CN101443887B - Pulsed growth of GAN nanowires and applications in group III nitride semiconductor substrate materials and devices - Google Patents

Pulsed growth of GAN nanowires and applications in group III nitride semiconductor substrate materials and devices Download PDF

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CN101443887B
CN101443887B CN2007800169465A CN200780016946A CN101443887B CN 101443887 B CN101443887 B CN 101443887B CN 2007800169465 A CN2007800169465 A CN 2007800169465A CN 200780016946 A CN200780016946 A CN 200780016946A CN 101443887 B CN101443887 B CN 101443887B
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nano
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gan
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CN101443887A (en
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S·M·赫尔西
X·王
X·孙
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University of New Mexico rainforest innovation company
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STC UNM
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Abstract

Exemplary embodiments provide semiconductor devices including high-quality (i.e., defect free) group III-N nanowires and uniform group III-N nanowire arrays as well as their scalable processes for manufacturing, where the position, orientation, cross-sectional features, length and the crystallinity of each nanowire can be precisely controlled. A pulsed growth mode can be used to fabricate the disclosed group III-N nanowires and/or nanowire arrays providing a uniform length of about 10 nm to about 1000 microns with constant cross-sectional features including an exemplary diameter of about 10-1000 nm. In addition, high-quality GaN substrate structures can be formed by coalescing the plurality of GaN nanowires and/or nanowire arrays to facilitate the fabrication of visible LEDs and lasers. Furthermore, core-shell nanowire/MQW active structures can be formed by a core-shell growth on the nonpolar sidewalls of each nanowire.

Description

The pulsed growth of GAN nano wire and application and device in the III of family nitride semiconductor substrate materials
Government rights
Contract number HR0011-05-1-0006 that the present invention utilizes government to be supported in to be authorized by Defense Advanced Research Project Agency/Army Research Institute and the contract number F49620-03-1-0013 that is authorized by Science Institute of air force and the contract number FA9550-06-1-0001 realization of getting off.Government can have specific right in the present invention.
Related application
The application requires in the U.S. Provisional Patent Application sequence number 60/780 of submission on March 10th, 2006,833, the sequence number of submitting on May 8th, 2,006 60/798,337, the sequence number of submitting on May 25th, 2,006 60/808, the sequence number 60/889 that on February 12nd, 153 and 2007 submitted to, 363 priority, it all is merged in by reference at this.
Technical field
The present invention relates generally to semi-conducting material, device, with and manufacture method, relate in particular to semiconductor nanowires and semiconductor nanowires active device.
Background technology
The nano wire (nanowire) that is made of the III-N of family alloy (for example GaN) provides possibility for new semiconductor device configuration, for example nanoscale opto-electronic device.For example, the GaN nano wire can provide big band gap, high-melting-point and chemical stability, and this is useful for the device that operates in corrosivity or the hot environment.GaN than large band gap with and relevant alloy also allow to be manufactured on light source in the visual range, this uses for display and illumination is useful.In addition, the unique geometry of each nano wire provides possibility for explore new device example in photonic propulsion and transmitting device.In order to realize this possibility fully, need scaleable (scalable) process make the high-quality III-N of family nano wire and/or nano-wire array, wherein accurately and as one man control geometry, position and the degree of crystallinity of each nano wire.
Conventional nano wire manufacturing institute based on be that vapour-liquid is consolidated (VLS (vapor-liquid-solid)) growth mechanism, and relate to use such as the catalyst of Au, Ni, Fe or In.Yet, because these conventional Catalytic processes can not be controlled the position and the consistency of formed nano wire, so produced problem.Utilizing another problem of conventional Catalytic processes is that catalyst is mixed in the nano wire inevitably.This has reduced the crystalline quality of formed nanostructure, and this application to them has caused restriction.
Therefore, need overcome these problems of prior art and other problem, and need provide high-quality nano wire and/or nano-wire array with and scaleable manufacture method.Also expect to provide nano wire opto-electronic device and manufacturing thereof in addition based on high-quality nano wire and/or nano-wire array.
Summary of the invention
According to different embodiment, this instruction comprises the method that is used to make nano wire.In the method, can on substrate, form the selective growth mask.Described selective growth mask can include the hole of a plurality of patternings, and the hole of described patterning exposes a plurality of parts of substrate.Semi-conducting material can utilize on each of a plurality of parts of selectivity non-pulse formula growth pattern in the hole that is exposed to each patterning of this substrate then grows.This growth pattern can be converted to the pulsed growth pattern from non-pulse formula growth pattern.By continuing the pulsed growth of semi-conducting material, can form a plurality of semiconductor nanowires.
According to different embodiment, this instruction also comprises the III-N of family nano-wire array, and it can include the selective growth mask that is arranged on the substrate.Described selective growth mask can include the hole of a plurality of patternings, and it exposes a plurality of parts of this substrate.The III-N of family nano wire can be connected to a plurality of parts that this substrate exposes and from its extension and extend across the top of described selective growth mask.The III-N of this family nano wire can come directed along single direction, and can keep the section feature of one of selected a plurality of surf zones.
According to different embodiment, this instruction also comprises the GaN substrat structure.This GaN substrat structure can be in conjunction with the GaN film that forms by a plurality of flawless GaN nano wires.This GaN film can have about 10 7Cm -2Or lower defect concentration.
Other purpose and advantage of the present invention will be partly set forth and partly will be become apparent by this specification in hereinafter the explanation, perhaps can obtain understanding by practice of the present invention.Objects and advantages of the present invention will by the key element especially in the accompanying Claim book, set forth with and combination be implemented and obtained.
It should be understood that as requested above-mentioned summary and following detailed description all only are exemplary with indicative, and are not limitations of the present invention.
Description of drawings
A part and the combined accompanying drawing of forming this specification show several embodiments of the present invention, and are used to explain principle of the present invention together with the description.
Figure 1A-1C shows according to the typical semiconductor nano-wire devices of this instruction sectional view when different fabrication stage.
Fig. 2 shows the second typical semiconductor nano wire according to this instruction.
Fig. 3 shows according to this instruction and is used to utilize two growth period patterns to form the canonical process of a plurality of nano wires and/or nano-array.
Fig. 4 A-4C shows the 3rd typical semiconductor nano-wire devices according to this instruction.
Fig. 5 shows the 4th typical semiconductor nano-wire devices according to this instruction.
Fig. 6 A-6D shows according to the typical consequence that originally is taught in a plurality of orderly GaN nano-wire array of growing by two growth period patterns under the situation of not using catalyst.
Fig. 7 A-7D shows four kinds of exemplary variation according to the semiconductor device of this instruction, and described semiconductor device comprises the GaN substrat structure that forms by at a plurality of nano wires shown in Fig. 1-6 and/or nano-wire array.
Fig. 8 shows typical core-shell nano line/MQW (multiplequantum well (Multiple Quantum Well)) the active structure device according to this instruction.
Fig. 9 shows another the typical core-shell nano line/MQW active structure device according to this instruction.
Figure 10 A-10C shows according to this instruction and uses the typical nanowires LED device that forms at the core-shell nano line/MQW active structure shown in Fig. 8-9.
Figure 11 shows according to the typical nanowires laser device of this instruction use at the core-shell nano line/MQW active structure shown in Fig. 8-9.
Figure 12 shows according to this instruction use another typical nanowires laser device at the core-shell nano line/MQW active structure shown in Fig. 8-9.
Embodiment
Now will be in detail with reference to exemplary embodiments of the present invention, example wherein of the present invention is shown in the drawings.Under possible situation, all will use identical Reference numeral to represent identical or similar part in the accompanying drawing.In the following description book, with reference to the accompanying drawing of a part that forms specification, and the mode by example shows and can put into practice specific exemplary embodiments of the present invention in the accompanying drawings.These embodiment are enough at length set forth, put into practice the present invention to allow those skilled in the art, and it should be understood that the embodiment that can use other, and can under the situation that does not break away from category of the present invention, change.Thereby explanation hereinafter only is exemplary.
Though the present invention illustrates about one or more execution modes, can be under the situation of spirit that does not break away from appended claims and category to shown in example change and/or change.In addition, though can about in the several embodiments only one special characteristic of the present invention is disclosed, but this feature can be combined with other one or more features of other enforcements, and wherein said other embodiment can be desired and be favourable for any given or specific function.And, just in the specification of this detailed description and claims, use term " to comprise " (" including ", " includes "), " having " (" having ", " has "), " having " or its variation, these terms meaning is " to comprise " similarly with term that mode comprises.It is one or more that term " one of at least " is used for representing selecting being listd.
