention. Figure 14 is a block diagram of a printing step in the manufacture of laser-forming spheres structures, in which a head • N 10"colors" 102 is controlled by a head controller 104 and a computer 106. A substrate 110, such as a polymer or glass substrate of one meter by one meter (e.g., crosslinked polystyrene) (or other appropriate material) , it is placed on a cover XY 108 below the head 102. The head 102 includes a capillary dispenser 102a which can preferably be to move along a Z axis, to controllably place or print "points" of selected gain medium material, such as one or more of those previously listed, on a region of the surface of the substrate 110. Each point it can be considered as a micro laser capable of laser-type emission at a predetermined wavelength or "color". The illustrated modality shows three points to emit a? I,? 2 and? 3. In this way each region could contain a plurality of points and could be capable of emitting with a plurality of distinguishable wavelengths.

Fig. 15 is an enlarged cross-sectional view of a laminate material of laser-producing sphere structure with a cross-linked polymer resistant to solvents. In this case a sphere structure 120 • containing the three microllaser points of Figure 14 is contained between the protective substrates 122, 124 using a solvent-resistant crosslinked polymeric adhesive 126. In general, at least one of the protective substrates is substantially transparent (at the lengths of excitation wave and emission of interest) and is arranged between the surface that leads to microllaser points and the environment. Figure 16 shows the additional manufacturing steps of the laser forming sphere structure, wherein Figure 16a shows an integrated solid support, in which a functionalized support 130 (or growth matrix) is directly attached or grafted, Figure 16B shows a union of resin particles 132 (ie, the growth matrix or support functionalized in particulate form), such as a commercially available functionalized support of LLC Dynosphere, with a crosslinked adhesive • 126 through flexographic processes, of engraving, or an inverse analox roll process, and Figure 16C shows a modality that uses the direct graft of the functionalized support (growth matrix 130) on the protective substrate (122 or 124). Examples of suitable polymers for the protective layer 122 include poly (styrene-oxyethylene) (PS-PEG), aminomethylated polystyrene-PS, hydroxyethyl methacrylate-PE, methacrylic acid / dimethylacrylamide-PE and polyvinyl glass / polystyrene glass. In all these embodiments, a substrate is coded optically in accordance with the teachings of this invention so as to allow the sphere structure to be identified. Figure 16D shows a side and top view of a further embodiment 140 in which a functionalized support constituted of the resin spheres 144 are placed in the cavities formed in a frame 142 in combination with a coded film 146. The spheres 144 are they maintain in the cavity with a polymeric structure type mesh 148. Figure 16E shows a structure of mixed material of multiple fragments comprising a plurality of cavities covered with the structure type mesh 148. The structure • 10 mesh type 148 allows spheres 144 to come into contact with chemical compounds. The embodiment of Figures 16D and 16E allows the use of almost any commercial resin sphere, and therefore it is not necessary to fix the reaction medium to the coded substrate. A cavity space is provided to allow the resin to expand, and the size / volume of the cavity can be adjusted to accommodate almost any desired load. In general, the • modality of figures 16D and 16E provides a relatively simple construction. In another embodiment, the functionalized support, preferably in The shape of resin particles can be sprayed onto a sticky or "tacky" coded substrate layer (such as in the embodiment of Figure 16B), while in another embodiment the resin particles can be fluidized in air, and combine with optically encoded substrates "that have become sticky". In any case, the resin particles adhere to the surface of the substrate that has become sticky. Figure 17 is a top view of the substrate or wafer 110, such • as shown in Figure 14, which contains a plurality of regions that define each of the laser-forming sphere structures, and also shows the wavelength calibration and fragmentation in thin wafer sheets in structures of individual laser forming sphere 110a. In this case the particular wavelength signature of each sphere structure 110a can be read by illumination with an excitation source • 10 appropriate (for example, a laser), detecting the wavelengths emitted, and then cataloging and storing (possibly in LUT 80) the wavelength signature. Fragmentation in thin wafer sheets as individual laser sphere structures can be achieved by, for example, scratching or breaking, mechanical sawing or laser cutting, i.e. using techniques based on or similar to those used in semiconductor chip fabrication techniques. The embodiment of Figure 14 shows a technique for essentially stamping the desired individual micro-lasers on the surface of the substrate. For example, for each laser sphere structure, it is printed in a individual a subset of nine different micro-lasers from a set of, for example, 25 micro-lasers. It should be understood, however, that in accordance with a further embodiment of this invention the complete set of 25 micro-lasers could be provided on each laser sphere structure (e.g. on the wafer) and then selectively removed or deactivated. number of these. For example, a screen printing procedure could be used to simultaneously form a large number of • laser sphere structures on the wafer (see Figure 17), with each laser sphere structure initially comprising a complete complement of micro-lasers. Then some appropriate methods, such as laser-activated photobleaching or wear, can be used to selectively deactivate or eliminate those selected micro-lasers in each laser sphere structure, resulting in laser sphere structures that present • 10 each one its signature of multi wavelength emission characteristic. Having thus described a number of embodiments of this invention, reference will now be made to Figures 19-28 for a discussion of further embodiments of this invention. It should be indicated first that the description of the patent E.U.A: No. 5,448,582 issued September 5, 1995, entitled "Optical Sources Having a Strongly Scattering Gain Medium Providing Laser-like Action", by Nabil M.

