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US20020130311A1 - Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors and fabricating such devices - Google Patents

Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors and fabricating such devices Download PDF

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Publication number
US20020130311A1
US20020130311A1 US09/935,776 US93577601A US2002130311A1 US 20020130311 A1 US20020130311 A1 US 20020130311A1 US 93577601 A US93577601 A US 93577601A US 2002130311 A1 US2002130311 A1 US 2002130311A1
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US
United States
Prior art keywords
semiconductor
nanometers
doped
less
bulk
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US09/935,776
Other languages
English (en)
Inventor
Charles Lieber
Yi Cui
Xiangfeng Duan
Yu Huang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harvard College
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US09/935,776 priority Critical patent/US20020130311A1/en
Application filed by Individual filed Critical Individual
Assigned to PRESIDENT AND FELLOWS OF HARVARD COLLEGE reassignment PRESIDENT AND FELLOWS OF HARVARD COLLEGE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CUI, YI, DUAN, XIANGFENG, HUANG, YU, LIEBER, CHARLES M.
Priority to EP02759070A priority patent/EP1436841A1/fr
Priority to PCT/US2002/016133 priority patent/WO2003005450A2/fr
Priority to JP2003511316A priority patent/JP2004535066A/ja
Priority to AU2002324426A priority patent/AU2002324426B2/en
Priority to CA002447728A priority patent/CA2447728A1/fr
Priority to US10/196,337 priority patent/US7301199B2/en
Publication of US20020130311A1 publication Critical patent/US20020130311A1/en
Priority to US11/082,372 priority patent/US7211464B2/en
Priority to US11/172,408 priority patent/US20060175601A1/en
Priority to US11/386,080 priority patent/US20070281156A1/en
Priority to US11/543,746 priority patent/US20070032052A1/en
Priority to US11/543,326 priority patent/US7595260B2/en
Priority to US11/543,353 priority patent/US7915151B2/en
Priority to US11/543,336 priority patent/US7476596B2/en
Priority to US11/543,352 priority patent/US7666708B2/en
Priority to US11/543,337 priority patent/US8153470B2/en
Priority to US11/824,618 priority patent/US20070252136A1/en
Priority to US12/072,844 priority patent/US20090057650A1/en
Priority to JP2008156094A priority patent/JP2008300848A/ja
Assigned to NAVY, SECRETARY OF THE, UNITED STATES OF AMERICA reassignment NAVY, SECRETARY OF THE, UNITED STATES OF AMERICA CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: HARVARD UNIVERSITY
Priority to US12/459,177 priority patent/US20100155698A1/en
Priority to US13/490,325 priority patent/US20120329251A1/en
Abandoned legal-status Critical Current

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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]

Definitions

  • the present invention relates generally to sub-microelectronic semiconductor devices, and more particularly to nanometer-scale semiconductor articles, for example, nanowires, doped to provide n-type and p-type conductivity, the growth of such articles, and the arrangement of such articles to fabricate devices.
  • Typical state-of-the-art semiconductor fabrication facilities involve relatively high cost, and require a clean room and the use of toxic chemicals such as hydrogen fluoride. While semiconductor and microfabrication technology is well-developed, there is a continuing need for improvements, preferably including smaller-scale, environmentally-friendly fabrication, at lower cost.
  • a free-standing bulk-doped semiconductor comprising at least one portion having a smallest width of less than 500 nanometers.
  • the semiconductor comprises: an interior core comprising a first semiconductor; and an exterior shell comprising a different material than the first semiconductor.
  • the semiconductor is elongated.
  • a ratio of the length of the section to a longest width is greater than 4:1, or greater than 10:1, or greater than 100:1, or even greater than 1000:1.
  • At least one portion of the semiconductor has a smallest width of less than 200 nanometers, or less than 150 nanometers, or less than 100 nanometers, or less than 80 nanometers, or less than 70 nanometers, or less than 60 nanometers, or less than 40 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers.
  • the semiconductor comprises a semiconductor from a group consisting of: Si, Ge, Sn, Se, Te, B, Diamond, P, B—C, B—P(BP6), B—Si, Si—C, Si—Ge, Si—Sn and Ge—Sn, SiC, BN/BP/BAs, AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, BN/BP/BAs, AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, ZnO/ZnS/ZnSe/ZnTe, CdS/CdSe/CdTe, HgS/HgSe/HgTe, BeS/BeSe/BeTe/MgS/MgS/Mg
  • the semiconductor comprises a dopant from a group consisting of: a p-type dopant from Group III of the periodic table; an n-type dopant from Group V of the periodic table; a p-type dopant selected from a group consisting of: B, Al and In; an n-type dopant selected from a group consisting of: P, As and Sb; a p-type dopant from Group II of the periodic table; a p-type dopant selected from a group consisting of: Mg, Zn, Cd and Hg; a p-type dopant from Group IV of the periodic table; a p-type dopant selected from a group consisting of: C and Si.; or an n-type is selected from a group consisting of: Si, Ge, Sn, S, Se and Te.
  • the semiconductor is part of a device.
  • the semiconductor is n-doped.
  • the semiconductor is either lightly n-doped or heavily n-doped.
  • the semiconductor is p-doped.
  • the semiconductor is either lightly p-doped or heavily p-doped.
  • the semiconductor is a single crystal.
  • the semiconductor is magnetic; the semiconductor comprises a dopant making the semiconductor magnetic the semiconductor is ferromagnetic; the semiconductor comprises a dopant that makes the semiconductor ferromagnetic; and/or the semiconductor comprises manganese.
  • an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers.
  • the semiconductor is free-standing.
  • the semiconductor comprises: an interior core comprising a first semiconductor; and an exterior shell comprising a different material than the first semiconductor.
  • a ratio of the length of the section to a longest width is greater than 4:1, or greater than 10:1, or greater than 100:1 or even greater than 1000:1.
  • At least one longitudinal section of the semiconductor has a smallest width of less than 200 nanometers, or less than 150 nanometers, or less than 100 nanometers, or less than 80 nanometers, or less than 70 nanometers, or less than 60 nanometers, or less than 40 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers.
  • At least one longitudinal section of the semiconductor has a largest width of less than 200 nanometers, or less than 150 nanometers, or less than 100 nanometers, or less than 80 nanometers, or less than 70 nanometers, or less than 60 nanometers, or less than 40 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers.
  • the semiconductor comprises a semiconductor from a group consisting of: Si, Ge, Sn, Se, Te, B, Diamond, P, B—C, B—P(BP6), B—Si, Si—C, Si—Ge, Si—Sn and Ge—Sn, SiC, BN/BP/BAs, AIN/AIP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, BN/BP/BAs, AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, ZnO/ZnS/ZnSe/ZnTe, CdS/CdSe/CdTe, HgS/HgSe/HgTe, BeS/BeSe/BeTe/MgS/MgS/MgS/MgS/M
  • the semiconductor comprises a dopant from a group consisting of: a p-type dopant from Group III of the periodic table; an n-type dopant from Group V of the periodic table; a p-type dopant selected from a group consisting of: B, Al and In; an n-type dopant selected from a group consisting of: P, As and Sb; a p-type dopant from Group II of the periodic table; a p-type dopant selected from a group consisting of: Mg, Zn, Cd and Hg; a p-type dopant from Group IV of the periodic table; a p-type dopant selected from a group consisting of: C and Si.; or an n-type dopant is selected from a group consisting of: Si, Ge, Sn, S, Se and Te.
  • the semiconductor is part of a device.
  • the semiconductor is n-doped.
  • the semiconductor is either lightly n-doped or heavily n-doped.
  • the semiconductor is p-doped.
  • the semiconductor is either lightly p-doped or heavily p-doped.
  • the semiconductor is a single crystal.
  • a doped semiconductor comprising a single crystal.
  • the semiconductor is bulk-doped.
  • the semiconductor is elongated.
  • a ratio of the length of the section to a longest width is greater than 4:1, or greater than 10:1, or greater than 100:1, or even greater than 1000:1.
  • At least one portion of the semiconductor has a smallest width of less than 200 nanometers, or less than 150 nanometers, or less than 100 nanometers, or less than 80 nanometers, or less than 70 nanometers, or less than 60 nanometers, or less than 40 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers.
  • the semiconductor comprises a semiconductor from a group consisting of: Si, Ge, Sn, Se, Te, B, Diamond, P, B—C, B—P(BP6), B—Si, Si—C, Si—Ge, Si—Sn and Ge—Sn, SiC, BN/BP/BAs, AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, BN/BP/BAs, AlN/AIP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, ZnO/ZnS/ZnSe/ZnTe, CdS/CdSe/CdTe, HgS/HgSe/HgTe, BeS/BeSe/BeTe/MgS/MgS/MgS/MgS/M
  • the semiconductor comprises a dopant from a group consisting of: a p-type dopant from Group III of the periodic table; an n-type dopant from Group V of the periodic table; a p-type dopant selected from a group consisting of: B, Al and In; an n-type dopant selected from a group consisting of: P, As and Sb; a p-type dopant from Group II of the periodic table; a p-type dopant selected from a group consisting of: Mg, Zn, Cd and Hg; a p-type dopant from Group IV of the periodic table; a p-type dopant selected from a group consisting of: C and Si.; or an n-type dopant is selected from a group consisting of: Si, Ge, Sn, S, Se and Te.
  • a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers, where a phenomena produced by a section of the bulk-doped semiconductor exhibits a quantum confinement caused by a dimension of the section.
  • the longitudinal section is capable of emitting light in response to excitation, wherein a wavelength of the emitted light is related to the width.
  • the wavelength of the emitted light is a function of the width; the longitudinal section is capable of transporting electrical carriers without scattering; the longitudinal section is capable of transporting electrical carriers such that the electrical carriers pass through the longitudinal section ballistically; the longitudinal section is capable of transporting electrical carriers such that the electrical carriers pass through the longitudinal section coherently; the longitudinal section is capable of transporting electrical carriers such that the electrical carriers are spin-polarized; and/or the longitudinal section is capable of transporting electrical carriers such that the spin-polarized electrical carriers pass through the longitudinal section without losing spin information.
  • a solution comprising one or more doped semiconductors, wherein at least one of the semiconductors is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers.
  • At least one portion of the at least one semiconductor has a smallest width of less than 200 nanometers, or less than 150 nanometers, or less than 100 nanometers, or less than 80 nanometers, or less than 70 nanometers, or less than 60 nanometers, or less than 40 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers.
  • the at least one semiconductor comprises a semiconductor from a group consisting of: Si, Ge, Sn, Se, Te, B, Diamond, P, B—C, B—P(BP6), B—Si, Si—C, Si—Ge, Si—Sn and Ge—Sn, SiC, BN/BP/BAs, AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, BN/BP/BAs, AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, ZnO/ZnS/ZnSe/ZnTe, CdS/CdSe/CdTe, HgS/HgSe/HgTe, BeS/BeSe/BeTe/MgS
  • the at least one semiconductor comprises a dopant from a group consisting of: a p-type dopant from Group III of the periodic table; an n-type dopant from Group V of the periodic table; a p-type dopant selected from a group consisting of: B, Al and In; an n-type dopant selected from a group consisting of: P, As and Sb; a p-type dopant from Group II of the periodic table; a p-type dopant selected from a group consisting of: Mg, Zn, Cd and Hg; a p-type dopant from Group IV of the periodic table; a p-type dopant selected from a group consisting of: C and Si.; or an n-type is selected from a group consisting of: Si, Ge, Sn, S, Se and Te.
  • a device comprising one or more doped semiconductors, wherein at least one of the semiconductors is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers.
  • the device comprises at least two doped semiconductor, wherein both of the at least two doped semiconductors is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers.
  • the at least two bulk-doped semiconductors are in physical contact with each other; a first of the at least two bulk-doped semiconductors is of a first conductivity type, and a second of the at least two bulk-doped semiconductors is of a second conductivity type; the first conductivity type is n-type, and the second type of conductivity type is p-type; and/or the at least two bulk-doped semiconductors form a p-n junction.
  • the device comprises one or more of the following:. a switch; a diode; a Light-Emitting Diode; a tunnel diode; a Schottky diode; a Bipolar Junction Transistor; a Field Effect Transistor; an inverter; a complimentary inverter; an optical sensor; a sensor for an analyte (e.g., DNA); a memory device; a dynamic memory device; a static memory device; a laser; a logic gate; an AND gate; a NAND gate; an EXCLUSIVE-AND gate; an OR gate; a NOR gate; an EXCLUSIVE-OR gate; a latch; a register; clock circuitry; a logic array; a state machine; a programmable circuit; an amplifier; a transformer; a signal processor; a digital circuit; an analog circuit; a light emission source; a photoluminescent device; an electroluminescent device; a rectifier; a
  • one of the device components may include the at least one semiconductor.
  • a plurality of the components of the device may include at least one semiconductor, where, for each device component, the at least one semiconductor is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers.
  • the at least one semiconductor is elongated.
  • a ratio of the length of the section to a longest width is greater than 4:1, or greater than 10:1, or greater than 100:1 or even greater than 1000:1.
  • At least one portion of the at least one semiconductor has a smallest width of less than 200 nanometers, or less than 150 nanometers, or less than 100 nanometers, or less than 80 nanometers, or less than 70 nanometers, or less than 60 nanometers, or less than 40 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers.
  • the at least one semiconductor comprises a semiconductor from a group consisting of: Si, Ge, Sn, Se, Te, B, Diamond, P, B—C, B—P(BP6), B—Si, Si—C, Si—Ge, Si—Sn and Ge—Sn, SiC, BN/BP/BAs, AlN/AIP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, BN/BP/BAs, AIN/AIP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, ZnO/ZnS/ZnSe/ZnTe, CdS/CdSe/CdTe, HgS/HgSe/HgTe, BeS/BeSe/BeTe/MgS/M
  • the at least one semiconductor comprises a dopant from a group consisting of: a p-type dopant from Group III of the periodic table; an n-type dopant from Group V of the periodic table; a p-type dopant selected from a group consisting of: B, Al and In; an n-type dopant selected from a group consisting of: P, As and Sb; a p-type dopant from Group II of the periodic table; a p-type dopant selected from a group consisting of: Mg, Zn, Cd and Hg; a p-type dopant from Group IV of the periodic table; a p-type dopant selected from a group consisting of: C and Si.; or an n-type is selected from a group consisting of: Si, Ge, Sn, S, Se and Te.
  • the device comprises another semiconductor that is electrically coupled to the at least one bulk-doped semiconductor.
  • the device comprises another semiconductor that is optically coupled to the at least one bulk-doped semiconductor. In yet another aspect of this embodiment, the device comprises another semiconductor that is magnetically coupled to the at least one bulk-doped semiconductor.
  • the device comprises another semiconductor that physically contacts the at least one bulk-doped semiconductor.
  • the at least one semiconductor is coupled to one or more of: an electrical contact; an optical contact; or a magnetic contact.