Though digital scope and parameter that big category of the present invention is set forth all are approximations, the digital value of being set forth in specific examples is as far as possible accurately reported.Yet any digital value must include certain error inherently, and it comes from the standard deviation that is occurred in they corresponding thermometricallies.And, any and all subranges that all are understood to include wherein to be comprised in these disclosed all scopes.For example, the scope of " less than 10 " can be included in any and all subranges between (comprising) minimum value of zero and the maximum 10, also promptly, have and be equal to or greater than zero minimum value and be equal to or less than peaked any and all subranges of 10, for example 1 to 5.
Exemplary embodiments provides semiconductor device, its include the III-N of the family nano wire of high-quality (also being zero defect) and the consistent III-N of family nano-array, with and scaleable manufacturing process, wherein the position of each nano wire, direction, section feature, length and/or degree of crystallinity can be accurately controlled.Especially, can use the selective growth pattern to form a plurality of nano wires and/or nano-wire array, wherein be the growth pattern conversion from the selective growth pattern to the pulsed growth pattern after described selective growth pattern.Section feature, for example sectional dimension (for example diameter or width) and the cross sectional shape of each nano wire that is obtained by the selective growth pattern can come continued growth to be held by using the pulsed growth pattern.Like this, just can form nano wire with high-aspect-ratio (aspect ratio).In exemplary embodiments, the length of each nano wire for example can be that for example about 10nm was to about 100 microns between about 10nm arrived about 1000 microns.
In addition, can form the III-N of high-quality family film, for example high-quality GaN film by termination with in conjunction with a plurality of nano wires and/or nano-wire array.These GaN films can be used as the GaN substrat structure, so that make the device based on GaN, for example are used to manifest the visual LED and the laser of solid-state illumination and the industry of UV transducer.
In addition, because the nano wire and/or the nano-array of each pulsed growth can provide nonpolar sidewall, so when setting up the active shell structure of MQW on the next sidewall of use nucleocapsid growth, be favourable at each nano wire.This core-shell nano/MQW active structure can be used in the nano level efficiency light electronic device, for example nanowire LED and/or nano wire laser.
As used in this, term " nano wire (nanowire) " is commonly referred to as the conductor or the semi-conducting material of any elongation that includes at least one reduced size of being less than or equal to about 1000nm (for example one of sectional dimension, such as width or diameter).In different embodiment, reduced size (minor dimension) can be less than about 100nm.In other different embodiment, described reduced size can be less than about 10nm.Described nano wire can have about 100 or bigger length-width ratio (for example long: wide and/or large-size: reduced size).In different embodiment, this length-width ratio can be about 200 or bigger.In other different embodiment, this length-width ratio can be about 2000 or bigger.In exemplary embodiments, the nano wire cross section can be highly asymmetric, makes can be significantly smaller than 1000nm on a direction of sectional dimension, and this size can be far longer than 1000nm in vertical direction.
Equally, term " nano wire " also comprises the structure of the elongation of other similar sizes, comprising but be not limited to nanoshafts, nano-pillar, nanoneedle, nano rod and nanotube (for example single-walled nanotube or many walls nanotube) and their fibers form that work by different way and that derive, for example nanofiber of forms such as line, silk, fiber.
Nano wire can have different cross sectional shapes, for example rectangle, polygon, square, ellipse or circle.Therefore, nano wire can have three-dimensional (3D) shape of cylinder and/or taper.In different embodiment, a plurality of nano wires for example can be parallel to each other substantially, arc, sinusoid etc.
Nano wire can/from support forming, wherein this support can comprise selected surf zone, wherein nano wire can be connected to this zone and from its extension (for example growth).The support of nano wire can also comprise the substrate that is made of multiple material, and described material comprises Si, SiC, sapphire, such as III-V semiconducting compound, metal, pottery or the glass of GaN or GaAs.The support of nano wire can also be included in the selective growth mask that forms on the substrate.In different embodiment, the support of nano wire can also comprise the resilient coating that is arranged between selective growth mask and the substrate.
In different embodiment, nano wire active device (nanowire active device), for example nanowire LED or nano wire laser can use nano wire and/or nano-wire array to form.In different embodiment, nano wire and/or nano-wire array and nano wire active device can use III-V compound semiconductor materials system to form, for example the III-N of family compound-material system.The example of the III of family element can comprise Ga, In or Al, and it can be formed by the typical III forerunner of family (precursor), for example trimethyl gallium (TMGa) or triethyl-gallium (TEGa), trimethyl indium (TMIn) or trimethyl aluminium (TMAI).Typical N forerunner for example can be ammonia (NH 3).Other family's V elements also can be used, for example P or As, and the wherein typical V forerunner of family is for example tert-butyl group phosphorus (TBP) or arsine (AsH 3).
Hereinafter, the III-N of family semiconducting alloy composition can be described by the combination of the III-N of family element, for example GaN, AlN, InN, InGaN, AlGaN or AlInGaN.Usually, the element in the composition can make up with different molal fractions (molar fraction).For example, semiconducting alloy composition InGaN can represent In xGa 1-xN, wherein molal fraction x can be any number less than 1.00.In addition, according to the molal fraction value, can assign to make different active devices by similar one-tenth.For example, In 0.3Ga 0.7N (wherein x is about 0.3) can be used in the MQW active region of LED and be used to launch blue light, and In 0.43Ga 0.57N (wherein x is about 0.43) can be used in the MQW active region of LED and be used for transmitting green light.
In different embodiment, nano wire, nano-array and/or nano wire active device can comprise the alloy of family, comprising: from the p type alloy of subgroup II (for example Mg, Zn, Cd and Hg); P type alloy from subgroup IV (for example C); Perhaps selected n type alloy from the family that comprises Si, Ge, Sn, S, Se and Te.
In different embodiment, nano wire and/or nano-wire array and nano wire active device can have high-quality heterostructure, and form by different crystal techniques, described crystal technique is including, but not limited to metal organic chemical vapor deposition (MOCVD (metal-organic chemical vapor deposition)) (being also known as organic metal vapour phase epitaxy (OMVPE (organometallic vapor phase epitaxy))), molecular beam epitaxy (MBE), source of the gas MBE (GSMBE), the organic MBE of metal (MOMBE), atomic layer epitaxy (ALE), or hydride gas-phase epitaxy (HVPE).
In different embodiment, can use the multistage growth pattern, for example two growth period patterns are used for the high quality crystal growth of nano wire and/or nano-wire array and nanometer active device.For example, can use phase I growth pattern (for example selective growth pattern) to come to form the condition that provides as the nucleus of growth selectivity and nano wire and/or nano-array.In the selective growth pattern, can use the MOCVD of standard crystal growing method, for example standard come with for example about 10nm or bigger expectation thickness make the growth of nano wire hold and.
The second stage growth pattern can be set up process, continuing the growth of each nano wire, and keeps its section feature from first growth pattern, and the length of any desired is provided.This second stage growth pattern can be employed by the growth pattern conversion, and wherein said growth pattern conversion can finish the phase I growth pattern.In this second stage growth pattern, can use pulsed growth pattern, for example pulsed MOCVD growth.
" pulsed growth pattern (pulsed growth mode) " refers to following process at this employed term, and the III of family and family's V precursor gas alternately are incorporated in the crystal growth reactor in designed sequence in this process.For example, TMGa and NH 3Can be with acting on the forerunner who typically forms GaN nano wire and/or nano-wire array and/or GaN nano wire active device.In the pulsed growth pattern, TMGa and NH 3Can alternately be introduced in order, promptly introduce TMGa in stage (for example about 20 seconds) sometime with designed flow velocity (for example about 10sccm), afterwards with designed flow velocity (for example about 1500sccm) at stage time (for example about 30 seconds) introducing NH 3In different embodiment, can carry out (for example repeating) one or more sequence cycles for the designed length of each nano wire.In different embodiment, the growth rate of each nano wire can be relevant with direction.
In different embodiment, when forming disclosed nano wire, nano-array and/or nano wire active device, can relate to dielectric material.For example, described selective growth mask can be made by dielectric material during forming a plurality of nano wires and/or nano-array.In another example, dielectric material can be used for the electric insulation such as the active device of nanowire LED and/or nano wire laser.As used in this, dielectric material can include but are not limited to: silicon dioxide (SiO 2), silicon nitride (Si 3N 4), silicon oxynitride (SiON), fluorine silica (SiOF), silicon oxide carbide (SiOC), hafnium oxide (HfO 2), hafnium silicate (HfSiO), hafnium silicate nitride (HfSiON (nitride hafnium-silicate)), zirconia (ZrO 2), aluminium oxide (Al 2O 3), barium strontium titanate (BST), lead zirconate titanate (PZT), zirconium silicate (ZrSiO 2), tantalum oxide (TaO 2) or other insulating material.According to other different embodiment, can use the conducting metal growth mask, be used for the selective growth of disclosed nano wire such as tungsten.
In Figure 1A-1C, Fig. 2-3, Fig. 4 A-4C, Fig. 5 and Fig. 6 A-6D, illustrated nano wire and/or nano-wire array semiconductor device exemplary embodiments with and scaleable growth course.