• Lawandy is incorporated herein by reference in its entirety in the present invention. The description of the U.S. patent is also incorporated for reference in its entirety in the present invention. No. 5,434,878, issued on 18 July 20, 1995, entitled "Optical Gain Medium Having Doped Nanocrystals of Semiconductors and also Optical Scatterers", by Nabil M. Lawandy. This aspect of the invention uses sphere structures that contain an optical gain means that is capable of exhibiting laser-like activity (e.g., emission in a narrow band of wavelengths when excited by an excitation energy source). However unlike the structures described in the patent • E.U.A. No. 5,448,582, the sphere structures in accordance with the teachings of this invention do not require the presence of a dispersion phase or scattering sites to generate the narrow band of emissions. In contrast, the optical gain medium that provides the amplified spontaneous emission in response to illumination may also respond to, for example, size restrictions, structural constraints, constraints of • 10 geometry and / or mismatches of the refractive index to emit the narrow band of emissions. In other words, restraints in size, structural constraints, constraints on geometry and / or refraction index mismatches are used to provide at least one mode in the structure of the sphere that favors at least one band. narrow wavelengths over other wavelengths, allowing the energy emitted in the narrow band of wavelengths to be added constructively. In other words, size constraints, structural constraints, geometry constraints and / or refractive index mismatches are used to provide the presence of amplified spontaneous emission (ASE) in response to a lighting step. It should be mentioned that ASE can be provided within a mode, but that does not require a way to have ASE. In general, ASE can occur in an amplified medium in a homogeneous and non-homogeneous manner.