  • a conductivity of the at least one semiconductor is controllable in response to a signal.
  • the conductivity of the at least one semiconductor is controllable to have any value within a range of values; the at least one semiconductor is switchable between two or more states; the at least one semiconductor is switchable between a conducting state and an insulating state by the signal; two or more states of the at least one semiconductor are maintainable without an applied signal; the conductivity of the at least one semiconductor is controllable in response to an electrical signal; the conductivity of the at least one semiconductor is controllable in response to an optical signal; the conductivity of the at least one semiconductor is controllable in response to a magnetic signal; and/or the conductivity of the at least one semiconductor is controllable in response to a signal of a gate terminal.
  • the device comprises two or more separate and interconnected circuits, at least one of the circuits not comprising a bulk-doped semiconductor that comprises at least one portion having a smallest width of less than 500 nanometers.
  • a collection of reagents for growing a bulk-doped semiconductor that comprises at least one portion having a smallest width of less than 500 nanometers, the collection comprising a semiconductor reagent and a dopant reagent.
  • the at least one semiconductor is elongated.
  • a ratio of the length of the section to a longest width is greater than 4:1, or greater than 10:1, or greater than 100:1 or even greater than 1000:1.
  • At least one portion of the at least one semiconductor has a smallest width of less than 200 nanometers, or less than 150 nanometers, or less than 100 nanometers, or less than 80 nanometers, or less than 70 nanometers, or less than 60 nanometers, or less than 40 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers.
  • the at least one semiconductor comprises a semiconductor from a group consisting of: Si, Ge, Sn, Se, Te, B, Diamond, P, B—C, B—P(BP6), B—Si, Si—C, Si—Ge, Si—Sn and Ge—Sn, SiC, BN/BP/BAs, AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, BN/BP/BAs, AIN/AIP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, ZnO/ZnS/ZnSe/ZnTe, CdS/CdSe/CdTe, HgS/HgSe/HgTe, BeS/BeSe/BeTe/MgS/
  • the at least one semiconductor comprises a dopant from a group consisting of: a p-type dopant from Group III of the periodic table; an n-type dopant from Group V of the periodic table; a p-type dopant selected from a group consisting of: B, Al and In; an n-type dopant selected from a group consisting of: P, As and Sb; a p-type dopant from Group II of the periodic table; a p-type dopant selected from a group consisting of: Mg, Zn, Cd and Hg; a p-type dopant from Group IV of the periodic table; a p-type dopant selected from a group consisting of: C and Si.; or an n-type is selected from a group consisting of: Si, Ge, Sn, S, Se and Te.
  • a semiconductor is doped during growth of the semiconductor.
  • the semiconductor is free-standing; the semiconductor has a smallest width of no more than 100 nanometers; an extent of the doping is controlled; the doped semiconductor is grown by applying energy to a collection of molecules, the collection of molecules comprising molecules of the semiconductor and molecules of a dopant; an extent of the doping is controlled; a ratio of an amount of the semiconductor molecules to an amount of the dopant molecules is controlled.
  • the molecules are vaporized using a laser to form vaporized molecules; the semiconductor is grown from the vaporized molecules; the vaporized molecules are condensed into a liquid cluster; the semiconductor is grown from the liquid cluster; growing the semiconductor is performed using laser-assisted catalytic growth; the collection of molecules comprises a cluster of molecules of a catalyst material; a width of the semiconductor is controlled;
  • the width of the semiconductor is controlled by controlling a width of the catalyst cluster.
  • the act of doping includes performing chemical vapor deposition on at least the molecules; the grown semiconductor has at least one portion having a smallest width of less than 20 nanometers; the grown semiconductor has at least one portion having a smallest width of less than 10 nanometers; and/or the grown semiconductor has at least one portion having a smallest width of less than 5 nanometers.
  • the grown semiconductor is magnetic; the semiconductor is doped with a material that makes the grown semiconductor magnetic; the grown semiconductor is ferromagnetic; the semiconductor is doped with a material that makes the grown semiconductor ferromagnetic; the semiconductor is doped with manganese.
  • the at least one semiconductor is elongated.
  • a ratio of the length of the section to a longest width is greater than 4:1, or greater than 10:1, or greater than 100:1 or even greater than 1000:1.
  • At least one portion of the at least one semiconductor has a smallest width of less than 200 nanometers, or less than 150 nanometers, or less than 100 nanometers, or less than 80 nanometers, or less than 70 nanometers, or less than 60 nanometers, or less than 40 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers.
  • the at least one semiconductor comprises a semiconductor from a group consisting of: Si, Ge, Sn, Se, Te, B, Diamond, P, B—C, B—P(BP6), B—Si, Si—C, Si—Ge, Si—Sn and Ge—Sn, SiC, BN/BP/BAs, AlN/AIP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, BN/BP/BAs, AIN/AIP/AIAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, ZnO/ZnS/ZnSe/ZnTe, CdS/CdSe/CdTe, HgS/HgSe/HgTe, BeS/BeSe/BeTe/MgS/MgS/Mg
  • the at least one semiconductor comprises a dopant from a group consisting of: a p-type dopant from Group III of the periodic table; an n-type dopant from Group V of the periodic table; a p-type dopant selected from a group consisting of: B, Al and In; an n-type dopant selected from a group consisting of: P, As and Sb; a p-type dopant from Group II of the periodic table; a p-type dopant selected from a group consisting of: Mg, Zn, Cd and Hg; a p-type dopant from Group IV of the periodic table; a p-type dopant selected from a group consisting of: C and Si.; or an n-type is selected from a group consisting of: Si, Ge, Sn, S, Se and Te.
  • a device is fabricated.
  • One or more semiconductors are contacted to a surface, where at least one of the semiconductors is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers.
  • the surface is a substrate; prior to contacting the surface, at least one of the semiconductors is grown by applying energy to molecules of a semiconductor and molecules of a dopant; a solution is contacted comprising the one or more semiconductors to the surface; one or more of the semiconductors are aligned on the surface using an electric field; an electric field is generated between at least two electrodes and one or more of the semiconductors are positioned between the electrodes; another solution comprising one or more other semiconductors is contacted to the surface, where at least one of the other semiconductor is a bulk-doped semiconductor comprising at least one portion having a smallest width of less than 500 nanometers; the surface is conditioned to attach the one or more contacted semiconductors to the surface; forming channels on the surface; patterns are formed on the surface; one or more of the semiconductors are aligned on the surface using an electric field; the at least one semiconductor is elongated.
  • a ratio of the length of the section to a longest width is greater than 4:1, or greater than 10:1, or greater than 100:1 or even greater than 1000:1.
  • At least one portion of the at least one semiconductor has a smallest width of less than 200 nanometers, or less than 150 nanometers, or less than 100 nanometers, or less than 80 nanometers, or less than 70 nanometers, or less than 60 nanometers, or less than 40 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers.
  • the at least one semiconductor comprises a semiconductor from a group consisting of: Si, Ge, Sn, Se, Te, B, Diamond, P, B—C, B—P(BP6), B—Si, Si—C, Si—Ge, Si—Sn and Ge—Sn, SiC, BN/BP/BAs, AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, BN/BP/BAs, AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, ZnO/ZnS/ZnSe/ZnTe, CdS/CdSe/CdTe, HgS/HgSe/HgTe, BeS/BeSe/BeTe/MgS
  • the at least one semiconductor comprises a dopant from a group consisting of: a p-type dopant from Group III of the periodic table; an n-type dopant from Group V of the periodic table; a p-type dopant selected from a group consisting of: B, Al and In; an n-type dopant selected from a group consisting of: P, As and Sb; a p-type dopant from Group II of the periodic table; a p-type dopant selected from a group consisting of: Mg, Zn, Cd and Hg; a p-type dopant from Group IV of the periodic is table; a p-type dopant selected from a group consisting of: C and Si.; or an n-type is selected from a group consisting of: Si, Ge, Sn, S, Se and Te.
  • generating light is generated by applying energy to one or more semiconductors causing the one or more semiconductors to emit light, wherein at least one of the semiconductors is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers.
  • the at least one semiconductor is elongated.
  • a ratio of the length of the section to a longest width is greater than 4:1, or greater than 10:1, or greater than 100:1 or even greater than 1000:1.
  • At least one portion of the at least one semiconductor has a smallest width of less than 200 nanometers, or less than 150 nanometers, or less than 100 nanometers, or less than 80 nanometers, or less than 70 nanometers, or less than 60 nanometers, or less than 40 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers.
  • the at least one semiconductor comprises a semiconductor from a group consisting of: Si, Ge, Sn, Se, Te, B, Diamond, P, B—C, B—P(BP6), B—Si, Si—C, Si—Ge, Si—Sn and Ge—Sn, SiC, BN/BP/BAs, AlN/AIP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, BN/BP/BAs, AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb, ZnO/ZnS/ZnSe/ZnTe, CdS/CdSe/CdTe, HgS/HgSe/HgTe, BeS/BeSe/BeTe/MgS/
  • the at least one semiconductor comprises a dopant from a group consisting of: a p-type dopant from Group III of the periodic table; an n-type dopant from Group V of the periodic table; a p-type dopant selected from a group consisting of: B, Al and In; an n-type dopant selected from a group consisting of: P, As and Sb; a p-type dopant from Group II of the periodic table; a p-type dopant selected from a group consisting of: Mg, Zn, Cd and Hg; a p-type dopant from Group IV of the periodic table; a p-type dopant selected from a group consisting of: C and Si.; or an-type is selected from a group consisting of: Si, Ge, Sn, S, Se and Te.
  • the at least one semiconductor is a bulk-doped;
  • the semiconductor comprises a direct-band-gap semiconductor; a voltage is applied across a junction of two crossed semiconductors, each semiconductor having a smallest width of less than 500 nanometers; each semiconductor has a smallest width of less than 100 nanometers; a wavelength of the emitted light is controlled by controlling a dimension of the at least one semiconductor having a smallest width of less than 100 nanometers; the semiconductor is elongated, and a width of the elongated semiconductor is controlled; the semiconductor has a property that a mass of the semiconductor emits light at a first wavelength if the mass has a minimum shortest dimension, and the controlled dimension of the semiconductor is less than the minimum shortest dimension.
  • a device having at least a doped semiconductor component and one or more other components is fabricated.
  • a semiconductor is doped during its growth to produce the doped semiconductor component, and the doped semiconductor component is attached to at least one of the one or more other components.
  • the doped semiconductor is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers.
  • the semiconductor component is at least part of a nanowire; the semiconductor is doped during growth of the semiconductor.
  • a process for controllably assembling a semiconductor device having elongated elements with a characteristic dimension in a transverse direction of the element on a nanometer scale comprising: producing at least one first elements of a first doping type, orienting said first element in a first direction, and connecting said first element to at least one first contact to allow an electrical current to flow through the first element.
  • the process further comprises producing at least one second elements of a second doping type, orienting said second element in a second direction different from the first direction, enabling an electrical contact between the first element and the second element, and connecting said second element to at least one second contact to allow an electrical current to flow between the first and second element;
  • the process further comprises connecting said first element to spaced-apart contacts and arranging a gate electrode proximate to the first element between the spaced-apart contacts, thereby forming an FET;
  • the first doping type is one of n-type or p-type;
  • the second doping type is n-type if the first doping type is p-type, and p-type if the first doping type is n-type;
  • the first element is oriented by applying at least one of an electric field or a fluid flow;
  • the first element is suspended in the fluid flow;
  • the first element is oriented by applying a mechanical tool;
  • the second element is oriented by applying at least one of an electric field or
  • a semiconductor device comprising: a silicon substrate having an array of metal contacts; a crossbar switch element formed in electrical communication with the array and having a first bar formed of a p-type semiconductor nanowire, and a second bar formed of an n-type semiconductor nanowire and being spaced away from the first bar and being disposed transversely thereto.
  • the second bar is spaces between 1-10 nm from the first bar.
  • a method for manufacturing a nanowire semiconductor device comprising positioning a first nanowire between two contact points by applying a potential between the contact points; positioning a second nanowire between two other contact points.
  • a method for manufacturing a nanowire semiconductor device comprising forming a surface with one or more regions that selectively attract nanowires.
  • a method for manufacturing a light-emitting diode from nanowires the diode having an emission wavelength determined by a dimension of a p-n junction between two doped nanowires.
  • a method for manufacturing a semiconductor junction by crossing a p-type nanowire and an n-type nanowire.
  • a method of assembling one or more elongated structures on a surface comprising acts of: flowing a fluid that comprises the one or more elongated structures onto the surface; and aligning the one or more elongated structures on the surface to form an array of the elongated structures.
  • flowing comprises flowing the fluid in a first direction and aligning comprises aligning the one or more elongated structures as the fluid flows in the first direction to form a first layer of arrayed structures
  • the method further comprises changing a direction of the flow from the first direction to a second direction, and repeating the acts of flowing and aligning; at least a first elongated structure from the first layer contacts at least a second elongated structure from the second array; one of the first and second elongated structures is doped semiconductor of a first conductivity type and another of first and second elongated structures is doped semiconductor of a second conductivity type; the first conductivity type is p-type and the second conductivity type is n-type, and wherein the first and second elongated structures form a p-n junction; the surface is a surface of a substrate; the method further comprises transferring the array of elongated structures from the surface of the substrate to a surface of another substrate; transferring comprises stamping; the one
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than less
  • elongated structures are at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers, and wherein the method comprises acts of conditioning the surface with one or more functionalities that attract the one or more elongated structures to particular positions on the surface, and aligning the one or more elongated structures by attracting the one or more elongated structures to the particular positions using the one or more functionalities.
  • the act of conditioning comprises conditioning the surface with one or more molecules; the act of conditioning comprises conditioning the surface with one or more charges; the act of conditioning comprises conditioning the surface with one or more magnetos; the act of conditioning comprises conditioning the surface with one or more light intensities; conditioning the surface with one or more functionalities that attract the one or more elongated structures to particular positions on the surface using chemical force; the act of conditioning comprises conditioning the surface with one or more functionalities that attract the one or more elongated structures to particular positions on the surface using optical force; the act of conditioning comprises conditioning the surface with one or more functionalities that attract the one or more elongated structures to particular positions on the surface using electrostatic force; and/or the act of conditioning comprises conditioning the surface with one or more functionalities that attract the one or more elongated structures to particular positions on the surface using magnetic force.
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers;
  • a method of assembling a plurality of elongated structures on a surface wherein one or more of the elongated structures are at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers, and wherein the method comprises acts of: depositing the plurality of elongated structures onto the surface; and electrically charging the surface to produce electrostatic forces between two or more of the plurality of the elongated structures.
  • the electrostatic forces cause the two or more elongated structures to align themselves; the electrostatic forces cause the two or more elongated structures to align themselves into one or more patterns; and/or the one or more patterns comprise a parallel array.
