CN104637788A - Selective area growing method for III-nitride micro graphic structure and structure - Google Patents
Selective area growing method for III-nitride micro graphic structure and structure Download PDFInfo
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- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 10
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 6
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/0254—Nitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
Abstract
The invention discloses a selective area growing method for III-nitride micro graphic structure and a structure. A carbon nanotube array is taken as a micrometer/nanometer composite size mask; nanometer grade growing windows in bundle clusters and micrometer grade growing windows among the bundle clusters are arranged at intervals; according to the remarkable difference between the growth rates of III-nitride in the micrometer grade growing windows and the nanometer grade growing windows, an III-nitride dual-size micro graphic structure in which micro graphic structures which are the same in shapes and are different in sizes are arranged at intervals can be made on the micrometer/nanometer composite size mask. By adopting the carbon nanotube mask, the advantage of nanoheteroepitaxy can be brought into full play, the crystal quality of a micro graphic structural material is improved, and the residual stress is lowered; the nanotube has the characteristics of high thermal conductivity and high electrical conductivity, so that the heat dissipation of subsequently-manufactured micro-electron and photoelectron devices and the improvement on the electric property are facilitated.
Description
Technical field
The present invention relates to semi-conductor photoelectronic technology, particularly relating to a kind of take carbon nano-tube as selective area growth method and the structure of the two size microcosmos pattern structure of group III-nitride of mask, shape and size controllable precise.
Background technology
Group III-nitride is the semi-conducting material that a class has application prospect, except the thin-film material of routine, in recent years, the group III-nitride of various micron or nanoscale and the thin-film material of the graphic structure with this micron or nanoscale also show superior performance and apply possibility widely.Above-mentioned microstructure comprises the column structure etc. of the groove structure of one dimension, two-dimentional island structure or three-dimensional.This type of thin-film material with microcosmos pattern structure both can be used as graphics template to obtain high-quality thin film material, also can be directly used in and prepare micron, the microelectronics of nanoscale, opto-electronic device.
The current method preparing group III-nitride microcosmos pattern structure mainly contains:
(1) using plasma strengthens method deposition of silica or the silicon nitride dielectric layers such as chemical vapour deposition (CVD) PECVD, by means such as photoetching, nano impression, electron beam exposures, insulating barrier is etched into layout again, then obtains the thin-film material with microcosmos pattern structure with selective area growth method;
(2) adopt without masking method, using metal materials such as undersized nickel, iron as catalyst, or prepare the thin-film material with microcosmos pattern structure by stress modulation etc. in self assembly mode.
Above-mentioned two classes have in method, and the thin-film material that the former obtains has the advantages such as uniformity is good, controllability is good, but complex process, with high costs, and are still difficult to obtain the microcosmos pattern structure of characteristic size at below 100nm on a large scale at present.Although the latter's technique is comparatively simple, without the need to preparing mask, obtained microcosmos pattern structural homogeneity is poor, poor controllability, poor repeatability.
Summary of the invention
In order to solve above problems of the prior art, the present invention proposes a kind of using carbon nano pipe array as mask, growth has the selective area growth method of the group III-nitride of the microcosmos pattern structures such as the cylinder of micron or nanoscale, cone, inverted trapezoidal or bar shaped; The method has the advantages such as with low cost, technique is simple, environmental protection, and the shape of figure and size adjustable, controllable precise flexibly.
One object of the present invention is the mask structure providing the two size microcosmos pattern structure selective area growth method of a kind of group III-nitride.
The selective area growth structure of the two size microcosmos pattern structure of group III-nitride of the present invention comprises: the two size microcosmos pattern structure of substrate, carbon nano-tube mask and group III-nitride; The carbon nano-tube mask that substrate is laid is made up of single or multiple lift carbon nano-tube film, every one deck carbon nano-tube film is carbon nano pipe array arranged in parallel, these carbon nano-tube assemble formation bundle clustering architecture arranged in parallel mutually, micron order growth window is formed between adjacent bundle bunch, form nanoscale growth window between the multiple carbon nano-tube arranged in parallel in bundle bunch inside, thus form nanoscale growth window and micron order growth window micrometer/nanometer compound size mask alternately; Carbon nano-tube mask grows the two size microcosmos pattern structure of group III-nitride.
