This application claims priority from German Patent Application No. DE 10 2016 225 344.1, which was filed on Dec. 16, 2016, and is incorporated herein in its entirety by reference.
Embodiments of the present invention relate to a polychromator and the manufacturing method thereof. Advantageous embodiments relate to a system for analyzing electromagnetic radiation and to devices for producing same.
Specific substance properties, e.g., the carbon dioxide concentration of respiratory air, the humidity of wood or paper, or the composition of plastics may often be analyzed by means of comparatively simple optical methods, e.g., with the aid a polychromator. In a large amount of application cases, comparatively simple information may be used for controlling an operating sequence or a process. Controlling drying of raw paper or determining the colorific value of wood, or wood pellets, are based on determining humidity. Just like determining the content of carbon dioxide in air, spectral-analytic system may provide accurate measurement values in said application cases merely by evaluating only two spectral bands—a measurement band and a reference band.
What is typical for said applications and many other examples of applications is the critical cost situation regarding the system. Low-cost systems make a decisive contribution to keeping manufacturing costs low. What is relevant is the respective total cost of ownership (TCO), which includes service and operating costs. Often, there are solutions which are technically feasible but involve too much expenditure in the long term. For example, commercially available near-infrared spectrometers are problematic because of their high investment costs; other approaches based, e.g., on optical filters or LED light sources are often limited in terms of reliability or long-term stability.
What is desirable is a system approach which is characterized by a small amount of expenditure in terms of manufacturing and operation and performs simple spectral-analytical measurement with reliability and long-term stability. The selection of the spectral bands considered should be easily adaptable within the context of the manufacturing process, the level of variability should be as large as possible, and the overall solution should be small, robust and low-cost.
Conventional technology discloses numerous methods of detecting chemical composition. Problems provided in a gaseous, liquid or dissolved form may be analyzed by means of chromatographic methods. Measurement is generally destructive.
Radiographic methods, e.g., X-ray florescence analyses (XRF) or atomic absorption spectrometry (AAS) involve a large amount of expenditure and represent potential health hazards.
Optical spectroscopy is a widely employed method both for utilization in laboratories and for performing field measurements. Complex spectral-analytical measurement tasks are typically performed by using spectrometers. Said spectrometers are available in manifold variants and for various spectral ranges. However, specifically within the range of near-infrared and infrared wavelengths, which range is important for analyzing organic compounds and water, spectrometers are expensive and often too sensitive for being used in the field and in production. Miniaturized variants of spectrometers, which are mainly based on designs having fixed gratings and detector lines, may reduce said disadvantage but are still too expensive for many applications.
System approaches based on interferometers, so called Fabry-Perot filters, are often critical with regard to vibrations occurring during use. Other approaches using spectral filters exhibit disadvantages regarding reliability and long-term stability. This also applies to approaches wherein light of different wavelengths is generated, for example, by selected LEDs.
Conventional technology also describes so-called polychromators which, similar to spectrometers, split up incident light into its spectral constituents but then will detect said incident light only at selected points of the spectrum in that a single detector is positioned at the appropriate location behind a suitably configured gap for aperture limitation. Such systems have so far been used mainly in the field of very high resolutions with very large designs. Miniaturization has been limited due to the adjustment expenditure which has so far been involved in order to achieve the desired level of precision.
According to an embodiment, a polychromator may have: a substrate; and a functional element having an optical spectral decomposition action and being configured to spectrally decompose electromagnetic radiation originating from an entry opening, a spectrally decomposed spectrum being obtained, and to direct the spectrally decomposed spectrum onto a spatial area of the substrate, wherein the substrate includes at least two transparent zones at different positions within the spatial area, so that two different spectral components of the spectrum are detectable at the two transparent zones.
According to another embodiment, a method of producing a polychromator including a substrate and a functional element having an optical spectral decomposition action configured to spectrally decompose electromagnetic radiation originating from an entry opening, a spectrally decomposed spectrum being obtained, and to direct the spectrally decomposed spectrum onto a spatial area of the substrate, may have the steps of: forming the substrate such that at least two transparent zones are configured at different positions, two different spectral components of the spectrum being detectable at the two transparent zones.
