US20150349281A1 - Organic schottky diodes - Google Patents
Organic schottky diodes Download PDFInfo
- Publication number
- US20150349281A1 US20150349281A1 US14/294,929 US201414294929A US2015349281A1 US 20150349281 A1 US20150349281 A1 US 20150349281A1 US 201414294929 A US201414294929 A US 201414294929A US 2015349281 A1 US2015349281 A1 US 2015349281A1
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- US
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- Prior art keywords
- diode
- conductor
- layer
- organic
- substrate
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- 238000002347 injection Methods 0.000 claims abstract description 24
- 239000007924 injection Substances 0.000 claims abstract description 24
- 239000004020 conductor Substances 0.000 claims abstract description 23
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 13
- -1 polyethylene terephthalate Polymers 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229920000547 conjugated polymer Polymers 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims description 4
- 125000005259 triarylamine group Chemical group 0.000 claims description 4
- 239000002042 Silver nanowire Substances 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims 2
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 1
- HMPRYWSTSPTPFI-UHFFFAOYSA-N [Li].[F] Chemical compound [Li].[F] HMPRYWSTSPTPFI-UHFFFAOYSA-N 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000327 poly(triphenylamine) polymer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/20—Organic diodes
- H10K10/23—Schottky diodes
-
- H01L51/0579—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66083—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by variation of the electric current supplied or the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched, e.g. two-terminal devices
- H01L29/6609—Diodes
- H01L29/66143—Schottky diodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/86—Types of semiconductor device ; Multistep manufacturing processes therefor controllable only by variation of the electric current supplied, or only the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched
- H01L29/861—Diodes
- H01L29/872—Schottky diodes
-
- H01L51/0002—
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
Abstract
An organic diode has a substrate, a first conductor layer on the substrate, an organic semiconductor layer on the first conductor layer, and a second conductor layer on the organic substrate layer, wherein one of the conductor layers has an injection enhancement.
Description
- Schottky diodes typically have a metal-semiconductor junction rather than a semiconductor-semiconductor junction. They typically have a low forward voltage drop. These diodes may consist of organic materials. Organic Schottky diodes may have an organic semiconductor layer sandwiched between a single or multi-layered stack of injecting contact (IC) and a blocking contact (BC), designated IC/OSL/BC. An example of such a diode is shown in
FIG. 1 .FIG. 1 shows a prior art embodiment of an organic Schottkydiode 10. The diode has an injectingcontact 14 on asubstrate 12. Theorganic semiconductor layer 16 resides on the injecting contact layer. The blockingcontact 18 resides on the organic semiconductor layer. Materials for the organic semiconductor layer include both p-type and n-type organic semiconducting polymeric or molecular materials and the IC and BC can each consist of at least a conductive layer such as indium-tin-oxide (ITO), gold, silver, copper, aluminum, nickel, and palladium. - Solution processing techniques, such a printing, spin coating, etc., work well with organic polymer Schottky diode processes. Because of this, these have become prevalent, including those based on pi conjugated polymers such as poly(phenylene vinylenes) (PPVs) and poly(thiophenes) such as ITO/PPV/A1, ITO/PEDOT-PSS/MEH-PPV/Au, ITO/MEH-PPV:C60/Ca, ITO/P3HT/Au and the like. Recently poly(triarylamine) (PTAA) and its derivatives have become one of the most popular semiconducting polymer classes, because of their ease of processing, stability and outstanding charge transport properties.
-
FIG. 1 shows a prior art embodiment of an organic Schottky diode. -
FIG. 2 shows an embodiment of an organic Schottky diode having an injection enhancement. -
FIG. 3 shows another embodiment of an organic Schottky diode having an injection enhancement. -
FIG. 4 shows another embodiment of an organic Schottky diode having an injection enhancement. -
FIG. 5 shows another embodiment of an organic Schottky diode having an injection enhancement. -
FIGS. 6 and 7 show linear plot and a log plot of voltage versus current density for a first embodiment of an organic Schottky diode. -
FIGS. 8 and 9 show linear plot and a log plot of voltage versus current density for a second embodiment of an organic Schottky diode. -
FIG. 2 shows an embodiment of an organic Schottkydiode 20. The diode has asubstrate 22, afirst conductor 24, asemiconductor 26 and asecond conductor 28, similar to the prior structure. In this embodiment, theconductor layer 24, sometimes referred to as the injecting contact layer, has an injection enhancement layer between the conductor and the semiconductor layer. The injection enhancement layer modifies the work function of the conductive layer to achieve, ideally, an Ohmic contact. - The conductor layer may consist of silver, gold, copper, nickel, aluminum, indium-tin-oxide, conductive carbon materials, silver nanowires, etc. The organic semiconductor layer may consist of pi conjugated polymers such as poly(triarylamines) (PTAA), poly(phenylene vinylenes), poly(thiophenes), triarylamine containing polymers, ferrocene containing polymers, polysilanes, and triarylamine molecularly doped polymers. The injection enhancement layer and injection enhancement additive include TCNQ (tetracyanoquinodimethane) and its derivatives, LiF (lithium fluorine), Li2CO3 (lithium carbonate), CsF (cesium fluoride), Cs2CO3 (cesium carbonate). Substrate materials may include high temperature thermal plastics, such as PET (polyethylene terephthalate) and PEN (polyethylene napthalate), glass and silicone.