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers;
  • a method of assembling a plurality of elongated structures on a surface wherein one or more of the elongated structures are at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers, and wherein the method comprises acts of: dispersing the one or more elongated structures on a surface of a liquid phase to form a Langmuir-Blodgett film; compressing the Langmuir-Blodgett film; and transferring the compressed Langmuir-Blodgett film onto a surface.
  • the surface id the surface of a substrate.
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than less
  • a method of assembling a plurality of one or more elongated structures on a surface wherein at least one of the elongated structures are at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers, and wherein the method comprises acts of: dispersing the one or more elongated structures in a flexible matrix; stretching the flexible matrix in a direction to produce a shear force on the one or more elongated structures that causes the at least one elongated structure to align in the direction; removing the flexible matrix; and transferring the at least one aligned elongated structure to a surface.
  • the direction is parallel to a plane of the surface
  • the act of stretching comprises stretching the flexible matrix with an electrically-induced force
  • the act of stretching comprises stretching the flexible matrix with an optically-induced force
  • the act of stretching comprises stretching the flexible matrix with a mechanically-induced force
  • the act of stretching comprises stretching the flexible matrix with a magnetically-induced force
  • the surface is a surface of a substrate
  • the flexible matrix is a polymer.
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers;
  • a system for growing a doped semiconductor comprising: means for providing a molecules of the semiconductor and molecules of a dopant; and means for doping the molecules of the semiconductor with the molecules of the dopant during growth of the semiconductor to produce the doped semiconductor.
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers;
  • a system for assembling one or more elongated structures on a surface comprising: means for flowing a fluid that comprises the one or more elongated structures onto the surface; and means for aligning the one or more elongated structures on the surface to form an array of the elongated structures.
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than less
  • a system for assembling one or more elongated structures on a surface wherein one or more of the elongated structures are at least one of the following: is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers, and wherein the system comprises: means for conditioning the surface with one or more functionalities that attract the one or more elongated structures to particular positions on the surface, and means for aligning the one or more elongated structures by attracting the one or more elongated structures to the particular positions using the one or more functionalities.
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers;
  • a system for assembling a plurality of elongated structures on a surface wherein one or more of the elongated structures are at least one of the following: is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers, and wherein the system comprises means for depositing the plurality of elongated structures onto the surface; and means for electrically charging the surface to produce electrostatic forces between two or more of the plurality of the elongated structures.
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than less
  • a system for assembling a plurality of elongated structures on a surface wherein one or more of the elongated structures are at least one of the following: is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers, and wherein the system comprises: means for dispersing the one or more elongated structures on a surface of a liquid phase to form a Langmuir-Blodgett film; means for compressing the Langmuir-Blodgett film; and means for transferring the compressed Langmuir-Blodgett film onto a surface.
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than less
  • a system for assembling a plurality of one or more elongated structures on a surface wherein at least one of the elongated structures are at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers, and wherein the system comprises: means for dispersing the one or more elongated structures in a flexible matrix; means for stretching the flexible matrix in a direction to produce a shear force on the one or more elongated structures that causes the at least one elongated structure to align in the direction; means for removing the flexible matrix; and means for transferring the at least one aligned elongated structure to a surface.
  • At least one of the elongated structures are semiconductors; at least one of the elongated structures are doped semiconductors; at least one of the elongated structures are bulk-doped semiconductors; at least one of the structures is a doped single-crystal semiconductor; at least one of the structures is an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers; at least one of the structures is a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than 500 nanometers; at least one of the structures is a doped semiconductor that is at least one of the following: a single crystal, an elongated and bulk-doped semiconductor that, at any point along its longitudinal axis, has a largest cross-sectional dimension less than 500 nanometers, and a free-standing and bulk-doped semiconductor with at least one portion having a smallest width of less than less
  • FIG. 1 is a perspective view of an example of a semiconductor article, or nanowire, in accordance with an embodiment of the invention
  • FIG. 2 is a simplified schematic diagram of an example of a laser assisted catalytic growth process for fabrication of semiconductor nanowires
  • FIG. 3 is a schematic diagram that illustrates nanowire growth
  • FIG. 4 is a schematic diagram that illustrates an example of a method for controlling nanowire diameter
  • FIG. 5 is a schematic diagram that illustrates nanowire fabrication by deposition on the edge of surface steps
  • FIG. 6 is a schematic diagram that illustrates nanowire growth by vapor deposition in or on an elongated template
  • FIGS. 7 A- 7 E illustrate orthogonal assembly of semiconductor nanowires to form devices
  • FIGS. 8 A- 8 C show silicon nanowire current as a function of bias voltage for different doping levels and gate voltages
  • FIGS. 9A and 9B show silicon nanowire current as a function of bias voltage for different phosphorous doping levels and gate voltages
  • FIGS. 10A and 10B show energy band diagrams for p-type and n-type silicon nanowire devices, respectively;
  • FIGS. 11A and 11B show temperature dependent current-voltage curves recorded on a heavily boron doped silicon nanowire
  • FIG. 12 is a schematic diagram that depicts the use of monodispersed gold colloids as catalysts for the growth of well-defined GaP semiconductor nanowires;
  • FIG. 13A shows a FE-SEM image of nanowires synthesized from 28.2 nanometer colloids
  • FIG. 13B shows a TEM image of another wire in the sample
  • FIGS. 14 A- 14 C show histograms of measured diameters for wires grown from different diameter colloids
  • FIG. 14D shows a histogram of diameters for wires grown using the previous method without colloids, in which the laser is used to both generate the gold nanoclusters and the GaP reactants;
  • FIG. 15 shows a pseudobinary phase diagram for gold and gallium arsenide
  • FIGS. 16 A- 16 C show FE-SEM images of different nanowires prepared by laser assisted catalytic growth
  • FIG. 17A shows a diffraction contrast TEM image of an approximately 20 nanometer diameter gallium arsenide nanowire
  • FIGS. 17 B- 17 D show high resolution TEM images of different diameter nanowires
  • FIG. 18A shows a FE-SEM image of CdSe nanowires prepared by laser assisted catalytic growth
  • FIG. 18B shows a diffraction contrast TEM image of an 18 nanometer diameter CdSe nanowire
  • FIG. 18C shows a high resolution TEM image of an approximately 13 nanometer diameter CdSe nanowire
  • FIG. 19 is a schematic diagram showing GaN nanowire growth by laser assisted catalytic growth
  • FIG. 20A shows a FE-SEM image of bulk GaN nanowire synthesized by laser assisted catalytic growth
  • FIG. 20B shows a PXRD pattern recorded on bulk GaN nanowires
  • FIG. 21A shows a diffraction contrast TEM image of a GaN nanowire that terminates in a faceted nanoparticle of higher contrast
  • FIG. 21B shows an HRTEM image of another GaN nanowire with a diameter of approximately 10 nanometers
  • FIGS. 22 A- 22 C illustrate doping and electrical transport of InP nanowires
  • FIGS. 23 A- 23 D illustrate crossed nanowire junctions and electrical properties
  • FIGS. 24 A- 24 D illustrate optoelectrical characterization of nanowire P-N junctions
  • FIG. 25A shows an EL image taken from a p-type Si and n-type GaN nanojunction
  • FIG. 25B shows current as a function of voltage for various gate voltages
  • FIG. 25C shows an EL spectrum for the nanojunction of FIGS. 25A;
  • FIGS. 26 A- 26 D illustrate parallel and orthogonal assembly of nanowires with electric fields
  • FIGS. 27 A- 27 F illustrate crossed silicon nanowire junctions
  • FIGS. 28 A- 28 D illustrate n + pn crossed silicon nanowire bipolar transistors
  • FIGS. 29 A- 29 D illustrate complementary inverters and tunnel diodes
  • FIGS. 30A and 30B are schematics of fluidic channel structures for flow assembly
  • FIGS. 31 A- 31 D illustrate parallel assembly of nanowire arrays
  • FIGS. 32 A- 32 D illustrate assembly of periodic nanowire arrays
  • FIGS. 33 A- 33 E illustrate layer-by-layer assembly and transport measurements of crossed nanowire arrays.
  • the present invention provides, in one aspect, techniques for controlled doping of materials such as semiconductors at a very small spatial scale, and arrangement of doped materials in position relative to each other to create useful devices.
  • One set of embodiments involves doping of a semiconductor, with a dop ant (e.g., boron, aluminum, phosphorous, arsenic, etc.) selected according to whether an n-type or p-type semiconductor is desired.
  • a dop ant e.g., boron, aluminum, phosphorous, arsenic, etc.
  • this invention involves controlled doping of semiconductors selected from among indium phosphide, gallium arsenide, gallium nitride, cadmium selenide, and zinc selenide.
  • Dopants including, but not limited to, zinc, cadmium, or magnesium can be used to form p-type semiconductors in this set of embodiments, and dopants including, but not limited to, tellurium, sulfur, selenium, or germanium can be used as dopants to form n-type semiconductors from these materials.
  • These materials define direct band gap semiconductor materials and these and doped silicon are well known to those of ordinary skill in the art.
  • the present invention contemplates use of any doped silicon or direct band gap semiconductor materials for a variety of uses.
  • a “width” of an article is a distance of a straight line from a point on a perimeter of the article through the center of the article to another point on the perimeter of the article.
  • a “width” or “cross-sectional dimension” at a point along the longitudinal axis of an elongated article is a distance along a straight line that passes through the center of the cross-section at the point and that connects two points on the perimeter of the cross section.
  • an “elongated” article e.g., semiconductor or section thereof
  • a ratio of the length of the article to the largest width at the point is greater than 2:1.
  • the “longitudinal axis” of an elongated article is an axis along a largest dimension of the article.
  • the “length” of an elongated article is a distance along the longitudinal axis from end to end of the article.
  • a “longitudinal section” of an elongated article is a portion of the elongated article along the longitudinal axis of the elongated article than can have any length greater than zero and less than or equal to the length of the article.
  • a “cross-section” at a point along the longitudinal axis of an elongated article is a plane at the point across the elongated article that is orthogonal to the longitudinal axis of the article.
  • a “cylindrical” article is an article having an exterior shaped like a cylinder, but does not define or reflect any properties regarding the interior of the article.
  • a cylindrical article may have a solid interior or may have a hollowed-out interior.
  • a “nanowire” or “NW” is an elongated semiconductor, i.e., a nanoscale semiconductor, that at any point along its length has at least one cross-sectional dimension and, in some embodiments, two orthogonal cross-sectional dimensions less than 500 nanometers, preferably less than 200 nanometers, more preferably less than 150 nanometers, still more preferably less than 200 nanometers, even more preferably less than 70, still more preferably less than 50 nanometers, even more preferably less than 20 nanometers, still more preferably less than 10 nanometers, and even less than 5 nanometers.
  • Th e cross-section of the elongated semiconductor may have any arbitrary shape, including, but not limited to, circular, square, rectangular, elliptical. Regular and irregular shapes are included.
  • a “nanotube” or “NT” is a nanowire that has a hollowed-out core.
  • a “bulk-doped” article is an article for which a dopant is incorporated substantially throughout the crystalline lattice of the article, as opposed to an article in which a dopant is only incorporated in particular regions.
  • some articles such as carbon NTs typically are doped after the base material is grown, and thus the dopant only extends a finite distance from the surface or exterior of the carbon NT into the interior of the crystal line lattice.
  • carbon NTs are often combined as nested tubes forming alternating layers of base material and doped base material such that the dopant is not incorporated throughout the crystal line lattice of the base material.
  • nanowire As used herein to describe a “nanowire” or “NW”, “doped” means bulk-doped. Accordingly, as used herein, a “doped nanowire” or “doped NW” is a bulk-doped nanowire.
  • an “array” of articles comprises a plurality of the articles.
  • a “crossed array” is an array where at least one of the articles contacts either another of the articles or a signal node (e.g., an electrode).
  • a first article e.g., a nanowire or larger-sized structure “coupled” to a second article is disposed such that the first article either physically contacts the second article or is proximate enough to the second article to influence a property (e.g., electrical property, optical property, magnetic property) of the second article.
  • a property e.g., electrical property, optical property, magnetic property
  • the present invention contemplates, in one aspect, an elongated semiconductor that has a smallest width of less than 500 nanometers that is doped in any way (n-type or p-type).
  • the semiconductor may have a smallest width less than about 200 nanometers, less than about 150 nanometers, or less than about 100 nanometers.
  • the semiconductor has a smallest width of less than about 80 nanometers, more preferably less than about 70 nanometers, preferably less than about 50 nanometers. Smaller widths, such as those with at least one dimension of less than about nanometers, less than about 10 nanometers, or less than about 5 nanometers also are included.
  • two orthogonal cross-sectional dimensions of the elongated semiconductor may be less than the values given above.
  • the aspect ratio i.e., the ratio of semiconductor length to largest width, is greater than 2:1. In other embodiments, the aspect ratio may be greater than 4:1, greater than 10:1, greater than 100:1 or even greater than 1000:1. Semiconductors such as these, at very small dimensions, find a variety of uses as described below.
  • FIG. 1 is a perspective diagram illustrating an example of a cylindrical semiconductor L1, for example, a wire-like semiconductor such as a nanowire.
  • the cylindrical semiconductor L1 has a length L2 and a longitudinal axis L3.
  • the cylindrical semiconductor LI has a plurality of widths L4 across cross-section L6, where one of the widths L4 is a smallest width at the point L5.
  • Such semiconductors may be free-standing.
  • a “free-standing” article is an article that at some point in its life is not attached to another article or that is in solution.
  • such a semiconductor may be a bulk-doped semiconductor.
  • a “bulk-doped semiconductor” article e.g. article or section of an article
  • NTs typically are doped after the semiconductor is grown, and thus the dopant only extends a finite distance from the surface or exterior of the nanotube into the interior of the crystalline lattice.
  • NTs are often combined as nested tubes (i.e.
  • cylinders forming alternating layers of semiconductor and doped semiconductor such that the dopant is not incorporated throughout the crystalline lattice of the semiconductor.
  • dopant is not incorporated throughout the crystalline lattice of the semiconductor.
  • the semiconductor may be doped during growth of the semiconductor. Doping the semiconductor during growth may result in the property that the doped semiconductor is bulk-doped. Further, such doped semiconductors may be controllably doped, such that a concentration of a dopant within the doped semiconductor can be controlled and therefore reproduced consistently, making possible the commercial production of such semiconductors.
  • a variety of devices may be fabricated using semiconductors such as those described above. Such devices include electrical devices, optical devices, mechanical devices or any combination thereof, including opto-electronic devices and electromechanical devices.
  • a field effect transistor is produced using a doped semiconductor having a smallest width of less than 500 nanometers or other width described above.
  • the doped semiconductor can be either a p-type or n-type semiconductor, as is known by those of ordinary skill in the art in FET fabrication. While FETs are known using nanotubes, to the inventors' knowledge, prior arrangements select nanotubes at random, without control over whether the nanotube is metallic or semiconducting. In such a case a very low percentage of devices are functional, perhaps less than one in twenty, or one in fifty, or perhaps approximately one in one hundred.