Substrate adopts the material that can realize group III-nitride growth, as gallium nitride substrate, Sapphire Substrate, silicon carbide substrates, silicon substrate etc., or substrate adopts the compound substrate that grown the template layer of thickness between 10nm ~ 100 μm on gallium nitride substrate, Sapphire Substrate, silicon carbide substrates or silicon substrate, the material of template layer adopts one or more the alloy in gallium nitride GaN, aluminium nitride AlN and indium nitride InN.
When preparing above-mentioned mask structure, first in the growth substrates of carbon nano pipe array, by the nano grade iron powder of electron-beam evaporation one deck marshalling, size uniform as catalyst, again by low-pressure chemical vapor deposition LPCVD method, using acetylene as carbon source under low pressure and high temperature, grow by standard orderly, array that carbon nano-tube arranged in parallel forms, then it can be used as one deck carbon nano-tube film to be transferred on the substrate of growth group III-nitride.Carbon nano-tube mask is made up of single or multiple lift carbon nano-tube film, every one deck carbon nano-tube film is as the criterion orderly, arranged in parallel carbon nano pipe array, carbon nano-tube wherein can be single wall or many walls, single-root carbon nano-tube between 10 ~ 100nm, these carbon nano-tube can be assembled mutually, form bundle clustering architecture arranged in parallel.Distance between bundle bunch inner adjacent carbon nanotubes is between 10 ~ 500nm, and this, for the growth of follow-up group III-nitride, defines nanoscale growth window; The diameter of every a bundle bunch is between 1 ~ 10 μm, and the distance between adjacent bundle bunch is between 1 ~ 20 μm, and this, for the growth of follow-up group III-nitride, defines micron order growth window.Thus, nanoscale growth window and micron order growth window can alternately, and cover structure forms micrometer/nanometer compound size mask.The present invention is directed to different substrates, the difference according to Substrate orientation and group III-nitride growth pattern selects different carbon nano-tube mask structures.Carbon nano-tube mask can comprise single or multiple lift carbon nano-tube film, and the laying number of plies is more, and in mask, the size of growth window is less, also namely by controlling the carbon nano-tube film number of plies of laying, can change the duty ratio of mask.Therefore accurately can control mask dimensions as required, improve the crystal mass of epitaxial film.Every one deck carbon nano-tube film is all as the criterion orderly, arranged in parallel carbon nano pipe array, then can be parallel to each other as required between multilayer carbon nanotube films, vertical or be crossed as acute angle arrangement, thus construct the geometric mask structures of arbitrary plane such as there is rectangle, hexagon, parallelogram with multilayer carbon nanotube films.
As mentioned above, in carbon nano-tube mask structure of the present invention, nanoscale growth window in existing bundle bunch, also have micron order growth window between bundle bunch, the two alternately.In nanoscale growth window, the growth rate of group III-nitride is less than the growth rate of group III-nitride in micron order growth window.Utilize the significant difference of the growth rate of group III-nitride in micron order growth window and nanoscale growth window, can obtain two kinds on above-mentioned micrometer/nanometer compound size mask shape is identical and the two size microcosmos pattern structure of microcosmos pattern structure group III-nitride alternately that size is different.Further, by controlling growth conditions, change the ratio of group III-nitride cross growth speed and longitudinal growth speed, above-mentioned size difference can be made to be embodied in laterally, vertical or horizontal with on longitudinal direction, namely highly identical and diameter different, highly different and diameter is identical or highly all different from diameter two size microcosmos pattern structures.Utilize mask structure and the growing method of above-mentioned uniqueness, obtain the two size microcosmos pattern structure of group III-nitride, this is that additive method is unapproachable.
Another object of the present invention is the selective area growth method providing the two size microcosmos pattern structure of a kind of group III-nitride.
