Transition metal-containing ceramic or carbonaeous material are formed from novel linear polymers containing a random distribution of repeating acetylenic units, organotransition metal complexes, siloxane, boron, silicon, and/or carborane-siloxane units. The precursor thermosets are formed by crosslinking of the linear polymers through the acetylenic units in the polymer backbone. The ceramics may also be formed directly by pyrolysis of the linear polymers. The preceramic polymers are potentially useful for fabricating ceramic fibers and composite materials having enhanced strength, hardness and toughness as well as superior mechanical, optical, electrical and/or magnetic properties.

1. Field of the Invention
This invention relates to a new class of transition metal containing linear polymers of varying molecular weight that are useful for conversion to high temperature thermosets and ceramics. These new materials have repeat units that contain alkynyl groups for cross-linking purposes along with organotransition metal complexes, silyl, siloxyl, boranyl, or di(silyl or siloxyl)carborane units. These novel linear polymers with the metal units in the backbone are soluble in most organic solvents and can be easily fabricated from the melt into shaped components, which enhance their importance for high temperature structural, magnetic, and microelectronic applications. Cross-linking of alkynyl groups is known to occur by either photochemical or thermal processes.
2. Technology Background
The incorporation of transition metals into a polymer structure has long been seen as a good way of preparing materials with different properties from conventional carbon-based polymers. Small molecule transition metal complexes and solid state compounds possess an array of interesting high temperature, hardness, redox, magnetic, optical, electrical, and catalytic properties. In addition, the rich diversity of coordination numbers and geometries available for transition elements offer the possibility of accessing polymers with unusual conformational, mechanical, and morphological characteristics.
The development of polymers with transition metals in the main chain structure would be expected to provide access to processable, specialty materials with similarly attractive physical properties that would be of interest as pyrolytic precursors to metal-containing ceramics. Transition metal-based polymers might also function as processable precursors for making metal-containing ceramic films and fibers with high stability and desirable physical properties. Most transition metal-based polymers reported to date, however, do not contain units for conversion to a thermoset and thus afford low char yields at elevated temperatures.
Despite early synthetic problems of constructing macromolecular chains, researchers have now prepared a variety of metal-containing polymers with novel properties. Ferrocene-based polymers appear to be particularly promising as reported by Ian Manners in Chain Metals, Chemistry In Britain, January 1996, pp. 46-49. Because of ferrocene""s ability to release and accept an electron reversibly, there is considerable interest in developing these materials as electrode mediators and in energy storage devices.
These mediators, for example, facilitate electron transfer between an enzyme such as glucose oxidase, where the redox active sites are buried in a protein sheath and an electrode. Ferrocene-based polymers have been successfully used as electron relays in electrochemical biosensors for measuring glucose levels. Scientists have also fabricated microelectrochemical devices such as diodes using ferrocene-based polymers.
Other studies have reported on the formation of Fexe2x80x94Sixe2x80x94C materials from the pyrolysis of iron containing polymers. See, for example: (1) Tang, B. Z.; Petersen, R.; Foucher, D. A.; Lough, A.; Coombs, N.; Sodhi, R.; Manners, I. J Chem. Soc., Chem Commun. 1993, 523-525; (2) Peterson, R; Foucher, D. A.; Tang, B. Z.; Lough, A.; Raju, N. P.; Greedan, J. E.; Manners, I. Chem. Mater. 1995, 7, 2045-2053; and (3) Ungurenasu, C. Macromolecules 1996, 29, 7297-7298; (4) Hodson, A. G. W; Smith, R. A. Transition Metal Functionalised Polysiloxanes as Precursors to Magnetic Ceramics, Faculty of Applied Sciences, University of the West of England, Bristol, BS16 1QY.
Spirocyclic [1]-ferrocenophanes have been reported to function as convenient cross-linking agents for poly(ferrocenes) via thermal ring-opening copolymerization reactions by MacLachlan, M. J.; Lough, A. J.; and Manners, I, in Macromolecules, 1996, 29, 8562-8564.
The use of ring-opening polymerization (ROP), a chain growth process, is reported by I. Manners in Polyhedron, Vol. 15, No. 24. pp 4311-4329, 1996 to allow access to a range of high molecular-weight polymers with skeletal transition metal atoms having novel properties.
Several poly(ferrocenylsilanes) have been synthesized and converted into ceramics upon heating to 1000xc2x0 C. under inert conditions. See, for example, Pudelski, J. K.; Rulkens, R.; Foucher, D. A.; Lough A. J.; MacDonald, P. M. and Manners, I., Macromolecules, 1995, 28, 7301-7308. The ceramic yields by thermogravimetric analysis (TGA), however, were in the range of 17 to 63%.
Alternative transition metals such as ruthenium have also been reported as being incorporated into a metallocenophane structure by Nelson, J. A.; Lough, A. J., and Manners, I in xe2x80x9cSynthesis and Ring-Opening Polymerization of Highly Strained, Ring-Titled[2]Ruthenocenophanesxe2x80x9d Angew. Chem., Int. Ed. Engl. 1994, 33, 989-991 and in xe2x80x9cSynthesis, Structures, and Polymerization Behavior of Di-silane-Bridged and Bis (disilane)-Bridged[2]Ruthenocenophanesxe2x80x9d in Organometallics 1994, 13, 3703-3710. Novel ruthenium or iron containing tetraynes as precursors of mixed-metal oligomers are reported in Organometallics 1996, 15, 1530-1531. Mixed valence diferrocenylacetylene cation compounds have been reported in the Journal of the American Chemical Society, 96:21, 1974, pp. 6788-6789.
The synthesis and characterization of linear boron-silicon-diacetylene copolymers is reported by R. A. Sundar and T. M. Keller in Macromolecules 1996, 29, 3647-3650. Additionally, the efficient, xe2x80x9cone-potxe2x80x9d synthesis of silylene-acetylene and disilylene-acetylene preceramic polymers from trichloroethylene is reported in the Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 28, 955-965 (1990).
Furthermore, the preparation and reactions of decachloroferrocene and decachlororuthenocene is disclosed in the Journal of the American Chemical Society, 95, 870-875 (1973). Symmetrically disubstituted ferrocenes are discussed in the Journal of Organometallic Chemistry, 27 (1971) pp. 241-249 as well as ferrocenyl-acetylene being disclosed in the J. Organometal. Chem., 6 (1966) pp. 173-180 and 399-411. Ferrocenyl- and 2-thienylarylacetylenes are reported by M. D. Rausch; A. Siegal and L. P. Kelmann in J. of Org. Chem. 1966, Vol. 31 p. 2703-2704.
Ferrocenyl ethylene and acetylene derivatives are also reported by P. L. Pauson and W. E. Watts in J. Chem. Soc. 1963, 2990-2996. Studies on the reactions of ferrocenylphenylacetylene and diferrocenyl-acetylene are reported in the Journal of Organometallic Chemistry, 149 (1978) 245-264. The chemistry of xcfx80-bridged analogues of biferrocene and biferrocenylene is discussed in the Journal of Organic Chemistry, Vol. 41, No. 16, 1976, 2700-2704. The synthesis of 1xe2x80x2, 6xe2x80x2-bis(ethynyl)-biferrocene and metal complexes referring to non-linear optics is presented in Polyhedron, Vol. 14, No. 19, pp. 2759-2766 (1995).
In addition to these documents discussing the various compounds and polymers, the catalytic graphitization by iron of isotropic carbon is reported in Carbon, Vol. 21, No. 1, pp. 81-87, 1983. Preceramic polymer routes to silicon carbide are disclosed by Richard M. Laine in Chem. Mater. 1993, 5, 260-279; and the comprehensive chemistry of polycarbosilanes, polysilazanes and polycarbosilazanes as precursors of ceramics is thoroughly reported in Chem. Rev., 1995, 95, 1443-1477.
U.S. Pat. Nos. 4,800,221 and 4,806,612 also respectively disclose silicon carbide preceramic polymers and preceramic acetylenic polysilanes which may be converted into ceramic materials.
U.S. Pat. Nos. 5,241,029 and 5,457,074 disclose diorganosilacetylene and diorganosilvinylene polymers which can be thermally converted into silicon carbide ceramic materials.
U.S. Pat. No. 4,851,491 discloses polyorganoborosilane ceramic polymers which are useful to generate high temperature ceramic materials upon thermal degradation. U.S. Pat. No. 4,946,919 also relates to boron-containing ceramics formed from organoboron preceramic polymers which are carboralated acetylenic polymers.
U.S. Pat. Nos. 5,272,237; 5,292,779; 5,348,917; 5,483,017 disclose carborane-(siloxane or silane)-unsaturated hydrocarbon based polymers reported to be useful for making high temperature oxidatively stable thermosets and/or ceramics.
U.S. Pat. No. 5,552,505 discloses copolymers formed from aromatic acetylenic monomers or prepolymers formed therefrom and carborane-(siloxane or silane)-unsaturated hydrocarbon polymers reportedly useful to form articles, adhesives, matrix materials, or coatings, or which may be pyrolyzed to form carbon-ceramic composites. Each of the documents cited herein contains valuable information and each is incorporated herein by reference in its entirety and for all purposes.
Most of the carborane-siloxane and/or carborane-silane polymers made by others have elastomeric properties rather than properties of more rigid polymeric products like thermosetting polymers or ceramics. There is a need for polymers that behave less like elastomeric polymers and more like thermosets and which, upon pyrolysis, form ceramics.
There is, therefore, a need for oxidatively stable materials having thermosetting properties for making rigid components therefrom which withstand high temperatures and which have high strength and high hardness properties and/or which optionally may have magnetic properties.
Furthermore, there is a need for transition metal-based polymers which contain units for conversion to thermosets and which afford high char yields at elevated temperatures. There is also a need for such polymers which would be useful precursors to novel materials unavailable from other sources, and which may exhibit unique nonlinear optical (NLO) properties.
It is therefore an object of the present invention to provide polymers having backbones incorporated with organotransition metals complexes along with silicon, acetylenic, and/or boron units which are useful as precursors to novel materials unavailable from other sources.
It is another object of the present invention to provide polymers having backbones incorporated with organotransition metal complexes along with silicon, acetylenic, and/or boron units which can be readily converted into high temperature thermosets.
It is another object of the present invention to provide polymers having backbones incorporating organotransition metal complexes along with silicon, acetylenic, and/or boron units which can readily be converted into high temperature materials which exhibit high strength properties, high hardness values, and electrical and/or magnetic properties.
It is yet another object of the present invention to provide transition metal based polymers which contain inorganic units and units for conversion to thermoset polymers and which afford high char yields at elevated temperatures.
It is still another object of the present invention to permit the formulation of ceramics containing a variable and controllable amount of metal and various cluster sizes.
These and other objectives are accomplished by first forming polymers having the following general composition:
wherein:
x is greater than or equal to one;
z is greater than or equal to one;
w is greater than or equal to one;
y is greater than or equal to one;
a is greater than or equal to one;
R1, R2, R3, R4, R5, R6, R7, and R8 may be the same or different and wherein each equal H, unsubstituted or substituted hydrocarbon moieties, unsubstituted or substituted alkyl or arylamino moieties; unsubstituted or substituted alkyl or aryl phosphino moieties; halogen;
M=Fe, Ru, Os, or a combination thereof; and
E is
xe2x80x83wherein:
f is greater than or equal to zero;
g is greater than or equal to one;
h is greater than or equal to one;
p is greater than or equal to zero;
q is greater than or equal to zero;
s is greater than or equal to zero and is greater than or equal to one when q is greater than or equal to one;
t is greater than or equal to zero
k=3 to 16;
R9, R10, R11, R12 may be the same or different and wherein each=H, unsubstituted hydrocarbon moieties or substituted hydrocarbon moieties; and
R13=unsubstituted or substituted hydrocarbon moieties.
As suggested above, R1 through R13 may each be one of any monovalent organic group, or, in the case of R1-R12, may be hydrogen. R1 through R13 may be aromatic, aliphatic, or include both aliphatic and aromatic moieties. R1 through R13 may be saturated or include unsaturation. In all cases, R1 through R13 may be halo-substituted. The carborane may be ortho meta or para.
Also, throughout the specification and claims, it should be understood that the value of E, and its associated variables, may differ at each occurance of E within the polymer, within the definitions provided for E and its associated variables. Thus, throughout the specification and claims, it should be understood that E and the variables included therein do not represent singular and constant values throughout the polymer. Instead, E and the variables included therein represent values that may vary, within the proscribed limits, throughout the polymer.
Typical groups for R9-R12 are, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl and tolyl. More often, R9-R12 are hydrogen, methyl, or ethyl. Most often R9-R12 are hydrogen or methyl.
Typically, R13 is methyl, ethyl, n-propyl, isopropyl, and the like, or phenyl, tolyl, and the like; most typically wherein R13 is methyl, ethyl or phenyl.
A typical xe2x80x9cExe2x80x9d component may have k=3 to 12; a more typical xe2x80x9cExe2x80x9d component having k=5 to 10; the even more typical xe2x80x9cExe2x80x9d component having k=8 to 10; and the most typical xe2x80x9cExe2x80x9d component having k=10.
Typical ranges for xe2x80x9cfxe2x80x9d include 0 to 10; more typically 0 to 6; and most typically from 0 to 2.
Typical ranges for xe2x80x9cgxe2x80x9d include 1 to 10; more typically 1 to 6; and most typically from 1 to 2.
Typical ranges for xe2x80x9chxe2x80x9d include 1 to 50; more typically 1 to 20; and most typically from 1 to 5.
Typical ranges for xe2x80x9cpxe2x80x9d include 0 to 50; more typically 0 to 20; and most typically from 0 to 5.
Typical ranges for xe2x80x9cqxe2x80x9d include 0 to 10 more typically 0 to 4; and most typically from 0 to 2.
Typical ranges for xe2x80x9csxe2x80x9d include 0 to 10; more typically 1 to 6; and most typically from 1 to 2.
Typical ranges for xe2x80x9ctxe2x80x9d include 0 to 10; more typically 0 to 6; and most typically from 0 to 2.
Typical ranges for xe2x80x9cwxe2x80x9d in these organometallic polymers, thermosets, and ceramics are from 1 to 100; more typically from 1 to 50; more often typically from 1 to 20; even more often from 1 to 10; and most often 1 to 3.
Typical ranges for xe2x80x9cyxe2x80x9d in these organometallic polymers, thermosets, are from 1 to 100; more typically from 1 to 50; more often from 1 to 20; even more often 1 to 10; and most often 1 to 3.
Typical ranges for xe2x80x9czxe2x80x9d in these organometallic polymers, thermosets, and ceramics are from 1 to 100; more typically from 1 to 80; more often from 1 to 50; even more often 1 to 30; and most often 1 to 20.
Typical xe2x80x9cMxe2x80x9d components of these novel organometallic polymers, thermosets and ceramics include transition metals; more typically being Fe, Ru, Os or combinations thereof; most typically being Fe, Ru or combinations thereof; most preferred being Fe. Different amounts of iron can be added to these polymers, thermosets, and ceramics depending on the additive compounds or combination of compounds, for example, ferrocene, biferrocene, triferrocene, and the like may be incorporated. Typically xe2x80x9caxe2x80x9d in these polymers, thermosets and ceramics may range from 1 to 20; more typically being from 1 to 10; more often being from 1 to 8; even more often being from 1 to 5; most often being from 1 to 3.
It should be understood that the general formula for the polymers describes both random and block copolymers. Throughout the specification and the claims that follows, the general polymer formula provided above will be used to represent a polymer having the structural elements shown, independent of the nature of the terminal groups. It should be further understood that a group described as xe2x80x9csubstitutedxe2x80x9d may be, for example, halo or haloalkyl substituted, unless otherwise explicitly stated.
The following general reaction represented in Scheme 1 illustrates the synthesis of the metallocene polymers containing acetylenic and inorganic units; the formation of thermosets therefrom; and the ultimate formation of the novel ceramics. In Scheme 1, X is a leaving group, such as a halogen, tosylate, and trifluoromethane sulfonate. Where EX2 in Scheme 1 is a mixture of various compounds in which E and X meet the above-provided definitions, E and its associated variables will have different values at different occurances within the polymer. Of course, each E, and its associated variable within the polymer, will meet the definitions provided for them in the present application.