Figure 1A-1C shows according to the sectional view that originally is taught in different fabrication stage typical semiconductor nano-wire devices 100.For what those of ordinary skills should understand easily be, represent the summary-type schematic illustrations at the nano-wire devices shown in Figure 1A-1C 100, and can increase other layer/nano wire, perhaps can remove or change existing layer/nano wire.
As shown in Figure 1A, this nano-wire devices 100 can comprise the hole 138 of substrate 110, selective growth mask 135 and a plurality of patternings.The hole 138 of described selective growth mask 135 and a plurality of patternings can be arranged on this substrate 110, and wherein the hole 138 of a plurality of patternings can intersperse among among the described selective growth mask 135.
This substrate 110 can be any substrate of the III-N of family material of can growing on it.In different embodiment, this substrate 110 can include but are not limited to: sapphire, carborundum, silicon, silicon-on-insulator (SOI (silicon-on-insulator)), such as III-V semiconducting compound, metal, pottery or the glass of GaN or GaAs.
Described selective growth mask 135 can be by forming formed dielectric layer (not shown) patterning (pattern) and etching on this substrate 110.In different embodiment, this dielectric layer can be made by any dielectric material, and uses the known technology of those of ordinary skill in the art to form.This dielectric layer can use one or more interference photoetching technologies (IL (interferometric lithography)) to come patterning then, described interference photoetching technology comprises immersion interference photoetching technology and non-linear interference photoetching technology, nano imprint lithography (NL) and electron beam lithography, and it can produce nanostructure or nanostructured pattern on wide and macroscopical zone.After patterning, etch process, for example reactive ion etching can be used to form the hole 138 of a plurality of patternings.This etch process can be in lower floor, also be that the surface of substrate 110 stops, and expose a plurality of surface portions 139 of this substrate 110.In different embodiment, described selective growth mask 135 can be the conducting metal growth mask of for example being made by tungsten, provides selective growth in order to as desired for the pulsed nanowire growth.
The hole 138 of described a plurality of patternings can have the thickness identical with described selective growth mask 135, for example is about 30nm or littler, and has the sectional dimension of about 10nm to about 1000nm, as diameter.As another example, described diameter can be about 10nm to about 100nm.In typical embodiment, the hole 138 of described a plurality of patternings can have hexagonal array, wherein pitch (pitch) (also i.e. the interval of center to center between the hole of any two adjacent patternsization) from about 50nm to about 10 μ m.In different embodiment, can form the array in the hole 138 of a plurality of patternings.Afterwards, the nanoscale features in the hole 138 of described a plurality of patternings can be passed to the process that subsequently technology is used to form nano wire and/or nano-wire array.
In different embodiment, before the growth subsequently of nano wire and/or nano-wire array, can on the device shown in Figure 1A 100, carry out different decontamination procedures.For example, described decontamination procedure can comprise that device outer (ex-situ) purifies (also promptly purifying outside execution of growth reactor), is that (in-situ) purifies (also promptly carry out and purify) in the device in growth reactor afterwards.According to the material that is used for selective growth mask 135, can use different purification methods.In exemplary embodiments, silicon nitride selective growth mask can purify by the standard external purifying, is afterwards to carry out purifying in the device in about 3 minutes by device 100 being encased in the typical MOCVD reactor and being heated to about 950 ℃ at the following device 100 of hydrogen that flows.This hydrogen reduction atmosphere (hydrogen-reducing-atmosphere) can remove at the device 100 lip-deep native oxides of not expecting (native oxide).According to the combination of materials of this substrate 110 and selective growth mask 135, those of ordinary skill in the art it will be understood that and can use alternative decontamination procedure.
In Figure 1B, a plurality of nanostructure nuclear (nanostructure nuclei) 140 can optionally grow from a plurality of surface portions 139 that exposed of substrate 110, to fill each in described a plurality of patterned holes 138, the hole of wherein said patterning can limit by described selective growth mask 135.Described selective growth mask 135 can be used as the selective growth mould, in order to its nano-pattern from the hole 138 of described a plurality of patternings negatively (negatively) copy to a plurality of nanostructures nuclears 140.Like this, the position of each in the described a plurality of nanostructure nuclear 140 and section feature, just can determine such as shape and size by the position and the section feature of each patterned holes in the hole 138 of described a plurality of patternings.For example, the hole 138 of described a plurality of patternings can comprise that size is about the hexagonal array of 250nm.Described hexagonal array can be passed to then and has with 250nm or smaller szie is similar or the growth of a plurality of nanostructures of smaller szie nuclear 140.In another example, if the one or more holes in the hole of described a plurality of patternings 138 roughly are that for example diameter typically is about the circle of 100nm, the one or more nuclears in so described a plurality of nanostructures nuclears 140 just can be with about 100nm or littler similar growth in thickness in circular port.Therefore, described a plurality of nanostructure nuclears 140 can be positioned at the position of good definition, and are shaped corresponding to the hole 138 by described selective growth mask 135 defined a plurality of patternings.In different embodiment, described a plurality of nanostructure nuclears 140 for example can form by the MOCVD technology of standard.
Like this, can be at the device shown in Figure 1B 100 as the support of nano wire and/or nano-wire array, it can comprise a plurality of selected surf zones (also being each surface of described a plurality of nanostructure nuclears 140).A plurality of nano wires and/or nano-wire array can be grown from described a plurality of selected surf zones then.In different embodiment, described selective growth mask 135 can remove by suitable etch process, to expose a plurality of nanostructure nuclears 140 after forming a plurality of nano wires.
In Fig. 1 C, before outstanding a plurality of nanostructure nuclears 140 from the top of selective growth mask 135, for example, can form a plurality of nano wires 145 by the growth that continues described a plurality of nanostructure nuclears 140 by finishing the selective growth pattern and adopting the pulsed growth pattern.Described a plurality of nano wire 145 can be examined 140 same material by nanostructure and constitute, for example GaN, AlN, InN, InGaN, AlInGaN or AlGaN.In different embodiment, can form heterostructure and form in a plurality of nano wires 145 each.In different embodiment, can join n type and/or p type alloy in described a plurality of nano wire 145 according to desired application.
By before the top of described selective growth mask 135 highlights, being converted to the pulsed growth pattern in the growth of described a plurality of nanostructures nuclear 140, the feature such as cross sectional shape and size of each in described a plurality of nano wire 145 can be held, up to the length that reaches expectation.That is to say that it is constant, same or similar with the section feature in hole 138 that the section feature of nano wire 145, for example shape and/or size can keep basically.In different embodiment, the length of each nano wire can be the micron number magnitude, according to appointment 20 μ m or bigger.
In different embodiment, can in nano-wire devices, form resilient coating.Fig. 2 shows the second typical semiconductor nano-wire devices 200 that comprises resilient coating according to this instruction.As shown in the figure, this nano-wire devices 200 can comprise and is arranged in substrate (for example substrate 110) and the selective growth mask (resilient coating 220 between the selective growth mask 135 (see Figure 1A-1C)) for example.In different embodiment, this resilient coating 220 can be the planar semiconductor film, and it is for example made by the MOCVD of for example standard by GaN, AlN, InN, InGaN, AlInGaN or AlGaN.In different embodiment, the thickness of this resilient coating 220 for example can arrive about 10 μ m for about 100nm.In different embodiment, this resilient coating 220 can be doped with n type or p type alloy, so that provide to the electrical connection of the low side of each nano wire of described a plurality of nano wires 140.Can use known various alloys for those of ordinary skills.
In different embodiment, the orientation of described a plurality of nanostructure nuclears 140 can be controlled along single direction, and this orientation again can be by controlling in the hole 138 of directed described a plurality of patternings along single crystallization direction consciously.For example, the hole 138 of described a plurality of patternings can be come directed along the single direction of resilient coating 220 as shown in FIG. 2 and consciously.In exemplary embodiments, during the IL patterning, the hole in selective growth mask 135 can be consciously along the GaN resilient coating＜1 100〉direction is come directed.In another exemplary embodiments, when this GaN resilient coating is grown, between GaN resilient coating and sapphire structure cell (unit cell), can have 30 ° of rotations on Sapphire Substrate about the c axle.
Fig. 3 shows and is used for using two growth period patterns to form the canonical process of a plurality of nano wires and/or nano-wire array according to this instruction.Fig. 3 especially shows the precursor gas flow curve (comprising first flow curve 302 and second flow curve 306) during selective growth 310 and pulsed growth subsequently 320, and wherein said selective growth 310 and pulsed growth subsequently 320 for example are used to form as at a plurality of nano wires 145 as shown in Fig. 1-2.As shown, described selective growth 310 can be passed through at t change-over time 1The place begins pulsed growth 320 (also being the growth pattern conversion) and finishes.Described pulsed growth 320 can also comprise a plurality of pulsed sequences, for example first sequence cycles 324, second sequence cycles 328 and/or other sequence cycles.In different embodiment, it is second sequence cycles 328 that this first sequence cycles 324 can be repeated.
