CN102605422B - For mask and the using method thereof of growing epitaxial structure - Google Patents
For mask and the using method thereof of growing epitaxial structure Download PDFInfo
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- CN102605422B CN102605422B CN201110025710.6A CN201110025710A CN102605422B CN 102605422 B CN102605422 B CN 102605422B CN 201110025710 A CN201110025710 A CN 201110025710A CN 102605422 B CN102605422 B CN 102605422B
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Abstract
The present invention relates to a kind of mask for growing epitaxial structure and using method thereof.This mask comprises: a carbon nanotube layer, and this carbon nanotube layer has multiple opening, thus the epitaxial growth plane of substrate can be exposed by the plurality of opening portion, some growth epitaxial film being exposed by this mask from the epitaxial growth plane of described substrate by this opening.The using method of this mask comprises the following steps: provide a substrate, and this substrate has the epitaxial growth plane of a support outer layer growth; Arrange a mask in the epitaxial growth plane of described substrate, this mask comprises: a carbon nanotube layer, and this carbon nanotube layer comprises multiple opening, thus the epitaxial growth plane of substrate is exposed by the plurality of opening portion; And at the epitaxial growth plane grown epitaxial layer of described substrate.
Description
Technical field
The present invention relates to a kind of mask for growing epitaxial structure and using method thereof.
Background technology
Epitaxial structure, especially heteroepitaxial structure is one of main raw making semiconducter device.Such as, in recent years, the gallium nitride epitaxial slice preparing photodiode (LED) becomes the focus of research.
Described gallium nitride epitaxial slice refers under certain condition, and by gallium nitride material molecule, regular arrangement, oriented growth is in sapphire substrates.But the preparation of high-quality gallium nitride epitaxial wafer is the difficult point of research always.Due to gan and the lattice parameter of sapphire substrates and the difference of thermal expansivity, thus epitaxial layer of gallium nitride is caused to there is more dislocation defects.And there is larger stress between epitaxial layer of gallium nitride and sapphire substrates, stress is got over conference and is caused epitaxial layer of gallium nitride to break.This heteroepitaxial structure ubiquity lattice mismatch phenomenon, and easily form the defects such as dislocation.
Prior art provides a kind of method improving above-mentioned deficiency, and it adopts non-smooth sapphire substrates epitaxial growth of gallium nitride.But prior art adopts the microelectronic techniques such as photoetching form groove at process for sapphire-based basal surface thus form non-smooth epitaxial growth plane usually.The method is complex process not only, and cost is higher, and can pollute sapphire substrates epitaxial growth plane, thus affects the quality of epitaxial structure.
Summary of the invention
In sum, necessaryly provide a kind of mask for growing epitaxial structure and using method thereof, and adopt this mask that preparation method's technique of epitaxial structure can be made simple, with low cost, and can not pollute the epitaxial growth plane of substrate.
A kind of mask for growing epitaxial structure, this mask comprises: a carbon nanotube layer, and this carbon nanotube layer is the self supporting structure of continuous print entirety, there is multiple opening, the epitaxial growth plane of substrate is exposed by the plurality of opening portion, by the some growth that this mask makes epitaxial film be exposed from the epitaxial growth plane of described substrate by this opening, described carbon nanotube layer comprises carbon nano-tube film or carbon nano tube line, and described opening is the micropore or gap that exist between carbon nanotube adjacent in gap between described carbon nano tube line or described carbon nano-tube film.
A kind of mask for growing epitaxial structure, this mask comprises: a carbon nanotube layer, this carbon nanotube layer is the self supporting structure of continuous print entirety, comprise multiple aligning and the carbon nanotube extended along the direction being parallel to carbon nanotube layer surface, and between the plurality of carbon nanotube, there is multiple opening, the epitaxial growth plane of substrate is exposed by the plurality of opening portion, by the some growth that this mask makes epitaxial film be exposed from the epitaxial growth plane of described substrate by this opening, described opening is the gap between micropore or adjacent carbon nanotubes that in described carbon nanotube layer, multiple adjacent carbon nanotube surrounds.
A using method for aforementioned mask, it comprises the following steps: provide a substrate, and this substrate has the epitaxial growth plane of a support outer layer growth; In the epitaxial growth plane of described substrate, one mask is set, this mask comprises: a carbon nanotube layer, this nanotube layer is the self supporting structure of continuous print entirety, comprise multiple aligning and the carbon nanotube extended along the direction being parallel to carbon nanotube layer surface, and between the plurality of carbon nanotube, there is multiple opening, the epitaxial growth plane of substrate is exposed by the plurality of opening portion; And at the epitaxial growth plane grown epitaxial layer of described substrate.
Compared with prior art, the present invention adopts a patterned carbon nanotube layer to be arranged at described substrate epitaxial growth plane grown epitaxial layer as mask, and described mask can be laid immediately on the epitaxial growth plane of substrate, and technique is simple, with low cost.This mask comprises multiple opening thus the epitaxial growth plane of substrate is exposed by the plurality of opening portion.Described substrate be used for grown epitaxial layer time, after described epitaxial film can only grow from the epitaxial growth plane exposed, laterally overgrown is connected as a single entity, thus the contact area between the epitaxial film of growth and substrate is reduced, thus reduce the stress between process of growth epitaxial layers and substrate.Meanwhile, mask can effectively suppress dislocation defects to extend to epitaxial surface, thus decreases the defect of epitaxially deposited layer, can be directly used in the epitaxial film of growing high-quality.
Accompanying drawing explanation
The process flow sheet of the preparation method of the heteroepitaxial structure that Fig. 1 provides for the embodiment of the present invention.
Fig. 2 is the stereoscan photograph of the carbon nano-tube film adopted in the embodiment of the present invention.
Fig. 3 is the structural representation of the carbon nanotube fragment in the carbon nano-tube film in Fig. 2.
Fig. 4 is the stereoscan photograph of the multilayer that adopts in embodiment of the present invention carbon nano-tube film arranged in a crossed manner.
Fig. 5 is the stereoscan photograph of the carbon nano tube line of the non-twisted adopted in the embodiment of the present invention.
Fig. 6 is the stereoscan photograph of the carbon nano tube line of the torsion adopted in the embodiment of the present invention.
Fig. 7 is epitaxially deposited layer process of growth schematic diagram in the embodiment of the present invention.
Fig. 8 is the stereoscan photograph in heteroepitaxial structure cross section prepared by first embodiment of the invention.
Fig. 9 is the transmission electron microscope photo of heteroepitaxial structure interface prepared by first embodiment of the invention.