  • the present invention contemplates controlled doping of nanowires such that a fabrication process can involve fabricating functional FETs according to a technique in which much greater than one in fifty devices is functional.
  • the technique can involve doping a nanowire, then fabricating an FET therefrom.
  • the invention also provides lightly-doped complementary inverters (complementary metal oxide semiconductors) arranged simply by contact of an n-type semiconductor with a p-type semiconductor, for example by arrangement of crossed n-type and p-type semiconducting nanowires as shown below.
  • lightly-doped complementary inverters complementary metal oxide semiconductors
  • tunnel diodes with heavily-doped semiconducting components.
  • a tunnel diode can be arranged similarly or exactly the same as a complementary inverter, with the semiconductors being heavily doped rather than lightly doped. “Heavily doped” and “lightly doped” are terms the meaning of which is clearly understood by those of ordinary skill in the art.
  • One important aspect of the present invention is the ability to fabricate essentially any electronic device that can benefit from adjacent n-type and p-type semiconducting components, where the components are pre-fabricated (doped, in individual and separate processes with components separate from each other when doped) and then brought into contact after doping.
  • This is in contrast to typical prior art arrangements in which a single semiconductor is n-doped in one region and p-doped in an adjacent region, but the n-type semiconductor region and p-type semiconducting regions are initially adjacent prior to doping and do not move relative to each other prior to or after doping. That is, n-type and p-type semiconductors, initially in non-contacting arrangement, are brought into contact with each other to form a useful electronic device.
  • any device can be made in accordance with this aspect of the invention that one of ordinary skill in the art would desirably make using n-type and p-type semiconductors in combination.
  • Examples of such devices include, but are not limited to, field effect transistors (FETs), bipolar junction transistors (BJTs), tunnel diodes, complementary inverters, light emitting devices, light sensing devices, gates, inverters, AND, NAND, OR, and NOR gates, latches, flip-flops, registers, switches, clock circuitry, static or dynamic memory devices and arrays, state machines, gate arrays, and any other dynamic or sequential logic or other digital devices including programmable circuits.
  • analog devices and circuitry including but not limited to, amplifiers, switches and other analog circuitry using active transistor devices, as well as mixed signal devices and signal processing circuitry.
  • Electronic devices incorporating semiconductor nanowires can be controlled, for example, by electrical, optical or magnetic signals.
  • the control may involve switching between two or more discrete states or may involve continuous control of nanowire current, i.e., analog control.
  • the devices may be controlled as follows:
  • the device is switchable in response to biological and chemical species, for example, DNA, protein, metal ions. In more general sense, these species are charged or have dipole.
  • the device is switchable in response to the mechanical stretching, vibration and bending.
  • the device is switchable in response to the temperature.
  • the device is switchable in response to the environmental pressure.
  • the device is switchable in response to the movement of environmental gas or liquid.
  • crossed p/n junctions which can be junctions of crossed n-type and p-type nanowires.
  • Crossed p/n junctions are defined by at least one n-type semiconductor and at least one p-type semiconductor, at least one portion of each material contacting at least one portion of the other material, and each semiconductor including portions that do not contact the other component. They can be arranged by pre-doping the nanowires, then bringing them into proximity with each other using techniques described below.
  • Light-emission sources are provided in accordance with the invention as well, in which electrons and holes combine, emitting light.
  • One type of light-emission source of the invention includes at least one crossed p/n junction, in particular, crossed p-type and n-type nanowires. In this and other arrangements of the invention using crossed nanowires, the wires need not be perpendicular, but can be.
  • forward biased positive charge applied to the p-type wire and a negative charge applied to the n-type wire
  • electrons flow toward the junction in the n-type wire and holes flow toward the junction in the p-type wire.
  • holes and electrons combine, emitting light.
  • Other techniques may be used to cause one or more nanowires, or other semiconductors to emit light, as described below in more detail.
  • the wavelength of light emission can be controlled by controlling the size of at least one, and preferably both components that are crossed to form the light-emitting junction. For example, where nanowires are used, a nanowire with larger smallest dimension (broader wire) will provide emission at a lower frequency. For example, in the case of indium phosphide, at size scales associated with typical fabrication processes, the material emits at 920 nanometers. At the size scales of the present invention the wavelength of emission can be controlled to be at wavelengths shorter than 920 nanometers, for example between 920 and 580 nanometers. Wavelengths can be selected within this range, such as 900, 850, 800, 750, 700 nanometers, etc., depending upon wire size.
  • one aspect of the invention involves a semiconductor light-emission source that emits at a higher frequency than the semiconductor causing emission emits in its bulk state such increase of the frequency of emission of light is often referred to herein as quantum confinement.
  • “Bulk state”, in this context, means a state in which it is present as a component, or a portion of a component having a smallest dimension of greater than 500 nanometers. “Bulk state” also can be defined as that state causing a material's inherent wavelength or frequency of emission. The present invention provides for such control over emission frequency of essentially any semiconducting or doped semiconducting material.
  • Assembly, or controlled placement of nanowires on surfaces can be carried out by aligning nanowires using an electrical field.
  • An electrical field is generated between electrodes, nanowires are positioned between the electrodes (optionally flowed into a region between the electrodes in a suspending fluid), and will align in the electrical field and thereby can be made to span the distance between and contact each of the electrodes.
  • individual contact points are arranged in opposing relation to each other, the individual contact points being tapered to form a point directed towards each other.
  • An electric field generated between such points will attract a single nanowire spanning the distance between, and contacting each of, the electrodes.
  • individual nanowires can readily be assembled between individual pairs of electrical contacts.
  • Crossed-wire arrangements including multiple crossings (multiple parallel wires in a first direction crossed by multiple parallel wires in a perpendicular or approximately perpendicular second direction) can readily be formed by first positioning contact points (electrodes) at locations where opposite ends of the crossed wires desirably will lie. Electrodes, or contact points, can be fabricated via typical microfabrication techniques.
  • a nanowire solution can be prepared as follows. After nanowires are synthesized, they are transferred into a solvent (e.g., ethanol), and then are sonicated for several seconds to several minutes to obtain a stable suspension.
  • a solvent e.g., ethanol
  • Another arrangement involves forming surfaces including regions that selectively attract nanowires surrounded by regions that do not selectively attract them.
  • —NH 2 can be presented in a particular pattern at a surface, and that pattern will attract nanowires or nanotubes having surface functionality attractive to amines.
  • Surfaces can be patterned using known techniques such as electron-beam patterning, “soft-lithography” such as that described in International Patent Publication No. WO 96/29629, published Jul. 26, 1996, or U.S. Pat. No. 5, 512,131, issued April 30, 1996, each of which is incorporated herein by reference. Additional techniques are described in U.S. Patent Application Serial No. 60/142,216, filed Jul.
  • Fluid flow channels can be created at a size scale advantageous for placement of nanowires on surfaces using a variety of techniques such as those described in International Patent Publication No. WO 97/33737, published September 18, 1997, and incorporated herein by reference. Other techniques include those described in U.S. Patent Application Serial No. 09/578,589, filed May 25, 2000, and incorporated herein by reference.
  • FIGS. 7 A- 7 E show one such technique for creating a fluid flow channel using a polydimethyl siloxane (PDMS) mold.
  • PDMS polydimethyl siloxane
  • the flow channel arrangement can include channels having a smallest width of less than 1 millimeter, preferably less than 0.5 millimeter, 200 microns or less. Such channels are easily made by fabricating a master by using photolithography and casting PDMS on the master, as described in the above-referenced patent applications and international publications. Larger-scale assembly is possible as well. The area that can be patterned with nanowire arrays is defined only by the feature of the channel which can be as large as desired.
  • Semiconductor nanowires have a crystalline core sheathed with 1-10 nm thick of amorphous oxide. This allows surface modification to terminate the surface with various functional groups. For example, we can use molecules, one end of which is alkyloxysilane group (e.g. —Si(OCH3)) reacting with nanowire surface, the other end of which comprise (1)—CH3,—COOH, —NH2,—SH, —OH, hydrazide, and aldehyde groups. (2) light activatable moieties: aryl azide, fluorinated aryl azide, benzophenone etc.
  • the substrate and electrodes are also modified with certain functional groups to allow nanowires to specifically bind or not bind onto the substrate/electrodes surface based on the their interaction.
  • Surface-functionalized nanowires can also be coupled to the substrate surface with functional cross-linkers, e.g. (1) Homobifunctional cross-linkers, comprising homobifunctional NHS esters, homobifunctional imidoesters, homobifunctional sulfhydryl-reactive linkers, difluorobenzene derivatives, homobifunctional photoactive linkers, homobifunctional aldehyde, bis-epoxides, homobifunctional hydarzide etc. (2) Heterobifuntional cross-linkers (3)Trifuntional cross-linkers.
  • Homobifunctional cross-linkers comprising homobifunctional NHS esters, homobifunctional imidoesters, homobifunctional sulfhydryl-reactive linkers, difluorobenzene derivatives, homobifunctional photoactive linkers, homobifunctional aldehyde, bis-epoxides, homobifunctional hydarzide etc.
  • the assembly of nanowires onto substrate and electrodes can also be assisted using bimolecular recognition.
  • Some good bio-recognitions are: DNA hybridization, antibody-antigen binding, biotin-avidin (or streptavidin) binding.
  • SiNWs elongated nanoscale semiconductors
  • LCG laser assisted catalytic growth
  • a composite target that is composed of a desired material (e.g. InP) and a catalytic material (e.g. Au) creates a hot, dense vapor which quickly condenses into liquid nanoclusters through collision with the buffer gas. Growth begins when the liquid nanoclusters become supersaturated with the desired phase and continues as long as the reactant is available. Growth terminates when the nanowires pass out of the hot reaction zone or when the temperature is turned down.
  • Au is generally used as catalyst for growing a wide range of elongated nanoscale semiconductors.
  • the catalyst is not limited to Au only.
  • a wide rage of materials such as (Ag, Cu, Zn, Cd, Fe, Ni, Co . . . ) can be used as the catalyst.
  • any metal that can form an alloy with the desired semiconductor material, but doesn't form more stable compound than with the elements of the desired semiconductor can be used as the catalyst.
  • the buffer gas can be Ar, N2, and others inert gases. Sometimes, a mixture of H2 and buffer gas is used to avoid un-desired oxidation by residue oxygen. Reactive gas can also be introduced when desired (e.g. ammonia for GaN). The key point of this process is laser ablation generates liquid nanoclusters that subsequently define the size and direct the growth direction of the crystalline nanowires.
  • the diameters of the resulting nanowires are determined by the size of the catalyst cluster, which in turn can be varied by controlling the growth conditions (e.g. background pressure, temperature, flow rate . . . ). For example, lower pressure generally produces nanowires with smaller diameters. Further diameter control can be done by using uniform diameter catalytic clusters.
  • nanowires with uniform size (diameter) distribution can be produced, where the diameter of the nanowires is determined by the size of the catalytic clusters, as illustrated in FIG. 4.
  • nanowires with different lengths can be grown.
  • nanowires can be flexibly doped by introducing one or more dopants into the composite target (e.g. (Ge for n-type doping of InP).
  • the doping concentration can be controlled by controlling the relative amount of doping element, typically 0-20%, introduced in the composite target.
  • Laser ablation may be used as the way to generate the catalytic clusters and vapor phase reactant for growth of nanowires and other related elongated nanoscale structures. but fabrication is not limited to laser ablation. many ways can be used to generate vapor phase and catalytic clusters for nanowire growth (e.g. thermal evaporation).
  • C—CVD catalytic chemical vapor deposition
  • the reactant molecules e.g., silane and the dopant
  • the reactant molecules are from vapor phase molecules (as opposed to vapor source from laser vaporization.
  • nanowires can be doped by introducing the doping element into the vapor phase reactant (e.g. diborane and phosphane for p-type and n-type doped nanowire).
  • the doping concentration can be controlled by controlling the relative amount of the doping element introduced in the composite target. It is not necessary to obtain elongated nanoscale semiconductors with the same doping ratio as that in the gas reactant. However, by controlling the growth conditions (e.g. temperature, pressure . . . ), nanowires with same doping concentration can be reproduced. And the doping concentration can be varied over a large range by simply varying the ratio of gas reactant (e.g. 1 ppm-10%).
  • nanowires of any of a variety of materials can be grown directly from vapor phase through a vapor-solid process.
  • nanowires can also be produced by deposition on the edge of surface steps, or other types of patterned surfaces, as shown in FIG. 5.
  • nanowires can be grown by vapor deposition in/on any general elongated template, for example, as shown in FIG. 6.
  • the porous membrane can be porous silicon, anodic alumina or diblock copolymer and any other similar structure.
  • the natural fiber can be DNA molecules, protein molecules carbon nanotubes, any other elongated structures.
  • the source materials can be came from a solution phase rather than a vapor phase. While in solution phase, the template can also be column micelles formed by surfactant molecules in addition to the templates described above.
  • elongated nanoscale semiconductors including semiconductor nanowires and doped semiconductor nanowires
  • Such bulk-doped semiconductors may include various combinations of materials, including semiconductors and dopants. The following are non-comprehensive lists of such materials. Other materials may be used. Such materials include, but are not limited to:
  • BN/BP/BAs AlN/AlP/AlAs/AlSb, GaN/GaP/GaAs/GaSb, InN/InP/InAs/InSb,
  • any combination of two or more of the above compound e.g.: AlGaN, GaPAs, InPAs, GaInN, AlGaInN, GaInAsP . . . )
  • any combination of two or more of the above compound e.g.: (ZnCd)Se, Zn(SSe). . . )
  • II-IV-V 2 BeSiN2, CaCN2, ZnGeP2, CdSnAs2, ZnSnSb2 . . .
  • I-IV 2 -V 3 CuGeP3, CuSi2P3. . .
  • I-III-VI 2 Cu, Ag)(Al, Ga, In, Tl, Fe)(S, Se, Te)2
  • IV 3 -V 4 Si3N4, Ge3N4 . . .
  • III 2 -VI 3 Al2O3, (Al, Ga, In)2(S, Se, Te)3 . . .
  • a p-type dopant may be selected from Group III, and an n-type dopant may be selected from Group V.
  • a p-type dopant may be selected from the group consisting of B, Al and In, and an n-type dopant may be selected from the group consisting of P, As and Sb.
  • a p-type dopant may be selected from Group II, including Mg, Zn, Cd and Hg, or Group IV, including C and Si.
  • An n-type dopant may be selected from the group consisting of Si, Ge, Sn, S, Se and Te. It will be understood that the invention is not limited to these dopants.
  • Single crystal n-type and p-type silicon nanowires have been prepared and characterized by electrical transport measurements.
  • a “single crystal” item is an item that has covalent bonding, ionic bonding, or a combination thereof throughout the item. Such a single crystal item may include defects in the crystal, but is distinguished from an item that includes one or more crystals, not ionically or covalently bonded, but merely in close proximity to one another.