In the exemplary embodiments that is used to form GaN nano wire and/or nano-wire array, this first flow curve 302 can (TMGa) be drawn for first precursor gas, for example trimethyl gallium, and this second flow curve 306 can be second precursor gas, for example ammonia (NH 3) drawn.During this selective growth 310, typical GaN nano wire and/or nano-wire array can form in the MOCVD reactor, and wherein this reactor comprises constant flow rate and is about the first precursor gas TMGa of 10sccm and the second precursor gas NH that constant flow rate is about 1500sccm 3This means that during this selective growth 310, described precursor gas (also is TMGa and NH 3) can be continuously rather than pulsed ground flow (also be III of family and the V of family precursor gas be provided for substrate together with continuous, non-pulse formula growth pattern).And, the V of family precursor gas (NH for example 3) and the III of family precursor gas (for example TMGa) can side by side be introduced into, and the ratio of the III of V/ family of family is as remaining about 100 to about 500.In exemplary embodiments, the ratio of the III of V/ family of family can remain about 150.In addition, other reactor conditions of selective growth 310 for example can comprise about 1015 ℃ to the reactor pressure of about 1060 ℃ initial reaction temperature, about 100Torr and hydrogen/nitrogen carrier gas mixing with about 4000sccm laminar flow.Can use any suitable MOCVD reactor, Veeco TurboDisk model P75MOCVD reactor for example, wherein between depositional stage substrate by high speed rotating.
During pulsed growth 320, such as first precursor gas of TMGa with such as NH 3Second precursor gas can in designed sequence (for example shown in first sequence cycles 324), alternately be introduced in the growth reactor.In different embodiment, the duration of each alternate steps can influence the growth of nano wire and/or nano-wire array in the pulsed sequence, and this can also be at the particular reactor geometry and be optimised.For example, in the first pulsed sequence cycles 324, TMGa can be introduced at for example about 20 seconds (not shown) of section sometime with the flow velocity of about 10sccm, for example be that (for example mixing of hydrogen/nitrogen) removed in carrier gas in 10 seconds afterwards, do not introduce precursor gas in the meantime, and introduce NH with the flow velocity of about 1500sccm in the time period of all 30 seconds (not shown) according to appointment afterwards 3, for example be that (for example mixing of hydrogen/nitrogen) removed in the carrier gas in 10 seconds under the situation that does not relate to precursor gas afterwards.Can also use other pulse duration according to reactor configurations, for example 15-40 is used for the III of family reactant second, and 15-40 is used for the V of family reactant second, and 5-15 is used for introducing removing gas between the step at each reactant second.In different embodiment, can repeat such as the pulsed sequence of first sequence cycles 324, up to reaching GaN nano wire measured length really.For example, can be repeated be second sequence cycles 328, the 3rd sequence cycles (not shown) or the like to this sequence cycles 324.In each sequence cycles, the V of family precursor gas (NH for example 3) and the III of family precursor gas (for example TMGa) can have effective V/III ratio, its value for example from about 60 to about 300 scope.In different embodiment, the temperature of pulsed growth 320, reactor pressure and carrier gas stream can remain with for the identical setting of selective growth 310.Those of ordinary skill in the art it should be understood that disclosed growth parameter(s) is exemplary, and can change according to employed particular reactor.
In different embodiment, change-over time (t 1) can determine by the duration of selective growth 310.This change-over time (t 1) can depend on the growth rate in each hole (for example each in the hole 138 at a plurality of patternings shown in Fig. 1-2).The growth rate in each hole can depend on again every kind of precursor gas air-flow (for example shown in flow curve 302 and 304) and as described in the geometry in each hole in the hole 138 of a plurality of patternings.Because for example from TMGa and/or NH 3Growth medium can be deposited on the selective growth mask and open wells in, so this geometry dependence can take place.During selective growth 310, the culture medium (nutrient) that is deposited on the selective growth mask can have high surface mobility, and can leave mask surface, if perhaps enough near from open wells, so just be diffused in this hole, and help growth rate in this hole.Thereby this appositional growth speed contribution can change according to the size in hole and the distance between the hole.In the exemplary embodiments that is used to form a plurality of GaN nano wires and/or nano-wire array, can (also be t in 1 minute duration of selective growth 1=1 minute) carry out the growth pattern conversion afterwards, this can be decided by the GaN growth rate in the hole of patterning according to experience.For example, the GaN growth rate can be about 0.6 μ m/hr, and the hole of patterning can be the form of hexagonal array, and described hexagonal array has the pitch of diameter and the about 1 μ m of about 200nm.
In different embodiment, the growth of described a plurality of nano wires and/or nano-wire array can be affected by when implementing the growth pattern conversion.For example, can give prominence to selective growth mask top (for example at 135 shown in Fig. 1-2) in the growth of a plurality of nanostructure nuclears 140 and implement the growth pattern conversion afterwards.In different embodiment, according to being to have grown in nanowire core to give prominence to selective growth mask top " before " (for example as shown in Fig. 1-2) or implement the growth pattern conversion, can be that nano wire and/or nano-wire array obtain different configuration/sizes at " afterwards ".
Fig. 4 A-4C shows typical semiconductor nanowires device 400, and it is given prominence to selective growth mask top " afterwards " and carries out growth pattern conversion and form by having grown in nanowire core.For what those of ordinary skill in the art should understand easily be, the nano-wire devices shown in Fig. 4 A-4C 400 representative be the vague generalization indicative icon, and can increase other layer/nano wire, perhaps can remove or change existing layer/nano wire.
In Fig. 4 A, this device 400 can comprise to as among Fig. 1 C for the similar structure shown in the device 100, and by in Fig. 1 C, form for the similar manufacturing process shown in the device 100.As shown, this device 400 can comprise substrate 410, selective growth mask 435 and a plurality of nanostructure nuclear 440.Selective growth mask 435 and a plurality of nanostructure nuclear 440 can form on this substrate 410, and wherein a plurality of nanostructure nuclears 440 can intersperse among among the selective growth mask 435.
This substrate 410 can be any substrate similar to the substrate 110 of device 100, the III-N of the family material of wherein can growing on described substrate 110.This substrate 410 for example can be sapphire, carborundum or silicon.Equally, described a plurality of nanostructure nuclear 440 can similarly constitute with a plurality of nanostructures nuclears 140 at the device shown in Figure 1B 100.For example, described a plurality of nanostructure nuclear 440 can form by the hole (not shown) that at first forms a plurality of patternings that limited by selective growth mask 435 on substrate 410.In the hole of described a plurality of patternings each then can by use such as the MOCVD of standard therein growing semiconductor material (for example GaN) be filled.Described a plurality of nanostructure nuclear 440 can have the thickness of described selective growth mask 435, for example about 30nm, and have the sectional dimension of for example about 10nm to about 200nm, for example width or diameter.And as another example, the width of this sectional dimension or diameter can for about 10nm to about 100nm.
In Fig. 4 B, when the growth pattern conversion was carried out at a plurality of nanostructure nuclears 440 tops " afterwards " of giving prominence to out selective growth mask 435, this device 400 can comprise from a plurality of nanostructures examined 440 side direction and orthotropic a plurality of nanostructure 442.For example, each in described a plurality of nanostructure 442 can laterally grow, extending transversely and partly on the surface of selective growth mask 435, grow.In different embodiment, described a plurality of nanostructures 442 can comprise pyramid (pyramid-shaped) structure, thereby the top crystal face is provided.For example, a plurality of GaN pyramid nanostructures can comprise (0001) top surface, and the size of this top surface can be controlled by the growth range of each nanostructure.Especially at the commitment of growth, when a plurality of nanostructure 442 side direction were also partly grown on the surface of selective growth mask 435, this top surface size can increase, and wideer than the sectional dimension of described a plurality of nanostructures nuclears 440.When continued growth, the top surface size can descend, and makes that the tip (point) of top surface size can be less than the size of a plurality of nanostructure nuclears 440.Therefore, the size of each pyramid top surface can be controlled by for example finishing the growth that selective growth pattern (also promptly implement growth pattern conversion) stops a plurality of pyramid nanostructures.In different embodiment, typical pyramid top surface can be cut the top, so and each size of being cut the top surface on top can be held, be used for to use the pulsed growth pattern to carry out the growth of nano wire and/or nano-wire array subsequently.In different embodiment, the top surface diameter that the quilt of each in described a plurality of nanostructures 442 is cut the top can be controlled as less than each the diameter in a plurality of nanostructures nuclears 440.In different embodiment, the top surface of each in described a plurality of nanostructures 442 can have typical cross sectional shape, for example square, polygon, rectangle, ellipse and circle.