Embodiments of the present invention provide a polychromator comprising a substrate and a functional element having an optical spectral decomposition action, e.g., a grating or a prism. The functional element having an optical spectral decomposition action is configured to spectrally decompose electromagnetic radiation originating from an entry opening, e.g. light which originates from a suitable radiation source and is reflected by a sample, so that a spectrally decomposed spectrum being obtained, and to direct the spectrally decomposed spectrum onto a spatial area of the substrate. The substrate comprises at least two transparent zones at different positions within the spatial area, so that two different spectral components of the spectrum are detectable at the two transparent zones, e.g. (aperture) diaphragms. The two transparent zones may have two detectors associated therewith for this purpose. By means of this embodiment, evaluation of a spectrum with a small number of spectral bands is possible; low-cost manufacturing may be achieved by using a substrate which has the transparent zones (gaps or pinholes) introduced therein, e.g., by means of lithography. This production process is not only low-cost, but also very reliable and highly precise so as to produce the exact positions for the desired spectral bands.
Embodiments of the present invention are based on the finding that by using a substrate, advantageously a one-part substrate such as a semiconductor substrate, for example, which is workable by means of semiconductor production technologies, highly accurate distances between two transparent zones (opening, gap), in particular two aperture openings, may be set. When using said substrate, which has been manufactured in this manner, in combination with a functional element having an optical spectral decomposition action, such as a periodic element, for example, an apparatus, or a polychromator, may thus be adjusted to exactly two characteristic spectral components, so that an apparatus for evaluating a spectrum having two or more spectral bands will be obtained by means of low-cost but nevertheless highly precise and, consequently, also highly accurate means. Depending on the distance selected, a modified apparatus may thus be provided for examining a modified spectrum and/or for optimizing the apparatus in terms of other spectral components to be evaluated.
As was already indicated, the at least two different positions each have a wavelength associated with them; in accordance with further embodiments, the distance is selected at least such that it corresponds to at least a spectral wavelength distance.
In accordance with further embodiments, rather than the two transparent zones, respectively, it is also possible to provide three transparent zones in combination with three detectors, or even more transparent zones in combination with more detectors, so that even a spectrum having more than two spectral bands is easily detectable.
In accordance with further embodiments, a radiation source having an optional beam former such as a diaphragm, a microlens, or other aperture openings, for example, may be provided at the entry opening. Also in accordance with a further embodiment, it is advantageous here that the beam former, or the diaphragm, be arranged within the one substrate. So as to then emit the light beam out of the plane, so that said light beam will be found again in an unfolded form within the same plane, said unfolding will occur with the aid of the spectrally acting functional element, e.g., in reflection. For the embodiment which is introduced here and has the one substrate which also has the transparent zone provided therein, further reflection means (further optical functional elements) will then be provided which reflect the beam (electromagnetic radiation), e.g., prior to or following the unfolding. In accordance with an advantageous variant, the functional elements having a spectrally decomposing action are configured as reflective gratings; the electromagnetic radiation will then be reflected prior to and following the unfolding, so that the electromagnetic radiation may be directed back to the one substrate.
In accordance with a further embodiment, provision may also be made for so-called “duplicating means”, e.g., for utilization of a perpendicularly illuminated grating, and diffraction of light in opposite directions in accordance with positive and negative diffraction orders in accordance with the grating equation, so that the one beam is unfolded onto two spatial areas, namely to a first spatial area and a further spatial area. Both in the first and in the further spatial area, the substrate comprises one or more transparent zones, so that in the event that specific spectral components are associated with the respective positions, additional spectral components for additional spectral lines may thus be examined. This is advantageous in particular when the spectral lines to be examined are very close together, so that it would typically be no longer possible, with a compact apparatus, to resolve the individual spectral lines. This is why in accordance with advantageous embodiments, the transparent zone has such a position within the further area that the spectral component to be detected lies between the two spectral components (which belong to the at least two transparent zones within the first area). In accordance with an advantageous variant, the apparatus includes only a substrate wherein the transparent zones are provided for the first area and the further area. Advantageously, a diaphragm may also be provided between the two areas, through which diaphragm the radiation source emits the electromagnetic radiation. In this embodiment, mirrors are employed.
In accordance with a further advantageous embodiment, the one substrate also includes the functional means which cause splitting of the spectrum. In this manner, it can be ensured that any mutual positioning may be accurately produced by means of highly standardized semiconductor production methods.