The perspective view of the heteroepitaxial structure that Figure 10 provides for first embodiment of the invention.
Figure 11 is the diagrammatic cross-section of the XI-XI along the line of the heteroepitaxial structure shown in Figure 10.
The perspective view of the heteroepitaxial structure that Figure 12 provides for second embodiment of the invention.
The perspective view of the heteroepitaxial structure that Figure 13 provides for third embodiment of the invention.
Main element nomenclature
Heteroepitaxial structure 10,20,30
Substrate 100,200,300
Epitaxial growth plane 101
Carbon nanotube layer 102,202,302
Hole 103
Epitaxially deposited layer 104,204,304
Opening 105
Hetero epitaxy crystal grain 1042
Hetero epitaxy film 1044
Carbon nanotube fragment 143
Carbon nanotube 145
Embodiment
The mask for growing epitaxial structure provided below with reference to the accompanying drawing detailed description embodiment of the present invention and using method thereof.For the ease of understanding technical scheme of the present invention, first the present invention introduces a kind of preparation method of heteroepitaxial structure.
Refer to Fig. 1, the embodiment of the present invention provides a kind of preparation method of heteroepitaxial structure 10, and it specifically comprises the following steps:
S10 a: substrate 100 is provided, and this substrate 100 has the epitaxial growth plane 101 that a support epitaxially deposited layer 104 grows;
S20 a: carbon nanotube layer 102 is set in the epitaxial growth plane 101 of described substrate 100, this carbon nanotube layer 102 is as mask;
S30: grow epitaxially deposited layer 104 in the epitaxial growth plane 101 of substrate 100.
In step S10, described substrate 100 provides the epitaxial growth plane 101 of epitaxially deposited layer 104.The epitaxial growth plane 101 of described substrate 100 is surfaces that molecule is level and smooth, and eliminates the impurity such as oxygen or carbon.Described substrate 100 can be single or multiple lift structure.When described substrate 100 is single layer structure, this substrate 100 can be a single crystal structure body, and has the epitaxial growth plane 101 of a crystal face as epitaxially deposited layer 104.The material of the substrate 100 of described single layer structure can be GaAs, GaN, Si, SOI, AlN, SiC, MgO, ZnO, LiGaO
2, LiAlO
2or Al
2o
3deng.When described substrate 100 is multilayered structure, its needs comprise the above-mentioned single crystal structure body of at least one deck, and this single crystal structure body has the epitaxial growth plane 101 of a crystal face as epitaxially deposited layer 104.The material of described substrate 100 can be selected according to the epitaxially deposited layer 104 that will grow, and preferably, makes described substrate 100 have close lattice parameter and thermal expansivity with epitaxially deposited layer 104.Thickness, the size and shape of described substrate 100 are not limit, and can select according to actual needs.Described substrate 100 is not limited to the above-mentioned material enumerated, and supports that the substrate 100 of the epitaxial growth plane 101 that epitaxially deposited layer 104 grows all belongs to protection scope of the present invention as long as have.
In step S20, described carbon nanotube layer 102 is the continuous print one-piece construction comprising multiple carbon nanotube.In described carbon nanotube layer 102, multiple carbon nanotube extends along the direction being basically parallel to carbon nanotube layer 102 surface.When described carbon nanotube layer 102 is arranged at the epitaxial growth plane 101 of described substrate 100, in described carbon nanotube layer 102, the bearing of trend of multiple carbon nanotube is basically parallel to the epitaxial growth plane 101 of described substrate 100.The thickness of described carbon nanotube layer is 1 nanometer ~ 100 micron, or 1 nanometer ~ 1 micron, or 1 nanometer ~ 200 nanometer, and preferably thickness is 10 nanometer ~ 100 nanometers.Described carbon nanotube layer 102 is a patterned carbon nanotube layer 102.Described " graphically " refers to that described carbon nanotube layer 102 has multiple opening 105, and the plurality of opening 105 runs through described carbon nanotube layer 102 from the thickness direction of described carbon nanotube layer 102.When the epitaxial growth plane 101 that described carbon nanotube layer 102 covers described substrate 100 is arranged, thus make the epitaxial growth plane 101 of described substrate 100 to should the part of opening 105 be exposed to be convenient to grow epitaxially deposited layer 104.Described opening 105 can be micropore or gap.Described opening 105 is of a size of 10 nanometer ~ 500 micron, and described size refers to the spacing of the aperture of described micropore or the width in described gap.Described opening 105 is of a size of 10 nanometer ~ 300 micron or 10 nanometer ~ 120 micron or 10 nanometer ~ 80 micron or 10 nanometer ~ 10 micron.The size of opening 105 is less, is conducive to the generation reducing dislocation defects in the process of grown epitaxial layer, to obtain high-quality epitaxially deposited layer 104.Preferably, described opening 105 is of a size of 10 nanometer ~ 10 micron.Further, the dutycycle of described carbon nanotube layer 102 is 1:100 ~ 100:1, or 1:10 ~ 10:1, or 1:2 ~ 2:1, or 1:4 ~ 4:1.Preferably, described dutycycle is 1:4 ~ 4:1.After so-called " dutycycle " refers to that this carbon nanotube layer 102 is arranged at the epitaxial growth plane 101 of substrate 100, this epitaxial growth plane 101 is by the area ratio of carbon nanotube layer 102 part occupied and the part exposed by perforate 105.
Further, described " graphically " refer to that the arrangement mode of multiple carbon nanotube in described carbon nanotube layer 102 is orderly, well-regulated.Such as, in described carbon nanotube layer 102, the axis of multiple carbon nanotube is all basically parallel to the epitaxial growth plane 101 of described substrate 100 and extends substantially in the same direction.Or the axis of multiple carbon nanotube can extend along two or more direction substantially regularly in described carbon nanotube layer 102.Or, axial crystal orientation extension or the angled extension in crystal orientation with substrate 100 along substrate 100 of multiple carbon nanotube in described carbon nanotube layer 102.The adjacent carbon nanotube extended in the same direction in above-mentioned carbon nanotube layer 102 is joined end to end by Van der Waals force.
Under there is at described carbon nanotube layer 102 prerequisite of foregoing opening 105, in described carbon nanotube layer 102 multiple carbon nanotube also can lack of alignment, random arrangement.
Preferably, described carbon nanotube layer 102 is arranged at the whole epitaxial growth plane 101 of described substrate 100.Carbon nanotube in described carbon nanotube layer 102 can be one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes, and its length and diameter can be selected as required.