wherein all variables are as described above.
Throughout the specification and claims, it should be understood that the the structure
represents a complex structure consisting of a plurality of cross-linked acetylenic moieties. The structure shown is not intended to be representative of the actual cross-links existing within that structure. In reality, the cross-linked acetylenic moiety may include several different cross-linking structures such as those shown below:

Linear metallocene polymers containing acetylenic and inorganic units and thermosets and ceramics therefrom

The United States of America as represented by the Secretary of the Navy


The present invention provides a reflection-type three-dimensional display system. The present invention comprises an image providing device that provides elemental images; an image displaying device that displays the elemental images; a projective lens system that is located along the same axis as the image providing device; and a concave mirror array that is located along the same axis as the projective lens system. The projective lens system projects the image that is displayed by the image displaying device to the concave mirror array, and the concave mirror array reflects and integrates the projected image and therefore displays the three-dimensional image.

(a) Field of the Invention
The present invention relates generally to three-dimensional display system. More particularly, the present invention relates to three-dimensional display system of reflection-type.
(b) Description of the Related Art
Among the technologies that display three-dimensional image, IP(lntegral Photography) which uses a lens array was first proposed by Lippmann in 1908. IP has not attracted much attention due to the limitation of the image capturing and displaying device. Recently IP begins to be studied extensively with the development of the high resolution image capturing and displaying device.
FIG. 1 shows the basic principle of the IP. IP consists of two functional parts (pickup/display) as shown in FIG. 1. In pickup part, many perspectives (that are called elemental images) of the three-dimensional object from various directions which are formed by the elemental lenses that constitute the lens array are captured and stored by the image capturing device. In display part, the reverse process of the pickup is performed. That is, the elemental images that were stored by the image capturing device are displayed by image displaying device, and the rays from the elemental images retrace through the lens array to integrate the three-dimensional image at the position where the original three-dimensional object was.
FIG. 2 is a more detailed image that depicts the image reconstruction principle of the IP. The elemental images which are displayed on the image displaying device (FIG. 2(a)) are integrated by the lens array (FIG. 2(b)) around the image plane position (FIG. 2(c)) of the lens array. The depth of the three-dimensional image is adjusted according to the spacing between the elemental images and therefore three-dimensional image can be displayed.
While conventional IP using the film as the pickup and displaying device could not display animation, a developed IP using the charge coupled device (CCD) camera and flat display panel (such as liquid crystal display (LCD) or cathode ray tube (CRT)) can display three-dimensional animation as well as still three-dimensional image. FIG. 3 shows the setup of the IP adopting the CCD camera and LCD panel as the pickup and display device respectively.
Three-dimensional display based on the IP can display three-dimensional image without any viewing aids (such as glasses) and provides continuous viewpoints However, realization of large size three-dimensional display based on the IP is difficult because large size lens array which is a major component of IP can not be readily made.