A further embodiment relates to a method of manufacturing the above-explained polychromator. In particular, the method includes the step of forming the substrate, so that at least two transparent zones are configured, and arranging the substrate within the spatial area, so that the at least two transparent zones are arranged at different positions along the spatial area. In accordance with an optional variant, the step of forming may be supported by lithography steps or at least one lithography step or the step of laser cutting or etching. In accordance with one embodiment, the method also includes the step of dicing the substrate as a multitude of contiguous substrates (wafer).
Embodiments of the present invention will be detailed subsequently referring to the appended drawings, in which:
Before embodiments of the present invention will be explained below by means of the accompanying drawings, it shall be noted that elements and structures which have identical actions are provided with identical reference numerals.
The optional radiation source 12, which is arranged in front of an entry opening 12b for the beam 13 (electromagnetic radiation), may be a light source, for example, which illuminates a sample or a gas column whose back-scattered and or transmitted light enters the polychromator. Alternatively, only one entry opening may be provided via which electromagnetic radiation, or the light of any origin, enters the polychromator 10. An entry opening is understood to mean not only a “mechanical” opening, but also an optical opening, e.g., chromium-on-glass substrate having a patterned gap, i.e., generally a transparent zone. A transparent zone 12b and 16a/16b, respectively, is an area whose light/radiation transmission is higher than that of the surroundings. Light includes a broad spectral range, e.g., from 780 nm to 6000 nm.
Within element 14, the beam 13 is spectrally split up by a suitable means, e.g., a grating or a prism. As a result of the splitting, the unfolded spectrum enters an image plane and/or an area of the substrate 16 at different spatial angles. In other words, this means that the different spectral components are imaged onto the substrate 16 at different spatial angles. A functional element having an optical spectral decomposition action 14 is understood to mean an element configured to image/deflect a frequency range, e.g., a visible range and/or an infrared spectral range and/or an ultraviolet spectral range, in different directions in a frequency-selective manner.
This (first) area of the substrate 16, e.g., made of silicon or any other semiconductor material with or without lateral structures (BSOI wafer), is provided with reference numeral 16s and represents the distribution of the intensity of all functions of the wavelength. Selecting the target area is possible in each case by specifying spatial coordinates which correlate with the minimum and maximum wavelengths, respectively, of a spectral band which are to be considered. The substrate 16 includes several different bands, such as the two bands associated with the diaphragms 16a and 16b. Depending on the spatial arrangement of said transparent zones, or diaphragms, 16a and 16b, different spectral bands and/or spectral components/spectral lines may be examined. The dimensions (diameters and widths) of the diaphragms 16a and 16b may vary, so that it will not be mandatory for said diaphragms to have identical dimensions. What is important in terms of positioning of the diaphragms 16a and 16b is that they are arranged precisely for the specified spectral bands and/or spectral (atomic or molecular) transitions.
This substrate 16 is manufactured, for example, by using processes of semiconductor production or production methods generally used in microsystems technology, including, e.g., lithography steps. Such production technologies ensure precise positioning of the at least two gaps 16a and 16b (aperture diaphragms). By means of such production methods, the extreme requirements in terms of precision that are placed upon the locations and widths of the gaps 16a and 16b can be met, said technology also entailing the miniaturization system approach for achieving very small sizes, or very compact designs. It is difficult or not all possible to implement such a system in a profitable manner by using the usual means of precision engineering.
Optional detectors 18a and 18b are arranged behind the gaps 16a and 16b, i.e., are associated with them, so that they may detect the unfolded electromagnetic radiation 15 entering through the transparent zones 16a and 16b. The detectors may be identical or different, for example, and may be configured to detect the radiation at least in the area associated with the positions of the transparent zones 16a and 16b.
In accordance with further embodiments, it shall be noted that the positional deviation of the gaps 16a and 16b is clearly smaller than the dimensions of the gaps, i.e., their widths per se. Alternatively, it would also be possible to specify the resulting inaccuracy in terms of width and/or position in relation to the wavelength of the spectral bands to be analyzed.