The sphere structure according to this aspect of the invention is thus comprised of a matrix phase, for example a polymer or glass, which is substantially transparent at the wavelengths of interest, and an amplification phase of electromagnetic radiation. (gain), for example a dye or a rare earth metal ion. The amplification (gain) phase is placed within a structure, in accordance with the teachings of this invention, wherein the structure has a predetermined size, or structural characteristics or geometry and / or a refractive index that differ from the refractive index of the environment within which the sphere structure is intended to be used. The structure tends to confine and possibly guide the emission of electromagnetic radiation from the amplification phase (gain) and could favor the creation of at least one mode, or the creation of amplified spontaneous emission (ASE). In either case, the emission may be contained within a narrow range of wavelengths, eg, a few nanometers wide, and is considered in the present invention as a narrowband emission. The matrix phase may comprise the material forming the structure of the sphere, such as a polymeric planchette containing the amplification phase of electromagnetic radiation (gain). Figure 19 illustrates a first embodiment of this aspect of the invention. A substrate, such as a polymer or glass substrate 10 includes a plurality of embedded stretched bodies or filaments 212 that include a host material, such as a textile fiber or a polymer fiber, that is coated or impregnated with a colorant or some other material able to amplify the light. The filaments 212 have electro-optical properties consistent with the laser action; that is, an output emission that exhibits both a spectral line width collapse and a temporary collapse to an input pumping energy above a threshold value level. In response to illumination with laser light, such as the duplicated frequency light (ie, 532 nm) from the Nd: YAG laser 214, filaments 212 emit a wavelength? which is characteristic of the chromic dye or other material comprising the illuminated filaments 212. A reflective coating can be applied so as to increase the emission from the filaments 212. An optical detector 214, which can include a selective filter of length of wave, can it be used to detect the emission at the wavelength? The emission can also be detected visually, assuming that it lies within the visible portion of the spectrum. In any case, the detection of the emission at the characteristic wavelength? it indicates at least the presence of the sphere structure, and an identity of the sphere structure is also possible. As discussed above, the addition of multiple wavelength emission allows a larger number of spheres to be individually coded and identified. In this case the filaments 212 can be selected from different groups of filaments, with each group having a characteristic wavelength emission. Figure 25 illustrates a number of illustrative dyes that are suitable for the practice of this invention, and shows their relative energy output as a wavelength function. The teachings of this invention are not limited to use with only the dyes shown in Figure 25. • Figure 20a is an enlarged elevation view of a small disc-shaped structure, also referred to as a planchette 212A. The planchette 212A may be provided with a functionalized support layer or region and may be used as a sphere structure, or it may be added to a larger sphere structure substrate material to optically code the sphere structure further. big. The planchette • 212A has, for example, a circular cylindrical shape with a diameter (D) and a thickness (T) that is smaller than the dimensions of the substrate material to which the tablet will be added. For example, both D and T can be significantly less than 100 micras. In addition, and in accordance with this invention, T and pD, the perimeter, may be selected to have values that are a function of a desired emission wavelength, such as one half wavelength or some multiple of one half wavelength. To this end, the planchette 212A is comprised of a polymer, or a glass, or some other suitable material, which contains an optical amplification (gain) material, such as one of the dyes shown in FIG. 25. A surface of Planchette 212A may be provided with a reflective coating. It is also preferred that the refractive index (n) of the planchette 212A be different from the refractive index (n ') of the desired substrate material (ie the planchette 212A does not coincide in index with the surrounding substrate).

A planchette can also be designed so that the ASE through the thickness T creates a narrow band emission, or so that the ASE along an internal reflection path, such as the perimeter, leads to • narrow band emission. Figure 20B depicts a fiber embodiment, in which the diameter (DM) of fiber 212B is made to have a value that is a function of the desired emission wavelength, such as a half wavelength or some multiple of one half wavelength. As in the planchette embodiment of Figure 20A, the fiber 212B comprises a polymer, or a glass or • some other suitable material, containing an optical emitter, such as one of the dyes shown in Figure 25. It is also again preferred that the refractive index (n) of the fiber 212B be different from the refractive index ( n ') of the desired substrate material so that the fiber 212B is non-coincident in index with the surrounding substrate. In this modality the radiation electromagnetic that is emitted by the dye is confined to the fiber and propagated in it. Due at least in part to the diameter of the fiber 212B a • narrow band of wavelengths is preferred over other wavelengths, and the energy in this band of wavelengths accumulates over time, relative to the other wavelengths. Preferably the DM diameter is made a function of the emission wavelength of the selected dye. The end result is a narrow band emission of the fiber 212B, when the dye contained in the matrix material of the fiber 212B is stimulated by an external laser source. A plurality of different fibers 212B, having a characteristic emission wavelength, can be added to the substrate material of a sphere to optically code the sphere identification. Figure 20C depicts a distributed feedback pattern (DFB) of the sphere structure or an emission structure that is designed to be incorporated within a larger sphere structure. In the DFB mode a periodic structure composed of regions of first and second refractive indices (ni and n2) alternate along the length of the structure of DFB 212C. Preferably neither is not equal to n2 and neither are • 10 equal to n '. The thicknesses of each of the regions may be a quarter of a wavelength, or a multiple of a quarter of a wavelength, of the desired emission wavelength to provide a mode for the desired emission wavelength. Figure 23 represents the maximum emission point of the dye selected, in any of the modalities of Figures 20A-20E, before (B) and after (A) of the collapse of spectrum made possible by the • structure that has a predetermined size, or structural features, or geometry, and / or a refractive index that differs from the refractive index of the substrate or environment within which the structure is designed to be used. In general, and for the case of spontaneous emission amplified for high gain, half amplified homogeneously, the general expression is (for a cylinder type geometry): ?? / ?? or = 1 / sqrt (2gL), where g is the gain (for example 200 cm "1), and L is a length that results in narrow band emission.The structure can include a propagation mode, and the mode can help guide the electromagnetic radiation, but • the mode is not necessarily for the ASE to occur. For a dye, the gain g is approximately 200 cm "1, as well as for a line width collapse of 10 times (/ / o = 0.1), L is approximately 2.5 mm.

