Gas-phase synthesis of epitaxial semiconductor wires from seed crystals
10036101 ยท 2018-07-31
Assignee
Inventors
- Lars Samuelson (Malmo, SE)
- Martin Magnusson (Malmo, SE)
- Knut Deppert (Lund, SE)
- Magnus Heurlin (Furulund, SE)
Cpc classification
C30B29/40
CHEMISTRY; METALLURGY
B82Y30/00
PERFORMING OPERATIONS; TRANSPORTING
C30B25/00
CHEMISTRY; METALLURGY
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
C30B25/00
CHEMISTRY; METALLURGY
B82Y30/00
PERFORMING OPERATIONS; TRANSPORTING
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
C30B29/40
CHEMISTRY; METALLURGY
Abstract
The present invention provides a method and a system for forming wires (1) that enables a large scale process combined with a high structural complexity and material quality comparable to wires formed using substrate-based synthesis. The wires (1) are grown from catalytic seed particles (2) suspended in a gas within a reactor. Due to a modular approach wires (1) of different configuration can be formed in a continuous process. In-situ analysis to monitor and/or to sort particles and/or wires formed enables efficient process control.
Claims
1. A method for forming nanowires comprising: providing metal catalytic seed particles suspended in a gas, providing Group III and Group V gaseous precursors, that comprise constituents of the nanowires to be formed, dissolving the Group III material into the metal catalytic seed particles which comprise molten catalytic seed particles; making at least one seed crystal at the surface of the at least one catalytic seed particle, and growing epitaxially at least one nanowire crystal from the at least one formed seed crystal in a gas-phase synthesis including the gaseous precursors while the catalytic seed particles are suspended in the gas and the constituents of the nanowires to be formed are supersaturated in the at least one catalyst seed particle, wherein the at least one nanowire crystal is a III-V semiconductor crystal selected from gallium arsenide, gallium arsenide antimonide, gallium arsenide phosphide, indium gallium arsenide, aluminum gallium arsenide, gallium phosphide, indium gallium phosphide and indium phosphide.
2. The method of claim 1, wherein the nanowires are formed in a continuous process.
3. The method of claim 1, wherein the nanowires formed are carried by the gas.
4. The method of claim 1, wherein the growth conditions during growth of each nanowire are varied by controlling one or more of parameters associated with: precursor composition, precursor molar flow, carrier gas flow, temperature, pressure or dopants, such that a nanowire segment is axially grown on a previously formed nanowire portion in a longitudinal direction thereof, or a shell is radially grown on the previously formed nanowire portion in a radial direction thereof, or material is added as a combination of axial and radial growth.
5. The method of claim 4, wherein the growth conditions are varied to obtain heterostructures with respect to composition, doping, conductivity type within each nanowire.
6. The method of claim 4, wherein the growth conditions are varied over time by controlling one or more of parameters associated with: precursor composition, precursor molar flow, carrier gas flow, temperature, pressure or dopants, or the size distribution of the catalytic seed particles is varied, such that nanowires with different properties are formed.
7. The method of claim 1, wherein the catalytic seed particles are provided as an aerosol that is mixed with the gaseous precursors.
8. The method of claim 1, wherein the catalytic seed particles are provided by formation from gaseous reactants that comprises at least one of the constituents of the catalytic particles.
9. The method claim 1, wherein the gas containing the catalytic seed particles flows sequentially through one or more reaction zones, each reaction zone contributes to the nanowire growth by adding material to the nanowire, and the nanowires grown after passage through each reaction zone are carried by the gas.
10. The method of claim 1, wherein the catalytic seed particles are charged.
11. The method of claim 1, further comprising in-situ analysis of the nanowires formed.
12. The method of claim 11, further comprising controlling the nanowire growth by feedback from in-situ analysis parameters without interrupting the nanowire forming process.
13. The method of claim 11, wherein the in-situ analysis comprises illumination of the nanowires formed and detection of luminescence from the nanowires to determine optical properties of the nanowires.
14. The method of claim 1, further comprising depositing and aligning the nanowires from the gas phase on a substrate.
15. The method of claim 1, wherein the nanowires comprise a first portion and a second portion, wherein the first portion has a first composition or a first conductivity type and the second portion has a second composition or a second conductivity type, wherein the first composition or the first conductivity type is different from the second composition or the second conductivity type.