Can be at the device 400 shown in Fig. 4 B as the support of nano wire and/or nano-wire array, it can also comprise a plurality of selected surf zones (also being the surface of each top surface of described a plurality of nanostructure 442).A plurality of nano wires and/or nano-wire array then can be from a plurality of selected surf zones growths, and keep each the section feature (for example size and dimension) in described a plurality of selected surf zone.
In Fig. 4 C, a plurality of nano wires 445 can form by the growth that utilizes the pulsed growth pattern to continue semi-conducting material from a plurality of selected surf zone of device 400 (also promptly from each top surfaces of a plurality of nanostructures 442).Therefore, described a plurality of nano wires 445 can be separately regularly, and have from about 20 representative diameter to about 500nm scope, and have typical cross sectional shape, for example square, polygon, rectangle, ellipse and circle.
Use the pulsed growth pattern by the top " afterwards " of giving prominence to out selective growth mask 435 at semiconductor material growing, described a plurality of nano wires 445 can be on the top surface of the typical pyramid-shaped structures of described a plurality of nanostructures 442 and be formed.The feature of each in described a plurality of nano wire 445, can keep constant with the top surface of being cut the top such as cross sectional shape and size, up to the length that reaches expectation.In different embodiment, the length of each nano wire can be controlled in the order of magnitude of micron, for example about 20 μ m or higher.
Fig. 5 shows another typical semiconductor nano-wire devices 500 according to this instruction, and it comprises resilient coating.As shown in the figure, this nano-wire devices 500 can comprise the resilient coating 520 that is arranged between substrate (for example substrate 410) and the selective growth mask (for example the selective growth mask 435).This resilient coating 520 can be the layer similar with the resilient coating 220 shown in Fig. 2.This resilient coating 520 can be a flat film, and it for example uses the MOCVD such as standard to constitute by GaN, AlN, InN or AlGaN.In different embodiment, the thickness of this resilient coating 520 can for about 100nm to about 10 μ m.In different embodiment, this resilient coating 520 can be doped with n type or p type alloy, so that provide to the electrical connection of each nano wire low side.
Fig. 6 A-6D shows according to the typical consequence that originally is taught in a plurality of orderly GaN nano wire of growing by the multistage growth pattern under the situation of not using catalyst and/or nano-wire array (nanostructure nuclear 140,440 and nano wire 145,445 do not use under the situation that is deposited on the metallic catalyst on the substrate grow).As shown in Fig. 6 A-6D, a plurality of GaN nano wires 610 can be grown with position, orientation, length, section feature (for example size and/or shape) and the big consistency of degree of crystallinity.As described herein, in certain embodiments, the position of each nano wire and size can be corresponding to the position and the sizes in each hole in the hole 138 of a plurality of patternings shown in Fig. 1-2.In other embodiments, the position of each nano wire and size can be corresponding to position and the sizes at each top surface of a plurality of nanostructures 442 shown in Fig. 4-5.
Fig. 6 A shows nearly (close-up) scanning electron micrograph (SEM (scanning electron micrograph)) result of typical GaN nano wire 610, and Fig. 6 B shows the SEM result of the long-range order of GaN nano wire 610.In different embodiment, each GaN nano wire can have independent crystallization property.
Fig. 6 C shows the orientation of GaN nano wire 610 can be along single crystallization direction, for example along (0001) crystallization direction of typical GaN nano wire 610.In addition, little central authorities (0001) top surface of each nano wire can be by the inclination { 1 on each nano wire top 1The 02} face limits.
Fig. 6 D is the vertical view of typical GaN nano wire 610, and it shows the hexagonal symmetry of the side wall surface of each GaN nano wire.Side wall surface (sidewall facet) can be perpendicular to having { 1 1The direction of the selective growth mask 620 of 00} system (family) side wall surface.In different embodiment, the diameter of typical GaN nano wire 610 can be about 1000nm or littler.
Consistency in the side direction nano wire shape (for example section feature) shown in Fig. 6 A-6D has shown that the GaN growth rate can only take place in vertical direction, also promptly in (0001) and { 1 1On the 02} top surface.For example, the vertical-growth speed of a plurality of GaN nano wires 610 of pulsed growth for example can be about 2 μ m/hr or higher.On the other hand, { 1 1GaN growth rate on the 00} side wall surface (also being lateral) can be ignored substantially regardless of their great areas.In exemplary embodiments, when using 30nm selective growth mask, GaN nano wire 610 can be grown to the length with about 20 μ m or higher unanimity, and keeps the diameter of about 250nm or littler unanimity.In different embodiment, the existence of hydrogen can be used to control the nanowire geometry shape in carrier gas mixture.
In addition, can be high-quality at the GaN nano wire 610 of the typical unanimity shown in Fig. 6 A-6D, promptly there is not screw dislocation (TD (threading dislocation)) substantially yet.For example, even the GaN resilient coating 220 below being arranged in selective growth mask 135 and/or 435 and/or 520 can observe screw dislocation, in the GaN nano wire 145 and/or 445 shown in Fig. 2 and Fig. 5, can not observe screw dislocation, this is to have left nano wire because of thinking that these dislocations turn to, and ends at the surface under growth mask.In addition, flawless GaN nano wire 610 can be grown on the different substrates, for example sapphire, such as the carborundum of 6H-SiC or such as the silicon of Si (111).
In different embodiment, consistent can be used to make the high quality GaN substrat structure with high quality GaN nano wire and/or nano-wire array.The GaN substrate of viable commercial is expected, makes visual LED and the laser that is used to manifest solid-state illumination and the industry of UV transducer because the GaN substrate can make things convenient for greatly.And the GaN substrate can also be used in other relevant application, for example high power (hi-power) RF circuit and device.
In different embodiment, the GaN substrat structure can form by using such as the technology end of nano heterogeneous extension (nanoheteroepitaxy) and in conjunction with a plurality of GaN nano wires (for example at a plurality of GaN nano wires shown in Fig. 1-6).Fig. 7 A-7D shows four kinds of typical semiconductor device, and it comprises respectively the formed GaN substrat structure 712,714,715 and 717 of a plurality of GaN nano wires by device 100 (seeing Fig. 1 C), device 200 (see figure 2)s, device 400 (seeing Fig. 4 C) and device 500 (see figure 5)s.
For example, can change the GaN growth conditions, allowing growing into suitable height after, and form GaN substrat structure (for example substrate 712,714,715 or 717) then in conjunction with formed a plurality of nano wires (for example 145 or 445).The GaN substrat structure can be the flat film of continuous, extension and complete combination.Described " suitable height " can determine at the combination of every kind of nano wire (for example GaN) and substrate (for example SiC or Si), and can be the height of the defect concentration of the GaN film (also being the GaN substrat structure) that allows to reduce greatly the top combination.In addition, described " suitable height " can be the height that can keep the machine robust structure for the semiconductor device (for example at the device shown in Fig. 7 A-7D) that is drawn.In different embodiment, because in a plurality of GaN nano wires (for example 145 or 445), do not have the spiral defective, so so the combination of GaN substrat structure (for example substrate 712,714,715 or 717) can take place and provide the GaN that comprises extremely low defect concentration substrat structure, for example about 10 on the top of described a plurality of nano wires 7Cm -2Or it is lower.
According to the different embodiment of nano wire formation technology, described processing step (for example formation of the pulsed growth of the selective growth of deposition, patterning and etching selectivity growth mask, nanowire core, nano wire and typical GaN substrat structure) can be scaled to big Substrate Area.Described processing step can also easily expand to the manufacturing requirement that comprises automatic processing of wafers, and can expand to the large-size wafer and be used for from the photonic crystal effect of the light extraction of visual and near UV LED in order to foundation.
Fig. 8-12 shows the exemplary embodiments of the nano wire active device that comprises nanowire LED and nano wire laser and shows its scaleable manufacturing process.In different embodiment, the disclosed III-N of family nano wire and nano-wire array (for example GaN nano wire and/or nano-wire array) provide unique attribute can for its active device.This is because the GaN nano wire of each pulsed growth can have { 1 1The sidewall of 00} system, and the normal of each described side plane can be the nonpolar direction of the III-N of family material.Thereby can on these sides of each GaN nano wire, form the high-quality quantum III-N of family trap, for example quantum InGaN/GaN trap, quantum AlGaN/GaN trap or other quantum III-N trap.
For example, when during the pulsed growth pattern, other precursor gas (for example trimethyl aluminium (Al) or trimethyl indium (In)) being added to typical MOCVD gas during the stage, can obviously change the nanowire growth behavior.In this case, even the little molfraction (for example about 1%) that is added to the Al or the In of GaN nano wire and/or nano-wire array also can cause each GaN nano wire lateral growth, and wherein its sectional dimension (for example width and diameter) increases in time.This lateral growth behavior can allow to make the nucleocapsid heterostructure, also, comprises such as the quantum well of the typical material of InGaN and AlGaN alloy and can grow in the heart and with its encirclement in each GaN nanowire core.Thereby described nucleocapsid growth can be created core-shell nano line/MQW active structure for luminescent device.