Reflecting three-dimensional display system


The invention is in general directed to the rapid exponential amplification of short DNA or RNA sequences at a constant temperature.

The field of in vitro diagnostics is quickly expanding as the need for systems that can rapidly detect the presence of harmful species or determine the genetic sequence of a region of interest is increasing exponentially. Current molecular diagnostics focus on the detection of biomarkers and include small molecule detection, immuno-based assays, and nucleic acid tests. The built-in specificity between two complementary nucleic acid strands allows for fast and specific recognition using unique DNA or RNA sequences, the simplicity of which makes a nucleic acid test an attractive prospect. Identification of bacterial and viral threat agents, genetically modified food products, and single nucleotide polymorphisms for disease management are only a few areas where the advancement of these molecular diagnostic tools becomes extremely advantageous. To meet these growing needs, nucleic acid amplification technologies have been developed and tailored to these needs of specificity and sensitivity.
Historically, the most common amplification technique is the polymerase chain reaction (PCR), which has in many cases become the gold standard for detection methods because of its reliability and specificity. This technique requires the cycling of temperatures to proceed through the steps of denaturation of the dsDNA, annealing of short oligonucleotide primers, and extension of the primer along the template by a thermostable polymerase. Though many new advances in engineering have successfully shortened these reaction times to 20-30 minutes, there is still a steep power requirement to meet the needs of these thermocycling units.
Various isothermal amplification techniques have been developed to circumvent the need for temperature cycling. From this demand, both DNA and RNA isothermal amplification technologies have emerged.
Transcription-Mediated Amplification (TMA) employs a reverse transcriptase with RNase activity, an RNA polymerase, and primers with a promoter sequence at the 5′ end. The reverse transcriptase synthesizes cDNA from the primer, degrades the RNA target, and synthesizes the second strand after the reverse primer binds. RNA polymerase then binds to the promoter region of the dsDNA and transcribes new RNA transcripts which can serve as templates for further reverse transcription. The reaction can produce a billion fold amplification in 20-30 minutes. This system is not as robust as other DNA amplification techniques and is therefore, not a field-deployable test due to the ubiquitous presence of RNAases outside of a sterile laboratory. This amplification technique is very similar to Self-Sustained Sequence Replication (3SR) and Nucleic Acid Sequence Based Amplification (NASBA), but varies in the enzymes employed.
Single Primer Isothermal Amplification (SPIA) also involves multiple polymerases and RNaseH. First, a reverse transcriptase extends a chimeric primer along an RNA target. RNaseH degrades the RNA target and allows a DNA polymerase to synthesize the second strand of cDNA. RNaseH then degrades a portion of the chimeric primer to release a portion of the cDNA and open a binding site for the next chimeric primer to bind and the amplification process proceeds through the cycle again. The linear amplification system can amplify very low levels of RNA target in roughly 3.5 hrs.
The Q-Beta replicase system is a probe amplification method. A probe region complementary to the target of choice is inserted into MDV-1 RNA, a naturally occurring template for Q-Beta replicase. Q-Beta replicates the MDV-1 plasmid so that the synthesized product is itself a template for Q-Beta replicase, resulting in exponential amplification as long as the there is excess replicase to template. Because the Q-Beta replication process is so sensitive and can amplify whether the target is present or not, multiple wash steps are required to purge the sample of non-specifically bound replication plasmids. The exponential amplification takes approximately 30 minutes; however, the total time including all wash steps is approximately 4 hours.
Numerous isothermal DNA amplification technologies have been developed as well. Rolling circle amplification (RCA) was developed based on the natural replication of plasmids and viruses. A primer extends along a circular template resulting in the synthesis of a single-stranded tandem repeat. Capture, washing, and ligation steps are necessary to preferentially circularize the template in the presence of target and reduce background amplification. Ramification amplification (RAM) adds cascading primers for additional geometric amplification. This technique involves amplification of non-specifically sized strands that are either double or single-stranded.
Helicase-dependent amplification (HDA) takes advantage of a thermostable helicase (Tte-UvrD) to unwind dsDNA to create single-strands that are then available for hybridization and extension of primers by polymerase. The thermostable HDA method does not require the accessory proteins that the non-thermostable HDA requires. The reaction can be performed at a single temperature, though an initial heat denaturation to bind the primers generates more product. Reaction times are reported to be over 1 hour to amplify products 70-120 base pairs in length.
Loop mediated amplification (LAMP) is a sensitive and specific isothermal amplification method that employs a thermostable polymerase with strand displacement capabilities and four or more primers. The primers are designed to anneal consecutively along the target in the forward and reverse direction. Extension of the outer primers displaces the extended inner primers to release single strands. Each primer is designed to have hairpin ends that, once displaced, snap into a hairpin to facilitate self-priming and further polymerase extension. Additional loop primers can decrease the amplification time, but complicates the reaction mixture. Overall, LAMP is a difficult amplification method to multiplex, that is, to amplify more than one target sequence at a time, although it is reported to be extremely specific due to the multiple primers that must anneal to the target to further the amplification process. Though the reaction proceeds under isothermal conditions, an initial heat denaturation step is required for double-stranded targets. Amplification proceeds in 25 to 50 minutes and yields a ladder pattern of various length products.
Strand displacement amplification (SDA) was developed by Walker et. al. in 1992. This amplification method uses two sets of primers, a strand displacing polymerase, and a restriction endonuclease. The bumper primers serve to displace the initially extended primers to create a single-strand for the next primer to bind. A restriction site is present in the 5′ region of the primer. Thiol-modified nucleotides are incorporated into the synthesized products to inhibit cleavage of the synthesized strand. This modification creates a nick site on the primer side of the strand, which the polymerase can extend. This approach requires an initial heat denaturation step for double-stranded targets. The reaction is then run at a temperature below the melting temperature of the double-stranded target region. Products 60 to 100 bases in length are usually amplified in 30-45 minutes using this method.
These and other amplification methods are discussed in, for example, VanNess, J, et al., PNAS 2003. Vol. 100, no 8, p 4504-4509; Tan, E., et al., Anal. Chem. 2005, 77, 7984-7992; Lizard, P., et al., Nature Biotech. 1998, 6, 1197-1202; Notomi, T., et al., NAR 2000, 28, 12, e63; and Kurn, N., et al., Clin. Chem. 2005, 51:10, 1973-1981. Other references for these general amplification techniques include, for example, U.S. Pat. Nos. 7,112,423; 5,455,166; 5,712,124; 5,744,311; 5,916,779; 5,556,751; 5,733,733; 5,834,202; 5,354,668; 5,591,609; 5,614,389; 5,942,391; and U.S. patent publication numbers US20030082590; US20030138800; US20040058378; and US20060154286.
There is a need for a quicker method of amplification of single-stranded and double-stranded nucleic acid target sequences that can be performed without temperature cycling and that is suitable for shorter target sequences.

This patent is subject to a terminal disclaimer.

Nicking and extension amplification reaction for the exponential amplification of nucleic acids


A reticle provides an image pattern and compensates for a lens error in a photolithographic system. The reticle is structurally modified using image displacement data indicative of the lens error. The reticle can be structurally modified by adjusting the configuration (or layout) of radiation-transmitting regions, for instance by adjusting a chrome pattern on the top surface of a quartz base. Alternatively, the reticle can be structurally modified by adjusting the curvature of the reticle, for instance by providing a chrome pattern on the top surface of a quartz base and grinding away portions of the bottom surface of the quartz base. The image displacement data may also vary as a function of lens heating so that the reticle compensates for lens heating associated with the reticle pattern.