The selective area growth method of the two size microcosmos pattern structure of group III-nitride of the present invention, comprises the following steps:
1) substrate is chosen:
Substrate adopts the material that can realize group III-nitride growth, as gallium nitride substrate, Sapphire Substrate, silicon carbide substrates, silicon substrate etc.; Or substrate adopts the compound substrate that grown the template layer of thickness between 10nm ~ 100 μm on gallium nitride substrate, Sapphire Substrate, silicon carbide substrates or silicon substrate, the material of template layer adopts one or more the alloy in GaN, AlN and InN;
2) on substrate, carbon nano-tube mask is laid:
The carbon nano-tube film grown is peeled off from its growth substrates, then according to needing to lay single or multiple lift carbon nano-tube film on substrate, form carbon nano-tube mask, in the carbon nano-tube mask of final formation, carbon nano-tube arranged in parallel can be assembled mutually, form bundle clustering architecture arranged in parallel, the spacing in every a bundle bunch between carbon nano-tube is nanometer scale, forms nanoscale growth window; Spacing between adjacent bundle bunch is micron dimension, forms micron order growth window, and nanoscale growth window and micron order growth window can alternately, and cover structure forms micrometer/nanometer compound size mask;
3) on the substrate having laid carbon nano-tube mask, the two size microcosmos pattern structure of growth group III-nitride:
Adopt metal-organic chemical vapor deposition equipment MOCVD or the two size microcosmos pattern structure of molecular beam epitaxy MBE technology growth group III-nitride.
Wherein, in step 2) in, in carbon nano-tube mask, carbon nano-tube can be single wall or many walls, and the diameter of single-root carbon nano-tube is between 10 ~ 100nm, and the distance between adjacent carbon nano-tube, between 10 ~ 500nm, forms nanoscale growth window; The diameter of every a bundle bunch is between 1 ~ 10 μm, and the distance between adjacent bundle bunch, between 1 ~ 20 μm, forms micron order growth window.For different substrates, the difference according to Substrate orientation and crystal growth mode selects different carbon nano-tube mask structures.Carbon nano-tube mask can comprise single or multiple lift carbon nano-tube film, every one deck carbon nano-tube film is all as the criterion orderly, arranged in parallel carbon nano pipe array, then can be parallel to each other as required between multilayer carbon nanotube films, vertical or be crossed as acute angle arrangement, thus construct the geometric mask structures of arbitrary plane such as there is rectangle, hexagon, parallelogram with multilayer carbon nanotube films.
Step 3) in, be mainly divided into two-step growth, be first low temperature buffer layer growth, carry out the high growth temperature of group III-nitride subsequently.MOCVD is adopted to grow group III-nitride, low temperature buffer layer is using III metallorganic as III source, its flow is 10 ~ 200sccm, using ammonia as group V source, its flow is 50 ~ 8000sccm, and growth temperature is between 500 ~ 600 DEG C, and pressure is between 100 ~ 400Torr, carrier gas is hydrogen, and buffer layer thickness scope is 10 ~ 500nm; Carry out the high growth temperature of group III-nitride subsequently, using hydrogen, nitrogen or the mist of the two as carrier gas, using III metallorganic as III source, its flow is 10 ~ 500sccm, using ammonia as group V source, its flow is 50 ~ 8000sccm, and group V source and III source molal quantity ratio V/III scope are 10 ~ 5000, growth temperature is between 900 ~ 1100 DEG C, and pressure is between 75 ~ 500Torr.By changing above-mentioned growth conditions, the two size microcosmos pattern structure of group III-nitride of micron or nanoscale can be grown.
In step 3) in, if first passed into ammonia or nitrogen before growth group III-nitride, carry out high-temperature ammonolysis, then form the column figure that end face is plane; If do not pass into ammonia or nitrogen before growth group III-nitride, do not carry out high-temperature ammonolysis, then form the taper figure that end face is wedge angle.