Figure 20D illustrates a top view of a planchette 212A, as in Figure 20A, or an end view of the fiber 212B in which the planchette or fibers are sectorized (for example four sectors) and is capable of emitting • 10 multiple wavelengths (??). Figure 20E illustrates a top view of a planchette 212A, as in Figure 20A, or an end view of the fiber 212B, in which the planchette or fiber is radially structured so as to be capable of emitting multiple wavelengths. Said multi-wavelength modalities in themselves lead to the coding of wavelength of Information, such as sphere identification information, as discussed above and will be discussed in further detail below. Figure 21 illustrates an embodiment of a structure in which one or more regions (for example three) 222, 224, 226 each include, for example, one or more colorants either alone or in combination with one or more rare earths that are selected to provide a desired wavelength? -i,? 2,? 3. An underlying substrate, such as a thin layer of transparent polymer 228, lies on top of a reflective layer 230. The reflective layer 230 may be a thin layer of sheet metal, and may be corrugated or otherwise formed or patterned as is desired The structure can be cut into thin strips that can be used to form the filaments 212 shown in Figure 19. Under a low illumination level provided by, for example, a UV lamp, a broadband fluorescent emission can be obtained. characteristic (eg, a few dozens of nanometers or larger) of the colorant and / or phosphorus particles. However, when excited by the laser 214 the structure emits a characteristic narrow band emission (e.g., less than 10 nm) at each of the wavelengths? I,? 2,? 3. The presence of these three wavelengths can be detected with the detector or detectors 216, in combination with suitable optical bandpass filters (see also figure 26), thus also providing identification of the sphere containing the structure . Alternatively, a spectrum analyzer (see also figure 27), such as a monolithic detector arrangement with, for example, an optical wedge, can be used to detect the spectrum. The output of the spectrum analyzer is then analyzed to determine maximum points? and derivatives, and can be compared with the default search box (see also the modality described above with respect to figure 18). If desired, a suitable coating 232 can be applied to the regions 222, 224 and 226. The coating 232 can provide, for example, UV stability and / or protection from abrasive forces. A thin transparent coating of UV absorbing polymer is a suitable example, as are dyes, pigments and phosphors.