In different embodiment, can also set up the 3rd other growth conditions, in order to the nucleocapsid (core-shell) of after the disclosed two growth period patterns of use have been grown the GaN nano wire, grow typical InGaN and AlGaN alloy.The 3rd growth pattern can be with for example as Fig. 3 310 shown in the selective growth pattern in employed similar continuous growth.In other different embodiment, can use the pulsed growth pattern for the 3rd growth conditions.
In different embodiment, this core-shell nano line/MQW active structure can be used to provide nanoscale opto-electronic device efficiently, for example nanowire LED and/or nano wire laser.For example, core-shell nano line/MQW the active structure that is produced (promptly have MQW on the sidewall of each nano wire core (nanowire core) yet pressure vessel is arranged) can not have piezoelectric field, and also do not have relevant quantum limit Stark effect (QCSE (quantum confined Starkeffect)), this is because each nano wire core all has nonpolar sidewall.The elimination of QCSE can increase the radiation recombination efficient in the active region, to improve the performance of LED and laser.In addition, do not exist QCSE can also allow to use wide quantum well, this can improve based on the overlap integral of the laser of nano wire and chamber gain (cavity gain).Use another typical efficiencies income of core-shell nano line/MQW active structure to be, the active region area can significantly increase owing to unique nucleocapsid structure.
Fig. 8 shows the cross section hierarchy according to the typical core-shell nano line/MQW active structure device 800 of this instruction.For what those of ordinary skill in the art should understand easily be,, and can increase other material/layer/shell, perhaps can remove or change existing material/layer/shell at the vague generalization indicative icon of the device shown in Fig. 8 800 representative.
As shown, this device 800 can comprise substrate 810, doping resilient coating 820, selective growth mask 825, doped nanowire core 830 and shell structure 835, and this shell structure comprises the first doping shell 840, MQW shell structure 850, the second doping shell 860, the 3rd doping shell 870.
Described selective growth mask 825 can form on the doping resilient coating 820 on this substrate 810.Described doped nanowire core 830 can be connected to doping resilient coating 820, and extends through selective growth mask 825 from it, and wherein doped nanowire core 830 can insulate by selective growth mask 825.Shell structure 835 can be formed in order to give is had the doped nanowire core " dress shell " of nucleocapsid active structure, and this shell structure 835 can also be positioned on this selective growth mask 825.In addition, this shell structure 835 can form by deposition the 3rd doping shell 870 on the second doping shell 860, and wherein this second doping shell can form on the MQW shell structure 850 on the first doping shell 840.
Substrate 810 can be and the similar substrate of substrate 110 and 410 (seeing Fig. 1-2 and Fig. 4-5), and it includes but are not limited to: sapphire, carborundum, silicon and such as the III-V substrate of GaAs or GaN.
Described doping resilient coating 820 can form on this substrate 810.Described doping resilient coating 820 can be similar with resilient coating 220 and/or 520 (seeing Fig. 2 and Fig. 5).Described doping resilient coating 820 for example can be formed by the known various growing methods of those of ordinary skill in the art by GaN, AlN, InN, AlGaN, InGaN or AlInGaN.In different embodiment, doping resilient coating 820 can be to mix with the similar conduction type of doped nanowire core 830.In certain embodiments, doping resilient coating 820 can be removed from this device 800.
Described selective growth mask 825 can be and the similar selective growth mask of selective growth mask 135 and/or 435 (seeing Fig. 1-2 and Fig. 4-5) that forms on resilient coating 820.In different embodiment, this selective growth mask 825 can directly form on this substrate 810.This selective growth mask 825 can limit the selective growth of a plurality of nano wires and/or nano-wire array.This selective growth mask 825 can be formed by any dielectric material or other known growth mask materials of those of ordinary skill in the art.
Described doped nanowire core 830 can be used any nano wire in a plurality of nano wires that form in the two growth period patterns of the use shown in Fig. 1-2 and Fig. 4-7.Described doped nanowire core 830 for example can be formed by GaN, AlN, InN, AlGaN, InGaN or AlInGaN, and it can form the n type by the various impurity of doping such as silicon, germanium, selenium, sulphur and tellurium.In different embodiment, doped nanowire core 830 can form the p type by introducing beryllium, strontium, barium, zinc or magnesium.Can use other known alloys of those of ordinary skill in the art.In different embodiment, the height of doped nanowire core 830 can be limited with the approximate altitude of source structure device 800.For example, doped nanowire core 830 can have the height of about 1 μ m to about 1000 μ m.
When material GaN was used to described doped nanowire core 830, doped nanowire core 830 can have { 1 1The nonpolar side wall surface (also being " m " plane face) of 00} system.The shell 835 that comprises MQW shell structure 850 can be grown by the nucleocapsid on these faces, thereby and this device 800 can not have piezoelectric field, thereby and do not have a relevant quantum limit Stark effect (QCSE) yet.
When using the pulsed growth pattern, the first doping shell 840 can be grown on the nonpolar side wall surface of doped nanowire core 830 by typical nucleocapsid and form and cover on it.For example, this first doping shell 840 can form by adding a spot of Al during the pulsed growth of doped nanowire core 830, and forms the nucleocapsid heterostructure.The conduction type of this first doping shell 840 and doped nanowire core 830 can be similar, for example the n type.In different embodiment, the first doping shell 840 can comprise Al xGa 1-xThe material of N, wherein x can be any number less than 1.00, for example 0.05 or 0.10.
When using the pulsed growth pattern, MQW shell structure 850 can be on this first doping shell 840 be grown by typical nucleocapsid and is formed.Especially, this MQW shell structure 850 can form by adding a spot of Al and/or During the pulsed growth of the first doping shell 840, to continue to form the nucleocapsid heterostructure.In different embodiment, this MQW shell structure 850 for example can comprise Al xGa 1-xThe alternating layer of N and GaN, wherein x for example can be 0.05 or less than 1.00 any other the number.This MQW shell structure 850 can also comprise for example In xGa 1-xThe alternating layer of N and GaN, wherein x can be any number less than 1.00, for example from about 0.20 any number to about 0.45 the scope.
The second doping shell 860 can form on this MQW shell structure 850.This second doping shell 860 can be as the barrier layer of this MQW shell structure 850, and it has the enough thickness of for example about 500nm to 2000nm.This second doping shell 860 for example can be by Al xGa 1-xN forms, and wherein x can be any number less than 1.00, and for example 0.20 or 0.30.This second doping shell 860 can be to mix with the similar conduction type of the 3rd doping shell 870.
The 3rd doping shell 870 can form to be coated with source structure device 800 by continuing the nucleocapsid growth from this second doping shell 860.The 3rd doping shell 870 for example can be formed by GaN, and is doped to n type or p type.In different embodiment, if the first doping shell 830 is n shells, the second doping shell 860 and/or the 3rd doping shell 870 can be p shells and vice versa so.In different embodiment, the 3rd doping shell 870 can have about thickness of 50 to 500nm.
In different embodiment, when in large tracts of land, including many devices 800, can be electrically insulated from one another at the nucleocapsid active structure device 800 shown in Fig. 8 such as wafer.Fig. 9 shows the active structure device 900 according to this instruction, and it comprises dielectric material 910, and this dielectric material is deposited so that at the line of the core-shell nano shown in Fig. 8/MQW active structure difference mutually insulated.
As shown in FIG. 9, dielectric material 910 can be deposited on the selective growth mask 825, and side direction is connected with the sidewall of shell structure 835, and especially the sidewall with the 3rd doping shell 870 is connected.In different embodiment, dielectric material 910 can be any dielectric material that is used for electric insulation, for example silicon dioxide (SiO 2), silicon nitride (Si 3N 4), silicon oxynitride (SiON) or other dielectric materials.In certain embodiments, dielectric material 910 can be rectifiable (curable) dielectric.Dielectric material 910 can form with height or the thickness of expecting by for example chemical vapour deposition (CVD) (CVD (chemical vapor deposition)) or rotation (spin-on) technology.In different embodiment, the height/thickness of dielectric material 910 can further be conditioned from the part of the dielectric material top removal dielectric material that deposited by using the known etching of those of ordinary skill in the art for example or lifting from flow process.The thickness of this dielectric material 910 can be regulated according to the application-specific of using core-shell nano line/MQW active structure.
In different embodiment, different nanowire LEDs and nano wire laser can form by growing at the nucleocapsid shown in Fig. 8-9, and this is because the active shell structure of MQW can be established on the nonpolar sidewall of the nano wire of pulsed growth.For example, arrange with the pitch that equals λ/2 if nano wire is hexagonal array that wherein λ is the emission wavelength of typical LED or laser, this nano-wire array can provide bulk of optical feedback so, moves with excitation luminescence.Figure 10-12 show according to this instruction based on the typical nanoscale active device that forms in structure shown in Fig. 8-9.