  • Laser catalytic growth was used to introduce controllably either boron or phosphorous dopants during the vapor phase growth of SiNWs.
  • SiNWs were synthesized using the laser-assisted catalytic growth (LCG) we have described previously. Briefly, a Nd-YAG laser (532 nm; 8 ns pulse width, 300 mJ/pulse, 10 Hz) may be used to ablate a gold target, which produces gold nanocluster catalyst particles within a reactor. The SiNWs may be grown in a flow of SiH 4 as the reactant.
  • LCG laser-assisted catalytic growth
  • Such SiNWs may be doped with boron by incorporating B 2 H 6 in the reactant flow, and may be doped with phosphorous using a Au-P target (99.5:0.5 wt %, Alfa Aesar) and additional red phosphorous (99%, Alfa Aesar) at the reactant gas inlet.
  • TEM Transmission electron microscopy
  • TEM studies show that the boron and phosphorous-doped SiNWs are single crystals, although these measurements do not have sufficient sensitivity to quantify the boron or phosphorous doping level in individual wires.
  • a gate electrode is used to vary the electrostatic potential of the SiNW while measuring current versus voltage of the nanowire.
  • the change in conductance of SiNWs as function of gate voltage can be used to distinguish whether a given nanowire is p-type or n-type since the conductance will vary oppositely for increasing positive (negative) gate voltages.
  • FIGS. 8 A- 8 C Typical gate-dependent current versus bias voltage (I-V) curves recorded on intrinsic and B-doped SiNWs are shown in FIGS. 8 A- 8 C.
  • the two B-doped wires shown in FIGS. 8B and 8C were synthesized using SiH 4 : B 2 H 6 ratios of 1000:1 and 2:1, respectively.
  • the two terminal I-V curves are linear and thus suggest that the metal electrodes make ohmic contacts to the SiNWs.
  • the small nonlinearity observed in the intrinsic nanowire indicates that this contact is slightly nonohmic.
  • This latter point is further supported by I-V measurements on the heavily B-doped SiNWs show in FIG. 8C.
  • This wire has a very low resistivity of 6.9 ⁇ 10 ⁇ 3 ⁇ -cm and shows no dependence on V g ; that is, J-V data recorded with V g of 0 and 20 V are overlapping. These results are consistent with a high carrier concentration that is near the metallic limit.
  • the I-V data recorded on a typical heavily P-doped wire are linear, have a resistivity of 2.3 ⁇ 10 ⁇ 2 ⁇ -cm, and shows no dependence on V g .
  • the low resistivity (four orders of magnitude smaller than the lightly P-doped sample) and V g independence demonstrate that high carrier concentrations can also be created via P-doping of the SiNWs.
  • a p-type nanowire (a) and n-type nanowire (b) are contacted at both ends to metal electrodes.
  • the SiNW bands bend (up for p-type; down for n-type) to bring the nanowire Fermi level in line with that of the metal contacts.
  • V g >0 the bands are lowered, which depletes the holes in B-doped SiNWs and suppress conductivity, but leads to an accumulation of electrons in P-doped SiNWs and enhance the conductivity.
  • V g ⁇ 0 will raise the bands and increase the conductivity of B-doped (p-type) SiNWs and decrease the conductivity of the P-doped (n-type) nanowires.
  • the slopes of dI/dV g for the intrinsic (2.13 ⁇ 10 ⁇ 11 ) and B-doped (9.54 ⁇ 10 ⁇ 9 ) SiNW yield mobilities of 5.9 ⁇ 10 ⁇ 3 cm 2 /V-s and 3.17 cm 2 /V-s, respectively.
  • the mobility for the B-doped nanowire is comparable to that expected in bulk Si at a doping concentration of 10 20 cm ⁇ 3 .
  • the mobility is expected to increase with decreasing dopant concentration, although in our intrinsic (low dopant concentration) SiNW the mobility is extremely low. It is possible that the reduced mobility is due to enhanced scattering in the smaller diameter (intrinsic) SiNW. We believe that future studies of the mobility as a function of diameter (for constant dopant concentration) should illuminate this important point.
  • SiNWs Single crystal n-type and p-type silicon nanowires
  • Laser catalytic growth was used to introduce controllably either boron or phosphorous dopants during the vapor phase growth of SiNWs.
  • Two-terminal, gate-dependent measurements made on individual boron-doped and phosphorous-doped SiNWs show that these materials behave as p-type and n-type materials, respectively.
  • Estimates of the carrier mobility made from gate-dependent transport measurements are consistent with diffusive transport, and show an indication for reduced mobility in smaller diameter wires.
  • these studies show it is possible to incorporate high dopant concentrations in the SiNWs and approach the metallic regime.
  • Temperature-dependent measurements made on heavily doped SiNWs show no evidence for single electron charging at temperatures down to 4.2 K, and thus suggest that the SiNWs possess a high degree of structural and doping uniformity.
  • Crossed SiNW p-n junctions have been formed by directed assembly of p-type (n-type) SiNWs over n-type (p-type) SiNWs. Transport measurements exhibit rectification in reverse bias and a sharp current onset in forward bias. Simultaneous measurements made on the p-type and n-type SiNWs making up the junction demonstrate that the contacts to these nanowires are ohmic (nonrectifying), and thus that the rectifying behavior is due to the p-n junction between the two SiNWs.
  • FIG. 10A shows energy band diagrams for p-type SiNW devices.
  • FIG. 10B shows energy band diagrams for n-type SiNW devices. The diagrams show schematically the effect of V g on the electrostatic potential for both types of nanowires.
  • FIGS. 11A and 11B show temperature dependent I-V curves recorded on a heavily B-doped SiNW.
  • curves 1, 2, 3, 4, 5, and 6 correspond to temperatures of 295, 250, 200, 150, 100, and 50 K, respectively.
  • FIG. 11B shows I-V data recorded on the nanowire at 4.2 K.
  • High-resolution TEM shows that the wires are single crystal zinc blend with a [111] growth direction, and energy dispersive X-ray analysis confirms that the nanowire composition is stoichiometric GaP.
  • monodisperse nanocluster catalysts combined with the LCG method will enable the growth of a wide range of semiconductor nanowires with well-defined and controlled diameters, and thus opens up opportunities from fundamental properties of one-dimensional (1D) systems to the assembly of functional nanodevices.
  • T-wires have been fabricated by growing semiconductor quantum wells via molecular beam epitaxy, followed by cleavage and overgrowth on the cleaved surface, while “V-groove” nanowires have been prepared by etching trenches on a surface and then depositing a small amount of material into the resulting grooves.
  • V-groove nanowires have been prepared by etching trenches on a surface and then depositing a small amount of material into the resulting grooves.
  • One of the significant limitations of these approaches is that the nanowires are embedded in a substrate, which precludes the assembly of complex 2D and 3D nanostructures.
  • Template approaches have also been used for growing a wide-range of nanowires. These methods can provide good control over the length and diameter of nanowires, although they are limited in that polycrystalline structures are often produced.
  • GaP nanowires were grown by LCG using 8.4, 18.5, and 28.2 nm diameter gold colloids.
  • the catalyst nanoclusters are supported on a SiO 2 substrate and laser ablation is used to generate the Ga and P reactants from a solid target of GaP.
  • Field emission scanning electron microscopy demonstrates that nanowires with lengths exceeding 10 ⁇ m (FIG. 13A) were obtained using all three sizes of catalyst. Examination of the nanowire ends also shows the presence of the nanocluster catalyst (FIG. 13A, inset). Control experiments carried out without the Au colloids did not produce nanowires.
  • the FESEM images show that the nanowire diameter distributions are narrower than obtained in experiments without the colloid catalysts, although FESEM is not a good method for quantifying these distributions since small variations in the focal plane can produce significant changes in the observed diameter.
  • the chamber was evacuated to less than 100 mTorr, and then maintained at 250 Torr with an Airflow of 100 sccm.
  • the substrates were examined by FESEM (LEO 982).
  • FESEM EDAX analysis, nanowires were deposited onto copper grids after removal from the substrates by sonication in ethanol.
  • FIG. 12 is a schematic depicting the use of monodisperse gold colloids as catalysts for the growth of well-defined GaP semiconductor nanowires.
  • FIG. 13A shows a FESEM image of nanowires synthesized from 28.2 nm colloids (scale bar is 5 ⁇ m).
  • the inset is a TEM image of the end of one of these wires (scale bar is 50 nm).
  • the high contrast feature corresponds to the colloid catalyst at the end of the wire.
  • FIG. 13B shows a TEM image of another wire in this sample (scale bar is 10 nm).
  • the [111] lattice planes are resolved, showing that wire growth occurs along this axis, in agreement with earlier work. Measurement of the inter-plane spacing gives a lattice constant of 0.54 nm ( ⁇ 0.05 mn) for the wire, in agreement with the bulk value for GaP, 0.5451 nm.
  • FIGS. 14 A- 14 C show histograms of measured diameters for wires grown from 28.2 nm (FIG. 14A), 18.5 nm (FIG. 14B), and 8.4 nm (FIG. 14C) colloids.
  • the solid line shows the distribution of wire.
  • FIG. 14D shows a histogram of diameters for wires grown using the previous method without colloids, in which the laser is used to both generate the Au nanoclusters and the GaP reactants.
  • the distribution is very broad (stan. dev. 23.9 nm) and the mean diameter (42.7 nm) greater than those synthesized using the predefined colloid catalyst.
  • the reported nanowire diameters correspond to the crystalline cores.
  • the amorphous oxide layers on the surface of all nanowires are relatively uniform from wire to wire within the same experiment, but vary from 2-6 nm in thickness between syntheses.
  • Nanowires of binary group III-V materials GaAs, GaP, InAs and InP
  • ternary Ill-V materials GaAs/P, InAs/P
  • binary II-VI compounds ZnS, ZnSe, CdS, and CdSe
  • binary SiGe alloys have been prepared in bulk quantities as high purity (>90%) single crystals.
  • the nanowires have diameters varying from three to tens of nanometers, and lengths extending to tens of micrometers. The synthesis of this wide range of technologically important semiconductor nanowires can be extended to many other materials and opens up significant opportunities in nanoscale science and technology.
  • Nanowires and nanotubes have been the focus of considerable attention, because they have the potential to answer fundamental questions about one-dimensional systems and are expected to play a central role in applications ranging from molecular electronics to novel scanning microscopy probes.
  • To explore such diverse and exciting opportunities requires nanowire materials for which the chemical composition and diameter can be varied.
  • considerable effort has been placed on the bulk synthesis of nanowires, and while advances have been made using template, laser ablation, solution, and other methods, in no case has it been demonstrated that one approach could be exploited in a predictive manner to synthesize a wide range of nanowire materials.
  • LCG laser-assisted catalytic growth
  • semiconductor nanowires of the Ill-V materials GaAs, GaP, GaAsP, InAs, InP and InAsP, the II-VI materials ZnS, ZnSe, CdS and CdSe, and IV-IV alloys of SiGe can be synthesized in high yield and purity using this approach.
  • Compound semiconductors, such as GaAs and CdSe, are especially interesting targets since their direct band gaps give rise to attractive optical and electrooptical properties.
  • the nanowires have been prepared as single crystals with diameters as small as 3 nm, which places them in a regime of strong radial quantum confinement, and lengths exceeding 10 ⁇ m.
  • the prediction of growth conditions for binary and more complex nanowires using the LCG method is, in principle, significantly more difficult than previous studies of elemental Si and Ge nanowires due to the complexity of ternary and higher order phase diagrams.
  • this complexity can be greatly reduced by considering pseudobinary phase diagrams for the catalyst and compound semiconductor of interest.
  • the pseudobinary phase diagram of Au-GaAs shows that Au-Ga-As liquid and GaAs solid are the principle phases above 630° C. in the GaAs rich region (FIG. 15). This implies that Au can serve as a catalyst to grow GaAs nanowires by the LCG method, if the target composition and growth temperature are set to this region of the phase diagram.
  • the structure and composition of the GaAs nanowires have been characterized in detail using transmission electron microscopy (TEM), convergent beam electron diffraction (ED) and energy dispersive X-ray fluorescence (EDX).
  • TEM studies show that the nanowires have diameters ranging from 3 nm to ca 30 nm.
  • a typical diffraction contrast image of a single 20 nm diameter wire (FIG. 17A) indicates that the wire is single crystal (uniform contrast) and uniform in diameter.
  • the Ga:As composition of this wire determined by EDX, 51.4:48.6, is the same, within limits of instrument sensitivity, as the composition obtained from analysis of a GaAs crystal standard.
  • the ED pattern recorded perpendicular to the long axis of this nanowire can be indexed for the ⁇ 112>zone axis of the ZB GaAs structure, and thus shows that growth occurs along the [111] direction.
  • Extensive measurements of individual GaAs nanowires show that growth occurs along the ⁇ 111>directions in all cases.
  • This direction and the single crystal structure are further confirmed by lattice resolved TEM images (e.g., FIG. 17B) that show clearly the (111) lattice planes (spacing 0.32+/ ⁇ 0.01 nm; bulk GaAs, 0.326 nm) perpendicular to the wire axis.
  • the nanowires produced by MOCVD method are distinct from the materials reported in this communication in several regards, including (1) the MOCVD nanowires are produced on surfaces and not in the bulk quantities required for assembly, (2) the MOCVD nanowires taper significantly from the base to their ends (that is, they do not have uniform diameters), and (3) the smallest nanowire diameters, 10-15 nm, are significantly larger than the 3-5 nm diameters achieved in our work. Lastly, as described below, it is important to recognize that our LCG method is readily extended to many different materials (e.g., Table-1) simply by producing solid targets of the material of interest and catalyst.
  • FIGS. 18A and 18C demonstrate that these materials are single crystals with a W-type structure and ⁇ 110>growth direction that is clearly distinguished from the ⁇ 111>is direction of ZB structures.
  • Studies of CdS nanowires show somewhat more complex behavior; that is, W-type nanowires with growth along two distinct ⁇ 100>and ⁇ 002>directions.
  • the ⁇ 002>direction assigned for a minority of CdS nanowires could correspond to the ⁇ 111>direction of a ZB structure.
  • X-ray diffraction measurements made on bulk nanowire samples are consistent with the W assignment.
  • previous studies of W-type CdS and CdSe nanoclusters showed elongation along the ⁇ 002>direction.
  • systematic studies of nanowire structure as a function of growth temperature should help to elucidate the origin of these results for CdS, and could also provide insight into how nanowire growth direction might be controlled.
  • the apparatus and general procedures for LCG growth of nanowires have been described previously.
  • the targets used in syntheses consisted of (material) 0.95 Au 0.05 .
  • Specific temperatures used for the growth of different nanowire materials are given in Table-1.
  • the nanowire products were collected at the down-stream cold end of the furnace.