The present invention adopts the micrometer/nanometer compound size mask be made up of single or multiple lift carbon nano-tube film, utilize the difference of the growth rate of group III-nitride in micron order growth window and nanoscale growth window, obtain the group III-nitride microcosmos pattern structure be of different sizes.
Advantage of the present invention:
With regard to preparation technology, the preparation of carbon nano-tube mask in the present invention has that technique is simple, with low cost, the advantage of environmental protection.
With regard to the character of mask and function, compared to the mask material such as silicon dioxide, silicon nitride, carbon nano-tube has the following advantages:
(1) stable chemical nature, high temperature resistant, surface cleanliness is high;
(2) mask regions in carbon nano-tube mask and window region change in size scope are larger, most I to nanoscale, maximum can to micron order, therefore obtained dimension of picture excursion is greatly and controlled flexibly;
(3) the mask pattern flexible shapes of carbon nano-tube mask is controlled, can construct the geometric mask structures of arbitrary plane such as having rectangle, hexagon, parallelogram as required with multilayer carbon nanotube films;
(4) what is particularly worth mentioning is that, in carbon nano-tube mask structure of the present invention, nanoscale growth window in existing bundle bunch, also have micron order growth window between bundle bunch, the two alternately.When above-mentioned mask structure carries out the growth of III-nitride material, utilize the growth rate difference of group III-nitride in two kinds of growth window, obtained two kinds shape is identical and the two size microcosmos pattern structure of microcosmos pattern structure group III-nitride alternately that size is different.
(5) adopt carbon nano-tube mask, the advantage of nanoheteroepitaxy can be given full play to, improve the crystal mass of microcosmos pattern structural material, reduce residual stress;
(6) because carbon nano-tube has, thermal conductivity is high, conductivity high, is conducive to follow-up obtained microelectronics, the heat radiation of opto-electronic device and the lifting of electrical properties.
Accompanying drawing explanation
Fig. 1 is the schematic diagram laying carbon nano-tube mask according to an embodiment of the two size microcosmos pattern structure selective area growth method of group III-nitride in the present invention;
Fig. 2 is the explosive view laying carbon nano-tube mask according to the embodiment one of the two size microcosmos pattern structure selective area growth method of group III-nitride in the present invention;
Fig. 3 is the schematic diagram of the two size micron six prism microcosmos pattern structure of GaN prepared according to the embodiment one of the two size microcosmos pattern structure selective area growth method of group III-nitride in the present invention, wherein, a () is end view, (b) is vertical view;
Fig. 4 is the schematic diagram of the two size micron hexagonal pyramid microcosmos pattern structure of GaN prepared according to the embodiment two of the two size microcosmos pattern structure selective area growth method of group III-nitride in the present invention;
Fig. 5 is the schematic diagram of the two size micron inverted trapezoidal microcosmos pattern structure of GaN prepared according to the embodiment three of the two size microcosmos pattern structure selective area growth method of group III-nitride in the present invention;
Fig. 6 is the schematic diagram of the two size six prism microcosmos pattern structure of GaN micrometer/nanometer prepared according to the embodiment four of the two size microcosmos pattern structure selective area growth method of group III-nitride in the present invention.
Embodiment
Below in conjunction with accompanying drawing, by embodiment, the present invention will be further described.
As shown in Figure 1, lay two-layer carbon nano-tube film on substrate 1 as carbon nano-tube mask 2, two-layer carbon nano-tube film is orthogonal, every one deck carbon nano-tube film comprises multiple bundle clustering architecture arranged in parallel, micron order growth window 31 is formed between adjacent bundle bunch, each bundle bunch comprises many carbon nano-tube arranged in parallel, nanoscale growth window 32 is formed between adjacent carbon nano-tube, the arrangement that nanoscale growth window is alternate with micron order growth window, forms micrometer/nanometer compound size mask.