Figure 10 A-10C shows according to the typical nanowires LED device 1000 of this instruction use at the core-shell nano line/MQW active structure shown in Fig. 8-9.
In different embodiment, this nanowire LED device 1000 can be manufactured, and it comprises and for example formedly on device 900 electrically contacts.Electrically contact and can include conductive structure, wherein said conductive structure by such as the metal of titanium (Ti), aluminium (Al), platinum (Pt), nickel (Ni) or gold (Au) with a plurality of multiple layer combination, use the known technology of those of ordinary skill in the art to form such as Al/Ti/Pt/Au, Ni/Au, Ti/Al, Ti/Au, Ti/Al/Ti/Au, Ti/Al/Au, Al or Au.
In Figure 10 A, this device 1000 can comprise conductive structure 1040, and wherein this conductive structure is on the surface of device 900, also promptly form on each surface at the 3rd doping shell 870 of dielectric material 910 and shell structure 835.This conductive structure 1040 can be the hyaline layer of p electrode that is used for the LED device 1000 of manufacturing subsequently.In exemplary embodiments, this conductive structure 1040 (or p electrode) for example can be the layered metal combination of Ti/Au.
In different embodiment, device 1000 can also comprise dielectric layer 1010, and wherein this dielectric layer has adjustable thickness (or height).By regulating the thickness of this dielectric layer 1010, the yardstick (for example thickness or height) of the conductive structure 1040 (or p electrode) that forms on the sidewall of shell structure 835 or along its sidewall can be regulated according to desired should being used for of nano wire active device.For example, thick dielectric layer 1010 can be restricted to the top of the nucleocapsid structure active device of nanowire LED for example and/or nano wire laser to conductive structure 1040 (or p electrode).Alternately, the thin dielectric layer of being regulated 1010 can allow this conductive structure 1040 (or p electrode) to have bigger thickness or height (the also yardstick that promptly increases), and this can reduce the impedance of active device.But in different embodiment, the big thickness of this conductive structure 1040 (or p electrode) can be thought and helps loss such as the active device of laser cavity.For those of ordinary skill in the art known be that the optimum performance of this conductive structure 1010 (or p electrode) can balance each other with desired cavity loss by the impedance of active device is descended and obtain.
In different embodiment, in this conductive structure 1040 (or p electrode) can be in from about 1 μ m to the scope of about 9 μ m along the thickness of shell structure 835 sidewalls of typical LED device 1010, to obtain the high efficiency performance.In different embodiment, LED device 1000 can have the total height of for example about 10 μ m.
In Figure 10 B, device 1000 can also comprise p electrode 1045, dielectric 1015 and selective exposure mask 1025, and wherein this selective exposure mask has the groove 1035 that etches into selective growth mask 825 (seeing Figure 10 A).
This p electrode 1045 and following dielectric 1015 can form by patterning and etching conductive structure 1040 and dielectric layer 1010 (seeing Figure 10 A).Therefore, the part (not shown) on the surface of this selective growth mask 835 can be exposed, and is separated by the dielectric on the both sides of each nucleocapsid structure 1015.After this patterning and etch process, the expose portion on the surface by passing selective growth mask 825 forms groove 1035 can form selective exposure mask 1025, and wherein each side of nucleocapsid active structure can comprise at least one groove 1035.Therefore, the surface portion of following resilient coating 820 can be as the end of groove 1035.
In different embodiment, the thickness of selective exposure mask 1025 may be critical for the performance of LED device 1000.For example, thickness is that the thickness of the silicon nitride selective growth mask of 30nm may be enough thick so that bear about 20 volts or higher voltage before LED device 1000 punctures.In different embodiment, this selective exposure mask 1025 can have about 30nm or littler thickness.Yet will be understood that in nano wire and nano wire active device technology, those of ordinary skill in the art can easily provide thicker selective growth mask.
In Figure 10 C, device 1000 can comprise n electrode 1080, and wherein this n electrode is formed in order to guarantee the conducting between n side contacts and central conductive region, and this central authorities' conductive region comprises doping resilient coating 820 and nano wire core 803.This central authorities' conductive region for example can be heavily doped n +The GaN zone.In different embodiment, this n electrode 1080 can comprise the conductive structure that forms by on each surface that electrode material is deposited to selective exposure mask 1025 and these groove 1035 bottoms.In exemplary embodiments, this n electrode 1080 can be made up, be formed such as Al/Ti/Pt/Au by for example layered metal.
At 1099 places, the light that the nanowire LED device 1000 in Figure 10 C is produced can be extracted by substrate 820, and wherein this substrate can be transparent when green and blue wavelength.In different embodiment, the light output that can more spread at the top side (not shown) of this device 1000 is because this nanowire LED device 1000 can be enough little of to carry out abundant diffraction.This diffused light output may be favourable in some solid-state illuminations are used.
Like this, disclosed nanowire LED device 1000 is compared the attribute that can provide unique with the LED device of routine.At first, it can have higher brightness, can be increased to for example about 10 times because nucleocapsid growth active region area (also being that MQW has the pressure vessel area) is compared with the planar LED structure of routine.The second, can improve light extraction to increase the delivery efficiency of this LED.This be because most of normal direction that the geometry of this LED device can make the active region area in wafer surface, also be substrate surface.Can trend towards a LED light at the restricted area of MQW active region either side is directed on the vertical direction.The 3rd, because the position of each in a plurality of nano wires and/or the nano-wire array and the high accuracy of diameter, the array of formed LED device 1000 can also be configured to photonic crystal, and this can further improve high output couple efficiency.The 4th, the nanowire LED impedance can reduce greatly owing to the increase of the contact area of electrical-contact area, for example p electrode 1045.At last, because this LED device 1000 can provide specific light power with higher brightness, so can handle more device on given wafer, this can reduce manufacturing cost, and increases manufacturing efficient.For example, in order to allow Metal Contact, this LED device 1000 can comprise the pitch interval (also i.e. the interval of the center to center between any two adjacent nanowires devices) of for example about 100 μ m.So 4 inches wafers can comprise a plurality of nanowire LED devices 1000, for example about 780,000 devices or more, wherein these devices can be side by side manufactured.In different embodiment, pitch interval can further be lowered to allow single 4 inches wafers to hold for example more than 1,000,000 LED devices 1000.
Figure 11-12 shows according to this instruction and uses as the typical nanowires laser device at the nucleocapsid grown nano wire/MQW active structure as shown in Fig. 8-10.Because the side wall surface of nano wire and/or nano-wire array be on the grade of atomic monolayer, have flatness accurately { the 1100} face is so can form the high-quality MQW active region of laser device on these good flat " sidewall substrates ".In addition, the cycle of the unanimity of the vertical orientated and nano wire of side wall surface and length can be provided for etching or cutting face to form the high-efficiency method of optics cavity.The consistent cycle can allow directly to set up structure photon crystal optics chamber.
As shown in Figure 11, nano wire laser device 1100 can be by using nucleocapsid grow nanowire/MQW active structure to make as the laser active structure in the technology shown in Fig. 8-10.This nano wire laser device 1100 can comprise the shell structure 1135 of polishing, the p electrode 1145 and the passivation layer 1195 of polishing, wherein this passivation layer can form on each surface of shell structure 1135 that polishes and the p electrode 1145 that polishes, to cover this laser active structure.
The p electrode 1145 of the shell structure 1135 of described polishing and polishing can polish and form by (with respect to as the substrate 810 of the bottom) top to all core-shell nano line/MQW active structures (also being the laser active structure) as shown in Fig. 10 C.Can utilize etched dielectric 1015 to use various polishing technologies, for example chemical machinery polishing as mechanical support.
This polishing step can be used for polishing at one time a plurality of laser faces, and can not reduce the manufacturability of this nano wire laser device 1100.For example, a plurality of nano wire laser devices 1100, for example about 780,000 or more can formation on 4 inches wafers are to obtain high manufacturing efficient.In different embodiment, this pitch interval can further be dwindled, and holds for example more than 1,000,000 laser devices 1100 to allow single 4 inches wafers.
In different embodiment, along the sidewall of the shell structure 1135 of polishing and the yardstick (for example thickness or height) of the p electrode 1145 of the described polishing that forms can be below regulating the thickness of etched dielectric 1015 regulate, to obtain the optimum performance of laser device 1100.In different embodiment, when total height is about 10 μ m, can be in from about 1 μ m to the scope of about 5 μ m along p electrode 1145 thickness of the described polishing of shell structure 1135 sidewalls of as shown in Figure 11 polishing.