  • the nanowire samples were characterized using X-ray diffraction (SCINTAG XDS 2000), FE-SEM (LEO 982), and TEM (Philips 420 and JEOL 2010). Electron diffraction and composition analysis (EDX) measurements were also made on the TEMs. Samples for TEM analysis were prepared as follows: samples were briefly sonicated in ethanol, which suspended the nanowire material, and then a drop of suspension was placed on a TEM grid and allowed to dry.
  • Template mediated methods using membranes and nanotubes have been used to prepare a number of materials.
  • these nanowires typically have diameters >10 nm, which are larger than those desired for strong quantum confinement effects, and often have polycrystalline structures that make it difficult to probe intrinsic physical properties.
  • Table 1 is a summary of single crystal nanowires synthesized. The growth temperatures correspond to ranges explored in these studies.
  • the minimum (Min.) and average (Ave.) nanowire diameters (Diam.) were determined from TEM and FE-SEM images. Structures were determined using electron diffraction and lattice resolved TEM imaging: ZB, zinc blende; W, wurtzite; and D, diamond structure types. Compositions were determined from EDX measurements made on individual nanowires. All of the nanowires were synthesized using Au as the catalyst, except GaAs, for which Ag and Cu were also used. The GaAs nanowires obtained with Ag and Cu catalysts have the same size, structure and composition as those obtained with the Au catalyst. Growth Min.
  • FIG. 15 shows a pseudobinary phase diagram for Au and GaAs.
  • the liquid Au—Ga—As component is designated by L.
  • FIGS. 16 A- 16 C show FE-SEM images of GaAs (FIG. 16A), GaP (FIG. 16B) and GaAs 0.6 P 0.4 (FIG. 16C) nanowires prepared by LCG.
  • the scale bars in FIGS. 16 A- 16 C are 2 ⁇ m.
  • the insets in FIGS. 16 A- 16 C are TEM images of GaAs, GaP and GaAs 0.6 P 0.4 nanowires, respectively.
  • the scale bars in are all 50 nm.
  • the high contrast (dark) features correspond to the solidified nanocluster catalysts.
  • FIG. 17A shows a diffraction contrast TEM image of a ca. 20 nm diameter GaAs nanowire.
  • the inset shows a convergent beam electron diffraction pattern (ED) recorded along the ⁇ 112>zone axis.
  • the [111] direction of the ED pattern is parallel to the wire axis, and thus shows that growth occurs along the [111] direction.
  • the scale bar corresponds to 20 nm.
  • FIG. 17B shows a high-resolution TEM image of a ca. 20 nm diameter GaAs nanowire.
  • FIGS. 17C and 17D show high-resolution TEM images of 10 and 6 nm diameter, respectively, GaAs 0.6 P 0.4 nanowires.
  • the (111) lattice planes (perpendicular to the wire axes) are clearly resolved in all three nanowires.
  • the scale bars in FIGS. 17C and 17D are 5 nm.
  • FIG. 18A shows a FE-SEM image of CdSe nanowires prepared by LCG.
  • the scale bar corresponds to 2 ⁇ m.
  • the inset in FIG. 18A is a TEM image of an individual CdSe nanowire exhibiting nanocluster (dark feature) at the wire end. EDX shows that the nanocluster is composed primarily of Au.
  • the scale bar is 50 nm.
  • FIG. 18B shows a diffraction contrast TEM image of a 18 nm diameter CdSe nanowire. The uniform contrast indicates that the nanowire is single crystal.
  • the inset in FIG. 1 8 B is an ED pattern, which has been indexed to the wurtzite structure, recorded along the ⁇ 001>zone axis.
  • the [110] direction of the ED pattern is parallel to the wire axis, and thus shows that growth occurs along the [110] direction.
  • the scale bar is 50 nm.
  • FIG. 18C shows a high-resolution TEM image of a ca. 13 nm diameter CdSe nanowire exhibiting well-resolved (100) lattice planes.
  • the experimental lattice spacing, 0.36 ⁇ 0.01 nm is consistent with the 0.372 nm separation in bulk crystals.
  • the 300 orientation (100) lattice planes with respect to the nanowire axis is consistent with the [110] growth direction determined by ED.
  • the scale bar corresponds to 5 nm.
  • Single crystalline GaN nanowires have been synthesized in bulk quantities using laser-assisted catalytic growth (LCG).
  • Laser ablation of a (GaN, Fe) composite target generates liquid nanoclusters that serve as catalytic sites confining and directing the growth of crystalline nanowires.
  • Field emission scanning electron microscopy shows that the product primarily consists of wire-like structures, with diameters on the order of 10 nm, and lengths greatly exceeding 1 ⁇ m.
  • Powder X-ray diffraction analyses of bulk nanowire samples can be indexed to the GaN wurtzite structure, and indicate >95% phase purity.
  • Nanostructured GaN materials have attracted extensive interest over the past decade due to their significant potential for optoelectronics. These studies have primarily focused on zero dimensional (0D) quantum dots and two dimensional (2D) quantum well structures, which can be readily synthesized using established methods. Investigations of one dimensional (1D) GaN nanowires, which could enable unique opportunities in fundamental and applied research, have been limited due to difficulties associated with their synthesis. Specifically, there has been only one report of GaN nanowire growth. In this work, carbon nanotubes were used as templates in the presence of Ga-oxide and NH 3 vapor to yield GaN nanowires. We have exploited predictable synthetic approach for GaN nanowire growth called laser-assisted catalytic growth (LCG).
  • LCG laser-assisted catalytic growth
  • a pulsed laser is used to vaporize a solid target containing desired material and a catalyst, and the resulting liquid nanoclusters formed at elevated temperature direct the growth and define the diameter of crystalline nanowires through a vapor-liquid-solid growth mechanism.
  • the catalyst used to define ID growth can be selected from phase diagram data and/or knowledge of chemical reactivity.
  • a related approach termed solution-liquid-solid phase growth has been used by Buhro and coworkers to prepare nanowires of several Ill-V materials in solution, although not nitrides.
  • LCG using a GaN/Fe target produces a high yield of nanometer diameter wire-like structures.
  • a typical FE-SEM image of the product produced by LCG (FIG. 20A) shows that the product consists primarily of 1D structures with diameters on the orders of 10 nm and lengths greatly exceeding 1 ⁇ m; that is, high aspect ratio nanowires.
  • the FE-SEM data also show that the products consist of ca. 90% nanowires, with the remaining being nanoparticles.
  • PXRD PXRD
  • the LCG experimental apparatus is similar to that reported previously.
  • the experimental system was evacuated to 30 mtorr, and then refilled with anhydrous ammonia gas. While the pressure and flow rate were maintained at ca. 250 torr and 80 sccm, respectively, the furnace temperature was increased to 900° C. at 30° C. /min.
  • a pulsed Nd-YAG laser (1064 nm, 8 ns pulse width, 10 Hz repetition, 2.5 W average power) was then used to ablate the target with a typical ablation duration of 5 min.
  • FIG. 20A shows a representative diffraction contrast image of one nanowire.
  • the uniform contrast along the wire axis indicates that the nanowire is a single crystal.
  • the nanoparticle (dark, high contrast feature) observed at the nanowire end is faceted as expected following crystallization of the liquid nanocluster (FIG. 19).
  • EDX to address the composition of the nanowires and terminal nanoparticles. Data recorded on the nanowire show only Ga and N in a ratio ca. the same as a GaN standard, while the nanoparticles contain Ga, N, and Fe. The presence of Fe (with Ga and N) only in the terminal nanoparticle confirms the catalytic nature of Fe in the synthesis.
  • the image which was recorded along the ⁇ 001>zone axis, shows clearly the single crystal structure of the nanowire and the lattice planes along the [100], [010] and [-110] directions. This image demonstrates that the [100] direction runs parallel to the wire axis, and thus confirms the [100] growth direction in GaN nanowires.
  • FIG. 19 is a schematic diagram showing GaN nanowire growth by laser-assisted catalytic growth.
  • FIG. 20A shows a FE-SEM (LEO 982) image of bulk GaN nanowires synthesized by LCG. The scale bar corresponds to 1 ⁇ m.
  • FIG. 20B shows a PXRD (Scintag, XDS2000) pattern recorded on bulk GaN nanowires. The numbers above the peaks correspond to the (hkl) values of the wurtzite structure.
  • FIG. 21A shows a diffraction contrast TEM (Philips, EM420) image of a GaN nanowire that terminates in a faceted nanoparticle of higher (darker) contrast.
  • the inset in FIG. 21A shows a CBED pattern recorded along ⁇ 001>zone axis over the region indicated by the white circle.
  • the white scale bar corresponds to 50 nm.
  • FIG. 21B shows a HRTEM (JEOL 2010) image of another GaN nanowire with a diameter of ca. 10 nm. The image was taken along ⁇ 001>zone axis.
  • the [100], [010] and [ ⁇ 110] directions are indicated with the [100] parallel to the wire axis.
  • the white scale bar corresponds to 5 nm.
  • Nanowires such as nanowires (NWs) and nanotubes (NTs)
  • NTs nanotubes
  • FETs field effect transistors
  • nanoscale structures as building blocks for bottom-up assembly of active devices and device arrays, which can eliminate the need for costly fabrication lines, will require that the electronic properties of the different blocks be both defined and controllable.
  • gate-dependent transport measurements demonstrate that indium phosphide (InP) NWs can be synthesized with controlled n-type and p-type doping, and can function as nanoscale FETs.
  • InP indium phosphide
  • the availability of well-defined n- and p-type materials has enabled the creation of p-n junctions by forming crossed NW arrays. Transport measurements reveal that the nanoscale p-n junctions exhibit well-defined current rectification.
  • Single crystal InP NWs have been prepared by a laser-assisted catalytic growth (LCG), which has been described previously.
  • the n-type and p-type InP NWs were prepared using tellurium (Te) and zinc (Zn) as dopants, respectively, and found to be of similar high quality as NWs produced without the addition of dopants.
  • Field emission scanning electron microscopy (FE-SEM) images of as-synthesized Zn-doped InP NWs (FIG. 22A) demonstrate that the wires extend up to tens of micrometers in length with diameters on the order of 10 nanometers.
  • High-resolution transmission electron microscopy (TEM) images (inset, FIG.
  • the doped NWs are single crystals with ⁇ 111>growth directions.
  • a 1-2 nm amorphous over-layer on the NWs is visible in TEM images. This thin layer is attributed to oxides formed when the NWs are exposed to air after synthesis.
  • the overall composition of individual NWs determined by energy dispersive X-ray (EDX) analysis was found to be 1:1 In:P, thus confirming the stoichiometric composition of the NWs.
  • EDX and other elemental analytic methods are, however, insufficiently sensitive to determine the doping level in individual NWs.
  • FIGS. 22B and 22C and 100c show the typical gate-dependent I-V curves obtained from individual Te- and Zn-doped NWs respectively.
  • the transport data (FIG. 22B) recorded on Te-doped NWs show an increase in conductance for V g >0, while the conductance decreases for V g ⁇ 0. These data clearly show that Te-doped InP NWs are n-type.
  • Gate-dependent transport data recorded on Zn-doped NWs show opposite changes in conductance with variation in V g compared to the n-type, Te-doped InP NWs. Specifically, for V g >0, conductance decreases and for V g ⁇ 0 conductance increases (FIG. 22C). These results demonstrate that the Zn-doped InP NWs are p-type.
  • the gate voltage can be used to completely deplete electrons and holes in n- and p-type NWs such that the conductance becomes immeasurably small.
  • the conductance of the NW in FIG. 22B can be switched from a conducting (on) to an insulating (off) state when V g is less than or equal to ⁇ 20 V, and thus it functions as a FET.
  • the conductance modulation can be as large as 4-5 orders of magnitude for some of the NWs.
  • the relatively large switching voltage is related to the thick (600 nm) oxide barrier used in our measurements.
  • This gate-dependent behavior is similar to that of metal-oxide-semiconductor (MOS) FETs and recent studies of semiconducting NT FETs.
  • MOS metal-oxide-semiconductor
  • An important distinction of our work with respect to NTs is that predictable semiconducting behavior can be achieved in every NW. Taken together, these results clearly illustrate that single crystal InP NWs can be synthesized with controlled carrier type. Because these NWs are produced in bulk quantities, they represent a readily available material for assembling devices and device arrays.
  • FIG. 23A shows a representative crossed NW device formed with a 29 nm and 40 nm diameter NW. The four arms are designated as A, B, C, D for the simplicity of discussion below.
  • the types of junctions studied are controllable for every experiment since we can select the types of NWs used to produce the crossed junction prior to assembly.
  • FIGS. 23B and 23C show the current-voltage (I-V) data recorded on n-n and p-p junctions, respectively.
  • the transport data recorded on the individual NWs AC, BD
  • curves 80, FIG. 23B and curve 82, FIG. 23C show linear or nearly linear I-V behavior.
  • FIG. 23D shows typical I-V behavior of a crossed NW p-n junction.
  • the linear I-V of the individual n- and p-type NWs components indicates ohmic contact between the NWs and metal electrodes.
  • Transport behavior across the p-n junction shows clear current rectification; i.e., little current flows in reverse bias, while there is a sharp current onset in forward bias.
  • the behavior is similar to bulk semiconductor p-n junctions, which form the basis for many critical electronic and optoelectronic devices.
  • rectification arises from the potential barrier formed at the interface between p- and n-type materials.
  • the barrier is reduced and a relatively large current can flow through the junction; on the other hand, only small current can flow in reverse bias since the barrier is further increased.
  • FIG. 24A shows an EL image taken from a typical NW p-n junction at forward bias, and the inset shows the PL image of a crossed NW junction.
  • the PL image clearly shows two elongated wire-like structures, and the EL image shows that the light comes from a point-like source. Comparison of the EL and PL images shows that the position of the EL maximum corresponds to the crossing point in the PL image, thus demonstrating the light indeed comes out from the NW p-n junction.
  • the I-V characteristic of the junction shows clear rectification with a sharp current onset at ⁇ 1.5 volts.
  • the EL intensity versus voltage curve of the junction shows significant light can be detected with our system at a voltage as low as 1.7 volts.
  • the EL intensity increases rapidly with the bias voltage, and resembles the I-V behavior.
  • the EL spectrum (FIG. 24C) shows a maximum intensity around 820 nm, which is significantly blue shifted relative to the bulk band gap of InP (925 nm). The blue-shift is due in part to quantum confinement of the excitons, although other factors may also contribute.
  • GaN is a direct wide bandgap semiconductor material, which emits light in the short wavelength (UV and blue) region at room temperature. Blue LEDs are important as emitters where strong, energy efficient and reliable light source are needed. Also it is important to enable production of full color LED displays and LED white lamp, since blue is one of the three primary colors (red, green and blue).
  • FIG. 25A shows an EL image taken from two P-type Si and N-type GaN crossed nanojunctions.
  • the p-Si is doped with Boron.
  • FIG. 25B shows current vs. voltage for various gate voltages.