Embodiment one
In the present embodiment, substrate adopts c surface sapphire substrate, substrate is laid three layers of carbon nano-tube film as carbon nano-tube mask, the two size micron six prism microcosmos pattern structure of preparation GaN.As shown in Figure 2, lay three layers of carbon nano pipe array 21 ~ 23 on substrate 1 respectively as carbon nano-tube mask, ground floor 21 is perpendicular to the second layer 22, and third layer 23 is perpendicular to the second layer; Every one deck carbon nano-tube film comprises multiple bundle clustering architecture arranged in parallel, each bundle bunch diameter between 2 ~ 4 μm, distance between adjacent bundle bunch is between 2 ~ 4 μm, as micron order growth window, distance in bundle bunch between adjacent carbon nano-tube is 200 ~ 500nm, as nanoscale growth window, form micron order growth window and nanoscale growth window micrometer/nanometer compound size mask alternately.
The selective area growth method of the two size micron six prism microcosmos pattern structure of GaN of the present embodiment, comprises the following steps:
1) substrate 1 adopts c surface sapphire substrate.
2) carbon nano-tube mask is laid on substrate 1:
In the growth substrates of carbon nano pipe array, by the nano grade iron powder of electron-beam evaporation one deck marshalling, size uniform as catalyst, again by LPCVD method, using acetylene as carbon source under low pressure and high temperature, grow accurate orderly, arranged in parallel carbon nano pipe array, then be laid on after being peeled off in the growth substrates of group III-nitride; The carbon nano-tube formed is Single Walled Carbon Nanotube, and the diameter of single-root carbon nano-tube is 20nm; Substrate is laid three layers of carbon nano-tube film 21 ~ 23 as carbon nano-tube mask, carbon nano pipe array in ground floor 21 is along the direction being parallel to substrate reference limit, and the carbon nano pipe array in the second layer 22 is along the direction being parallel to substrate reference limit perpendicular to the carbon nano pipe array edge in the direction third layer 23 on substrate reference limit; Final carbon nano pipe array forms bundle clustering architecture, each bundle bunch diameter between 2 ~ 4 μm, distance between adjacent bundle bunch is between 2 ~ 4 μm, as micron order growth window, distance in bundle bunch between adjacent carbon nano-tube is 200 ~ 500nm, as nanoscale growth window, form micrometer/nanometer compound size mask.
3) on the substrate having laid carbon nano-tube mask, the two size micron six prism microcosmos pattern structure of MOCVD technology epitaxial growth GaN is adopted:
A) in MOCVD reative cell, in a hydrogen atmosphere, air pressure is 100Torr, is warming up to 1050 DEG C and carries out situ cleaning process;
B) in a hydrogen atmosphere, air pressure is 300Torr, and temperature keeps 1050 DEG C, passes into ammonia as group V source, and its flow is 8000sccm, keeps 10 minutes, carries out high-temperature ammonolysis process to substrate;
C) in a hydrogen atmosphere, air pressure is 300Torr, and temperature is down to 530 DEG C, passes into trimethyl gallium TMGa as III source, its flow is 28sccm, pass into ammonia as group V source, its flow is 3420sccm, V/III is 2300, growth thickness is the low temperature GaN buffer of 30nm, then close III source, be warming up to 1050 DEG C, carry out annealing in process;
D) carrier gas is changed to nitrogen, air pressure is 200Torr, and temperature is down to 1000 DEG C, pass into trimethyl gallium TMGa as gallium source, its flow is 65sccm, passes into ammonia as group V source, its flow is 8000sccm, V/III is 2330, and growth thickness is 0.5 μm of high-quality GaN graphics template layer;
E) in a nitrogen atmosphere, air pressure is 200Torr, temperature is 1060 DEG C, pass into trimethyl gallium TMGa as gallium source, its flow is 65sccm, pass into ammonia as group V source, its flow is 150sccm, V/III is 45, in micron order growth window and nanoscale growth window, grow GaN micron six prism of two kinds of sizes respectively, be highly respectively 10 μm and 3 μm, the two diameter is about 3 microns, two kinds of micron six prism cover structures form the two size micron six prism microcosmos pattern structure of GaN, as shown in Figure 3.