1. Field of the Invention
The present invention relates to reticles, and more particularly to reticles used in photolithographic systems used for fabricating integrated circuit devices.
2. Description of Related Art
Integrated circuit device fabrication requires that precisely controlled quantities be introduced into or deposited onto tiny regions of a wafer or substrate. Photolithography is typically used to create patterns that define these regions. That is, photoresist is spin-coated onto the wafer, selectively exposed to radiation, and then developed. If positive photoresist is used then the developer removes the irradiated regions, whereas if negative photoresist is used then the developer removes the non-irradiated regions. After the photoresist is patterned, the wafer is subjected to an additive process (such as ion implantation) or a subtractive process (such as etching) using the photoresist as a mask.
Photolithographic systems typically use a radiation source and a lens in conjunction with a mask or reticle to selectively irradiate the photoresist. The radiation source projects radiation through the mask or reticle to the lens, and the lens focuses an image of the mask or reticle onto the wafer. A mask transfers a pattern onto the entire wafer (or another mask) in a single exposure step, whereas a reticle transfers a pattern onto only a portion of the wafer. Step and repeat systems transfer multiple images of the reticle pattern over the entire wafer using multiple exposures. The reticle pattern is typically 2.times. to 10.times. the size of the image on the wafer, due to reduction by the lens. However, non-reduction (1.times.) steppers offer a larger field, thereby allowing more than one pattern to be printed at each exposure.
The reticle is typically composed of quartz with relatively defect-free surfaces and a high optical transmission at the radiation wavelength. Quartz has a low thermal expansion coefficient and high transmission for near and deep ultraviolet light. Although quartz tends to be expensive, it has become more affordable with the development of high quality synthetic quartz material.
The reticle is prepared by cutting a large quartz plate which is polished and cleaned, and then coated with a mask forming material such as chrome or iron oxide. Chrome is the most widely used material and is typically deposited by sputtering or evaporation to a thickness of less than 1,000 angstroms. The chrome is then selectively removed to form the pattern. For instance, a very thin layer of photoresist is deposited on the chrome and patterned (either optically or by an electron beam) by imaging and exposing a set of accurately positioned rectangles, and then a wet etch is applied. Patterning the reticle for a complex VLSI circuit level may require in excess of 100,000 rectangle exposures over a 10 hour period. During this period, extreme temperature control is often necessary to prevent positional errors. As a result, the quality of the reticle cannot be ascertained until after the chrome is etched.
Lens errors in step and repeat systems are highly undesirable since they disrupt the pattern transfer from the reticle to the photoresist, which in turn introduces flaws into the integrated circuit manufacturing process. Lens errors include a variety of optical aberrations, such as astigmatism and distortion. Astigmatism arises when the lens curvature is irregular. Distortion arises when the lens magnification varies with radial distance from the lens center. For instance, with positive or pincushion distortion, each image point is displaced radially outward from the center and the most distant image points are displaced outward the most. With negative or barrel distortion, each image point is displaced radially inward toward the center and the most distant image points are displaced inward the most. Accordingly, the lens error is frequently measured so that corrections or compensations can be made.
A typical technique for evaluating lens errors includes performing a photoresist exposure and development using specially designed mask patterns to be used for evaluation purposes. After such an imaging process, the wafer is either subjected to an optical inspection or is further processed to form electrically measurable patterns. The use of photosensitive detectors fabricated on silicon to monitor optical systems is also known in the art.
U.S. Pat. No. 4,585,342 discloses a silicon wafer with radiation sensitive detectors arranged in a matrix, an x-y stage for positioning the wafer so that each one of the detectors is separately disposed in sequence in the same location in the field of projected radiation, and a computer for recording the output signals of the detectors in order to calibrate the detectors prior to evaluating the performance of an optical lithographic system.
U.S. Pat. No. 5,402,224 provides distortion inspection of an optical system by providing a test reticle with a measurement pattern arranged at a predetermined interval Sx, transferring a the pattern from a test reticle to a photosensitive substrate, shifting the test reticle and the substrate relative to one another by .DELTA.Tx (where .DELTA.Tx<Sx), transferring measurement pattern again from the test reticle to the substrate, measuring the relative displacement between the two formed patterns to provide differential coefficients on distortion characteristics, and integrating the differential coefficients to provide the distortion characteristics.
Replacing the lens in a step and repeat system is considered impractical since the lens is a large, heavy, integral part of the system. Furthermore, it is unlikely that a substitute lens will render subsequent corrections unnecessary.
U.S. Pat. No. 5,308,991 describes predistorted reticles which incorporate compensating corrections for known lens distortions. Lens distortion data is obtained which represents the feature displacement on a wafer as a function of the field position of the lens. The lens distortion data is used to calculate x and y dimensional corrections terms. The inverted correction terms are multiplied by a stage controller's compensation value to correctly position the reticle. In this manner, the reticle is positioned to compensate for the lens error. A drawback to this approach, however, is that a highly accurate reticle positioning apparatus is required.
Accordingly, a need exists for an improved technique that compensates for lens errors in photolithographic systems.

Reticle that compensates for radiation-induced lens error in a photolithographic system


A method of generating a high dynamic range image corresponding to a specific scene. The method includes shooting a specific scene to generate a base image; selecting a bright area and a dark area from the base image; determining base luminance according to the base image; shooting the specific scene to generate at least a first image, wherein average luminance of a part of the first image corresponding to the bright area of the base image is less than or equal to the base luminance; shooting the specific scene to generate at least a second image, wherein average luminance of a part of the second image corresponding to the dark area of the base image is greater than or equal to the base luminance; and combining at least the first image and the second image into a high dynamic range image corresponding to the specific scene.

1. Field of the Invention
The present invention relates to a high dynamic range image, and more particularly, to a method and system of generating a high dynamic range image corresponding to a specific scene.
2. Description of the Prior Art
In image processing technical fields, the ratio of the highest luminance to the lowest luminance in a scene is defined as a dynamic range of the scene. Typically, the dynamic range of the real world is over 50,000:1, and the dynamic range of the human vision system (HVS) is over 10,000:1. Moreover, in some specific lighting condition, human eyes can differentiate some 10,000 colors. Thus, human eyes can detect different luminance in the real word to a fairly satisfactory degree.
Image capturing devices (such as cameras) or image display devices (such as computer displays) commonly used for processing images, however, have a dynamic range far less than the dynamic range of the real world. Therefore, those image devices are unable to capture or display details of high luminance (i.e. over-exposure) or low luminance (i.e. under-exposure) parts in a scene in some condition. For example, an image capturing device or an image display device having a dynamic range of 255:0 may treat all pixels in a high luminance part in a scene as white pixels having grayscale values of (255, 255, 255), or treat all pixels in a low luminance part in a scene as black pixels having grayscale values of (0, 0, 0). In other words, those image devices are unable to record details of high luminance or low luminance parts in a scene.
Generally, an image having a high dynamic range is called a high dynamic range (HDR) image. Presently, there is no simple and direct way to capture or display an HDR image. Therefore, an alternative method to execute multiple exposures in a scene to capture a plurality of low dynamic range (LDR) images and then combine the LDR images into an HDR image of the scene is provided.
Traditionally, multiple exposures are executed in a scene to capture a plurality of LDR images until the amount of LDR images is sufficient to generate a satisfactory HDR image, thereby consuming a lot of shooting time and storage space for the LDR images.

Method and system of generating high dynamic range image corresponding to specific scene


A method and system for managing a plurality of credit card transactions within an integrated accounting environment. Embodiments of the present disclosure enable integration between financial institutions, organizational accounting systems, and disparate user workflows to overcome deficiencies of the prior art. Specific embodiments enable tracking of credit card charges, credits, and payments directly within an accounts payable interface, enabling the ability to view activity on the credit card account record, register, and vendor record. Methods and systems are operable to establish a real-time data transfer protocol between a financial institution and an organizational accounting application to integrate transaction data in real-time, define vendor association for transactions, and create a real-time credit card register to drive decision making across disparate user roles.

Credit card transactions are becoming an ever more prevalent method of making purchases by non-profit organizations, particularly small purchases of consumer type items needed on an immediate basis. Organizations need to maintain control and visibility over the continuously growing volume of these transactions. While numerous solutions exist to provide organizations with various means of importing credit card transactions into computer-based accounting applications, these solutions fail to provide real-time integration of credit card transactions within an accounts payable system, and require disconnected workflows between various stakeholders. Examples of such workflows include time consuming manual processes for tracking cardholders, receipts, and reconciling credit card transactions. Due to a lack of effective integration between prior art credit card management solutions and computer-based accounting applications, many organizations wait until a credit card statement is received at the end of each month to record credit card expenses within their accounting system. This results in lost receipts and delays to month-end close procedures. In addition, cardholders often do not have an efficient solution to record expense details and information. Likewise, it is inefficient for organizations to track spending by vendor within an integrated and scalable environment.
While numerous solutions exist to track credit card spending, these solutions fail to provide a meaning solution to integrate disparate user roles and accounting functions within an integrated credit card management system.

System and method for real-time integrated credit card management


A zirconia sol having zirconia crystals with an average primary particle size less than 20 nm is provided, wherein more than 90% of the zirconia crystals exist in the form of tetragonal and cubic crystal lattice structures. The zirconia sol has a transmittance more than 70% when the amount of the zirconia crystals in the zirconia sol is about 20 wt %.