16. The method of claim 1, wherein: the metal catalytic seed particles comprise gold catalytic seed particles; and dissolving the Group III material into the metal catalytic seed comprises dissolving gallium into gold catalytic seed particles to form Au-Ga seed particles.
17. The method of claim 16, wherein a gaseous precursor is mixed with the gold catalytic seed particles prior to initiation of nanowire growth.
18. The method of claim 1, wherein the nanowires comprise a pn or pin junction in which a p or n doped nanowire segment is grown axially on another one of the p or n doped segment.
19. The method of claim 1, wherein a ratio of the Group V precursor to the Group III precursor is between 0.2 and 5.
20. The method of claim 1, wherein growing epitaxially at least one nanowire crystal occurs at a reactor pressure of between 50 and 1100 mbar.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Preferred embodiments of the invention will now be described with reference to the accompanying drawings, wherein
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DETAILED DESCRIPTION OF EMBODIMENTS
(12) For the purpose of this application the term wire refers to an elongated object. As mentioned above, these wires may be of essentially nanometer dimensions in their width or diameter, commonly referred to as nanowires, nanowhiskers, nanorods, etc., however not limited to this.
(13) Referring to
(14) The growth, or at least part thereof, is performed at an elevated temperature, typically in a furnace or some other kind of reactor, and starts with an initiation of the growth by catalytic decomposition of the gaseous precursors 3, 4 on the surface of the catalytic seed particles 2 and nucleation. After nucleation the wire 1 grows directionally and forms an elongated object, i.e. a wire. Preferably the gas flows through the reactor and thereby carries at least the catalytic seed particles and thus the wires formed on the catalytic seed particles through the reactor.
(15) The method is described herein in terms of semiconductor materials, in particular III/V-materials, however not limited to this. By way of example,
(16) A basic system for forming wires in accordance with the present invention is schematically illustrated in
(17) In one embodiment of the method of the invention the wire growth is performed in one or more reactors arranged in sequence and/or in parallel, where a continuous flow of catalytic seed particles is supplied as an aerosol, which is mixed with gaseous precursors 3, 4, and then the gas mixture enters a first reactor of said one or more reactors where the wire growth is initiated. The catalytic seed particles 2 can also be formed by gaseous reactants inside said first reactor, thereby enabling a self-catalyzed wire growth. When performing the wire growth in a plurality of reactors, each reactor increases the complexity of the wires, e.g., to make pn-junctions or heterostructures in the axial or radial direction.
(18) The reactors, the means for providing catalytic seed particles, means for in-situ analysis, etc. of said system do not have to be separate chambers or arrangements. Preferably the system is a modular system combined in an in-line production apparatus. In particular, each reactor may comprise one or more reaction zones arranged in sequence and/or in parallel as described for the reactors above. Hence since a reaction zone has the same function as a reactor, these terms are interchangeably used hereinafter.
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(21) Although exemplified with GaAs, it should be appreciated that other III/V semiconductor materials as well as semiconductor materials comprising group II and group VI materials can be processed in the same way. For example the gaseous precursors of the above examples can be exchanged for TMIn and PH.sub.3 to form InP wires. As appreciated to a person skilled in the art the reactor configuration does not have to be changed to form wires from different gaseous precursors, the gaseous precursors are simply switched. Moreover, the processes such as those exemplified by
(22) The catalytic seed particles may consist of a single element, or a combination of two or more elements, to assist in the wire growth or dope the wire. Gaseous precursors may also be used to dope the wire.
(23) In case of pre-forming the catalytic seed particles said means for providing catalytic seed particles 9 may comprise a particle generator. The particle generator produces an aerosol of more or less size-selected particles by a range of prior art methods. Particle generation can be done by evaporation/condensation, spray or vapor pyrolysis, spark discharge, laser ablation, electrospraying of colloidal particles, etc. Size selection can be done by gas mobility classification, e.g. by using a DMA, virtual impaction, or simply well-controlled particle formation. For many applications, it is desirable that the aerosol particles be electrically charged, which can be accomplished by radioactive sources, corona discharge, thermal or optical emission of electrons, etc. A typical system for particle generation is described in Magnusson et al., Gold nanoparticles: production, reshaping, and thermal charging, J Nanoparticle Res 1, 243-251 (1999).