Described carbon nanotube layer 102 is used as the mask of growth epitaxially deposited layer 104.So-called " mask " refers to that this carbon nanotube layer 102 is for blocking the portion of epi aufwuchsplate 101 of described substrate 100, and expose portion epitaxial growth plane 101, thus make epitaxially deposited layer 104 only from the some growth that described epitaxial growth plane 101 exposes.Because carbon nanotube layer 102 has multiple opening 105, so this carbon nanotube layer 102 forms a patterned mask.After carbon nanotube layer 102 is arranged at the epitaxial growth plane 101 of substrate 100, multiple carbon nanotube extends along the direction being parallel to epitaxial growth plane 101.Because described carbon nanotube layer 102 forms multiple opening 105 in the epitaxial growth plane 101 of described substrate 100, thus make that the epitaxial growth plane 101 of described substrate 100 has a patterned mask.Be appreciated that, relative to microelectronic techniques such as photoetching, by arranging carbon nanotube layer 102 mask, to carry out epitaxially grown method technique simple, with low cost, not easily introduce in the epitaxial growth face 101 of substrate 100 and pollute, and environmental protection, the preparation cost of heteroepitaxial structure 10 can be greatly reduced.
Be appreciated that described substrate 100 and carbon nanotube layer 102 together constitute the substrate for growing heteroepitaxial structure.This substrate can be used for the epitaxially deposited layer 104 growing differing materials, as semiconductor epitaxial layers, metal epitaxial film or alloy epitaxial film.This substrate also can be used for growing homogeneity epitaxial layer, thus obtains a homogeneity epitaxial structure.
The epitaxial growth plane 101 of described substrate 100 is laid immediately on after described carbon nanotube layer 102 can be pre-formed.Described carbon nanotube layer 102 is a macrostructure, and described carbon nanotube layer 102 is the structure of a self-supporting.So-called " self-supporting " refers to that this carbon nanotube layer 102 does not need large-area carrier supported, as long as and relatively both sides provide support power can be unsettled on the whole and keep oneself state, when being placed on two supporters that (or being fixed on) interval specific range arranges by this carbon nanotube layer 102, the carbon nanotube layer 102 between two supporters can unsettled maintenance oneself state.Because carbon nanotube layer 102 is self supporting structure, the unnecessary epitaxial growth plane 101 being formed in substrate 100 by complicated chemical process of described carbon nanotube layer 102.Further preferably, described carbon nanotube layer 102 is the pure nano-carbon tube structure of multiple carbon nanotube composition.So-called " pure nano-carbon tube structure " refers to described carbon nanotube layer without the need to any chemically modified or acidification in whole preparation process, not containing modified with functional group such as any carboxyls.
Described carbon nanotube layer 102 can also be a composite structure comprising multiple carbon nanotube and adding material.Described adding material comprises that graphite, graphite are rare, one or more in silicon carbide, boron nitride, silicon nitride, silicon-dioxide, decolorizing carbon etc.Described adding material can also comprise in metallic carbide, metal oxide and metal nitride etc. one or more.Described adding material is coated at least part of surface of carbon nanotube in carbon nanotube layer 102 or is arranged in the opening 105 of carbon nanotube layer 102.Preferably, described adding material is coated on the surface of carbon nanotube.Due to, described adding material is coated on the surface of carbon nanotube, makes the diameter of carbon nanotube become large, thus the opening 105 between carbon nanotube is reduced.Described adding material can be formed at the surface of carbon nanotube by methods such as chemical vapour deposition (CVD), physical vapor deposition (PVD), magnetron sputterings.
The step of an organic solvent process can also be comprised after described carbon nanotube layer 102 being laid on the epitaxial growth plane 101 of described substrate 100, more combine closely to make carbon nanotube layer 102 and epitaxial growth plane 101.This organic solvent can to select in ethanol, methyl alcohol, acetone, ethylene dichloride and chloroform one or several mixing.Organic solvent in the present embodiment adopts ethanol.Organic solvent to be dropped in the whole carbon nanotube layer of carbon nanotube layer 102 surface infiltration 102 by test tube or substrate 100 to be immersed to fill in the container of organic solvent together with whole carbon nanotube layer 102 and infiltrates by this step with an organic solvent processed.
Described carbon nanotube layer 102 also can be grown directly upon the epitaxial growth plane 101 of described substrate 100 by methods such as chemical vapour depositions (CVD) or first be grown at silicon substrate surface, is then transferred to the epitaxial growth plane 101 of described substrate 100.
Particularly, described carbon nanotube layer 102 can comprise carbon nano-tube film or carbon nano tube line.Described carbon nanotube layer 102 can be the carbon nano-tube film of a single-layered carbon nanotube periosteum or multiple stacked setting.Described carbon nanotube layer 102 can comprise multiple carbon nano tube line of be arrangeding in parallel or multiple carbon nano tube line arranged in a crossed manner.When described carbon nanotube layer 102 is the carbon nano-tube film of multiple stacked setting, the number of plies of carbon nano-tube film is unsuitable too many, preferably, is 2 layers ~ 100 layers.When described carbon nanotube layer 102 is multiple carbon nano tube line be arranged in parallel, the distance between adjacent two carbon nano tube lines is 0.1 micron ~ 200 microns, preferably, is 10 microns ~ 100 microns.Space between described adjacent two carbon nano tube lines forms the opening 105 of described carbon nanotube layer 102.Gap length between adjacent two carbon nano tube lines can equal the length of carbon nano tube line.The epitaxial growth plane 101 that described carbon nano-tube film or carbon nano tube line can be laid immediately on substrate 100 forms described carbon nanotube layer 102.By controlling the distance between the number of plies of carbon nano-tube film or carbon nano tube line, the size of carbon nanotube layer 102 split shed 105 can be controlled.
The self supporting structure that described carbon nano-tube film is made up of some carbon nanotubes.Described some carbon nanotubes are that preferred orientation extends in the same direction.Described preferred orientation refers to the overall bearing of trend of most of carbon nanotube in carbon nano-tube film substantially in the same direction.And the overall bearing of trend of described most of carbon nanotube is basically parallel to the surface of carbon nano-tube film.Further, in described carbon nano-tube film, most carbon nanotube is joined end to end by Van der Waals force.Particularly, in the most of carbon nanotubes extended substantially in the same direction in described carbon nano-tube film, each carbon nanotube and carbon nanotube adjacent are in the direction of extension joined end to end by Van der Waals force.Certainly, there is the carbon nanotube of minority random alignment in described carbon nano-tube film, these carbon nanotubes can not form obviously impact to the overall orientation arrangement of carbon nanotube most of in carbon nano-tube film.Described self-supporting is that carbon nano-tube film does not need large-area carrier supported, as long as and relatively both sides provide support power can be unsettled on the whole and keep self membranaceous state, when being placed on two supporters that (or being fixed on) interval specific range arranges by this carbon nano-tube film, the carbon nano-tube film between two supporters can the membranaceous state of unsettled maintenance self.Described self-supporting mainly through exist in carbon nano-tube film continuously through Van der Waals force join end to end extend arrangement carbon nanotube and realize.