1. Field of the Invention
This invention relates in general to a metal oxide nanoparticle sol and a method for preparing the same. More particularly, the invention relates to a zirconia nanocrystal sol and a method for preparing the same.
2. Description of the Related Art
The incorporation of zirconia nanoparticles into organic matrix materials (e.g., polymers) can increase the refractive index of optically transparent materials. The degree to which the refractive index of the organic matrix may be increased is a function of the loading limit of the nanoparticles in the organic matrix and the refractive index of the zirconia nanoparticles.
The nature of the zirconia (e.g., crystallinity, crystal structure, particle size and degree of primary particle association) governs the optical transmission, refractive index and the loading limit of the nanoparticles in an organic polymer. For a material to remain optical transparent after the incorporation of nanoparticles, the size of the nanoparticles has to be smaller than ¼ of the wavelength of the incident light, so that light is not scattered. Therefore the requirement of transparency posts an upper limit to the size of the primary and the associated particles. To increase the refractive index of the matrix, the refractive index of the incorporated nanoparticles must be higher than the matrix. In this respect, crystalline zirconia has a higher reflective index than non-crystalline zirconia, and is thus preferred. The refractive index of the matrix can be increased substantially if the loading of zirconia is high. However, the loading limit of a zirconia in a polymer is a function of both particle association and particle size. As particle size increases and/or the association between particles increases, the loading limit of the zirconia in a polymer decreases. Therefore, a method for preparing a sol containing nano-crystalline zirconia without association or having only weak association is important and necessary.
A stable sol containing non- or weakly-associated zirconia nanocrystals is in general transparent to visible light. However, the pH range where the sol remains stable should be as close to neutral condition as possible, preferably in the range of pH 6˜9, for easier application in various fields.
In a prior art, U.S. Pat. No. 4,784,794, a method of preparing a translucent zirconia sol by treating zirconium chloride at 130° C. or higher is disclosed, but the pH value of the prepared product is lower than 7. Additionally, U.S. Pat. No. 6,376,590 discloses a method of preparing a zirconia sol having high dispersing zirconia crystals by using a zirconium salt solution containing polyether or an organic acid having ether group therein as the starting material. However, the method requires high (140˜250° C.) temperature and the pH value of the prepared product is lower than 7. Since the process temperature described in the above methods would require the employment of a high-pressure autoclave, a low temperature process for the preparation of zirconia sol is needed.

Zirconia sol and method for preparing the same


An electro-optical device copes with a decreased size of a pixel pitch by using a comparatively simple configuration in which a driving circuit system is formed on one substrate. In a scanning-line driving circuit, each transfer signal of a shift register is branched off into three signal components, and an enable circuit is provided for each signal component. During a pulse cycle of the transfer signal, one transfer signal is divided into three components while being sequentially shifted in the time domain in accordance with enable signals whose phases are sequentially shifted from each other, and the divided components are output as scanning signals. The same applies to a data-line driving circuit.

1. Field of Invention
The present invention relates to a driving circuit system for use in an active-matrix-type electro-optical device and for driving the electro-optical device, and also to an electro-optical device driven by this driving circuit system.
2. Description of Related Art
Generally, in an active matrix type electro-optical device, a plurality of scanning lines and a plurality of data lines are arranged in a matrix, and pixel electrodes are formed via switching elements, such as thin film diodes (hereinafter referred to as "TFDs") and thin film transistors (hereinafter referred to as "TFTs") in correspondence with the intersections of the matrix.
In the electro-optical device configured as described above, scanning signals are sequentially supplied to the respective scanning lines by a scanning-line driving circuit. More specifically, the scanning-line driving circuit has a Y-direction shift register formed of unit circuits in multiple stages in the Y direction (vertical direction), which is the direction in which the scanning lines are arranged. First, the Y-direction shift register sequentially transfers a start pulse, which is supplied from an external image signal processing circuit at the start of a vertical scanning period, based on the period of a Y-direction clock signal CLY (and its inverted signal CLY′), which is used as the reference of vertical scanning, output from the external image signal processing circuit. The Y-direction shift register then supplies transfer signals as scanning signals from the respective stages of the unit circuits to the corresponding scanning lines.
Meanwhile, the data lines are driven by a data-line driving circuit. That is, the data-line driving circuit is configured to supply sampling control signals to sampling switches, which sample an image signal supplied to an image signal line in correspondence with the individual data lines, in synchronization with the above-described operation of sequentially supplying scanning signals. More specifically, the data-line driving circuit has a multiple-stage X-direction shift register in the X direction (horizontal direction), which is the direction in which the data lines are arranged. First, the X-direction shift register sequentially transfers a start pulse, which is supplied from the external image signal processing circuit at the start of a horizontal scanning period, based on the period of an X-direction clock signal CLX (and its inverted signal CLX′), which is used as the reference of horizontal scanning, output from the image signal processing circuit. The X-direction shift register then outputs transfer signals as sampling control signals from the respective stages of the unit circuits to the sampling switches connected to the corresponding data lines. Subsequently, the sampling switches respectively sample the image signal supplied to the image signal line according to the sampling control signals and supply the sampled image signal to the corresponding data lines.
As discussed above, generally, in the active-matrix-type electro-optical device, vertical scanning based on a field unit or a frame unit, namely, field scanning or frame scanning, is performed in accordance with the scanning signals and sampling control signals sequentially output from the shift registers.
When being put into practical use, this type of electro-optical device often has a built-in driving circuit system in which the aforementioned scanning-line driving circuit and the data-line driving circuit are formed, together with the switching elements connected to the pixel electrodes, on one of a pair of substrates forming the electro-optical device. In this case, a small space occupied by peripheral circuits including the driving circuits makes it possible to miniaturize the entire device. Additionally, active elements, which form the peripheral circuits, are formed by the same process step as the switching elements for driving the pixel electrodes, thereby enhancing the manufacturing efficiency of the whole device and decreasing the cost.
The size of the substrates is a factor that defines the size of the entire electro-optical device. Accordingly, the formation of a large peripheral portion on which the scanning-line driving circuit and the data-line driving circuit are formed in the peripheral region on the substrates, in relation to a screen display portion, contradicts the basic demand in this technical field for miniaturizing the entire electro-optical device and increasing relatively the screen display portion in relation to the size of the electro-optical device.
Thus, for the formation of the driving circuits on the substrate, in the Y-direction shift register of the scanning-line driving circuit, the circuit pitch in the Y direction of each unit circuit (hereinafter simply referred to as the "circuit pitch of the Y-direction shift register") is adjusted to the same pitch as that of the scanning lines. Accordingly, the Y-direction width of the portion required for forming the scanning-line driving circuit can be set to be substantially equal to the Y-direction width of the screen display portion. Similarly, in the X-direction shift register of the data-line driving circuit, the circuit pitch in the X direction of each unit circuit (hereinafter simply referred to as the "circuit pitch of the X-direction shift register") and the pitch in the X direction of the sampling switches of the sampling circuit (hereinafter simply referred to as the "pitch of the sampling switch") are adjusted to be the same pitch as that of the data lines. Accordingly, the X-direction width of the portion required for forming the data-line driving circuit can be set to be substantially equal to the X-direction width of the screen display portion. This makes it possible to reduce the widths in the X direction and in the Y direction of the substrates, thereby preventing a large scale of substrates.
These days, there is an intense demand for a higher level of image quality in the electro-optical device. In order to implement higher-definition images, it is thus necessary to reduce the pixel pitch to a very small size and also to driving a greater number of scanning lines and data lines at a higher frequency.
However, each unit circuit of the above-described shift registers is provided with a plurality of relatively complicated active elements. For example, each unit circuit requires at least three clocked inverters, each formed of four TFTs, positive and negative power sources for each clocked inverter, and wiring patterns for supplying a clock signal and its inverted signal. Accordingly, in the configuration in which peripheral circuits, such as the driving circuits, are formed on the substrate of the electro-optical device, as the pixel pitch is becoming smaller, it is more difficult to adjust the circuit pitches of the above-described Y-direction and X-direction shift registers to the same pitches of the scanning lines and the data lines. For example, under current circumstances, the smallest-possible circuit pitch of the shift registers is, in a practical sense, about 20 μm, which hampers a decrease in the pixel pitch.

Driving circuit system for use in electro-optical device and electro-optical device


A solid fuel starter assembly is provided with an envelope component made of combustible material; a foldable chimney component made of combustible material and a tear off strip component made of material and attached to the envelope component. The foldable chimney component is disposed inside a package formed by the envelope component and the tear off strip. The chimney component is a foldable flue component in the shape of a pyramid or cone.

Numerous methods and devices have been described for igniting solid fuels such as charcoal. Perhaps the most common is the use of a flammable liquid such as charcoal starter fuel. Typically, charcoal starter fuel is a mixture of kerosene and naphtha. In addition to being highly flammable, these fuels are highly toxic if inhaled or ingested. Another device used frequently for igniting charcoal is an electric charcoal starter that typically comprises a coil through which an electric current is passed causing the coil to become hot. The heat is then transferred to the charcoal which is then ignited. A disadvantage of the electric charcoal starter is that it requires a nearby source of electricity, making it inconvenient for campers, or lighting charcoal in parks where there is no nearby source of electricity. Yet another device for igniting charcoal is a chimney starter. The chimney starter is typically a metal cylinder with an internal charcoal grate. Charcoal is placed into the top of the cylinder and a crumpled newspaper is placed under the grate. The newspaper is lit and lights the charcoal above. The "chimney effect" causes the charcoal to light from the bottom all the way up to the top. A disadvantage of the chimney starter is that it requires the manipulation of lighted charcoal and remains hot even after charcoal has been poured out. Additionally, these devices are bulky (for example, 10.5″×6.5″) and are inconvenient when carried a long distance.
Us Patent Application 2009/0095276 A1 (Published Apr. 16, 2009) ("Kaye") discloses a charcoal starter that is fully consumable through combustion. The starter takes the form of a container that includes one or more walls that define a top and bottom compartment. Solid fuel is deposited in the top compartment and kindling material is deposited in the bottom compartment. The divider allows for oxygenation and ventilation while also supporting the solid fuel in the top compartment. The starter is generally composed of a cardboard or other flammable, non-toxic material. The starter is configured such that solid fuel is supported in the top compartment for a period of time after the kindling material is lit and thereafter collapses and is completely consumed.
Kaye discloses a two-part embodiment comprising a first wall component 20 that includes a pair of substantially triangular divider elements. The first and second divider elements are formed in the wall and are each adapted to be folded relative to fold-lines. The device includes a pair of identical wall components with opposed engagement flaps to define a substantially rectangular apparatus. A disadvantage with the Kaye device is that the charcoal is confined within the walls of the device, cutting off side ventilation of the charcoals and when stacked the charcoals are not in an optimal pyramidal or conical stack. Additionally, the walls typically burn faster than the charcoal, resulting in the walls being consumed and the charcoal stack falling away from the kindling.