(24) As mentioned above, the system may comprise one or more reactors or reaction zones, where each reactor or reaction zone adds a new functional layer to the wires. Such a modular system is shown in
(25) For some growth conditions, additional modules may be added to the reactor or the reaction zone. For example a plasma generator may be added to modify the chemical reactions to enable higher reaction rates. This is important especially if the wire or layer formed on the wire is grown at low temperature by a stable precursor which usually requires a high temperature to decompose. A typical example where this may be useful is for growth of nitrides from ammonia.
(26) Before or between the reactors or reaction zones, further components may be placed, for example means for charging particles or wires. A tube-shaped absorption filter can be used to remove precursor molecules and small particles from the gas flow, by taking advantage of a comparatively low diffusion coefficient of the wires. Precursors and reactants can thereby be replaced, not only added, between the growth reactors. Size classification tools, such as DMA or virtual impactor, can also be used to refine the gas flow, i.e. the aerosol, or as in-situ analysis as explained below.
(27) Referring to
(28) By using a plurality means for in-situ analysis, such as the two in-situ DMAs of
(29) As mentioned above, said method and system of the invention can be used to form complex wire structures. By way of example,
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(31) The flexibility of the system allows for several in-situ analysis tools 12, to measure and monitor properties which are not obtainable using other wire growth techniques. This allows instant feedback to regulate the system, making it possible to continuously fine-tune material parameters in a way that is not possible in other methods.
(32) By way of example, wire size measurement and sorting is achievable by using a DMA. The DMA, or any other means for in-situ analysis, can be coupled either in series or in parallel, depending on if the measurement is to be invasive or non-invasive on the gas flow. Coupled in series a DMA can sort the wires in the aerosol by their size. The size and size distribution which is sorted depends on the properties and settings of the DMA. Coupled in parallel, a small aerosol flow can be extracted to the DMA for an almost non-invasive measurement. In this case the DMA can scan within its size detection range to give the size distribution of the aerosol. This can be done while only wasting a small part of the gas flow thus maintaining a high production rate of wires.
(33) By illuminating the gas flow, the optical properties of the wires can be studied in a non-invasive manner. The light source should preferably be a laser where the energy of the light is higher than the band gap of one or more materials that the wires consist of. By using a photodetector, the luminescence from the wires can be studied. This enables monitoring of the optical properties of the wires, which can be used to tune growth parameters to obtain the desired properties of the wires. This is in contrast to other growth methods in that the wires may be cooled down rapidly after each successive growth reactor or reaction zone and the temperature sensitive photoluminescence technique can be used between each step in the wire growth.
(34) Further possible in-situ optical methods include absorption spectroscopy, where the absorption path would ideally be along the wire flow; Raman spectroscopy (especially Coherent anti-Stokes Raman Spectroscopy, CARS), which can also be used inside reaction furnaces to study decomposition of molecules and temperature gradients; and X-ray powder diffraction on-the-fly.
(35) Depending on the type of wires being produced, different collection methods are possible. For charged wires, they are easily collected on any substrate by means of an electric field. The aerosol may be bubbled through a liquid to remove the wires from the gas flow, with or without surfactant molecules to keep the wires from agglomerating. Wires that are easily re-dispersed may be collected in a filter as a dry powder.
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(38) As a further example of wires formed by the method and the system of the invention
(39) The formation of GaAs nanowires typically takes place in the temperature regime between 380 C. and 700 C. depending on the desired shape and properties of the formed nanowires. A higher temperature typically results in a higher growth rate, i.e., longer nanowires for a set growth time, but also in a conical shape, along with effects on crystal structure and impurity incorporation. Besides temperature, the ratio of group V material precursor to group III material precursor, i.e., the V/III ratio, is important. If the V/III ratio is too low, typically below 0.2, the nanowire growth proceeds in a group III rich environment which can reduce the growth rate and material quality. If the V/III ratio is too high, typically above 5, the nanowires are difficult to nucleate since group III material can't be dissolved in the Au particles. Formation of GaAs nanowires typically takes place with a total pressure inside the reactor between 50 and 1100 mbar. A lower pressure reduces the supersaturation in the gas phase which can reduce parasitic gas phase reactions. A higher pressure increases the supersaturation in the gas phase which can increase the supersaturation in the Au particle and increase the growth rate. The pressure can also be used to control the residence time in the growth reactor.