- In some particular embodiments, the
conductor 24 consists of silver, and the injection enhancement layer consists of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimehane (F4-TCNQ). The other layers may consist of N,N′-Bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD), bisphenol A polycarbonate (PC), and (PTAA) polytriphenylamine. The diode would be Ag/F4-TCNQ/TPD:PC(1:1)/Ag. Another possibility would be Ag/F4-TCNQ/PTAA/Ag. The area of the TPD:PC diode is 1 mm2 and the polymer thickness is about 400 nm. The area of the PTAA diode is 2.5 mm2 and the PTAA layer thickness is about 1000 nm. -
FIGS. 3-5 show alternative embodiments of the diode structure. In thediode 30, theinjection enhancement layer 29 resides between thesemiconductor layer 26 and thesecond conductor layer 28. InFIGS. 4 and 5 , rather than an injection enhancement layer, it consists of an injection enhancement additive. The conductor is bulk modified by addition of the injection enhancement additive, which may consist of the same materials used in the injection enhancement layer.FIG. 4 shows adiode 40 has a lower conductor layer that has been bulk modifiedlayer 44 by an injection enhancement additive on the substrate.FIG. 5 shows adiode 50 in which the bulk modified layer resides above the semiconductor layer. In either case, the additive is referred to as an injection enhancement, either in layer or additive form. - The manufacture of these diodes may take many forms. The metal conductor is deposited on the substrate. Typically, this may be accomplished using several different processes, but the materials used here are particularly useful for printing or other solution processing. In the case of the injection enhancement layer, the process will deposit it on either the conductor layer or the substrate depending upon the structure of the diode. With the injection enhancement additive, the solution used to form the conductor layer has the additive mixed into it prior to deposition.
-
FIGS. 6 and 7 show the linear and log I-V plots for a diode consisting of Ag/F4-TCNQ/PTD:PC(1:1:)/Ag upon applying a forward bias showing at current density of 1.0×10−5 A/mm2 at 5 V.FIGS. 8 and 9 show linear and log I-V plots for a diode consisting of Ag/F4-TCNQ/PTAA/Ag. The plots show a rectifying effect upon applying a forward bias showing at a current density of 2.0×104 A/mm2. The resulting performance of this diode is approximately better than that for the TPD:PC. Without the injecting material, the device does not rectify. - The resulting diodes having an injection enhancement layer or additive has several advantages over other organic semiconductor layer diodes. For example, most organic diodes use different electrode materials with different work functions. With the use of injection enhancement layer or additive, the diode has near Ohmic contact, enabling the use of identical electrode materials. In one embodiment, for example, both electrodes consist of silver in the bulk metal, but the additives are tuned to enhance or block the charge injection.
- It will be appreciated that several of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also that various presently unforeseen or unanticipated alternatives, modifications, variations, or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims.
Claims (11)
1. An organic diode, comprising:
a substrate;
a first conductor layer on the substrate;
an organic semiconductor layer on the first conductor layer;
a second conductor layer on the organic semiconductor layer, wherein one of the conductor layers is comprised of a conductor mixed with an injection enhancement additive.
2. The diode of claim 1 , wherein the substrate comprises one of a high temperature thermal plastic, glass or silicone.
3. The diode of claim 2 , wherein the substrate comprises high temperature thermal plastic and is one of polyethylene terephthalate or polyethylene napthalate.
4. The diode of claim 1 , wherein the first conductor comprises one of silver, gold, copper, nickel, aluminum, indium-tin-oxide, conductive carbon materials, and silver nanowires.
5. The diode of claim 1 , wherein the second conductor comprises one of silver, gold, copper, nickel, aluminum, indium-tin-oxide, conductive carbon materials, and silver nanowires.