Particularly, the most carbon nanotubes extended substantially in the same direction in described carbon nano-tube film, and nisi linearity, can be suitable bend; Or and non-fully arranges according on bearing of trend, can be suitable depart from bearing of trend.Therefore, can not get rid of between carbon nanotube arranged side by side in the most carbon nanotubes extended substantially in the same direction of carbon nano-tube film and may there is part contact.
Refer to Fig. 2 and Fig. 3, particularly, described carbon nano-tube film comprise multiple continuously and the carbon nanotube fragment 143 of the direction detection extends.The plurality of carbon nanotube fragment 143 is joined end to end by Van der Waals force.Each carbon nanotube fragment 143 comprises multiple carbon nanotube 145 be parallel to each other, and the plurality of carbon nanotube 145 be parallel to each other is combined closely by Van der Waals force.This carbon nanotube fragment 143 has arbitrary length, thickness, homogeneity and shape.Described carbon nano-tube film obtains by directly pulling after part carbon nanotube selected from a carbon nano pipe array.The thickness of described carbon nano-tube film is 1 nanometer ~ 100 micron, and width is relevant with the size of the carbon nano pipe array pulling out this carbon nano-tube film, and length is not limit.There is micropore or gap between carbon nanotube adjacent in described carbon nano-tube film thus form opening 105, and the size in the aperture of this micropore or gap is less than 10 microns.Preferably, the thickness of described carbon nano-tube film is 100 nanometer ~ 10 micron.Carbon nanotube 145 in this carbon nano-tube film in the same direction preferred orientation extends.Described carbon nano-tube film and preparation method thereof specifically refers to applicant and applies on February 9th, 2007, in No. CN101239712B Chinese publication " carbon nano tube membrane structure and preparation method thereof " of bulletin on May 26th, 2010.For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the present patent application technology and disclose.
Refer to Fig. 4, when described carbon nanotube layer comprises the multilayer carbon nanotube film of stacked setting, the bearing of trend of the carbon nanotube in adjacent two layers carbon nano-tube film forms an intersecting angle α, and α is more than or equal to 0 degree is less than or equal to 90 degree (0 °≤α≤90 °).
For reducing the thickness of carbon nano-tube film, heat treated can also be carried out to this carbon nano-tube film further.Be destroyed when heating for avoiding carbon nano-tube film, the method for described heating carbon nano-tube film adopts Local heating method.It specifically comprises the following steps: local heating carbon nano-tube film, makes carbon nano-tube film oxidized at the part carbon nanotube of local location; The position that mobile carbon nanotube is locally heated, realizes the heating of whole carbon nano-tube film from local to entirety.Particularly, this carbon nano-tube film can be divided into multiple little region, adopt by local to overall mode, this carbon nano-tube film of ground, region-by-region heating.The method of described local heating carbon nano-tube film can have multiple, as LASER HEATING method, microwave heating method etc.In the present embodiment, be greater than 0.1 × 10 by power density
4this carbon nano-tube film is irradiated in watt/square metre laser scanning, by local to overall this carbon nano-tube film of heating.This carbon nano-tube film is by laser radiation, and part carbon nanotube is oxidized in a thickness direction, and meanwhile, the carbon nano-tube bundle that in carbon nano-tube film, diameter is larger is removed, and makes this carbon nano-tube film thinning.
Be appreciated that the method for above-mentioned laser scanning carbon nano-tube film is not limit, as long as can this carbon nano-tube film of uniform irradiation.Laser scanning can be carried out line by line along the orientation of carbon nanotube in parallel carbon nano-tube film, also can carry out by column along the orientation perpendicular to carbon nanotube in carbon nano-tube film.Have constant power, fixed wave length the speed of laser scanning carbon nano-tube film less, the heat that the carbon nano-tube bundle in carbon nano-tube film absorbs is more, and corresponding destroyed carbon nano-tube bundle is more, the less thick of the carbon nano-tube film after laser treatment.But if laser scanning speed is too little, hyperabsorption heat is burnt by carbon nano-tube film.In the present embodiment, the power density of laser is greater than 0.053 × 10
12watt/square metre, the diameter of laser facula is within the scope of 1 millimeter ~ 5 millimeters, and laser scanning irradiation time is less than 1.8 seconds.Preferably, laser apparatus is carbon dioxide laser, and the power of this laser apparatus is 30 watts, and wavelength is 10.6 microns, and spot diameter is 3 millimeters, and laser aid 140 is less than 10 mm/second with the speed of relative movement of carbon nano-tube film.
Described carbon nano tube line can be the carbon nano tube line of non-twisted or the carbon nano tube line of torsion.The carbon nano tube line of described non-twisted and the carbon nano tube line of torsion are self supporting structure.Particularly, refer to Fig. 5, the carbon nano tube line of this non-twisted comprises the carbon nanotube that carbon nano tube line length direction that multiple edge is parallel to this non-twisted extends.Particularly, the carbon nano tube line of this non-twisted comprises multiple carbon nanotube fragment, and the plurality of carbon nanotube fragment is joined end to end by Van der Waals force, and each carbon nanotube fragment comprises multiple being parallel to each other and the carbon nanotube of being combined closely by Van der Waals force.This carbon nanotube fragment has arbitrary length, thickness, homogeneity and shape.The carbon nanotube line length of this non-twisted is not limit, and diameter is 0.5 nanometer ~ 100 micron.The carbon nano tube line of non-twisted is for obtain carbon nano-tube film by organic solvent process.Particularly, organic solvent is infiltrated the whole surface of described carbon nano-tube film, under the capillary effect produced when volatile organic solvent volatilizees, the multiple carbon nanotubes be parallel to each other in carbon nano-tube film are combined closely by Van der Waals force, thus make carbon nano-tube film be punctured into the carbon nano tube line of a non-twisted.This organic solvent is volatile organic solvent, as ethanol, methyl alcohol, acetone, ethylene dichloride or chloroform, adopts ethanol in the present embodiment.By the carbon nano tube line of the non-twisted of organic solvent process compared with the carbon nano-tube film without organic solvent process, specific surface area reduces, and viscosity reduces.