Embodiment two
In the present embodiment, cancel the high-temperature ammonolysis process in embodiment one, i.e. cancellation step 3) in b) step, other steps, with embodiment one, can obtain the two size micron hexagonal pyramid microcosmos pattern structure of GaN, as shown in Figure 4.
Embodiment three
In the present embodiment, substrate adopts in c surface sapphire substrate, substrate is laid four layers of carbon nano-tube film as carbon nano-tube mask, the two size micron inverted trapezoidal microcosmos pattern structure of preparation GaN.
The selective area growth method of the two size micron inverted trapezoidal microcosmos pattern structure of GaN of the present embodiment, comprises the following steps:
1) substrate 1 adopts c surface sapphire.
2) carbon nano-tube mask is laid on substrate 1:
In the growth substrates of carbon nano pipe array, by the nano grade iron powder of electron-beam evaporation one deck marshalling, size uniform as catalyst, again by LPCVD method, using acetylene as carbon source under low pressure and high temperature, grow accurate orderly, arranged in parallel carbon nano pipe array, then be laid on after being peeled off in the growth substrates of group III-nitride; The carbon nano-tube formed is Single Walled Carbon Nanotube, and the diameter of single-root carbon nano-tube is 30nm; Substrate is laid the carbon nano-tube film of four layers respectively as carbon nano-tube mask, carbon nano pipe array in ground floor and third layer is all along the direction being parallel to substrate reference limit, and the carbon nano pipe array in the second layer and the 4th layer is all along the direction perpendicular to substrate reference limit; Final carbon nano pipe array forms bundle clustering architecture, each bundle bunch diameter be 5 μm, distance between adjacent bundle bunch is 5 μm, as micron order growth window, distance in bundle bunch between adjacent carbon nano-tube is 500nm, as nanoscale growth window, form micrometer/nanometer compound size mask.
3) on the substrate having laid carbon nano-tube mask, the two size inverted trapezoidal microcosmos pattern structure of MOCVD growing GaN is adopted:
A) in MOCVD reative cell, in a hydrogen atmosphere, air pressure is 100Torr, is warming up to 1050 DEG C and carries out situ cleaning process;
B) in a hydrogen atmosphere, air pressure is 300Torr, and temperature remains on 1060 DEG C, passes into ammonia as group V source, and its flow is 8000sccm, keeps 10 minutes, carries out high-temperature ammonolysis process to substrate;
C) in a hydrogen atmosphere, air pressure is 300Torr, temperature is down to 530 DEG C, passes into trimethyl gallium TMGa as III source, and its flow is 28sccm, pass into ammonia as group V source, its flow is 3420sccm, V/III is 2300, and growth thickness is the low temperature GaN buffer of 50nm, then close III source, be warming up to 1060 DEG C and carry out annealing in process;
D) carrier gas is changed to nitrogen, air pressure is 200Torr, is cooled to 1030 DEG C, pass into trimethyl gallium TMGa, its flow is 65sccm, passes into ammonia as group V source, its flow is 8000sccm, V/III is 2330, and growth thickness is the high-quality GaN graphics template layer of 0.7 μm;
In a nitrogen atmosphere, air pressure is 300Torr, be warming up to 1050 DEG C, pass into trimethyl gallium TMGa as gallium source, its flow is 65sccm, pass into ammonia as group V source, its flow is 150sccm, V/III is 45, adopt pulsed growth method, alternately pass into III source and group V source, and progressively strengthen ammonia flow in notch cuttype mode, V/III is made progressively to be enlarged to 300, the GaN inverted trapezoidal structure of two kinds of sizes is grown respectively in micron order growth window and nanoscale growth window, highly be respectively 8 μm and 2 μm, two kinds of inverted trapezoidal structure cover structures form the two size micron inverted trapezoidal microcosmos pattern structure of GaN, as shown in Figure 5.Embodiment four
In the present embodiment, substrate adopts on (111) crystal face silicon substrate, grown the compound substrate that AlN nucleating layer that thickness is 100nn and thickness are the AlGaN prestressed layer of 1 μm, compound substrate is laid three layers of carbon nano-tube film as carbon nano-tube mask, the two size micrometer/nanometer six prism microcosmos pattern structure of preparation GaN.