  • the nanojunction shows good rectification at different gate voltages.
  • the El spectrum shown in FIG. 25C shows light emission is about 380 nm and 470 nm.
  • a n-InP and p-Si nanojunction has good rectification.
  • E-field assembly of NWs between an array of electrodes demonstrates that individual NWs can be positioned to bridge pairs of diametrically-opposed electrodes and form a parallel array.
  • the alignment can be done in a layer-by-layer fashion to produce crossed NW junctions (FIG. 26D).
  • InP NWs were synthesized using LCG.
  • the LCG target typically consisted of 94% (atomic ratio) InP, 5% Au as the catalyst, and 1% of Te or Zn as the doping element.
  • the furnace temperature (middle) was set at 800° C. during growth, and the target was placed at the upstream end rather than middle of the furnace.
  • a pulsed (8 ns, 10 Hz) Nd-YAG laser (1064 nm) was used to vaporize the target. Typically, growth was carried out for 10 minutes with NWs collected at the downstream, cool end of the furnace.
  • Transport measurement on individual NWs were carried out using published procedures. Briefly, NWs were first dispersed in ethanol, and then deposited onto oxidized silicon substrates (600 nm oxide, 1-10 ⁇ cm resistivity), with the conductive silicon used as a back gate. Electrical contact to the NWs was defined using electron beam lithography (JEOL 6400). Ni/In/Au contact electrodes were thermally evaporated. Electrical transport measurements were made using home built system with ⁇ 1pA noise under computer control.
  • n-n and p-p junctions were obtained by random deposition.
  • the p-n junctions were obtained by layer-by-layer deposition.
  • a dilute solution of one type (e.g., n-type) of NW was deposited on the substrate, and the position of individual NWs was recorded.
  • a dilute solution of the other type (e.g., p-type) of NW was deposited, and the positions of crossed n- and p-type NWs were recorded.
  • Metal electrodes were then defined and transport behavior was measured.
  • EL was studied with a home-built micro-luminescence instrument. PL or scattered light (514 nm, Ar-ion laser) was used to locate the position of the junction. When the junction was located, the excitation laser was shut off, and then the junction was forward biased. EL images were taken with a liquid nitrogen cooled CCD camera, and EL spectra were obtained by dispersing EL with a 150 line/mm grating in a 300 mm spectrometer.
  • FIGS. 22 A- 22 C illustrate doping and electrical transport of InP NWs.
  • FIG. 22A shows a typical FE-SEM image of Zn-doped InP NWs. Scale bar is 10 ⁇ m. inset, lattice resolved TEM image of one 26 nm diameter NW. The (111) lattice planes are visible perpendicular to the wire axis. Scale bar is 10 nm.
  • FIGS. 22B and 22C show gate-dependent I-V behavior for Te- and Zn-doped NWs, respectively. The insets in FIGS. 22B and 22C show the NW measured with two terminal Ni/In/Au contact electrodes. The scale bars correspond to 1 ⁇ m. The diameter of the NW in FIG. 22B is 47 nm, while that in FIG. 22C is 45 nm. Specific gate-voltages used in the measurements are indicated on the right hand sides of the FIGS. on the corresponding I-V curves. Data were recorded at room temperature.
  • FIGS. 23 A- 23 D illustrate crossed NW junctions and electrical properties.
  • FIG. 23A shows a FE-SEM image of a typical crossed NW device with Ni/In/Au contact electrodes. The scale bar corresponds to 2 ⁇ m. The diameters of the NWs are 29 nm (A-C) and 40 nm (B-D); the diameters of the NWs used to make devices were in the range of 20-75 nm.
  • FIGS. 23 B- 23 D show I-V behavior of n-n, p-p and p-n junctions, respectively. The curves 80 and 82 correspond to the I-V behavior of individual n- and p-NWs in the junctions, respectively.
  • the curves 88 represent the I-V behavior across the junctions.
  • the current recorded for the p- and n- type NWs in FIG. 23D is divided by 10 for better viewing.
  • the solid lines represent transport behavior across one pair of adjacent arms, and the dashed lines represent that of the other three pairs of adjacent arms. Data were recorded at room temperature.
  • FIGS. 24 A- 24 D illustrate optoelectrical characterization of NW p-n junctions.
  • FIG. 24A is an EL image of the light emitted from a forward biased NW p-n junction at 2.5 V.
  • the inset in FIG. 24A shows the PL image of the junction. Both scale bars correspond to 5 ⁇ m.
  • FIG. 24B shows the EL intensity versus voltage.
  • the inset in FIG. 24B shows the I-V characteristics and the inset in the inset shows the FE-SEM image of the junction itself.
  • the scale bar corresponds to 5 ⁇ m.
  • the n-type and p-type NWs forming this junction have diameters of 65 and 68 nm, respectively.
  • FIG. 24C shows an EL spectrum of the junction shown in FIG.
  • FIG. 24A shows an EL spectrum recorded from a second forward biased crossed NW p-n junction.
  • the EL maximum occurs at 680 nm.
  • the inset in FIG. 24D shows the EL image and demonstrates that the EL originates from the junction region.
  • the scale bar is 5 ⁇ m.
  • the n-type and p-type NWs forming this junction have diameters of 39 and 49 nm, respectively.
  • FIGS. 26 A- 26 D illustrate parallel and orthogonal assembly of NWs with E-fields.
  • FIG. 26A is a schematic view of E-field alignment. The electrodes (orange) are biased at 50-100 V after a drop of NW solution is deposited on the substrate (blue)
  • FIG. 26B shows a parallel array of NWs aligned between two parallel electrodes. The NWs were suspended in chlorobenzene and aligned using an applied bias of 100 V.
  • FIG. 26C shows a spatially positioned parallel array of NWs obtained following E-field assembly using a bias of 80 V. The top inset in FIG. 26C shows 15 pairs of parallel electrodes with individual NWs bridging each diametrically opposed electrode pair.
  • FIG. 26A is a schematic view of E-field alignment. The electrodes (orange) are biased at 50-100 V after a drop of NW solution is deposited on the substrate (blue)
  • FIG. 26B shows a parallel array of NWs aligned between two parallel electrodes. The
  • FIGS. 26D shows a crossed NW junction obtained using layer-by-layer alignment with the E-field applied in orthogonal directions in the two assembly steps.
  • the applied bias in both steps was 80 V.
  • the scale bars in FIGS. 26 B- 26 D correspond to 10 ⁇ m.
  • Bottom-Up Assembly of Nanoscale Electronic Devices from Silicon Nanowires Four types of important functional nanodevices have been created by rational bottom-up assembly from p and n-type silicon nanowires (SiNWs) with well controlled dopant type and level. In all these devices, electrical transport measurements on individual p and n-type SiNWs suggested ohmic or nearly ohmic contact between SiNWs and leads.
  • n + pn crossed junctions were also assembled to create bipolar transistors, in which common base/emitter current gains as large as 0.94/16 were obtained.
  • Complementary inverters made of crossed lightly doped pn junctions showed clear output voltage inverse to input voltage with a gain of 0.13.
  • Tunnel diodes in form of heavily doped SiNW pn crosses showed negative differential resistance (NDR) behavior in forward bias with a peak-to-valley ratio (PVR) of 5 to 1.
  • Nanoscale structures as building blocks for the bottom-up assembly of integrated devices, where both the fabrication and assembly of individual blocks are expected to be cheap, can thus eliminate greatly the cost of fabrication lines while still maintaining some concepts that have proven successful in microelectronics.
  • One dimensional structures such as nanowires (NWs) and nanotubes (NTs) are ideal candidates as critical building blocks for nanoelectronics. How to construct the functional nanodevices and device arrays with these building blocks is essential to nano science and technology. NTs have been tested as field effect transistors, single electron transistors.
  • NT-NW heterojunctions NT intramolecular junctions and crossed junctions have also been demonstrated.
  • the use of NTs in rational assembly is limited by unpredictability of individual tube properties because the specific growth of metallic and semiconductor NTs is not controllable and controlled doping of semiconductor NTs is difficult.
  • SiNWs single crystal semiconductor SiNWs
  • the type of dopant p-type and n-type
  • the relative doping concentration from lightly to degenerately
  • the highly dense SiNW device arrays can be formed by the directed assembly of chemical assembly, for example, the specific peptide binding to semiconductor, DNA base matching interaction, and/or the ligand-receptor interaction.
  • understanding the electrical properties of individual bottom-up assembled active devices is the prerequisite.
  • n + pn crossed SiNW junctions to bipolar transistors which were demonstrated to have common base/emitter current gains as large as 0.94/16.
  • the inverters made of lightly doped pn crosses showed clearly the output voltage inverse to the input voltage with voltage gain of 0.13.
  • the results of tunnel diodes made of heavily doped pn crossed showed NDR behavior in forward bias with a PVR of 5 to 1.
  • the p-type and n-type SiNWs were synthesized by using diborane and phosphorus, respectively as doping source during laser-assisted catalytic growth of SiNWs. Metal leads contact with SiNWs on doped silicon substrate with 600nm thermal oxide were defined by electron beam lithography.
  • the pn, pp and nn junctions were formed by crossing one p-type and one n-type, two p-type and two n-type SiNWs, respectively.
  • the types of junctions were controlled by choosing the types of SiNWs used to create a given junction.
  • a typical field emission scanning electron microscopy (FE-SEM) image of cross junctions is shown in FIG. 27A, where the four contact leads are labeled as 1, 2, 3 and 4 for the convenience of discussion.
  • FIG. 27B shows current versus voltage (I-V) data on a pn crossed junction with diameters of p and n-type SiNWs as small as 20.3 nm and 22.5 nm, respectively.
  • I-V curve across junction shows little current in reverse bias (negative bias in our setup) and very sharp current onset in forward bias (positive bias).
  • single p (between leads 1-3) and n-type (between leads 2-4) SiNWs show linear I-V behavior (FIG. 27B curves 110 and 120, respectively), which suggests ohmic (not rectifying) contact between SiNWs and leads.
  • the p and n-type SiNWs were dispersed in to aceton separately. p-n junctions were obtained by sequential deposition.
  • the solution of one type of SiNWs e.g., n-type
  • the solution of the other type of SiNWs e.g., p-type
  • pp or nn junctions were obtained by depositing only one type of SiNWs : p-type or n-type. The junction positions were then recorded.
  • bipolar transistor As the basic unit of most semiconductor devices, pn junctions provide the characteristics needed for rectifiers, amplifiers, switching circuits and many other electronic circuit functions. Success in making pn junction from SiNW crosses provides us the possibility to make other important functional devices.
  • bipolar transistor To demonstrate we can create not only passive device: p-n diode, but also the active device, we constructed bipolar transistor, which is capable of current gain.
  • a bipolar transistor is a n + pn (FIG. 28A left) or p + np junction device, which requires high doping level in emitter, low doping in base and collector. Well control in doping of SiNWs provides us the capability to make this complex device.
  • FIG. 28B is a typical SEM image of bipolar transistors.
  • the SiNWs and junctions in transistors were first characterized individually. The I-V curves of three individual SiNWs are linear and the two individual junctions have correct rectifying behavior. Then the n + -type SiNW was used as emitter while the n-type as collector to do bipolar transistor measurements.
  • the emitter-base (E-B) is always forward biased to inject electrons into base region.
  • the transistor When the collector-base (C-B) voltage is greater than zero, the transistor is operated in the active mode, in which the C-B junction is reverse biased and only a very small leakage current will flow across the junction.
  • the electrons injected from emitter can diffuse through the base to reach the C-B junction space charge region and will be collected by collector.
  • the actual collector current depends only on the injected electrons from emitter and thus depends only on the E-B voltage. This is clearly seen in FIG. 28C regime II, where the collector current goes high with the forward E-B voltage while change slowly with C-B voltage which results from Early effect and the existence of slowly increasing leakage current with reverse bias. This demonstrates the transistor action: large current flow in a reverse biased collector junction can result from carriers injected from a nearby emitter junction.
  • n+pn bipolar transistors were fabricated by deposition and machanical manipulation. First, p-type SiNWs were deposited from solution onto the substrate. In the second step, the n + and n-type SiNWs were attached to sharp STM tips and released onto the p-type SiNWs under optical microscope.
  • the common base current gain of the bipolar transistor in active mode is as large as 0.94 (FIG. 28D) and the common emitter current gain is 16. Three important points are suggested from this large current gain.
  • the space charge region between base and collector has high efficiency to collect electrons and sweep them into collector, suggesting that the oxide barrier at the interface doesn't contribute significantly, which further confirms our analysis on single pn junctions.
  • Our bipolar transistor can be improved, for example, by reducing the base width, to approach the performace of the commercial one in which the typical common base current gain is larger than 0.99.
  • the output voltage is negative (zero) with the positive(negative) input voltage, which is the typical inverter behavior.
  • This behavior can explained like this: the depletion of n-type (p-type) wires by negative (positive) input makes the output equal to ground (bias).
  • the voltage gain is calculated as 0.13, the slope of voltage inversion. The gain is lower than that in commercial inverters which is larger than 1, but can be improved by using thinner gate oxide layer instead of the 600 nm oxide, which reduces the gate response of SiNWs, and using more lightly doped SiNWs, which needs more effort to make ohmic contact with and to be further investigated.
  • results described here demonstrate the bottom-up assembly of multiple types of nanoscale electronic devices from doped SiNWs with control over both dopant type and doping level.
  • the individual devices show predictable behaviors similar to the conventionally fabricated devices.
  • the mass production and high intergration of these functional nanodevices can be realized by chemical assembly assisted with electric field and flowing solution alignment, which will lead to exciting practical applications in nanoelectronics while avoiding high cost fabrication lines.
  • pn diode crosses can function as photodiodes and pn solar cells
  • bipolar transistor crosses can form phototransistors.
  • FIGS. 27 A- 27 F illustrate crossed SiNW junctions.
  • FIG. 27A shows a typical FE-SEM image of crossed NW junctions with Al/Au as contact leads.
  • the scale bar is 2
  • FIGS. 27 B- 27 D show I-V behavior of pn, pp and nn junctions, respectively.
  • the curves 110 and 120 correspond to the I-V behavior of individual p and n-type SiNWs in junctions, respectively.
  • the curves 130 represent the four-terminal I-V through pn junction in FIG. 27B and two terminal I-V through pp and nn junction in FIGS. 27C and 27D, respectively.
  • the solid line is I-V by following current between lead 1 and 2 and simultaneouly measuring the voltage between lead 3 and 4 while the dashed line correponds to that by following current between 1 and 4 and measuring voltage between 3 and 2.
  • FIGS. 27C and 27D the solid lines are I-V across one pair of adjacent leads (1-2) and the dashed lines are those across the other three pairs (1-4, 2-3, 3-4).
  • FIGS. 27E and 27F show the energy band diagrams of a pn junction under forward bias and reverse bias, respectively.
  • FIGS. 28 A- 28 D illustrate n + pn crossed SiNW bipolar transistors.