The carbon nano tube line of described torsion is that acquisition is reversed in described carbon nano-tube film two ends by employing one mechanical force in opposite direction.Refer to Fig. 6, the carbon nano tube line of this torsion comprises the carbon nanotube that multiple carbon nano tube line axial screw around this torsion extends.Particularly, the carbon nano tube line of this torsion comprises multiple carbon nanotube fragment, and the plurality of carbon nanotube fragment is joined end to end by Van der Waals force, and each carbon nanotube fragment comprises multiple being parallel to each other and the carbon nanotube of being combined closely by Van der Waals force.This carbon nanotube fragment has arbitrary length, thickness, homogeneity and shape.The carbon nanotube line length of this torsion is not limit, and diameter is 0.5 nanometer ~ 100 micron.Further, the carbon nano tube line of this torsion of volatile organic solvent process can be adopted.Under the capillary effect produced when volatile organic solvent volatilizees, carbon nanotube adjacent in the carbon nano tube line of the torsion after process is combined closely by Van der Waals force, and the specific surface area of the carbon nano tube line of torsion is reduced, and density and intensity increase.
Described carbon nano tube line and preparation method thereof refers to applicant and to apply on September 16th, 2002, in No. CN100411979C Chinese issued patents " a kind of Nanotubes and manufacture method thereof " of bulletin on August 20th, 2008, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd., and on December 16th, 2005 application, in No. CN100500556C Chinese issued patents " carbon nano-tube filament and preparation method thereof " of bulletin on June 17th, 2009, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..
In step S30, the growth method of described epitaxially deposited layer 104 can pass through one or more realizations in molecular beam epitaxy (MBE), chemical beam epitaxy method (CBE), reduced pressure epitaxy method, low temperature epitaxial method, selective epitaxy method, liquid deposition epitaxial method (LPE), metal organic vapor method (MOVPE), ultravacuum chemical Vapor deposition process (UHVCVD), hydride vapour phase epitaxy method (HVPE) and Metalorganic Chemical Vapor Deposition (MOCVD) etc.
Described epitaxially deposited layer 104 refers to that its material is different from substrate 100 by the single crystal structure body of epitaxial method growth in the epitaxial growth plane 101 of substrate 100, so claim epitaxially deposited layer 104.The thickness of the growth of described epitaxially deposited layer 104 can be prepared as required.Particularly, the thickness of the growth of described epitaxially deposited layer 104 can be 0.5 nanometer ~ 1 millimeter.Such as, the thickness of the growth of described epitaxially deposited layer 104 can be 100 nanometer ~ 500 micron, or 200 nanometer ~ 200 micron, or 500 nanometer ~ 100 micron.Described epitaxially deposited layer 104 can be semiconductor epitaxial film, and the material of this semiconductor epitaxial layers is GaMnAs, GaAlAs, GaInAs, GaAs, SiGe, InP, Si, AlN, GaN, GaInN, AlInN, GaAlN or AlGaInN.Described epitaxially deposited layer 104 can be a metal epitaxial film, and the material of this metal epitaxial film is aluminium, platinum, copper or silver.Described epitaxially deposited layer 104 can be an alloy epitaxial film, and the material of this alloy epitaxial film is MnGa, CoMnGa or Co
2mnGa.
Refer to Fig. 7, particularly, the process of growth of described epitaxially deposited layer 104 specifically comprises the following steps:
S31: along the epitaxial growth plane 101 direction nucleation being basically perpendicular to described substrate 100 and epitaxy forms multiple hetero epitaxy crystal grain 1042;
S32: described multiple hetero epitaxy crystal grain 1042 forms a continuous print hetero epitaxy film 1044 along the epitaxial growth plane 101 direction epitaxy being basically parallel to described substrate 100;
S33: described hetero epitaxy film 1044 forms an epitaxially deposited layer 104 along the epitaxial growth plane 101 direction epitaxy being basically perpendicular to described substrate 100.
In step S31, described multiple hetero epitaxy crystal grain 1042 starts growth in the epitaxial growth plane 101 of described substrate 100 by the part that the opening 105 of this carbon nanotube layer 102 exposes, and its direction of growth is basically perpendicular to the epitaxial growth plane 101 of described substrate 100, namely in this step, multiple hetero epitaxy crystal grain 1042 carries out longitudinal epitaxy.
In step S32, by controlling growth conditions, described carbon nanotube layer 102 to be covered by described multiple hetero epitaxy crystal grain 1042 along the direction isoepitaxial growth being connected of the epitaxial growth plane 101 being basically parallel to described substrate 100.That is, multiple hetero epitaxy crystal grain 1042 described in this step carries out laterally overgrown and directly closes up, and finally around carbon nanotube, forms multiple hole 103 and surrounded by carbon nanotube.Preferably, epitaxially deposited layer 104 interval of carbon nanotube and this carbon nanotube of encirclement is arranged.The shape of described hole is relevant with the orientation of the carbon nanotube in carbon nanotube layer 102.When carbon nanotube layer 102 be single-layered carbon nanotube periosteum or multiple be arranged in parallel carbon nano tube line time, described multiple hole 103 is the groove of substantially parallel setting.When carbon nanotube layer 102 be multilayer carbon nano-tube film arranged in a crossed manner or multiple carbon nano tube line arranged in a crossed manner time, described multiple hole 103 is trench network arranged in a crossed manner.