A further embodiment relates to a manufacturing method, in particular for manufacturing the substrate. As was already indicated above, said substrate is produced by means of production methods used in microsystems technology such as lithography or laser cutting, for example. In semiconductor production technology, further methods are known by means of which suitable substrates may be re-shaped in a structured manner by means of chemical etching from the front and/or rear sides. Stand-alone structures, diffraction gratings and gaps have been successfully produced by deep etching of silicon substrates (wafers). On the basis of their devices, spectroscopic instruments, i.e., so-called “scanning grating spectrometers”, have been successfully implemented (cf. Tino Pugner, Jens Knobbe, Heinrich Gruger, “Near-Infrared Spectrometer for Mobile Phone Applications”; Applied Spectroscopy 2016, vol. 70(5) 734-745). A next step comprises appropriately positioning the substrate 16 within the apparatus 10, e.g., opposite the functional element 14, so that the positions of the transparent zones 16a and 16b coincide with the spectral band desired accordingly.
It shall also be noted at this point that the method may include additional steps such as dicing the substrates, which have been processed in this manner, from a multitude of contiguous substrates (within a wafer). With regard to
The gaps 16a and 16b have the detectors 18a and 18b associated with them, which, as may be seen, in particular, in
With reference to
Reflection means (optical functional elements) 32′ are provided opposite the plane 30′ and/or the units 12′, 12b, 14′, and 16. Said reflection means 32′ include, in this embodiment, two curved (parabolic) mirror surfaces 32a′ and 32b′, which are oriented such that the light beam 13 from the source 12′ is reflected, via the grating 14′, as a light beam 15 unfolded by the grating 14′, onto the substrate 16 and/or into the spatial area 16s, where the transparent zones 16a and 16b are arranged. It shall be noted at this point that the depicted area 12s is “spatial” in a very strict sense only (in the area of a substrate thickness); however, the ratio between the thickness and the lateral dimensions in this case is very small, i.e. a surface. Imaging is useful only if it takes place within the range of an optical depth of focus. However, spectrally selective deflection of the radiation typically goes into different spatial areas (without necessarily being focused).
More specifically, the light beam 13 (cone) is reflected by the reflective face 32a′, while the unfolded cone of light 15 is reflected by the face 32b, wherein focusing may occur. The cone of light 15 includes the spectrally unfolded light beams (spectral components) 15a and 15b, both of which are projected onto different positions of the substrate 16 in the area 16s in a frequency-selective manner. In addition to beam focusing, which is advantageous in the case of gratings, an advantage of the reflection means 32′ is that all three of the radiation source 12′ comprising the diaphragms 12b, the grating 14′, and the substrate 16 are arranged on a plane 30, which significantly improves accurate positioning.
In accordance with embodiments, the reflective element 32′ is kept at an appropriate distance by means side panels 34′. At the lateral position of the grating 14′, the reflective element 32′ has a recess, since no reflection occurs here.
It shall be noted at this point that here, in the unfolded radiation spectrum 15, three spectral components which forward the split-up beam 13 to the detectors 18a to 18c are marked by reference numerals 15a to 15c. Further changes, e.g. on the reflection means 32′ and/or the grating 14′ or the radiation source 12′ are not mandatory here.
Based on the embodiment 10′,
Three specific applications of the polychromators explained above will be discussed below.
1. Gas analysis system (e.g. NDIR, non-dispersive infrared): concentration measurements, in particular those providing absolute values (% by volume), may be effected by means of absorption measurements along a gas column. For applications in gas analysis, a light path of a known length by means of which the specific absorption of a gas, e.g. CO2, in air is detected is relevant.
In an arrangement in accordance with 10, 10′, 10″, 10′″, a gas column is illuminated with the light of a light source 12, 12′ configured accordingly, e.g. a halogen lamp, and is analyzed by the polychromator. Due to the location of the grating 14, 14′ and the positions, or widths, of the gaps 16a to 16c, the spectral bands are selected at 3910 nm and 4220 nm (each having a width of from +/−30 nm to +/−50 nm), and the intensity is detected and converted to an electric signal by an infrared detector, advantageously a pyroelectric element or a thermopile. The signals are detected by an electronic evaluation circuit and evaluated within data processing means. By means of the intensities detected, a quantitative statement may be made regarding the carbon dioxide content of the analyzed air. If applied in indoor air monitoring, this may be advantageously used for recommending performing ventilation or for controlling corresponding ventilation means.