The selective area growth method of the two size micrometer/nanometer six prism microcosmos pattern structure of GaN of the present embodiment, comprises the following steps:
1) substrate adopts on (111) crystal face silicon substrate, grown that AlN nucleating layer that thickness is 100nn and thickness are 1 μm, the compound substrate of the AlGaN prestressed layer of Al content gradually variational.
2) in compound substrate, carbon nano-tube mask is laid:
In the growth substrates of carbon nano pipe array, by the nano grade iron powder of electron-beam evaporation one deck marshalling, size uniform as catalyst, again by LPCVD method, using acetylene as carbon source under low pressure and high temperature, grow accurate orderly, arranged in parallel carbon nano pipe array, then be laid on after being peeled off in the growth substrates of group III-nitride; The carbon nano-tube formed is Single Walled Carbon Nanotube, and the diameter of single-root carbon nano-tube is 20nm; Substrate lays three layers of carbon nano-tube film, the carbon nano pipe array in ground floor and third layer along the direction being parallel to substrate reference limit, the carbon nano pipe array in the second layer along the direction perpendicular to substrate reference limit; Final carbon nano-tube forms the structure of bundle bunch, and often the diameter of bundle bundle bunch is 1 μm, and the distance between adjacent bundle bunch is 2 μm, as micron order growth window, distance in bundle bunch between adjacent carbon nano-tube is 200nm, as nanoscale growth window, forms micrometer/nanometer compound size mask.
3) on the substrate having laid carbon nano-tube mask, the two size six prism microcosmos pattern structure of MOCVD technology epitaxial growth GaN micro-/ nano is adopted:
A) in MOCVD reative cell, in a hydrogen atmosphere, air pressure is 100Torr, is warming up to 1050 DEG C and carries out situ cleaning process;
B) in a hydrogen atmosphere, air pressure is 200Torr, and temperature keeps 1050 DEG C, passes into ammonia as group V source, and its flow is 8000sccm, keeps 10 minutes, carries out high-temperature ammonolysis process to substrate;
C) be that the hydrogen of 3:1 and the mist of nitrogen are as carrier gas with ratio, air pressure is 200Torr, temperature is 1050 DEG C, pass into TMGa as III source, its flow is 65sccm, pass into ammonia as group V source, its flow is 150sccm, V/III is 50, and pass into silane, its flow is 30sccm, highly identical and diameter is different GaN six prism is grown respectively in micron order growth window with nanoscale growth window, diameter 2 μm, the latter's diameter 300nm, highly be 2 μm, two kind of six prism structure cover structure forms the two size micrometer/nanometer microcosmos pattern structure of GaN, as shown in Figure 6.
It is finally noted that, the object publicizing and implementing mode is to help to understand the present invention further, but it will be appreciated by those skilled in the art that: without departing from the spirit and scope of the invention and the appended claims, various substitutions and modifications are all possible.Therefore, the present invention should not be limited to the content disclosed in embodiment, and the scope that the scope of protection of present invention defines with claims is as the criterion.
Claims (10)
1. a selective area growth method for the two size microcosmos pattern structure of group III-nitride, it is characterized in that, described selective area growth method comprises the following steps:
1) substrate is chosen:
Substrate adopts the material that can realize group III-nitride growth, as gallium nitride substrate, Sapphire Substrate, silicon carbide substrates, silicon substrate etc.; Or substrate adopts the compound substrate that grown the template layer of thickness between 10nm ~ 100 μm on gallium nitride substrate, Sapphire Substrate, silicon carbide substrates or silicon substrate, the material of template layer adopts one or more the alloy in GaN, AlN and InN;
2) on substrate, carbon nano-tube mask is laid:
The carbon nano-tube film grown is peeled off from its growth substrates, then according to needing to lay single or multiple lift carbon nano-tube film on substrate, form carbon nano-tube mask, in the carbon nano-tube mask of final formation, carbon nano-tube arranged in parallel can be assembled mutually, form bundle clustering architecture arranged in parallel, the spacing in every a bundle bunch between carbon nano-tube is nanometer scale, forms nanoscale growth window; Spacing between adjacent bundle bunch is micron dimension, forms micron order growth window, and nanoscale growth window and micron order growth window can alternately, and cover structure forms micrometer/nanometer compound size mask;
3) on the substrate having laid carbon nano-tube mask, the two size microcosmos pattern structure of growth group III-nitride:
Adopt metal-organic chemical vapor deposition equipment MOCVD or the two size microcosmos pattern structure of molecular beam epitaxy MBE technology growth group III-nitride.