In step S33, due to the existence of described carbon nanotube layer 102, the lattice dislocation between hetero epitaxy crystal grain 1042 and substrate 100 is stopped growing in the process forming continuous print hetero epitaxy film 1044.Therefore, the epitaxially deposited layer 104 of this step is equivalent to not have defective hetero epitaxy film 1044 surface to carry out isoepitaxial growth.Described epitaxially deposited layer 104 has less defect.In first embodiment of the invention, described substrate 100 is a sapphire (Al
2o
3) substrate, described carbon nanotube layer 102 is a single-layered carbon nanotube periosteum.This enforcement adopts MOCVD technique to carry out epitaxy.Wherein, high-purity ammonia (NH is adopted
3) as the source gas of nitrogen, adopt hydrogen (H
2) do carrier gas, adopt trimethyl-gallium (TMGa) or triethyl-gallium (TEGa), trimethyl indium (TMIn), trimethyl aluminium (TMAl) is as Ga source, In source and Al source.Specifically comprise the following steps.First, sapphire substrates 100 is inserted reaction chamber, be heated to 1100 DEG C ~ 1200 DEG C, and pass into H
2, N
2or its mixed gas is as carrier gas, high bake 200 seconds ~ 1000 seconds.Secondly, continue with entering carrier gas, and cool to 500 DEG C ~ 650 DEG C, pass into trimethyl-gallium or triethyl-gallium and ammonia, growing GaN low temperature buffer layer, its thickness 10 nanometer ~ 50 nanometer.Then, stop passing into trimethyl-gallium or triethyl-gallium, continue to pass into ammonia and carrier gas, temperature is elevated to 1100 DEG C ~ 1200 DEG C simultaneously, and constant temperature keeps 30 seconds ~ 300 seconds, anneals.Finally, the temperature of substrate 100 is remained on 1000 DEG C ~ 1100 DEG C, continue to pass into ammonia and carrier gas, again pass into trimethyl-gallium or triethyl-gallium simultaneously, at high temperature complete the laterally overgrown process of GaN, and grow high-quality GaN epitaxial layer.After sample grown, scanning electronic microscope (SEM) and transmission electron microscope (TEM) is used to observe sample and test respectively.Refer to Fig. 8 and Fig. 9, in heteroepitaxial structure prepared by the present embodiment, epitaxially deposited layer only grows from the position that the epitaxial growth plane of substrate does not have carbon nanotube layer, is then connected.The surface of described epitaxially deposited layer and substrate contact forms multiple hole, and described carbon nanotube layer is arranged in this hole, and and epitaxially deposited layer interval arrange.Particularly, can know that it sees the interface between GaN epitaxial layer and sapphire substrates from described Fig. 8, wherein, dark parts is GaN epitaxial layer, and light-colored part is sapphire substrates.The surface that described GaN epitaxial layer contacts with sapphire substrates has a round hole.Can see from described Fig. 9, in each hole, be provided with carbon nanotube.Carbon nanotube in described hole is arranged at process for sapphire-based basal surface, and and forms the GaN epitaxial layer interval of hole and arrange.
Refer to Figure 10 and Figure 11, be a kind of heteroepitaxial structure 10 that first embodiment of the invention prepares, it comprises: substrate 100, carbon nanotube layer 102 and an epitaxially deposited layer 104.Described substrate 100 has an epitaxial growth plane 101.Described carbon nanotube layer 102 is arranged at the epitaxial growth plane 101 of described substrate 100, and this carbon nanotube layer 102 has multiple opening 105, and the part of the opening 105 of the corresponding described carbon nanotube layer 102 of epitaxial growth plane 101 of described substrate 100 exposes.Described epitaxially deposited layer 104 is arranged at the epitaxial growth plane 101 of described substrate 100, and covers described carbon nanotube layer 102.Described carbon nanotube layer 102 is arranged between described epitaxially deposited layer 104 and substrate 100.
Described carbon nanotube layer 102 covers by described epitaxially deposited layer 104, and the multiple openings 105 permeating described carbon nanotube layer 102 contact with the epitaxial growth plane 101 of described substrate 100, i.e. in multiple openings 105 of described carbon nanotube layer 102, all infiltration has described epitaxially deposited layer 104.Carbon nanotube layer 102 interval on microcosmic of described epitaxially deposited layer 104 and its covering is arranged, namely the surface that described epitaxially deposited layer 104 contacts with substrate 100 forms multiple hole 103, described carbon nanotube layer 102 is arranged in this hole 103, particularly, the carbon nanotube in described carbon nanotube layer 102 is separately positioned in multiple hole 103.Described hole 103 is formed in the surface that epitaxially deposited layer 104 contacts with described substrate 100, is blind hole at this hole 103 of thickness direction of described epitaxially deposited layer 104.In each hole 103, carbon nanotube does not contact with described epitaxially deposited layer 104 all substantially.
Described carbon nanotube layer 102 is a self supporting structure.This carbon nanotube layer comprises carbon nano-tube film or carbon nano tube line.In the present embodiment, described carbon nanotube layer 102 is a single-layered carbon nanotube periosteum, this carbon nano-tube film comprises multiple carbon nanotube, and the axially preferred orientation extension in the same direction of the plurality of carbon nanotube, the adjacent carbon nanotube that bearing of trend is identical is joined end to end by Van der Waals force.Between the adjacent carbon nanotube perpendicular to bearing of trend, partial separation arranges and there is micropore or gap, thus forms opening 105.
Refer to Figure 12, be a kind of heteroepitaxial structure 20 that second embodiment of the invention prepares, it comprises: substrate 200, carbon nanotube layer 202 and an epitaxially deposited layer 204.The substrate 200 of the heteroepitaxial structure 20 in second embodiment of the invention and the material of epitaxially deposited layer 204, and substrate 200, carbon nanotube layer 202 are substantially identical with the heteroepitaxial structure 10 of the first embodiment with the position relationship of epitaxially deposited layer 204, its difference is, carbon nanotube layer 202 is multiple parallel and spaced carbon nano tube lines, forms micropore between adjacent carbon nano tube line.
Described carbon nano tube line can be the carbon nano tube line of non-twisted or the carbon nano tube line of torsion.Particularly, the carbon nano tube line of described non-twisted comprises the carbon nanotube that multiple carbon nano tube line length direction along this non-twisted extends.The carbon nano tube line of described torsion comprises the carbon nanotube that multiple carbon nano tube line axial screw around this torsion extends.
In second embodiment of the invention, described substrate 100 is an isolate supports (SOI:silicon on insulator) substrate, and described carbon nanotube layer 102 is multiple parallel and spaced carbon nano tube lines.This enforcement adopts MOCVD technique to carry out epitaxy.Wherein, adopt trimethyl-gallium (TMGa), trimethyl aluminium (TMAl) as the source material of Ga and Al respectively, ammonia (NH
3) as the source material of nitrogen, hydrogen (H
2) do carrier gas, use the heating of horizontal type level Reaktionsofen.Particularly, first multiple parallel and spaced carbon nano tube line is laid in the epitaxial growth plane 101 of SOI substrate 100.Then in the epitaxial growth plane 101 epitaxy GaN epitaxial layer of substrate 100, growth temperature 1070 DEG C, growth time 450 seconds, mainly carries out the longitudinal growth of GaN; Then keep chamber pressure constant, increase the temperature to 1110 DEG C, reduce Ga source flux simultaneously, and keep ammonia flow constant, to promote laterally overgrown, growth time is 4900 seconds; Finally, reduce temperature to 1070 DEG C, increase Ga source flux simultaneously and continue longitudinal growth 10000 seconds.