6. The diode of claim 1 , the organic semiconductor layer comprises pi conjugated polymers.
7. The diode of claim 1 , the pi conjugated polymer comprises one of poly(triarylamines), poly(phenylene vinylenes), poly(thiophenes), triarylamine containing polymers, ferrocene containing polymers, polysilanes, and triarylamine molecularly doped polymers.
8. (canceled)
9. (canceled)
10. The diode of claim 1 , wherein the injection enhancement comprises one of tetracyanoquinodimethane, a derivative of tetracyanoquinodimethane, lithium fluoride, lithium carbonate, cesium fluoride, and cesium carbonate.
11.-16. (canceled)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US14/294,929 US20150349281A1 (en) | 2014-06-03 | 2014-06-03 | Organic schottky diodes |
US15/837,843 US10283725B2 (en) | 2014-06-03 | 2017-12-11 | Organic Schottky diodes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/294,929 US20150349281A1 (en) | 2014-06-03 | 2014-06-03 | Organic schottky diodes |
Related Child Applications (1)
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US15/837,843 Division US10283725B2 (en) | 2014-06-03 | 2017-12-11 | Organic Schottky diodes |
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US20150349281A1 true US20150349281A1 (en) | 2015-12-03 |
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US14/294,929 Abandoned US20150349281A1 (en) | 2014-06-03 | 2014-06-03 | Organic schottky diodes |
US15/837,843 Active US10283725B2 (en) | 2014-06-03 | 2017-12-11 | Organic Schottky diodes |
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US15/837,843 Active US10283725B2 (en) | 2014-06-03 | 2017-12-11 | Organic Schottky diodes |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US10283725B2 (en) | 2014-06-03 | 2019-05-07 | Palo Alto Research Center Incorporated | Organic Schottky diodes |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US20080179742A1 (en) * | 2006-07-24 | 2008-07-31 | Interuniversitair Microelektronica Centrum (Imec) | Method and solution to grow charge-transfer complex salts |
Family Cites Families (8)
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US7193291B2 (en) | 2004-03-25 | 2007-03-20 | 3M Innovative Properties Company | Organic Schottky diode |
CN101506989B (en) * | 2006-07-31 | 2014-02-19 | 威世-硅尼克斯 | Molybdenum barrier metal for sic schottky diode and process of manufacture |
KR20100105678A (en) | 2007-12-14 | 2010-09-29 | 바스프 에스이 | Process for the preparation of semiconducting layers |
KR20110061099A (en) * | 2009-12-01 | 2011-06-09 | 삼성전기주식회사 | Substitutional electroless gold plating solution and method for forming the gold plating layer using the same |
KR101021280B1 (en) * | 2010-11-11 | 2011-03-11 | 한국기계연구원 | The preparing method for aluminum cathode using wetting process and the aluminum cathode thereby |
US8900985B2 (en) | 2012-10-15 | 2014-12-02 | Infineon Technologies Austria Ag | Self-doped ohmic contacts for compound semiconductor devices |
US20150349281A1 (en) | 2014-06-03 | 2015-12-03 | Palo Alto Research Center Incorporated | Organic schottky diodes |
GB201415708D0 (en) * | 2014-09-05 | 2014-10-22 | Cambridge Display Tech Ltd | Semiconductor doping |
-
2014
- 2014-06-03 US US14/294,929 patent/US20150349281A1/en not_active Abandoned
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2017
- 2017-12-11 US US15/837,843 patent/US10283725B2/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080179742A1 (en) * | 2006-07-24 | 2008-07-31 | Interuniversitair Microelektronica Centrum (Imec) | Method and solution to grow charge-transfer complex salts |
Non-Patent Citations (1)
Title |
---|
Humphrey et al, "Electrically conducting TCNQ derivatives of Copper Sulphur/Nitrogen Chelates; Structure of a Novel Semiconductor Complex. . .", J. Chem. Soc., Chem. Comm., 1988, Issue 20, pp. 1356-1358. * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10283725B2 (en) | 2014-06-03 | 2019-05-07 | Palo Alto Research Center Incorporated | Organic Schottky diodes |
Also Published As
Publication number | Publication date |
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US20180114932A1 (en) | 2018-04-26 |
US10283725B2 (en) | 2019-05-07 |
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Owner name: PALO ALTO RESEARCH CENTER INCORPORATED, CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HSIEH, BING R.;NG, TSE NGA;WHITING, GREGORY;SIGNING DATES FROM 20140528 TO 20140530;REEL/FRAME:033021/0291 |
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