For the case where the coating 232 is applied, the coating can be selected to be or contain a fluorescent material. In this case, the coating 232 can be excited with a UV source to provide broadband emission. The filaments 212 may comprise fibers such as nylon-6, nylon 6/6, PET, ABS, SAN and PPS. For example, a selected dye can be selected from Pyrrometene 567, Rhodamine 590 chloride, and Rhodamine 640 perchlorate. The selected dye can be formed into a compound with a selected polymer resin and then extruded. Wet spinning is another suitable technique for forming the fibers. A suitable dye concentration is 2 x 10"3 M. Extrusion at 250 ° C followed by cooling in a water bath is a suitable technique for forming the fibers 212. When used on a flat substrate the diameter is measured from properly, and according to the selected emission wavelength (s). An adequate inflow (pump 212) of excitation is on the scale of about 5 mJ / cm2. Two or more fibers, each containing a different colorant, can be braided together or otherwise connected to provide a composite fiber that exhibits emission at two or more wavelengths. Alternatively, the sectorized mode of Figure 20D, or the radial embodiment of Figure 20E, may be used. It must be realized that single-cut fibers constructed in this way can be used to create the 212A planchets. For example, Figure 24 illustrates the emission of a twisted pair of nylon fibers, excited in the 532 nm line of a double-stranded laser 212. frequency Nd: YAG, which contains 2 x 10"3 M Pirrometene 567 and Rhodamine 640 perchlorate with maximum emission points at 552 nm and 615 nm, respectively, by varying the types of fibers doped with dye in various combinations of braided fibers or combined in other ways, the resulting composite fibers 5 or filaments 212 make it possible to encode information optically, such as the identification of the sphere and / or some other information relating to the sphere, the characteristic emission lines may be spaced narrower than the shown in Figure 24. For example, in which the emission lines of individual fibers are of the order of 4 • 10 nm, one or more additional emission wavelengths can be spaced apart at intervals of approximately 6 nm. The dye can also be incorporated by a polymer coloring process with active sites and dyes specifically designed to bind to the active sites. 15 It is also within the scope of these techniques to provide a single fiber with two dyes, wherein the emission from a dye is used to • excite the other dye, and in which only the emission from the second dye may be visible. In a Rhodamine 640 embodiment, it is excited at 532 nm. The Rhodamine 640 emits 620 nm radiation which is absorbed by Nile blue, which in turn emits at 700 nm. Figure 22 illustrates a modality in which the polymer substrate 228 of Figure 21 is removed, and the regions 222, 224 and 226 are arranged directly on the reflective material layer 230 or other pattern material. In this embodiment it can be seen that a thickness modulation of the gain medium regions occurs, allowing multiple wavelengths to occur if multiple dyes are included. Figure 26 illustrates one embodiment of an apparatus suitable for reading spherical identifications according to one aspect of this invention. The sphere reading system 250 includes the laser 214, such as but not limited to a dual frequency laser Nd: YAG having a pulse output 214a. The ray 214a is directed to a mirror M and from there to the sphere structure • 10 210 that will be read (such as one of the flat sphere structures shown in Figures 14-17). The structure 210 may be disposed on a support 252. One or both of the mirror M and the support 252 may be capable of movement, allowing the beam 212a to scan over a population of the sphere structures 210. Assuming the sphere structure 210 includes the filaments 212, and / or planchettes 212a, or any of the other embodiments of sphere structures described, generate one or more wavelengths of • broadcast (for example,? A? N). A suitable bandpass filter F can be provided for each emission wavelength of interest (eg, F1 to Fn). The output of each filter F1-Fn is optically coupled through free space or through an optical fiber to a corresponding photodetector PD1 to PDn. The electrical outputs from PD1 to PDn are connected to a controller 254 having an output 254a to indicate identification or sphere identifications. The sphere identification can be declared when it is discovered that all the expected emission wavelengths are present, ie, when all or some subgroup of PD1 to PDn emits each, an electrical signal that exceeds some predetermined threshold. A further consideration may be an expected intensity of the detected wavelengths and / or a ratio of 5 individual wavelength intensities to one another. It should be realized that the support 252 could be a conveyor belt or some other mechanism for moving sphere structures or containers or cavities containing sphere structures of the stationary or scanned beam 212a. It must also be realized that a prism, wedge • 10 or grid could replace the individual filters F1-Fn, in which case the PD1-PDn photodetectors are spatially located to intercept the specific wavelength outputs of the prism or grid. The PD1-PDn photodetectors could also be replaced by one or more area image forming arrangements, such as a training arrangement image of silicon or CCD, as shown in figure 27. In this case it is expected that the arrangement will be illuminated in certain pixel locations • predetermined if certain emission wavelengths are present. It is assumed that the photodetector (s) or image formation arrangement (s) exhibits an adequate electrical response to the wavelength or wavelengths of interest. However, as noted above, it is possible to closely spaced the emission wavelengths (e.g., the emission wavelengths can be spaced at approximately 6 nm). This allows a plurality of emission wavelengths to be located within the maximum range of wavelength response capability of the selected detector (s). The controller 254 can be connected to the laser 214, mirror M, support 252, and other system components, such as a rotatable wedge that replaces the fixed filters F1-Fn, to control the operation of those various system components. Figure 27 is a simplified block diagram of a sphere reading system 250 'which is a further aspect of this invention. The apparatus of Figure 27 may be similar to that of Figure 26, however, controller 254 'may also emit a counting signal 254a', along with the sphere identification signal, and may also provide a signal to a mechanism diverter 253 to direct one or more spheres identified to a predetermined destination. In this embodiment it is assumed that the support 252 is a conveyor belt or some similar apparatus that transports spheres beyond the stationary or scanned beam 212a. It should be noted that the spheres could also be located in a flow channel and flow past the beam 212A. If only a counting function is used then a minimum of one wavelength (and therefore a photodetector) needs to be used, assuming that only one type of sphere will be counted. A wavelength could also be used in the case of identification, if it is assumed that a desired type of sphere emits a predetermined wavelength while other spheres do not emit at all or emit at a different wavelength. In this case, the diverter mechanism 253 can be activated whether the expected emission is present or not present. Figure 27 also shows the case where the photodetectors • Discretes of Figure 26 are replaced by a monolithic area arrangement 5 253 comprised of pixels 253a. The arrangement 253, in combination with some type of device for spatial distribution of the output spectrum on the array, such as a wedge 255, provides a spectrum analyzer in combination with the controller 254 '. That is, the spectrum (SP) emanating from the sphere structure 210 is detected and converted to an electrical signal for analysis by software in controller 254 '. For example, the maximum points in the spectrum are identified and associated with particular wavelengths by their locations on the 253 array. The information that is conveyed by the maximum wavelength points (and / or some other spectrum feature, such as maximum point width, or maximum point spacing, or the derivative) is then used to at least uniquely identify the sphere structure 210, and / or to detect a type • of sphere structure 210, and / or to determine some other information about sphere structure 210, and / or to count and / or classify sphere structures 210. 20 Additionally according to the teachings of this invention the coding of several substrates can be achieved by a strictly binary wavelength domain code, or by a method that also includes the amplitude of the signals.