Refer to Figure 13, third embodiment of the invention provides a kind of heteroepitaxial structure 30, and it comprises: substrate 300, carbon nanotube layer 302 and an epitaxially deposited layer 304.The substrate 300 of the heteroepitaxial structure 30 in third embodiment of the invention and the material of epitaxially deposited layer 304, and substrate 300, carbon nanotube layer 302 are substantially identical with the heteroepitaxial structure 20 of the second embodiment with the position relationship of epitaxially deposited layer 304, its difference is, carbon nanotube layer 302 is multiple intersection and spaced carbon nano tube line, particularly, the plurality of carbon nano tube line be arranged in parallel along first direction and second direction respectively, described first direction and second direction arranged in a crossed manner.Intersect and form an opening between four adjacent carbon nano tube lines.In the present embodiment, two adjacent carbon nano tube lines be arranged in parallel, and two carbon nano tube lines intersected are mutually vertical.Be appreciated that described carbon nano tube line also can adopt any interleaved mode to arrange, only carbon nanotube layer 302 need be made to form multiple opening, thus the epitaxy face portion of substrate 300 is exposed.
The heteroepitaxial structure 30 of third embodiment of the invention can adopt the method identical with the first embodiment or the second embodiment to prepare.
Fourth embodiment of the invention provides a kind of iso-epitaxy structure, and it comprises: a substrate, a carbon nanotube layer and an epitaxial film.Carbon nanotube layer in fourth embodiment of the invention can adopt above-mentioned first embodiment to the carbon nanotube layer of the 3rd embodiment, material and the position relationship of substrate, carbon nanotube layer and epitaxial film are substantially identical with the first embodiment, its difference is, described substrate is identical with the material of epitaxial film, thus forms a homogeneity epitaxial structure.Particularly, in the present embodiment, the material of described substrate and epitaxial film is GaN.
Fourth embodiment of the invention provides a kind of preparation method of iso-epitaxy structure further, and it specifically comprises the following steps:
S100 a: substrate is provided, and this substrate has the epitaxial growth plane of a support iso-epitaxy layer growth;
S200: one carbon nanotube layer is set in the epitaxial growth plane of described substrate, this substrate and carbon nanotube layer form a substrate jointly; And
S300: at the epitaxial growth plane growth homogeneity epitaxial layer of substrate.
The growth method of the homogeneity epitaxial layer of fourth embodiment of the invention is substantially identical with the growth method of the epitaxially deposited layer of the first embodiment, and its difference is, described substrate is identical with the material of epitaxial film, thus forms a homogeneity epitaxial structure.
The present invention adopts a carbon nanotube layer to be arranged at described substrate epitaxial growth plane grown epitaxial layer as mask to have and have with effect below:
The first, described carbon nanotube layer is a self supporting structure, can be laid immediately on the epitaxial growth plane of substrate, and form mask relative to prior art by techniques such as photoetching after deposition, present invention process is simple, with low cost, is conducive to volume production.
Second, described carbon nanotube layer is patterned structures, and its thickness, opening size all can reach nano level, described substrate be used for grown epitaxial layer time the hetero epitaxy crystal grain that formed there is less size, be conducive to the generation reducing dislocation defects, to obtain high-quality epitaxially deposited layer.
3rd, the opening size of described carbon nanotube layer is nano level, described epitaxial film grows from the epitaxial growth plane of the exposure corresponding with nano level opening, contact area between the epitaxial film of growth and substrate is reduced, reduce the stress between process of growth epitaxial layers and substrate, thus can the larger epitaxially deposited layer of growth thickness, can further improve the quality of epitaxially deposited layer.
In addition, those skilled in the art also can do other change in spirit of the present invention, and these changes done according to the present invention's spirit, all should be included in the present invention's scope required for protection certainly.
Claims (26)
1. the mask for growing epitaxial structure, this mask comprises: a carbon nanotube layer, and this carbon nanotube layer is the self supporting structure of continuous print entirety, there is multiple opening, the epitaxial growth plane of substrate is exposed by the plurality of opening portion, by the some growth that this mask makes epitaxial film be exposed from the epitaxial growth plane of described substrate by this opening, described carbon nanotube layer comprises carbon nano-tube film or carbon nano tube line, described opening is the micropore or gap that exist between carbon nanotube adjacent in gap between described carbon nano tube line or described carbon nano-tube film.
2., as claimed in claim 1 for the mask of growing epitaxial structure, it is characterized in that, described carbon nanotube layer is laid immediately on the epitaxial growth plane of described substrate.
3., as claimed in claim 1 for the mask of growing epitaxial structure, it is characterized in that, described opening is of a size of 10 nanometer ~ 500 micron.
4., as claimed in claim 3 for the mask of growing epitaxial structure, it is characterized in that, described opening is of a size of 10 nanometer ~ 120 micron.
5., as claimed in claim 4 for the mask of growing epitaxial structure, it is characterized in that, described opening is of a size of 10 nanometer ~ 80 micron.
6., as claimed in claim 5 for the mask of growing epitaxial structure, it is characterized in that, described opening is of a size of 10 nanometer ~ 10 micron.
7. the mask for growing epitaxial structure according to any one of claim 3 to 6, is characterized in that, the dutycycle of described carbon nanotube layer is 1:100 ~ 100:1.
8. the mask for growing epitaxial structure according to any one of claim 3 to 6, is characterized in that, the dutycycle of described carbon nanotube layer is 1:4 ~ 4:1.
9., as claimed in claim 1 for the mask of growing epitaxial structure, it is characterized in that, the thickness of described carbon nanotube layer is 1 nanometer ~ 100 micron.
10. as claimed in claim 1 for the mask of growing epitaxial structure, it is characterized in that, described carbon nanotube layer comprises at least one carbon nano-tube film, and this carbon nano-tube film comprises multiple carbon nanotube, and the axially preferred orientation extension in the same direction of described multiple carbon nanotube.
11., as claimed in claim 10 for the mask of growing epitaxial structure, is characterized in that, the described axis adjacent carbon nanotube that preferred orientation extends in the same direction is joined end to end by Van der Waals force.
12., as claimed in claim 10 for the mask of growing epitaxial structure, is characterized in that, described carbon nanotube layer comprises multiple carbon nanotube film-stack and arranges.
13., as claimed in claim 1 for the masks of growing epitaxial structure, is characterized in that, described carbon nanotube layer comprises multiple parallel and spaced carbon nano tube line.
14. as claimed in claim 1 for the mask of growing epitaxial structure, and it is characterized in that, described carbon nanotube layer comprises multiple carbon nano tube line arranged in a crossed manner.