2. Near-infrared measurement of water content: in the field of detecting the water content, or the degree of drying of wood, cardboard and paper, one typically uses spectral bands at three wavelengths, a reference band and a further band, which is correlated with hydrocarbons, being used in addition to a water band. Said bands may lie within the so-called near-infrared range from 780 nm to 2500 nm. Measurement is performed in reflection, the sample is illuminated by a suitable light source, and the back-scattered light is examined by the analysis system. By means of a system approach in accordance with 10 to 10′″, the gaps are placed, within the device 16 to 16″″, such that they correspond to the spectral bands. Three photodiodes in InGaAs technology are used for detecting the level of intensity.
What is advantageous as compared to an alternative solution, which is disclosed in conventional technology and uses three infrared LEDs for spectrally varying illumination of the sample, is the possibility of being able to accurately take into account the spectral transitions in accordance with their very nature by means of the locations and widths of the gaps, and to not be dependent on the technologically predefined emission line widths of LEDs. In addition, the problem of spectral long-term drift of infrared LEDs is solved.
3. Near-infrared analysis of plastics: the absorption spectra of numerous commonly used plastics such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polycarbonate (PC), polyethylene terephthalate (PET) and others differ specifically in the range of the C—C and the C—H bands between 1650 nm and 1780 nm. Identification of various plastics by means of a spectral analysis is possible on this basis. For example in the field of incoming goods inspection and of recycling, such analyses are very important. Appropriate system approaches have been provided, in a miniaturized design, for mobile use as portable devices (e.g. Phazir by Polychromix/Thermo Fischer), wherein the degree of miniaturization that has been reached and the system cost still have enormous potential for optimization. For this task, which is clearly more complex than the previous examples of application, evaluation of closely adjacent spectral lines may be advantageous. Due to the physical facts given in the implementation of the inventive approach, in particular the size of detectors and the consequent minimum distance of adjacent bands, it may be advantageous to use a specific implementation of the system which provides two separate spatial areas for placing exit gap devices and detectors, which placement may be addressed by using positive and negative first-order diffraction (which is possible only when using a grating as a diffractive element, and it is advantageous when the grating is symmetrical—e.g. an Si-etched V-stage grating).
The selection of the respective characteristic spectral ranges is illustrated by means of
The transparent zones 16a and 16b are provided in the area 16s, whereas the opening 16c″″ is provided within the area 16s″″. As may already be seen by means of the transparent zones 16a and 16b, said transparent zones are located very close to each other, so that the associated detectors 18a and 18b are arranged almost directly next to each other. In order to sample a spectral component (wavelength) located between those spectral components which belong to the transparent zones 16a and 16b, either the beam is unfolded even more or, as is the case here, the emitted beam is duplicated, so that a spectral band is detectable between the two spectral bands of the transparent zones 16a and 16b by means of the opening 16c″″.
Since in accordance with embodiments, the two functional elements/gratings 14a″″ and 14b″″ belong together, the structure may be described, in other words, as follows. The grating 14a″″+14b″″ is configured such that the entry gap 12b″″ is centrally provided within the grating 14a″″+14b″″, the light is converted to parallel beams via the oppositely located mirror 32a″″, which parallel beams will then perpendicularly impinge upon the grating 14a″″+14b″″. This is important in order to be able to symmetrically evaluate the positive and negative diffraction order. However, symmetry is not mandatory.
In accordance with advantageous embodiments, both the transparent zones 16c″″, 12b″″ as well as the transparent zones 16a and 16b are arranged within the same substrate 16″″. This is particularly advantageous since in this manner, the distances between the individual transparent zones 16a to 16c″″ and 12b″ may be accurately positioned with regard to one another.
In accordance with further embodiments, the substrate 16″″ as depicted here also includes the means for spectral unfolding, here the (planar) gratings 14a″″ and 14b″″ (either in combination with the exit gaps 16a, 16b and/or the entry gap 12b″″). Also in this embodiment is it advantageous that the positioning of the gratings 14a″ and 14b″ with regard to the transparent zones 16a to 16c″″ and/or 12b″″ may be adjusted with very high accuracy.
In accordance with embodiments, a simple opening for radiation impinging from outside may be provided instead of the radiation source 12″″.