  • FIG. 28A shows the common base configuration schematics of an n + pn bipolar transistor in semiconductor physics (left) and in crossed SiNW structure (right). The n+, p and n-type SiNWs function as emitter, base and collector, respectively. Base is grounded. Emitter is negatively biased at specific values. Collector voltage is scanned from postive to negative.
  • FIG. 28B shows a typical FE-SEM image of SiNW bipolar transistor. The scale bar is 5 ⁇ m.
  • FIG. 28 C shows a collector current vs collector-base voltage behavior recorded on an n+pn transistor with emitter and base SiNWs 15um apart.
  • Curve 1 to 4 correspond to the behavior at emitter-base voltages of ⁇ 1, ⁇ 2, ⁇ 3,-4V.
  • Regime I and II are separated by dashed line, correponding to saturation mode and active mode, respectively.
  • FIG. 28D shows common base current gain vs collector-base voltage.
  • FIGS. 29 A- 29 D illustrate complementary inverters and tunnel diodes.
  • FIG. 29A shows schematics of a complementary inverter structure in semicondutor physics (top) and that formed by a lightly doped pn cross (bottom). In bottom schematics, one end of n-type NW is biased at ⁇ 5V and one end of p-type NW is grounded. Input voltage is back gate voltage and the other ends of p and n-type NWs are shorted as output terminal.
  • FIG. 29B shows output voltage vs input voltage data in a pn cross inverter. The inset in FIG. 29B is the I-V curves of p-type NW in the inverter.
  • Curve 1 to 5 correspond to I-V at back gate voltage ⁇ 50, ⁇ 30, ⁇ 10, 0 and 10V, respectively.
  • the n-type NW in this inverter has similar I-V behavior and can be completely depleted at a gate voltage of ⁇ 30V.
  • FIG. 29C shows two terminal mearsurement data of a tunnel diode made from a heavily doped pn cross. The I-V behavior of individual p and n-type SiNWs have been tested to be linear. The inset in FIG. 29C spreads out the part of I-V curve showing NDR.
  • FIG. 29D shows the energy band diagrams of a crossed SiNW tunnel diode. At reverse bias (e.g. at position 1 in FIG.
  • NWs Nanowires
  • the substrate (silicon wafter) was covered by a self-assembled monolayer (SAM) with —NH2 termination.
  • SAM self-assembled monolayer
  • microfluidic molds are made of PDMS.
  • Patterning process I. a layer of PMMA was spin-coated on the substrate surface, then use EBL (Electron Beam Lithography) to write pattern, i.e. to selectively exposed Si surface which was later chemically functionalized. (as in 2).
  • EBL Electro Beam Lithography
  • Patterning process I. a layer of PMMA was spin-coated on the substrate surface, then use EBL (Electron Beam Lithography) to write pattern, i.e. to selectively exposed Si surface which was later chemically functionalized. (as in 2).
  • EBL Electro Beam Lithography
  • One-dimensional nanostructures such as nanowires and nanotubes, represent the smallest dimension for efficient transport of electrons and excitons, and thus are ideal building blocks for hierarchical assembly of functional nanoscale electronic and photonic structures.
  • nanowires can be assembled into parallel arrays with control of the average separation, and by combining fluidic alignment with surface patterning techniques that it is also possible to control periodicity.
  • complex crossed nanowire arrays can be prepared using layer-by-layer assembly with different flow directions for sequential steps. Transport studies show that the crossed nanowire arrays form electrically conducting networks, with individually addressable device function at each cross point.
  • Nanoscale materials for example, nanoclusters and nanowires (NWs)
  • NWs nanoclusters and nanowires
  • IDL one-dimensional nanostructures
  • NTs carbon nanotubes
  • the gallium phosphide (GaP), indium phosphide (InP) and silicon (Si) NWs used in these studies were synthesized by laser assisted catalytic growth, and subsequently suspended in ethanol solution.
  • PDMS poly(dimethylsiloxane)
  • FIG. 30A and 30B flat substrate
  • Parallel and crossed arrays of NWs can be readily achieved using single (FIG. 30A) and sequential crossed (FIG. 30B) flows, respectively, for the assembly process as described below.
  • FIG. 31A A typical example of parallel assembly of NWs (FIG. 31A) shows that virtually all the NWs are aligned along one direction; i.e. the flow direction. There are also some small deviations with respect to the flow direction, which we will discuss below. Examination of the assembled NWs on larger length scales (FIG. 31B) shows that the alignment readily extends over hundreds of micrometers. Indeed, alignment of the NWs has been found to extend up to millimeter length scales, and seem to be limited by the size of the fluidic channels, based on experiments carried out using channels with widths ranging from 50 to 500 ⁇ m and lengths from 6-20 mm.
  • the average NW surface coverage can be controlled by the flow duration (FIG. 31D).
  • flow duration (FIG. 31D).
  • a flow duration of 30 min produced a density of ca. 250 NWs/100 ⁇ m or an average NW/NW separation of ⁇ 400 nm.
  • Extended deposition time can produce NW arrays with spacings on the order of 100 nm or less.
  • the deposition rate and hence average separation versus time depends strongly on the surface chemical functionality. Specifically, we have shown that the GaP, InP and Si NWs deposit more rapidly on amino-terminated monolayers, which possesses a partial positive charge, than on either methyl-terminated monolayers or bare SiO 2 surfaces.
  • FIG. 31B Our general approach can be used to organize NWs into more complex crossed structures, which are critical for building dense nanodevice arrays, using the layer-by-layer scheme illustrated in FIG. 31B.
  • the formation of crossed and more complex structures requires that the nanostructure-substrate interaction is sufficiently strong that sequential flow steps do not affect preceding ones: we find that this condition can be achieved.
  • alternating the flow in orthogonal directions in a two-step assembly process yields crossbar structures (FIG. 33A and 33B).
  • FIGS. show that multiple crossbars can be obtained with only hundreds of nanometer separations between individual cross points in a very straightforward, low cost, fast and scalable process.
  • a periodic array can be easily envisioned using a patterned surface as described above.
  • these crossbar structures can yield functional devices (see below).
  • Electric fields can be used to align suspensions of semiconductor NWs into parallel NW arrays and single NW crosses, where patterned micro-electrode arrays are used to create a field pattern. Fringing fields and charging can, however, lead to significant complications in the assembly of multiple crosses at the submicron scale.
  • each layer is independent of the others, and thus a variety of homo- and hetero-junction configurations can be obtained at each crossed point by simply changing the composition of the NW suspension used for each step.
  • FIGS. 30A and 30B are schematics of fluidic channel structures for flow assembly.
  • FIG. 30A shows a channel formed when the PDMS mold was brought in contact with a flat substrate. NW assembly was carried out by flowing a NW suspension inside the channel with a controlled flow rate for a set duration. Parallel arrays of NWs are observed in the flow direction on the substrate when the PDMS mold is removed.
  • FIG. 30B illustrates that multiple crossed NW arrays can be obtained by changing the flow direction sequentially in a layer-by-layer assembly process.
  • FIGS. 31 A- 31 D illustrate parallel assembly of NW arrays.
  • FIGS. 31A and 31B are SEM images of parallel arrays of InP NWs aligned in channel flow. The scale bars correspond to 2 ⁇ m and 50 ⁇ m in FIGS. 31A and 31B, respectively.
  • the silicon (SiO 2 /Si) substrate used in flow assembly was functionalized with an amino-terminated self assembled monolayer (SAM) by immersion in a 1 mM chloroform solution of 3-aminopropyltriethoxysilane (APTES) for 30 min, followed by heating at 110° C. for 10 min. All of the substrates used in the following experiment were functionalized in a similar way unless otherwise specified.
  • SAM amino-terminated self assembled monolayer
  • APTES 3-aminopropyltriethoxysilane
  • FIG. 31C shows NW angular spread with respect to the flow direction vs. flow rate.
  • NWs e.g., see inset
  • the inset shows histogram of NW angular distribution at a flow rate of 9.40 mm/s.
  • FIG. 3 ID shows the average density of NW arrays vs. flow time. The average density was calculated by dividing the average number of NWs at any cross section of the channel by the width of the channel. All of the experiments were carried out with a flow rate of 6.40 mm/s.
  • FIGS. 32 A- 32 D illustrate assembly of periodic NW arrays.
  • FIG. 32A is a schematic view of the assembly of NWs onto a chemically patterned substrate.
  • the light gray areas correspond to amino-terminated surfaces, while the dark gray area corresponds to either methyl-terminated or bare surfaces. NWs are preferentially attracted to the amino-terminated regions of the surface.
  • FIGS. 32B and 32C show parallel arrays of GaP NWs aligned on poly(methylmethacrylate) (PMMA) patterned surface with 5 ⁇ m and 2 ⁇ m separation.
  • the dark regions in the image correspond to residual PMMA, while the bright regions correspond to the amino-terminated SiO 2 /Si surface.
  • the NWs are preferentially attracted to amino-terminated regions.
  • FIG. 32D shows parallel arrays of GaP NWs with 500 nm separation obtained using a patterned SAM surface.
  • the SiO 2 /Si surface was first functionalized with methyl-terminated SAM by immersing in pure hexamethyldisilazane (HMDS) for 15 min at 50° C., followed by 10 min at 110° C.
  • HMDS hexamethyldisilazane
  • FIGS. 33 A- 33 E illustrate layer-by-layer assembly and transport measurements of crossed NW arrays.
  • FIGS. 33A and 33B show typical SEM images of crossed arrays of InP NWs obtained in a two-step assembly process with orthogonal flow directions for the sequential steps. Flow directions are highlighted by arrows in the images.
  • FIG. 33C shows an equilateral triangle of GaP NWs obtained in three-step assembly process, with 60° angles between flow directions, which are indicated by numbered arrows. The scale bars correspond to 500 nm in the three images.
  • FIG. 33D shows an SEM image of a typical 2 ⁇ 2 cross array made by sequential assembly of n-type InP NWs using orthogonal flows.
  • Ni/In/Au contact electrodes which were deposited by thermal evaporation, were patterned by E-beam lithography.
  • the NWs were briefly (3-5 s) etched in 6% HF solution to remove the amorphous oxide outer layer prior to electrode deposition.
  • the scale bar corresponds to 2 ⁇ m.
  • FIG. 33E shows representative I-V curves from two-terminal measurements on a 2 ⁇ 2 crossed array.
  • the curves 210 represent the I-V of four individual NWs (ad, bg, cf, eh), and the curves 200 represent I-V across the four n-n crossed junctions (ab, cd, ef, gh).
  • Nanowires (or any other elongated structures) can be aligned by inducing a flow of nanowire solution on surface, wherein the flow can be a channel flow or flow by any other ways.
  • Nanowire arrays with controlled position and periodicity can be produced by patterning the surface of the substrate and/or conditioning surface of the nanowires with different functionalities.
  • the position and periodicity control is achieved by designing specific complementary forces (chemical or biological or electrostatic or magnetic or optical) between the patterned surface and wires, such as A wire goes to A' patterned area, B wire goes to B' patterned area, C wire goes to C+ patterned area, etc.
  • specific complementary forces chemical or biological or electrostatic or magnetic or optical
  • the surface of the substrate and/or nanowires can be conditioned with different molecules/materials, or different charges, different magnetos or different light intensities (eg. by interference/diffraction patterns from light beams.) or a combination of these.
  • As-assembled nanowire arrays could also be transferred to another substrate. (e.g. by stamping)
  • Nanowires can be assembled by complementary interaction. Flow is used for assembly of nanowires in the above methods, although it is not limited to flow only. Complementary chemical, biological, electrostatic, magnetic or optical interactions alone can also be exploited for nanowire assembly (although with less control).
  • Nanowires can be assembled using physical patterns. Deposit nanowire solution onto substrate with physical patterns, such as surface steps, trenches, etc.
  • Nanowires can be aligned along the corner of the surface steps or along the trenches.
  • Physical patterns can be formed by the natural crystal lattice steps or self-assembled diblock copolymer stripes, or imprinted patterns or any other patterns.
  • Nanowires may be assembled by electrostatic or magnetic force between nanowires. By introducing charge onto nanowire surface, electrostatic forces between nanowires can align them into certain patterns, such as parallel arrays.
  • Nanowires can be assembled using a LB film. Nanowires were first surface conditioned and dispersed to the surface of a liquid phase to form a Langmuir-Blodgett (LB) film. Nanowires can then be aligned into different patterns (such as parallel arrays) by compressing the surface. Then the nanowire patterns can be transferred onto desired substrate.
  • LB Langmuir-Blodgett
  • Nanowires can be assembled by shear stretching by dispersing nanowires in a flexible matrix (which could be polymers), followed by stretching the matrix in one direction, nanowires can be aligned in the stretching direction by the shear force induced. The matrix can then be removed and the aligned nanowire arrays can be transferred to desired substrate.
  • a flexible matrix which could be polymers
  • the stretching of the matrix can be induced by mechanical, electrical optical, magnetic force. And the stretching direction could be either in the plane of the substrate or not.
  • the means are not intended to be limited to the means disclosed herein for performing the recited function, but are intended to cover in scope any equivalent means, known now or later developed, for performing the recited function.

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AU2002324426A AU2002324426B2 (en) 2000-08-22 2002-05-20 Nanoscale wires and related devices
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US10/196,337 US7301199B2 (en) 2000-08-22 2002-07-16 Nanoscale wires and related devices
US11/082,372 US7211464B2 (en) 2000-08-22 2005-03-17 Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors and fabricating such devices
US11/172,408 US20060175601A1 (en) 2000-08-22 2005-06-30 Nanoscale wires and related devices
US11/386,080 US20070281156A1 (en) 2000-08-22 2006-03-21 Nanoscale wires and related devices
US11/543,337 US8153470B2 (en) 2000-08-22 2006-10-04 Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors, and fabricating such devices
US11/543,746 US20070032052A1 (en) 2000-08-22 2006-10-04 Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors, and fabricating such devices
US11/543,352 US7666708B2 (en) 2000-08-22 2006-10-04 Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors, and fabricating such devices
US11/543,326 US7595260B2 (en) 2000-08-22 2006-10-04 Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors, and fabricating such devices
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US11/543,336 US7476596B2 (en) 2000-08-22 2006-10-04 Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors, and fabricating such devices
US11/824,618 US20070252136A1 (en) 2000-08-22 2007-07-02 Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors and fabricating such devices
US12/072,844 US20090057650A1 (en) 2000-08-22 2008-02-27 Nanoscale wires and related devices
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US12/459,177 US20100155698A1 (en) 2000-08-22 2009-06-26 Nanoscale wires and related devices
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US7915151B2 (en) 2011-03-29
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US7476596B2 (en) 2009-01-13
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EP1314189A2 (fr) 2003-05-28
EP2360298A2 (fr) 2011-08-24
US20050164432A1 (en) 2005-07-28
JP2004507104A (ja) 2004-03-04
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US20070032052A1 (en) 2007-02-08
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