In the binary scheme the sphere structures or other structure substrates can be impregnated with combinations of N wavelengths of laser production of a total variety of M laser production wavelengths. The presence of a signal at a specific wavelength denotes a "1" while its absence denotes a "0". If M wavelength selections are available, for example in the form of 212B fibers or 212A planchets, then there is a total of 2M-1 possible codes. For example, M = 3 different wavelength fibers can create seven different codes. Additionally, if only N wavelengths at a time are incorporated in any given sphere or substrate structure, then there are: z7L =. M \ M (M - N) \ N \ possibilities, where! indicates factorials For example, with M = 5 different laser wavelengths to select from one you have: z- (1 fiber in each substrate) = 5 z- (2 fibers in each substrate) = 10 z- (3 fibers in each substrate) = 10 z- (4 fibers in each substrate) = 5 z- (all 5 fibers in a substrate) = 1 Increased coding capacity can be obtained by allowing more bits to be associated with each wavelength. This can be achieved by considering the signal levels at each wavelength, as indicated in Figure 28 for a specific wavelength? 0. The signal level can be directly controlled by the density of each of the coding transmitters in each substrate. For example, three bits at a given 0? Can be created as: "0", without emission at? 0"1", emission at a signal strength = A "2", emission at a signal strength = B > A, Where A is a selected signal level corresponding to a given charge of the laser production emitter. Also as an example, the information encoded in? 0 can be as follows "0", without emission to? 0 p + 1", emission at a signal strength = A p-1", emission at a signal strength = B > A Using an illustrative trinary scheme as described, M different wavelengths can create 3N-1 discrete codes. If discrete AND amplitude levels are selected, then there are YN-1 selections. In an illustrative multi-level coding scheme, a total of 26 codes are provided for M = 3, Y = 3, as opposed to seven in the strictly binary case. The teachings of this invention generally encompass the use of sphere structures, which are considered to be a multi-component material, fibers, such as polymer filaments and textile filaments, as well as planchets, which may be round bodies such as disk or polygonal which are placed on the substrate, and which may include a coating having the optical emitter. This invention therefore teaches a sphere structure comprising a gain means coupled to a structure that supports the creation of at least one mode for electromagnetic radiation. This invention further teaches a sphere structure comprising a gain means coupled to a structure having a dimension or length in one or more directions to produce and support amplified spontaneous emission (ASE). This invention additionally teaches a sphere structure comprising an optical gain means and a structure having limits imparting a total geometry to the structure which, in combination with at least one material property of the structure, supports an improvement in radiation electromagnetic radiation emitted from the gain means to favor the creation of at least one mode that improves an emission of electromagnetic radiation within a narrow band of wavelengths. Suitable forms, but not limiting, for the structure comprise elongated shapes, be able to join or adhere with a desired substance. The desired substance can be, for example, an organic or inorganic chemical compound, a genomic product or polymorphism, a fragment of DNA or RNA, a • bacteria, a virus, a protein or, in general, any desired element, compound, or structure or molecular or cellular sub-structure. Thus, although the invention has been shown and described in particular with respect to preferred embodiments thereof, it will be understood by those skilled in the art that changes in form and detail may be made thereto without departing from the spirit and scope of the invention. the invention. ^ 10 fifteen • twenty