It shall be noted at this point that in all of the embodiments of
In the embodiment of
The element having a spectrally decomposing action 14″″′, here a grating implemented to be reflective, is provided opposite the substrate 16″″′. In the intermediate area between the element having a spectrally decomposing action 14″″′ and the substrate 16″″′, a lens element 38″″′ is arranged which instead of the parabolic mirrors performs imaging (focusing) of the spectrum, which has been unfolded by means of the functional element 14″″′ (cf. 15″″′), onto the substrate 16″″′.
The mechanism which is operative in the examination, or the mode of operation, is comparable to the embodiments explained above, only the course of the beams is slightly changed. The beam 13″″ is emitted by the source 12″″ toward the element 14″″′ and is then reflected back in a spectrally decomposed manner (cf. 15″″′). In the unfolded spectrum 15″″′, the three spectral components imaged onto the transparent zones 16a, 16b and 16c″″ are marked by reference numerals 15a″″′, 15b″″′ and 15c″″′.
It shall be noted at this point that in case a prism is used as a spectrally unfolding element, means for focusing will not necessarily be provided. As an alternative to the general grating or to the prism, the following optical (dispersive) elements may also be provided: transmission grating, reflection grating, blazed grating, echelle grating, echelette grating, planar grating, concave grating, convex grating, holographic grating, prism.
Even if the spectrally unfolding element has been described as an element acting upon reflection, spectral unfolding may alternatively also occur in transmission, in accordance with embodiments.
It shall also be noted at this point that in accordance with further embodiments, a system is provided. The system serves to analyze electromagnetic radiation and consists of at least the following:
In accordance with embodiments, the system may comprise any of the following features:
Therefore, this generally means that the system is characterized in that
While this invention has been described in terms of several embodiments, there are alterations, permutations, and equivalents which fall within the scope of this invention. It should also be noted that there are many alternative ways of implementing the methods and compositions of the present invention. It is therefore intended that the following appended claims be interpreted as including all such alterations, permutations and equivalents as fall within the true spirit and scope of the present invention.
Number | Date | Country | Kind |
---|---|---|---|
10 2016 225 344 | Dec 2016 | DE | national |
Number | Name | Date | Kind |
---|---|---|---|
4468122 | Puryaev | Aug 1984 | A |
4995724 | Sonobe | Feb 1991 | A |
4997281 | Stark | Mar 1991 | A |
4999489 | Huggins | Mar 1991 | A |
5020910 | Dunn | Jun 1991 | A |
5159404 | Bittner | Oct 1992 | A |
5166755 | Gat | Nov 1992 | A |
5173748 | Bilhorn | Dec 1992 | A |
5420681 | Woodruff | May 1995 | A |
5528363 | Fachinger | Jun 1996 | A |
5550375 | Peters | Aug 1996 | A |
5559597 | Battey | Sep 1996 | A |
5623473 | Ichihara | Apr 1997 | A |
5657121 | Nishina | Aug 1997 | A |
5717487 | Davies | Feb 1998 | A |
5812262 | Ridyard | Sep 1998 | A |
5815278 | Johnston | Sep 1998 | A |
5825484 | Iwasaki | Oct 1998 | A |
5880834 | Chrisp | Mar 1999 | A |
6057925 | Anthon | May 2000 | A |
6081331 | Teichmann | Jun 2000 | A |
6100974 | Reininger | Aug 2000 | A |