Method and apparatus for lighting charcoal


A heat exchanger, a heat exchanger unit, and a refrigeration cycle apparatus in which frost melt water is inhibited from reaching an upper surface of a header include: heat transfer tubes arranged in parallel with each other; a fin connected to one of the heat transfer tubes; and a header connected to the heat transfer tubes and having a header end surface along a direction in which the heat transfer tubes are arranged in parallel. The fin has an edge facing the header and extends in a first direction perpendicular to the axes of the heat transfer tubes. An end portion of the fin projects in the first direction relative to the header end surface, and another end portion of the fin in the first direction is positioned closer in the first direction to the heat transfer tubes than the header end surface is.

There have been known heat exchangers including flat tubes that are heat transfer tubes whose sections each have a flat shape and a plurality of holes to improve heat exchange performance. Such a heat exchanger in which a plurality of flat tubes are arranged in parallel with each other such that their longitudinal tube axes are along the direction of gravity includes a header that distributes or collects fluid to be subjected to heat exchange at lower end portions in the direction of gravity of the flat tubes. In such a heat exchanger, frost melt water on surfaces of the flat tubes or fins is discharged in the direction of gravity along the flat tubes or the fins. For this reason, water easily remains on an upper surface of the header, in particular, joints between the header and the flat tubes, and easily remains between the upper surface of the header and the fins. There has been known a heat exchanger in which an upper surface of a header is inclined in the direction of gravity to facilitate discharge of frost melt water from the upper surface of the header (for example, see Patent Literature 1).

Heat exchanger, heat exchanger unit, and refrigeration cycle apparatus


A digital camera includes an imaging unit for generating image data, an emission unit for emitting a flash, a face detection unit for detecting face information in the image data, and an emission amount control unit for controlling the emission amount of a flash. A plurality of time points is set in a period from the time when generation of image data is started to the time when a flash is emitted, each as a time point where a detection result of the face detection unit is supplied to the emission control unit. The emission amount for the flash is obtained by selectively referring to the plurality of detection results and performing one of a plurality of arithmetic operations selected based on the referenced detection result.

1. Field of the Invention
The present invention relates to a digital camera that controls the emission amount of a flash using face information included in a subject, and a method therefor.
2. Description of the Related Art
Generally, digital cameras initiate image taking before the shutter release button is depressed, and exposure control and focus control are performed using the image obtained during that period. The image obtained during that period is also used for a flash control to obtain an adequate emission amount of a flash. In the past, the method in which the adequate amount of flash is obtained based on the overall brightness of the obtained image has been commonly used. Recently, however, a flash control method in which face detection is performed on the obtained image, and emission amount of the flash is controlled according to existence or nonexistence of a face, or the proportion of the detected face in the image.
For example, U.S. Patent Application Publication No. 20030071908 describes a method in which emission amount of a flash is reduced if a face is detected and the ratio of the face in the image is greater than or equal to a predetermined value. Further, U.S. Patent Application Publication No. 20060044422 describes a method in which emission amount of a flash is obtained using only the image data of a region corresponding to a face in the image, or using image data in which a region corresponding to a face in the image is weighted greater than for the other regions.
Further, when a person is imaged with a flash at night or in a dark place, the eyes of the person may sometimes be imaged in red or gold (hereinafter, collectively referred to as "red eye" including gold and other colors). It is known that the red eye phenomenon occurs when the pupils of the eyes are opened widely. Consequently, some digital cameras have a function to emit a flash to close the pupils to a certain degree prior (hereinafter referred to as "redeye reduction emission") to performing flash photography, and thereafter performing ordinary flash photography as described, for example, Japanese Unexamined Patent Publication No. 2001-215404.
The methods described in U.S. Patent Application Publication Nos. 20030071908 and 20060044422 may obtain an image of appropriate brightness without halation in the face portion or without the face portion becoming too dark, if the content of image data obtained for face detection is identical to the content of image data obtained for light control. But, the position of a face included in the image data obtained for light control may sometimes differ from the position of the face detected from the image data obtained for face detection, since the face detection is performed prior to exposure control and focus control. In this case, the emission amount obtained based on the data of a region extracted as the region corresponding to the face may not become an optimum amount. Further, a more inadequate emission amount may be set in comparison with a case where the emission amount is obtained without considering the face, depending on an object newly located in the region where the face was detected as a result of the change in the face position.
The aforementioned problem is particularly serious for flash photography involving the redeye reduction emission. The redeye reduction emission is primarily performed for closing the pupils to a certain degree, and the imaging is suspended for a certain time which is required by the pupils to contract in response to the redeye reduction emission, so that it is more likely that the aforementioned problem occurs in comparison with imaging without the redeye reduction emission.
It is an object of the present invention to provide a digital camera capable of invariably performing a flash emission with an appropriate amount by solving the problem arising from the movement of the subject or digital camera during the time frame between the face detection and light control in imaging involving the redeye reduction emission described above.

Digital camera and flash emission control method based on face detection


A system comprises a faceted structure imaging assembly and a faceted structure image analyzer. The system is configured to determine carat weight of a gemstone while in a mounted setting. In a first mode, the imaging assembly obtains a first image of a top gemstone surface. The image analyzer uses the first image to obtain at least one gemstone dimension, such as table and diameter dimensions. In a second mode, the imaging assembly obtains a second image of the top gemstone surface while a colored light pattern is reflected onto the gemstone. The image analyzer uses the second image to obtain at least one other gemstone dimension, such as crown and pavilion angles. The image analyzer uses the dimensions obtained from the first and second images to determine weight information of the gemstone. The system quickly determines gemstone weight reliably and consistently without skilled gemologists or removal from the setting.

Faceted structures are often mounted in jewelry and other accessories. Rings, bracelets, necklaces, glasses, and watches are commonly adorned with faceted structures that provide visual appeal to these items. The visual appeal results in part from the illumination properties of the faceted structure. As light enters the faceted structure, some of the entering light is internally reflected within the structure and redirected to the eye of an observer. This effect makes the faceted structure appear illuminated.
One popular type of faceted structure is a diamond gemstone. Quality of diamond gemstones is typically assessed by carat weight, color grade, clarity grade, and cut grade. Carat weight has units of metric carats. One carat is equal to 0.2 grams. The weight of a diamond gemstone is determined by first measuring a volume of the diamond gemstone. When the diamond gemstone is mounted in a setting, not all dimensions of the gemstone are readily available for measurement. Highly skilled gemologists are able to estimate the volume using calipers despite the gemstone being mounted in the setting. However, reliability is an issue. For example, one gemologist might have different estimates of volume than another gemologist. While variation in volume might appear slight, any variation in volume might have significant cost implications due to the extraordinary value of some diamonds. In addition, it is highly desirable to maintain the reputation of a gemologist and variations in weight estimation places the reputation of the gemologist in jeopardy.
Another way to ascertain the dimensions of the mounted gemstone is to remove the gemstone from the setting. After removal, the gemstone is weighed using a scale and the gemstone is re-mounted in the setting. Although this provides a precise estimate of gemstone volume and weight, this technique risks damage to the setting. Moreover, some items with mounted settings have significant emotional value as in the case of family heirlooms. Additionally, removal of the gemstone from the setting exposes the gemologists to risk of real or perceived loss of the gemstone.
Gemstone dimensions are often useful in other aspects of the gemstone industry. Gemstone dimensions are commonly used in identifying and tracking particular gemstones. For example, an entity that distributes gemstones might sell an item with a mounted gemstone to a customer. At some later time, the customer may return the item with the mounted gemstone for repair, trade-in, or consignment. It is usually desirable to validate that the item with the mounted gemstone is the same as the original item that was provided to the customer initially at the earlier date. However, due to the physical qualities of many settings, it is difficult to reliably and consistently obtain some of the critical dimensions of the mounted gemstone. A solution that overcomes these challenges is desirable.

Estimating gemstone weight in mounted settings


A low-cost high-speed device for correcting the marking position of a laser marker, which uses a smaller quantity of corrective data and a simplified arithmetic operations, wherein corrective values for design parameters for a lens are obtained on the basis of a production tolerance of the lens. The design parameters of the lens are corrected according to the corrective values, and the distance for the lens to move is calculated from the corrected design parameters of the lens and the distance to a desired marking position. A move command corresponding to the calculated distance is outputted to lens drive means, and a pattern of a divided image is marked in the desired position.