(40) It should be noted that parameters such as temperature, precursor flow, V/III ratio and pressure are dependent on the precursor molecules that are used since only the material that actually reaches the growth interface is incorporated. If a precursor can withstand higher temperatures without reacting, the nanowire-forming reaction most likely takes place at a higher temperature.
(41) The above discussion on growth parameters is valid mainly for single stage growth, where nucleation and wire growth take place in a single reaction zone. For multiple stage growth, the first nucleation stage should typically be done at a higher temperature, lower precursor flow and lower V/III ratio, compared to the subsequent growth steps.
(42) Compared with MOVPE nanowire formation in the described process typically takes place at a lower V/III ratio but at similar temperatures. Since parameters such as temperature, pressure, flows and V/III ratio are dependent on the exact chemistry used to form the nanowires it is understood that different materials may be formed at different parameters. For example III-nitrides may be formed at higher temperatures due to the higher stability of the NH.sub.3 precursor, while InAs growth is done at lower temperatures.
(43) Suitable materials for formation of the wires of the method and the system in accordance with the invention include, but are not limited to: InAs, InP, GaAs, GaP and alloys thereof (In.sub.xGa.sub.1-xAs.sub.yP.sub.1-y) InSb, GaSb and alloys thereof (In.sub.xGa.sub.1-xSb) AlP, AlAs, AlSb and alloys thereof for example AlP.sub.1-xAs.sub.x InGaAsP alloyed with Al, for example Al.sub.xGa.sub.1-xAs InGaAsP alloyed with Sb, for example GaAs.sub.ySb.sub.1-y InN, GaN, AlN and alloys thereof (In.sub.xGa.sub.1-xN) Si, Ge and alloys thereof, i.e. (Si.sub.xGe.sub.1-x) CdSe, CdS, CdTe, ZnO, ZnS, ZnSe, ZnTe, MgSe, MgTe and alloys thereof SiO.sub.x, C (Diamond), C (Carbon nanotube) SiC, BN
(44) Suitable materials for the catalytic seed particle include, but are not limited to: Au, Cu, Ag In, Ga, Al Fe, Ni, Pd, Pt Sn, Si, Ge, Zn, Cd Alloys of the above, e.g., AuIn, AuGa, AuSi
(45) Suitable gases for carrying the catalytic seed particles and the wires in the process include, but are not limited to: H.sub.2, N.sub.2 or a mixture thereof; or He, Ar.
(46) Suitable dopants include, but are mot limited to, for InGaAlAsPSb system: n-dopants: S, Se, Si, C, Sn; p-dopants: Zn, Si, C, Be AlInGaN system: n-dopants: Si; p-dopants: Mg Si: n-dopants: P, As, Sb; p-dopants: B, Al, Ga, In CdZnOSSeTe system: p-dopants: Li, Na, K, N, P, As; n-dopants: Al, Ga, In, Cl, I
(47) According to common nomenclature regarding chemical formula, a compound consisting of an element A and an element B is commonly denoted AB, which should be interpreted as A.sub.xB.sub.1-x
(48) It should be appreciated that the wire growth may comprise one or more etch steps, where material is removed rather than grown on the wires. Etching can also be used to decouple radial and axial growth, which for example enables lowering of the tapering of the wires or simple shape control of the wires.
(49) The size of the wires depends on many factors such as the materials forming the wires, the intended application for the wires and the requirement on quality of the wires formed. Preferably the wires have diameter of less than 10 m, and more preferably, in particular for formation of wires comprising lattice mismatched layers or segments, the wire diameter is less than 300 nm.
(50) Since the wires of the invention may have various cross-sectional shapes the diameter, which interchangeably is referred to as width, is intended to refer to the effective diameter.
(51) While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, on the contrary, it is intended to cover various modifications and equivalent arrangements within the appended claims.