This passivation layer 1195 can form on each surface of the polishing top of each laser active structure, the p electrode 1145 that is also promptly polishing and the shell structure 1135 that polishes.This passivation layer 1195 can be configured to avoids the 1100 unsuitable non-radiative compound or joint leakages (junction leakage) of nano wire laser device.In different embodiment, this passivation layer 1195 can be by for example forming with about thickness of 10 to about 100nm for the known any dielectric material of those of ordinary skill in the art.
In certain embodiments, can influence optical lasers process around the composition of the material of shell structure 1135 usefulness of the polishing in nano wire chamber (also being nano wire core 830) and refractive index at 1199 places.For example, when nano wire had the representative diameter of about 200nm, some in the optical lasers pattern may reside in outside this chamber.Thereby laser can to around the material in this chamber, also promptly to be used to the composition and the refractive index of material of each layer of the shell structure 1135 that polishes more responsive.
In other embodiments, because upward do not have physically lower face, so near selective growth mask 1025, may have effective change of refractive at laser optical cavity (yet being nano wire core 830).Because some optical lasers patterns can be positioned at outside this chamber, in fact can help (also promptly increasing) this variations in refractive index.In exemplary embodiments, this nano wire laser device 1100 (seeing Figure 11) can carry out tuned optical by regulating selective exposure mask 1025 at maximum reflectivity.For example, when this device was launched the blue light of 450nm, the optical thickness of the selective exposure mask 1025 of this laser device 1100 can be in the scope of about 220nm to 230nm.
Figure 12 shows another typical laser device 1200, wherein distributed Bragg reflector (DBR (distributed Bragg reflector)) mirror stack (mirror stack) 1220 can be arranged between the layer and this selective growth mask 1025 of substrate 810, and is relative with doping resilient coating 820 between these two layers that are arranged in laser device 1100 shown in Figure 11.
The DBR mirror stack that this DBR mirror stack 1220 can be an extension.This DBR mirror stack 1220 can comprise for example for example quarter-wave alternating layer of GaN and AlGaN.In different embodiment, this DBR mirror stack 1220 can be by tuning, to improve reflectivity and to increase the chamber Q of laser 1299.
In different embodiment, can provide low device resistance at all the nano wire active devices shown in Figure 10-12, because more resistive p electrodes (for example this p electrode 1045 and/or 1145) that can heterostructure can be positioned at bigger area place, wherein this bigger area is the periphery of each core-shell nano line/MQW active structure.For example, for LED device 1000 (shown in Figure 10), p electrode 1045 can be patterned in order to cover the top of this device 1000 fully, with further reduction device resistance.
Although for the purpose of setting forth has illustrated single nano wire in Fig. 8-12, but those of ordinary skill in the art it should be understood that the nucleocapsid growth technique on each nano wire of a plurality of nano wires of nanoscale active device and/or nano-wire array (for example shown in Fig. 1-6) and can carry out simultaneously in big area (for example entire wafer).
By considering that other embodiment of the present invention will be conspicuous for those skilled in the art in this disclosed specification of the present invention and practice.It is exemplary that this specification and example should be regarded as merely, and true scope wherein of the present invention and spirit illustrate by the following claim book.

Claims (25)

1. method that is used to make nano wire, it comprises:
Form the selective growth mask on substrate, wherein said selective growth mask comprises the hole of a plurality of patternings, and a plurality of parts of described substrate are exposed in the hole of described a plurality of patternings;
Use selectivity non-pulse formula growth pattern in order to growing semiconductor material on each of a plurality of parts that exposed in the hole at each patterning of substrate;
The growth pattern conversion of execution from non-pulse formula growth pattern to the pulsed growth pattern; And
Form a plurality of semiconductor nanowires by the pulsed growth pattern that continues described semi-conducting material.
2. method according to claim 1, wherein said substrate are included in the lip-deep resilient coating of support substrates, and described semi-conducting material is passed in the hole selective growth of a plurality of patternings on the described resilient coating.
3. method according to claim 1 and 2, wherein said substrate comprise selected one or more materials from the group that comprises Si, SiC, sapphire, GaN and GaAs.
4. method according to claim 1 and 2 also is included in the one or more process for purifying before the selectivity non-pulse formula growth of described semi-conducting material.
5. method according to claim 1 and 2, the hole of wherein said a plurality of patternings forms hexagonal array, and described hexagonal array has the diameter of 10nm to 1000nm and the 50nm pitch to 10 μ m.
6. method according to claim 1 and 2, the section feature of each in each in wherein said a plurality of semiconductor nanowires and the hole of described a plurality of patternings is similar.
7. method according to claim 6, wherein said section feature are selected shapes from the group that comprises polygon, rectangle, square, ellipse and circle.
8. the step of the growth pattern conversion from described non-pulse formula growth pattern to described pulsed growth pattern wherein before the growth of described semi-conducting material protrudes in described selective growth mask top, takes place to carry out in method according to claim 6.
9. method according to claim 1 and 2, the semi-conducting material that wherein is used for described a plurality of semiconductor nanowires comprises from selected one or more materials of the group that comprises GaN, AlN, InN, InGaN, AlInGaN and AlGaN.
10. method according to claim 1 and 2, wherein said selective growth comprise that the V of family and family's III precursor gas have from 100 to 500 V/III ratio.
11. method according to claim 1 and 2, wherein initial pulsed growth comprises with one or more sequence cycles the V of family of described semi-conducting material and the III of family precursor gas alternately is incorporated in the growth reactor that wherein said precursor gas comprises from 60 to 300 V/III ratio.
12. method according to claim 1 and 2, wherein said pulsed growth comprise 2 μ m/hr or higher vertical-growth speed.
13. method according to claim 1 and 2, each in wherein said a plurality of nano wires all has the length of 10nm to 100 μ m.
14. method according to claim 1 and 2, wherein:
Switch process from described non-pulse formula growth pattern to described pulsed growth pattern after protruding in described selective growth mask top, takes place in the growth of described semi-conducting material, in order to form a plurality of pyramid nanostructures of cutting the top that partly are arranged on the described selective growth mask surface; And
The step that forms a plurality of nano wires comprises: form semiconductor nanowires by the pulsed growth that continues described semi-conducting material on each of described a plurality of pyramid nanostructures, make that each the top surface of section feature and described a plurality of pyramid nanostructures of described semiconductor nanowires is similar.
15. method according to claim 14, wherein said semiconductor nanowires comprise than each the little sectional dimension of sectional dimension in the hole of described a plurality of patternings.
16. the III-N of the family nano-wire array by claim 1 or 2 described methods form comprises:
Support, it comprises a plurality of selected surf zones; And
Be connected in a plurality of selected surf zone of described support each and from the III-N of the family nano wire of its extension, the wherein said III-N of family nano wire is orientated along single direction, and keeps the section feature of one of described a plurality of selected surf zones.
17. nano-wire array according to claim 16 also comprises the GaN nano wire that is orientated along (0001) crystallization direction.
18. nano-wire array according to claim 16, the wherein said III-N of family nano wire comprises selected one or more materials from the group that comprises GaN, AlN, InN, InGaN, AlGaN and AlInGaN.
19. nano-wire array according to claim 16, the wherein said III-N of family nano wire comprise selected one or more cross sectional shapes from the group that comprises polygon, rectangle, square, ellipse and circle.
20. nano-wire array according to claim 16, the wherein said III-N of family nano wire also comprise 100 or higher length-width ratio and 250nm or littler sectional dimension.
21. nano-wire array according to claim 16, wherein said support comprises the III-N of family nanowire core, the described III-N of family nanowire core is arranged on each of a plurality of substrate parts by the selective growth mask that is arranged on the described substrate, and the surface of the wherein said III-N of family nanowire core comprises one of a plurality of selected surf zones of described support.
22. nano-wire array according to claim 21, wherein said support also comprises the III-N of pyramid family nanostructure, it is formed and partly is arranged on the described selective growth mask by the described III-N of family nanowire core, and the top surface of the wherein said pyramid III-N of family nanostructure comprises one of a plurality of selected surf zones of described support.
23. the III-N of family nano-wire array comprises:
Substrate;
Selective growth mask on described substrate, wherein said selective growth mask comprises the hole of a plurality of patternings, the hole of described a plurality of patternings exposes a plurality of parts of described substrate; And
Be connected in a plurality of parts of described substrate each and from the III-N of the family nano wire of its extension, the wherein said III-N of family nano wire is orientated along single direction, and keep the section feature of one of described a plurality of selected surf zones, and the wherein said III-N of family nano wire extends described selective growth mask top.
24.GaN substrat structure comprises:
By the described nano-wire array that comprises a plurality of GaN nano wires that method according to claim 1 and 2 forms, each in wherein said a plurality of GaN nano wires all is flawless; And
By the GaN film of described a plurality of GaN nano wire combination, wherein said GaN film has 10 7Cm -2Or lower defect concentration.
25. substrate, it comprises a plurality of nano wires that form by method according to claim 1 and 2.
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