A device whereby a desired pattern is marked onto a specimen by irradiating the specimen with laser light is disclosed in Japanese Patent Publication 4-39646.
In the device disclosed in this patent, reference marks are provided at prescribed intervals in the X direction at the specimen stage, photodetector elements are provided, laser light is scanned in the X direction prior to actual marking, the divergence .DELTA.X from the reference mark is determined for each reference mark from the timing at which light is received at each photodetector element, and the position of laser irradiation in the X direction is corrected for each reference mark on the basis of the divergence .DELTA.X for each reference mark.
However, in the aforementioned device, since the position is corrected in reference mark units, a memory having a very large memory capacity is required in order to record and store data on the divergence, .DELTA.X, for each reference mark, therefore leading to high costs. Furthermore, since it is necessary to read out and calculate computer data on the divergence, .DELTA.X, for each reference mark, time is required for processing and high-speed processing cannot be achieved.
On the other hand, in a laser marker already implemented by the present applicant, although the composition of the device, which is premised on the use of a liquid crystal mask, or the like, differs from the prior art laser marker described above, there is a demand for correction of the marking position to be carried out at low cost and high speed.
The present invention was devised in view of the foregoing, its object being to provide a laser marker wherein the marking position can be corrected by means of a simple calculational process using a small quantity of corrective data, thereby enabling reductions in cost and increases in speed to be achieved.

Marking position correcting device for laser marker


A Direct Memory Access (DMA) device includes a first buffer which holds a first transfer information required for a first transfer request, and a second buffer which holds a second transfer information required for a second transfer request, and a transfer request comparison circuit which determines whether or not a current transfer request, which is newly inputted, matches with the first transfer request or the second transfer request. The DMA device includes a priority determination circuit that, in case where the transfer request comparison circuit determines that the current transfer request is not matched with the first transfer request or the second transfer request, updates the second transfer information to a transfer information for the current transfer request when a priority of the current transfer request is higher than a priority of the second transfer request, and updates the first transfer information to the transfer information for the current transfer request when the priority of the current transfer request is lower than the priority of the second transfer request.

1. Field of the Invention
The present invention relates to microcomputers (hereafter, referred to as "micros") and in particular to a DMA (Direct Memory Access) device and a DMA transfer method incorporated in a micro.
2. Description of Related Art
With the aim of reducing load on CPU (Central Processor Unit) associated with increase in the number of peripheral I/Os (Input/Output Ports) incorporated in micros, there is demand for multichannel DMA. In general, a DMA device incorporates transfer information equivalent to the number of channels in DMA. Therefore, when the number of channels is increased, the amount of incorporated transfer information is increased and this leads to the expanded physical scale of the DMA.
As one means for avoiding the expansion of physical scale due to channel multiplication, there is a technique in which transfer information is placed in rewritable memory, such as RAM (Random Access Memory). At each time of transfer the transfer information is read from the RAM and the read information is placed in the DMA device to carry out DMA transfer.
In DMA of such a type that transfer information placed in RAM is read, the expansion of physical scale due to channel multiplication can be avoided. However, overhead due to reading of transfer information from RAM at each time of transfer is produced and this poses a problem of degradation in transfer performance.
In recent years, re-specification of data paths have been frequently carried out to cope with increase in micro clock frequency and this tends to increase clock counts in transfer. Because of bus multiplication in conjunction with diversification of peripheral I/Os and the complication of systems, it has been required to displace the access path from DMA to RAM to a different bus and overhead tends to further increase. For this reason, it is demanded to reduce overhead arising from reading of transfer information.
Description will be given to the configuration of a device disclosed in Patent Document (Japanese Patent Application Laid Open No. 2000-99452) with reference to FIG. 9, FIG. 10, and FIG. 11. As illustrated in FIG. 9, this device is comprised of: a first buffer including a DMA count register 91, a DMA command register 92, a DMA address register 93, a DMA offset register 94, and a request number register 81; a data bus 95 for carrying out data transfer; a transfer request signal 84; a request number 82 corresponding to the request signal 84; a request number comparator 83, and a DMA control circuit 99. This device is DMA of such a type that transfer information placed in RAM is read.
FIG. 10 illustrates an example of transfer information placed in RAM. One piece of transfer information is composed of transfer information TIA, TIB, TIC equivalent to 3 words. FIG. 11 illustrates an example of multiple pieces of transfer information placed in RAM. Transfer information items to be read are displaced in positions predetermined by a user program in the RAM like transfer information TIA000, TIB000, . . . .
Description will be given to the operation of the thus configured device. A transfer request is made by the transfer request signal 84. The request number corresponding to a transfer request signal 84 is given starting from the request number 82. At this time, at the request number comparator 83, the request number 82 is compared with a value stored in the request number register 81. Initially, the request number register 81 is empty and the result of comparison at the request number comparator 83 is disagreement. When the result of comparison is disagreement, the request number 82 is stored in the request number register 81 and transfer information corresponding to the request number 82 is read from the RAM.
First, transfer information TIA is read from the RAM and placed in the DMA count register 91 and the DMA command register 92. Subsequently, transfer information TIB and transfer information TIC are sequentially read from the DMA and placed in the DMA address register 93. Then DMA transfer is carried out.
When a transfer request whose request number is the same as the previous request number occurs, the request number 82 and a value stored in the request number register 81 are compared with each other at the request number comparator 83. Since the request number of the transfer request of this time is the same as the previous request number, the result of comparison is agreement. Therefore, reading of transfer information TIA, TIB, TIC is skipped and DMA transfer is immediately carried out.
When a transfer request whose request number is different from the previous request number occurs, the request number 82 and a value stored in the request number register 81 are compared with each other at the request number comparator 83. Since the request number of the transfer request of this time is different from the previous request number, the result of comparison is disagreement. Consequently, transfer information TIA, TIB, TIC are written back and saved to the RAM area corresponding to the previous request number because the transfer information TIA, TIB, TIC corresponding to the previous request number remain in the DMA device. Thereafter, the transfer information TIA, TIB, TIC corresponding to the request number 82 of this time are read and DMA transfer is carried out.
In the related art, as mentioned above, the request number comparator 83 determines whether or not to skip reading of transfer information according to whether or not the previous request number and the request number of this time are matched with each other.
FIG. 12 is a timing chart of an example where request numbers are matched with each other, illustrating how the effect of the related art is exerted. During period T0, first, request number 02 is inputted together with a transfer request. In response thereto, in the DMA device, request number 02 is set in the request number register 81 and transfer information TIA, TIB, TIC corresponding to request number 02 are read during period T02R. Thereafter, DMA transfer is carried out during period TDMA. When a request with request number 02, identical with the previous request number, occurs during period T1, the following processing is carried out: since the value in the request number register 81 and the request number in period T1 are identical with each other, reading of the transfer information TIA, TIB, TIC is skipped and the cycle in period TDMA is immediately carried out.
FIG. 13 illustrates an example where the previous request number and the request number are not matched with each other. In the related art, the following processing is carried out when a transfer request with request number 00 occurs during period T0: during period T00R, transfer information TIA, TIB, TIC corresponding to request number 00 are read and during period TDMA, DMA transfer is carried out. When a transfer request with request number 01 thereafter occurs during period T1, transfer information TIA, TIB, TIC corresponding to request number 00 is written back and saved during period T00W because request number 01 is different from the previous request number 00. During period T01R, transfer information items TIA, TIB, and TIC corresponding to request number 01 are read, and DMA transfer is carried out based on these items of transfer information.

DMA device having plural buffers storing transfer request information and DMA transfer method


An image processing method processes image data to be output to an image forming apparatus that is capable of making a two-way recording to form an image on a recording medium by recording in a forward path and a return path of a scan by an ink-jet recording head. The image processing method includes a halftone process that is based on an inclined line-group keytone and maintains keytone continuity, including a dither process in which the inclined line-group keytone appears at a stage where the recording in the forward path is made.