Claims (35)

6 NOVELTY OF THE INVENTION CLAIMS

1. - A structure, comprising: a core; at least one layer of gain medium disposed about said core to provide a characteristic emission wavelength; and a functionalized support for adhering to a desired substance.

2.- A structure that includes: a nucleus; a plurality of gain medium layers disposed around said core to provide a plurality of characteristic emission wavelengths, said plurality of gain medium layers being adjacent to insulating layers having a larger refractive index; and a functionalized support for adhering to a desired substance.

3. A multiple-spectrum light source comprising at least one laser pump, means for selectively providing at least one pump wavelength to a plurality of optical channels comprising at least one Raman-based resonator structure for generating at least one of red and blue light, and to illuminate at least one micro-laser sphere structure comprising a functionalized support for adhesion to a desired substance.

4. - A light source according to claim 3, further characterized in that the plurality of optical channels are a red channel, a green channel and a blue channel.

5. A light source according to claim 3, further characterized in that the outputs of the plurality of optical channels are provided to excite the sphere structure to emit a wavelength identification group.

6. A light source according to claim 5, further characterized in that it additionally comprises a spectrometer for • 10 solve and detect said emitted group of wavelengths.

7. A light source according to claim 6, further characterized in that it additionally comprises means for identifying an individual sphere structure according to the detected group of emitted wavelengths.

8. A method for manufacturing a laser sphere structure, comprising the steps of: providing a substrate; depositing a plurality of regions of optical gain material on a surface of said substrate, each region is comprised of a plurality of areas each containing optical gain material, each area being capable of emitting a predetermined wave length that differs from a wavelength emitted by others of the plurality of areas within said region; and physically dividing the substrate into a plurality of individual laser sphere structures of which it comprises at least one of said areas.

9. - A method according to claim 8, further characterized in that the deposition step uses a head structure to selectively print optical gain material in said areas, and a mechanism to cause relative movement between the head and the substrate.

10. A method according to claim 8, further characterized in that the deposition step deposits a complete complement of optical gain material in said plurality of areas, and further comprises a step of selectively removing or deactivating optical gain material. within selected areas.

11. A method according to claim 10, further characterized in that the step of removing selectively comprises a photo step to bleach the optical gain material in selected areas.

12. A method according to claim 10, further characterized in that the step of removing selectively comprises a photo-ablation step of the optical gain material in selected areas.

13.- A structure, comprising: a substrate; a plurality of areas on a surface of said substrate, each of said areas comprising an optical gain medium material capable of emitting a predetermined wavelength that differs from a wavelength emitted by others of said plurality of areas; and a functionalized support for adhesion to a desired substance.

14. - A structure according to claim 13, further characterized in that it additionally comprises a protective transparent substrate disposed between said surface and the environment.

15. A method for identifying a particular sphere in a population of spheres, comprising the steps of: providing a population of spheres each comprising a functionalized support and means for optically encoding identification information; use a sensor that responds to a desired sphere activity to identify a location of one or more areas of interest within the population; use the identified location to point an interrogation beam to a particular sphere; and determining an identification of the particular sphere from a plurality of wavelengths emitted by the particular sphere in response to the interrogation beam.

16. A method according to claim 15, further characterized in that the sensor comprises at least one of an optical energy detector, an ionizing radiation detector, or a thermal energy detector.

17. A method according to claim 15, further characterized in that the sensor is capable of operating with more than one sensitivity threshold.

18. A sphere comprising a functionalized support and further comprising a gain means coupled to a structure that supports the creation of at least one mode for electromagnetic radiation.

19. A sphere comprising a functionalized support and further comprising a gain means coupled to a structure having a dimension or length in one or more directions to produce or support amplified spontaneous emission (ASE).