6151112 | Atkinson | Nov 2000 | A |
6303934 | Daly | Oct 2001 | B1 |
6587198 | Olshausen | Jul 2003 | B2 |
6657723 | Cohen | Dec 2003 | B2 |
6661513 | Granger | Dec 2003 | B1 |
6744505 | Wang | Jun 2004 | B1 |
6813018 | Richman | Nov 2004 | B2 |
6862092 | Ibsen | Mar 2005 | B1 |
6886953 | Cook | May 2005 | B2 |
6917425 | Caruso | Jul 2005 | B2 |
6977727 | Lerner | Dec 2005 | B2 |
6980295 | Lerner | Dec 2005 | B2 |
6985226 | Lerner | Jan 2006 | B2 |
7034935 | Kruzelecky | Apr 2006 | B1 |
7041979 | Chrisp | May 2006 | B2 |
7075082 | Tsao | Jul 2006 | B2 |
7081955 | Teichmann | Jul 2006 | B2 |
7148488 | Horton | Dec 2006 | B2 |
7161673 | Da Silva | Jan 2007 | B2 |
7170600 | Nishii | Jan 2007 | B2 |
7180590 | Bastue | Feb 2007 | B2 |
7233394 | Odhner | Jun 2007 | B2 |
7236243 | Beecroft | Jun 2007 | B2 |
7239386 | Chrisp | Jul 2007 | B2 |
7330258 | Warren | Feb 2008 | B2 |
7345760 | Deck | Mar 2008 | B2 |
7382498 | Cook | Jun 2008 | B1 |
7483127 | Li | Jan 2009 | B1 |
7808635 | Chrisp | Oct 2010 | B2 |
7812949 | Delmas | Oct 2010 | B2 |
7817274 | Zhang | Oct 2010 | B2 |
8040507 | Shibayama | Oct 2011 | B2 |
8174695 | Choi | May 2012 | B2 |
8345226 | Zhang | Jan 2013 | B2 |
8390806 | Subramanian | Mar 2013 | B1 |
8861060 | Puegner | Oct 2014 | B2 |
9435689 | Comstock, II | Sep 2016 | B2 |
9488577 | Andre et al. | Nov 2016 | B2 |
9625317 | Correns | Apr 2017 | B2 |
10084239 | Shaver | Sep 2018 | B2 |
10444069 | Rolland | Oct 2019 | B2 |
10444145 | Maschhoff | Oct 2019 | B2 |
10520361 | Knobbe | Dec 2019 | B2 |
20060038997 | Julian | Feb 2006 | A1 |
20060082772 | Kehoe | Apr 2006 | A1 |
20070030483 | Everett | Feb 2007 | A1 |
20070152154 | DeCamp | Jul 2007 | A1 |
20070171415 | Chrisp | Jul 2007 | A1 |
20070194239 | McAllister | Aug 2007 | A1 |
20070211250 | Teichmann | Sep 2007 | A1 |
20070252989 | Comstock | Nov 2007 | A1 |
20070262405 | Furuyama | Nov 2007 | A1 |
20080013086 | Deck | Jan 2008 | A1 |
20090262346 | Egloff | Oct 2009 | A1 |
20100039643 | Park | Feb 2010 | A1 |
20100227200 | Miyata | Sep 2010 | A1 |
20120236382 | Puegner | Sep 2012 | A1 |
20130271759 | Fattal | Oct 2013 | A1 |
20140055845 | Jain | Feb 2014 | A1 |
20150022811 | Cornell | Jan 2015 | A1 |
20150116721 | Kats | Apr 2015 | A1 |
20150241277 | Correns | Aug 2015 | A1 |
20150288129 | Jain | Oct 2015 | A1 |
20160099701 | Rinaldi | Apr 2016 | A1 |
20160126381 | Wang | May 2016 | A1 |
20160158886 | Kumar | Jun 2016 | A1 |
20160178983 | Alloatti | Jun 2016 | A1 |
20160356649 | Yokino | Dec 2016 | A1 |
20170003169 | Shaltout | Jan 2017 | A1 |
20170030773 | Han | Feb 2017 | A1 |
20170082263 | Byrnes | Mar 2017 | A1 |
20170176689 | Popp | Jun 2017 | A1 |
20170194522 | Wang | Jul 2017 | A1 |
20170201658 | Rosenblatt | Jul 2017 | A1 |
20170322457 | Chanda | Nov 2017 | A1 |
20170346257 | Garnache-Creuillot | Nov 2017 | A1 |
20170370773 | Kim | Dec 2017 | A1 |
20180045953 | Fan | Feb 2018 | A1 |
20180059440 | Yu | Mar 2018 | A1 |
20180156949 | Tsai | Jun 2018 | A1 |
20180172517 | Grueger | Jun 2018 | A1 |
20180178571 | Zhu | Jun 2018 | A1 |
20180202918 | Tanaka | Jul 2018 | A1 |
20180231702 | Lin | Aug 2018 | A1 |
20180240653 | Akselrod | Aug 2018 | A1 |
20180246262 | Zhan | Aug 2018 | A1 |
20180252857 | Glik | Sep 2018 | A1 |
20180274750 | Byrnes | Sep 2018 | A1 |
Number | Date | Country |
---|---|---|
4434814 | Apr 1996 | DE |
3104147 | Dec 2016 | EP |
Number | Date | Country | |
---|---|---|---|
20180172517 A1 | Jun 2018 | US |