As image forming apparatuses such as printers, facsimile apparatuses, copying apparatuses and composite (or multi-function) apparatuses having the functions of the printer, facsimile apparatus and copying apparatus, there are the so-called ink-jet recording apparatuses which use an ink-jet recording head, for example. The ink-jet recording apparatus makes an image formation on a recording medium by ejecting ink from the ink-jet recording head onto the recording medium. The recording medium may be paper, OHP film or any suitable recording sheet onto which the ink may be adhered. The image formation includes various kinds of recording and printing of characters, images and/or photographs.
In such an ink-jet recording apparatus, increasing the resolution is one element for increasing the picture quality of the image that is formed on the recording medium. A pitch of nozzles of the recording head that ejects the ink may be reduced in order to obtain a high resolution. However, since there is a physical limit to reducing the nozzle pitch, the so-called interlace scanning is carried out so as to obtain a resolution that is an integer multiple of the nozzle pitch, with the sub scanning (or recording sheet feeding) accuracy and the impact dot diameter permitting.
Increasing the operation speed (or recording speed) of the ink-jet recording apparatus is another important element besides increasing the picture quality. Particularly in the case of a serial scan type image forming apparatus in which the recording head scans in a main scanning direction and the recording sheet is fed in a sub scanning direction, it is possible to achieve a recording speed that is approximately two times that of a one-way recording, by carrying out a two-way recording (or bi-directional recording) which ejects the ink onto the recording sheet during both a forward path (or down-path path) and a return path (or up-path) of the recording head scan in the main scanning direction.
But when the two-way recording is carried out, it is difficult to completely match the impact positions of the ink drops on the recording medium between the forward and return paths of the recording head, and a slight error occurs between the impact positions of the ink drops on the recording medium between the forward and return paths of the recording head. For this reason, when an attempt is made to simultaneously achieve a high-speed operation (or high-speed recording) and a high picture quality by simultaneously carrying out the interlace scanning and the two-way recording, the impact position error occurs for every other line (this impact position error will be referred to as a "two-way impact error") and the picture quality greatly deteriorates as a result.
Japanese Laid-Open Patent Applications No. 11-48587 and No. 2004-288627 propose preventing the picture quality from becoming deteriorated by the above two-way impact error, by providing a pattern that can easily correct the impact positions before a user uses the recording apparatus, and enabling the user to carry out a correction operation based on this pattern.
A Japanese Laid-Open Patent Application No.2004-9333 proposes another method that records the dots with a priority in the forward path of the main scan, and filling the dots in the return path for gradation levels amounting to 50% or more of the recording density of the dots.
Furthermore, a Japanese Laid-Open Patent Application No.2004-166163 proposes a gradation reproducing method which carries out a halftone process using a dither matrix, by reproducing the gradation level by an inclined line-group keytone.
In the ink-jet recording apparatus, the gradation image may be formed by forming four kinds of dot sizes (large, medium, small and nil) by selectively ejecting ink with three kinds of ink drop sizes, namely, large ink drop, medium ink drop and small ink drop. But in this case, the extent of the two-way impact error becomes different depending on the ink drop sizes.
For example, if the recording head that ejects the ink uses a piezoelectric element, the kinetic energy of the ink drop, the air resistance the ink drop receives during flight and a driving signal waveform applied to the piezoelectric element to eject the ink drop respectively differ depending on the ink drop size. As a result, the amount of impact position error of the ink drop that is ejected from the recording head differs depending on the ink drop size. Moreover, if the nozzle diameters are made different in order to eject the ink with the different ink drop sizes, the amount of impact position error of the ink drop that is ejected from the recording head is also affected by the precision with which the recording head is made.
In other words, when carrying out the two-way recording by selectively ejecting the ink with the different ink drop sizes, it is extremely difficult to accurately match the impact positions of the ink drops for all ink drop sizes.
For this reason, there is a limit to suppressing the picture quality deterioration caused by the two-way impact error even if the methods proposed in the Japanese Laid-Open Patent Applications No.11-48587 and No.2004-188627 are employed. Accordingly, when generating the image data, the halftone process must be carried out under the precondition that the two-way impact error will occur, but this precondition was not take into consideration by the conventional methods.
On the other hand, although the Japanese Laid-Open Patent Application No.2004-9333 proposes a suitable method from the point of view of suppressing the picture quality deterioration caused by the two-way impact error, the dots formed by the small ink drops will be arranged linearly along the main scanning direction for every other line at the gradation level where the recording density of the small ink drops is 50%, for example. But such a dot arrangement is easily affected by inconsistencies in the sub scanning direction and inconsistencies in the ink ejection of the nozzles, and another problem is introduced in that a banding is easily generated.
The dither process based on the inclined line-group keytone as proposed in the Japanese Laid-Open Patent Application No.2004-166163 will not easily generate the banding. However, another problem is introduced in that a disorder of the inclined line-group keytone is generated if the two-way impact error occurs.

Image processing method, printer driver, image processing apparatus, image forming apparatus and image forming system


The system to proctor an examination includes a first camera worn by the examination taking subject and directed to capture images in subject's field of vision. A second camera is positioned to record an image of the subject's face during the examination. A microphone captures sounds within the room, which are analyzed to detect speech utterances. The computer system is programmed to store captured images from said first camera. The computer is also programmed to issue prompting events instructing the subject to look in a direction specified by the computer at event intervals not disclosed to subject in advance and to index for analysis the captured images in association with indicia corresponding to the prompting events.

This section provides background information related to the present disclosure which is not necessarily prior art.
Online education offers the potential to greatly expand the reach of today's educational institutions, both by providing a wider range of educational resources to enrolled students and by making educational resources available through adult education programs to persons who are not formally enrolled in a college or university.
Testing is an important and necessary component of any educational program, and online educational programs are no exception. The mechanics of testing the student's knowledge become problematic with online programs because, with no human proctor present, there is no reliable way to ensure against cheating. When tests are administered in a controlled and proctored environment, such as in a classroom, the students can be monitored by a human proctor during the test. However, in online programs there may be no convenient way to provide the human proctor.
The same is true in testing situations outside the educational environment. For example governmental examinations and professional certification examinations also currently require a human proctor to ensure against cheating. The need for a human proctor increases the cost of testing and often restricts the venues available where testing can be administered. Limitations imposed by cost and available venue may dictate that a test be administered only at limited times. This places a burden on the student and limits the frequency with which testing can be performed.
To illustrate, in a government program designed to assess the skills and aptitudes of an entire population, testing may be practical only at selected time intervals, such as for example, once a year, for students entering high school that year. If testing could be conducted in a more distributed and frequent fashion, it would be possible to obtain a more granular and accurate assessment of the skills and aptitudes of the student population. With such more granular and accurate assessment the educational process could be more finely controlled. Current cost and venue demands make this impractical.

Board of Trustees of Michigan State University


A CIS-based thin film solar cell has a backside electrode layer that is divided by a pattern (P1), and a CIS-based light absorption layer, and a transparent conductive film are sequentially formed on a substrate. The backside electrode layer comprises an intermediate layer on the surface that is in contact with the CIS-based light absorption layer, the intermediate layer being composed of a compound of a metal that constitutes the backside electrode layer and a group VI element that constitutes the CIS-based light absorption layer; the intermediate layer comprises a first intermediate layer portion which is formed on the upper surface and a second intermediate layer portion which is formed on the lateral surface that and faces the pattern (P1); and the film thickness of the second intermediate layer portion is larger than the film thickness of the first intermediate layer portion.

Typically, a CIS-based thin film solar cell has an integrated structure, in which a backside electrode layer formed on a substrate is divided by a dividing groove referred to as pattern 1 (P1) and a CIS-based light absorption layer (hereinafter referred to as "light absorption layer") and transparent conductive film formed on the backside electrode layer are divided by dividing grooves referred to as pattern 2 (P2) and pattern 3 (P3), whereby a plurality of unit cells are connected in series.
In a prior art CIS-based thin film solar cell, a shunt path (20c) is formed through the light absorption layer between the adjacent regions of the backside electrode layer divided by pattern 1 (P1) and a leakage current flowing through the shunt path (20c) causes problems of reduction of conversion efficiency of a solar cell.
Several methods have been developed to obviate the aforementioned problems. One of the methods involves fabricating an insulating material between the adjacent regions of the backside electrode layer divided by pattern 1 (P1) to reduce the influence of leakage current on the shunt path (20c) (see, for example, Patent document 1.)
Other methods involve a process of expanding the width of pattern 1 (P1) to increase the distance between the regions of the backside electrode layer adjacent to pattern 1 (P1) thereby to reduce the influence of leakage current on the shunt path (20c).


A vibration generating apparatus with high yield, low cost, and can exhibit vibration tactile haptic effects even with variation in the natural frequency of a mechanical vibrator, including a damping system having a damping ratio ζ<1 to support a mechanical vibrator to a fastening part, and a magnetizing unit generating a dynamic magnetic field to vibrate the mechanical vibrator by non-contact, the mechanical vibrator generating a beat vibration by making the frequency of a drive voltage applied to the magnetizing unit, from a drive start or middle of drive, to be a non-resonant frequency out of a damped natural frequency of the mechanical vibrator, wherein the apparatus comprises a forced vibration control unit controlling to stop application of the drive voltage, in a beat wave defining an amplitude of the beat vibration, at a second valley part after a first peak part from the side of the drive start.

1. Field of the Invention
The present invention relates to a vibration generating apparatus which can be built into a mobile phone, touch panel, or other device, more particularly relates to a vibration generating apparatus which exhibits a vibration tactile haptic effects of instantaneous vibration.
2. Description of the Related Art
A vibration generating apparatus giving the vibration tactile haptic effects disclosed in Japanese Patent Publication (A) No. 2008-521597 employs a resonant forced vibration system. A signal generator generates an excitation use actuator signal of a first frequency the same as the natural frequency of the resonance actuator and excites the resonance actuator in the resonance state so as to sharply increase the acceleration instantaneously. After this, the signal generator generates a damping use actuator signal of a second frequency shifted from the first frequency by a 180 degree phase (waveform inverted) and dampens the resonance actuator to cause instantaneously damping.
As related art, there is Japanese Patent Publication (A) No. 2008-521597 (0033, FIG. 1)
The above resonance actuator is made to operate in a resonance mode using a forced vibration frequency the same as its natural frequency (resonant frequency), so while instantaneous excitation is easy in the excitation process which rapidly increases the acceleration, in the damping process for damping the once high acceleration resonance actuator, since the resonance actuator will have quite of a bit of variation in natural frequency for each specimen, even if the phase of the damping use actuator signal completely shifts by 180 degrees from the excitation use actuator signal, in reality there is no guarantee of a complete 180 degree shift with respect to the phase of the vibration and displacement of the resonance actuator. Due to this advanced phase difference or retarded phase difference which occurs unavoidably due to variations in the natural frequency, depending on the timing of the end of application of the damping use actuator signal, incomplete stopping of the mechanical vibrator or restart after stopping will be induced, so the free damping period remains longer until entering the insensitive zone and the sharpness of the damping becomes poor.