20. A sphere comprising a functionalized support and further comprising an optical gain means and a structure having limits that impart a total geometry to said structure which, in combination with at least one material property of said structure, supports an improvement of electromagnetic radiation emitted from the gain medium favoring the creation of at least one mode that improves an emission of electromagnetic radiation within a narrow band of wavelengths.

21. A sphere according to claim 20, further characterized in that suitable shapes for said structure comprise elongated, generally cylindrical shapes such as filaments, a spherical shape, a partially spherical shape, a toroidal shape, a cubic shape and a polyhedron shape. , and a disk shape.

22. A sphere according to claim 20, further characterized in that said structure comprises at least one of a monolithic structure or a multilayer structure or an ordered structure that can provide distributed optical feedback for the creation of a mode.

23. A method for identifying a sphere of a type comprising a functionalized support, comprising the steps of: providing the sphere as to understand an optical gain means and a structure for at least one of (a) favoring the creation of at least one mode or (b) support amplified spontaneous emission; illuminate the sphere with selected light to excite the gain medium; detecting an emission of at least one wavelength from the sphere in response to the illumination step; and identify the sphere from the detected emission.

24. A method according to claim 23, further characterized in that the step of providing provides at least one of a layer of polymer that functions as the structure that favors the creation of at least one mode; at least one filament; a multi-layered structure; a multi-layered structure comprising a reflective layer; and a multi-layered structure comprising a reflective layer which is in the form of a pattern and which modulates a thickness of an overlying layer.

25. A method according to claim 23, further characterized in that the structure has a refractive index that differs from a refractive index of an environment of the structure so that the structure does not coincide in index with the environment.

26.- A method according to claim 23, further characterized in that the structure comprises at least one filament, and in which the wavelength emitted is a function of a diameter of the filament.

27. - A method according to claim 23, further characterized in that the structure comprises a planchette, and in which the wavelength emitted is a function of the thickness of the planchette.

28.- A method according to claim 23, further characterized in that the structure comprises a structure DFB comprising alternating regions, and in which the wavelength emitted is a function of the individual thicknesses of the regions.

29. A method for processing a population of spheres of a type comprising a functionalized support, comprising the steps of: providing at least some spheres of the population such as to comprise an optical gain means and a structure coupled to said means of gain for at least one of (a) favoring the creation of at least one mode or (b) supporting amplified spontaneous emission, said structure encodes information that is manifested by an optical emission from said sphere; illuminate at least a portion of the population with selected light to excite the gain medium; detecting an emission of at least one wavelength from at least one sphere in response to the illumination step; and decoding the information that was encoded in the at least one sphere from the detected emission.

30. A method according to claim 29, further characterized in that the information is encoded using only wavelength coding or wavelength coding and signal level coding.

31. - A method according to claim 29, further characterized in that the information is encoded using at least one single level coding or multiple level coding.

32.- A method for identifying a particular sphere in a population of spheres in one of a combination chemistry, an exploration, or a genomic application, comprising the steps of: providing a population of spheres comprising each a functionalized support and means for optically coding identification information; using a sensor that responds to a desired sphere activity to identify a location of one or more spheres of interest within the population, said sensor comprising at least one of an optical energy detector, an ionization radiation detector, or a detector of thermal energy; use the identified location to point an interrogation laser beam to a particular sphere; and determining an identification of the particular sphere from a plurality of wavelengths emitted by the particular sphere in response to the interrogation laser beam.

33.- A method according to claim 32, further characterized in that the sensor is located inside or under a container containing the population of spheres.

34.- A method for identifying a particular sphere in a population of spheres used in a Lawn analysis comprising the steps of: providing a population of spheres each comprising a functionalized support and means for optically encoding identification information; use a sensor that detects sphere analysis activity to identify a location of one or more spheres of interest within the population, said sensor comprising at least one of an optical energy detector, an ionizing radiation detector, or an energy detector thermal use the identified location to point an interrogation laser beam to a particular sphere; and determining an identification of the particular sphere from a plurality of wavelengths emitted by the particular sphere in response to the interrogation laser beam.

35. A method according to claim 34, further characterized in that the sensor is located within or below a container containing the population of spheres.