2. selective area growth method as claimed in claim 1, is characterized in that, in step 2) in, carbon nano-tube is single wall or many walls, the diameter of single-root carbon nano-tube is between 10 ~ 100nm, and the distance between adjacent carbon nano-tube, between 10 ~ 500nm, forms nanoscale growth window.
3. selective area growth method as claimed in claim 1, is characterized in that, in step 2) in, the diameter of every a bundle bunch is between 1 ~ 10 μm, and the distance between adjacent bundle bunch, between 1 ~ 20 μm, forms micron order growth window.
4. selective area growth method as claimed in claim 1, is characterized in that, in step 3) in, be divided into two-step growth, first low temperature-grown buffer layer, carry out the two size microcosmos pattern structure of high growth temperature group III-nitride subsequently.
5. selective area growth method as claimed in claim 1, is characterized in that, in step 3) in, if first passed into ammonia or nitrogen before growth group III-nitride, carry out high-temperature ammonolysis, then form the column figure that end face is plane; If do not pass into ammonia or nitrogen before growth group III-nitride, do not carry out high-temperature ammonolysis, then form the taper figure that end face is wedge angle.
6. selective area growth method as claimed in claim 1, is characterized in that, in step 3) in, if first passed into ammonia or nitrogen before growth group III-nitride, carry out high-temperature ammonolysis, then form the column figure that end face is plane; If do not pass into ammonia or nitrogen before growth group III-nitride, do not carry out high-temperature ammonolysis, then form the taper figure that end face is wedge angle.
7. a selective area growth structure for the two size microcosmos pattern structure of group III-nitride, it is characterized in that, described selective area growth structure comprises: the two size microcosmos pattern structure of substrate, carbon nano-tube mask and group III-nitride; The carbon nano-tube mask that substrate is laid is made up of single or multiple lift carbon nano-tube film, every one deck carbon nano-tube film is carbon nano pipe array arranged in parallel, these carbon nano-tube assemble formation bundle clustering architecture arranged in parallel mutually, micron order growth window is formed between adjacent bundle bunch, form nanoscale growth window between the multiple carbon nano-tube arranged in parallel in bundle bunch inside, thus form nanoscale growth window and micron order growth window micrometer/nanometer compound size mask alternately; Carbon nano-tube mask grows the two size microcosmos pattern structure of group III-nitride.
8. selective area growth structure as claimed in claim 7, it is characterized in that, described carbon nano-tube is single wall or many walls, and the diameter of single-root carbon nano-tube is between 10 ~ 100nm, distance between adjacent carbon nano-tube, between 10 ~ 500nm, forms nanoscale growth window.
9. selective area growth structure as claimed in claim 7, is characterized in that, the diameter of every a bundle bunch is between 1 ~ 10 μm, and the distance between adjacent bundle bunch, between 1 ~ 20 μm, forms micron order growth window.
10. selective area growth structure as claimed in claim 7, it is characterized in that, described substrate adopts the one in gallium nitride substrate, Sapphire Substrate, silicon carbide substrates and silicon substrate, or substrate adopts the compound substrate that grown the template layer of thickness between 10nm ~ 100 μm on gallium nitride substrate, Sapphire Substrate, silicon carbide substrates or silicon substrate, the material of template layer adopts one or more the alloy in gallium nitride GaN, aluminium nitride AlN and indium nitride InN.
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