15. masks for growing epitaxial structure as described in claim 13 or 14, it is characterized in that, the diameter of described carbon nano tube line is 0.5 nanometer ~ 100 micron, and the distance between adjacent two carbon nano tube lines be arranged in parallel is 0.1 micron ~ 200 microns.
16. as claimed in claim 1 for the mask of growing epitaxial structure, and it is characterized in that, described carbon nanotube layer is a composite structure comprising multiple carbon nanotube and adding material.
17., as claimed in claim 16 for the masks of growing epitaxial structure, is characterized in that, described adding material comprises that graphite, graphite are rare, one or more in silicon carbide, boron nitride, silicon nitride, silicon-dioxide and decolorizing carbon.
18., as claimed in claim 16 for the masks of growing epitaxial structure, is characterized in that, described adding material comprise in metallic carbide, metal oxide and metal nitride one or more.
19. as claimed in claim 16 for the mask of growing epitaxial structure, and it is characterized in that, described adding material is coated at least part of surface of carbon nanotube or is arranged in the opening of carbon nanotube layer.
20. 1 kinds of masks for growing epitaxial structure, this mask comprises: a carbon nanotube layer, this carbon nanotube layer is the self supporting structure of continuous print entirety, comprise multiple aligning and the carbon nanotube extended along the direction being parallel to carbon nanotube layer surface, and between the plurality of carbon nanotube, there is multiple opening, the epitaxial growth plane of substrate is exposed by the plurality of opening portion, by the some growth that this mask makes epitaxial film be exposed from the epitaxial growth plane of described substrate by this opening, described opening is the gap between micropore or adjacent carbon nanotubes that in described carbon nanotube layer, multiple adjacent carbon nanotube surrounds.
The using method of 21. 1 kinds of masks for growing epitaxial structure as described in any one in claim 1 to 20, it comprises the following steps:
There is provided a substrate, this substrate has the epitaxial growth plane of a support outer layer growth;
In the epitaxial growth plane of described substrate, one mask is set, this mask comprises: a carbon nanotube layer, this nanotube layer is the self supporting structure of continuous print entirety, comprise multiple aligning and the carbon nanotube extended along the direction being parallel to carbon nanotube layer surface, and between the plurality of carbon nanotube, there is multiple opening, the epitaxial growth plane of substrate is exposed by the plurality of opening portion; And,
At the epitaxial growth plane grown epitaxial layer of described substrate.
22. as claimed in claim 21 for the using method of the mask of growing epitaxial structure, and it is characterized in that, described carbon nanotube layer comprises multiple carbon nanotube, and the plurality of carbon nanotube extends along the direction in the crystal orientation being parallel to substrate.
23., as claimed in claim 21 for the using method of the mask of growing epitaxial structure, is characterized in that, the some growth that described epitaxial film is exposed from the epitaxial growth plane of described substrate by this opening.
24. as claimed in claim 21 for the using method of the mask of growing epitaxial structure, and it is characterized in that, described epitaxial film and substrate form a heteroepitaxial structure.
25. as claimed in claim 21 for the using method of the mask of growing epitaxial structure, and it is characterized in that, described epitaxial film and substrate form a homogeneity epitaxial structure.
26. as claimed in claim 21 for the using method of the mask of growing epitaxial structure, it is characterized in that, the growth method of described epitaxial film comprise in molecular beam epitaxy, chemical beam epitaxy method, reduced pressure epitaxy method, low temperature epitaxial method, selective epitaxy method, liquid deposition epitaxial method, metal organic vapor method, ultravacuum chemical Vapor deposition process, hydride vapour phase epitaxy method and Metalorganic Chemical Vapor Deposition one or more.
Priority Applications (19)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110025710.6A CN102605422B (en) | 2011-01-24 | 2011-01-24 | For mask and the using method thereof of growing epitaxial structure |
| US13/273,252 US9024310B2 (en) | 2011-01-12 | 2011-10-14 | Epitaxial structure |
| US13/276,275 US20120175629A1 (en) | 2011-01-12 | 2011-10-18 | Semiconductor epitaxial structure |
| US13/276,302 US20120175743A1 (en) | 2011-01-12 | 2011-10-18 | Epitaxial structure |
| US13/276,280 US9196790B2 (en) | 2011-01-12 | 2011-10-18 | Method for making epitaxial structure |
| US13/276,278 US9515221B2 (en) | 2011-01-12 | 2011-10-18 | Epitaxial structure and method for making the same |
| US13/276,265 US8685773B2 (en) | 2011-01-12 | 2011-10-18 | Method for making semiconductor epitaxial structure |
| US13/276,309 US8906788B2 (en) | 2011-01-12 | 2011-10-18 | Method for making epitaxial structure |
| US13/276,285 US8455336B2 (en) | 2011-01-12 | 2011-10-18 | Method for making epitaxial structure |
| US13/275,564 US8633045B2 (en) | 2011-01-12 | 2011-10-18 | Method for making epitaxial structure |
| US13/276,251 US9466762B2 (en) | 2011-01-12 | 2011-10-18 | Base and method for making epitaxial structure using the same |
| US13/276,294 US20120178248A1 (en) | 2011-01-12 | 2011-10-18 | Method for making epitaxial structure |
| US13/276,283 US8936681B2 (en) | 2011-01-12 | 2011-10-18 | Method for making epitaxial structure using carbon nanotube mask |
| JP2011238660A JP5931402B2 (en) | 2011-01-24 | 2011-10-31 | Mask used for growing an epitaxial layer and method of using the same |
| US14/098,775 US9905726B2 (en) | 2011-01-12 | 2013-12-06 | Semiconductor epitaxial structure |
| US14/098,743 US9559255B2 (en) | 2011-01-12 | 2013-12-06 | Epitaxial structure |
| US14/098,767 US9219193B2 (en) | 2011-01-12 | 2013-12-06 | Method for making epitaxial structure |
| US15/263,338 US10177275B2 (en) | 2011-01-12 | 2016-09-12 | Epitaxial structure and method for making the same |
| US16/177,449 US10622516B2 (en) | 2011-01-12 | 2018-11-01 | Epitaxial structure and method for making the same |
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| CN102299056B (en) * | 2011-07-21 | 2013-11-06 | 北京大学 | Preparation method of III-nitride quantum dot structure |
| KR102114950B1 (en) | 2013-01-29 | 2020-05-26 | 삼성디스플레이 주식회사 | Mask for layer deposition and deposition apparatus having the same |
| CN104952983B (en) * | 2014-03-26 | 2018-07-10 | 清华大学 | The preparation method of epitaxial structure |
| CN108132582B (en) * | 2016-12-01 | 2020-06-09 | 清华大学 | Photoetching mask plate |
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