CN104637795A - Selective area growing method and structure for III nitride epitaxial film on silicon substrate - Google Patents
Selective area growing method and structure for III nitride epitaxial film on silicon substrate Download PDFInfo
- Publication number
- CN104637795A CN104637795A CN201510050080.6A CN201510050080A CN104637795A CN 104637795 A CN104637795 A CN 104637795A CN 201510050080 A CN201510050080 A CN 201510050080A CN 104637795 A CN104637795 A CN 104637795A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- tube
- growth
- mask
- epitaxial film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Recrystallisation Techniques (AREA)
Abstract
The invention discloses a selective area growing method and structure for an III nitride epitaxial film on a silicon substrate. A carbon nanotube array is taken as a micrometer/nanometer composite size mask, so that a high-quality III nitride epitaxial film can be obtained directly, and an III nitride epitaxial film which is bright on the surface, is high in quality and is low in stress can be obtained in a small thickness; the preparation of the carbon nanotube mask has the advantages of simple process, low cost, environmental friendliness, stable chemical stability, high temperature resistant, high surface cleanness and the like, and the has the advantages of flexible and accurately-controllable image sizes and shapes; moreover, a carbon nanotube mask can be inserted into the epitaxial film repeatedly to form a periodical carbon nanotube mask structure, so that the crystal quality of the III nitride epitaxial film is improved further; furthermore, the carbon nanotube has the characteristics of high thermal conductivity, high electric conductivity and the like, and can play roles in dissipating heat and extending current specific to subsequently-manufactured micro-electron or photoelectric devices.
Description
Technical field
The present invention relates to semi-conductor photoelectronic technology, particularly relate to a kind of selective area growth method and structure of the group III-nitride epitaxial film on a silicon substrate using carbon nano-tube as mask.
Background technology
Group III-nitride is the semi-conducting material that a class has application prospect, and because group III-nitride single crystalline substrate is difficult to preparation and with high costs, therefore at present nitride film obtains mainly through the epitaxy technology in foreign substrate.
Conventional backing material comprises sapphire, silicon nitride, silicon etc.Wherein, there is larger lattice mismatch and thermal mismatching in sapphire and group III-nitride, and its heat conduction and poorly conductive.With regard to silicon nitride, its mechanical performance is poor, price is high, and is still difficult to prepare large-sized substrate.Compared with above-mentioned two kinds of foreign substrate, although the lattice mismatch between silicon and group III-nitride and thermal mismatching larger, but have benefited from the extremely ripe development and apply of microelectronic, the monocrystalline quality of silicon is very high, with low cost, can large-sized substrate be prepared, and it is integrated to realize photoelectricity, this is all of value to the industrial applications realizing group III-nitride, and the high-quality epitaxial thin film material therefore preparing group III-nitride on a silicon substrate becomes study hotspot in recent years.
Due to large lattice mismatch and thermal mismatching, directly prepare group III-nitride epitaxial film on a silicon substrate, there is highdensity crystal defect, and very large stress can be produced, make film produce warpage and micro-crack, have a strong impact on device performance and application; In addition, can there is alloy reaction in silicon and gallium, destroys epitaxial loayer pattern.Therefore, when growing group III-nitride epitaxial film on a silicon substrate, except needs nucleating layer, also need to introduce complicated insert layer structure as prestressed layer, alleviate huge lattice mismatch and thermal mismatching.Conventional prestressed layer has low temperature AI N, low temperature SiN
x, Al
xga
1-xn graded bedding, AlGaN/GaN superlattice etc., wherein AlN and SiN
xthough Deng low temperature, non crystalline structure energy relaxed stress, epitaxial loayer pattern and crystal mass can be affected, and Al
xga
1-xthough N graded bedding, AlGaN/GaN superlattice etc. can relaxed stress, improve crystal mass, growth course is longer, complex structure and be difficult to control.In addition, the single effect of above-mentioned all kinds of prestressed layer is all limited, generally need to adopt multiple prestressed layer scheme could obtain the group III-nitride epitaxial film of better quality simultaneously, thus the complexity of epitaxial structure, growth time and preparation cost is added, partial offset group III-nitride silica-based epitaxially grown advantage, is unfavorable for that large-scale industrialization is applied.
In addition, also have at present and utilize selective area growth technology to improve the method for group III-nitride epitaxial film quality on silicon substrate.This type of technology can be divided into two kinds, and one is on a silicon substrate by various etch tool, prepares the patterned silicon substrate with groove structure or nano-pillar array structure, then carries out selective area growth; Another kind is on a silicon substrate with method deposition of silica or silicon nitride dielectric layers such as plasma enhanced chemical vapor deposition PECVD, and then by means etching insulating layer such as photoetching, nano impression, electron beam exposures, obtain the silicon substrate with mask pattern, then carry out selective area growth.Then above-mentioned two class methods all have following two shortcomings, and the first, complicated process of preparation, cost is higher, is unfavorable for large-scale industrial production; The second, after have employed selective area growth technology, still need to introduce one or more prestressed layers when epitaxial growth, the group III-nitride epitaxial film of better quality could be obtained.
Summary of the invention
In order to solve above problems of the prior art, the present invention proposes the selective area growth method based on the group III-nitride epitaxial film of micrometer/nanometer compound size mask on a kind of silicon substrate, using carbon nano pipe array as periodic micrometer/and nano combined size mask, without the need to Al
xga
1-xthe prestressed layer of all kinds of complexity such as N graded bedding, AlGaN/GaN superlattice, can obtain high-quality group III-nitride epitaxial film, has the advantages such as technique is simple, with low cost, environmental protection.
One object of the present invention is to provide the mask structure of group III-nitride epitaxial film selective area growth on a kind of silicon substrate.
On silicon substrate of the present invention, the selective area growth structure of group III-nitride epitaxial film comprises: substrate, carbon nano-tube mask and group III-nitride epitaxial film; 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 group III-nitride epitaxial film.
Substrate is used for growing group III-nitride, adopt crystal orientation to be the silicon substrate of <111>, <110> or <100>, or adopt the compound substrate of the aluminium nitride AlN nucleating layer of the thickness of epitaxial growth on a silicon substrate between 10 ~ 1000nm.
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 has micron order growth window between bundle bunch.According to existing research, in nanoscale growth window, the size of the one-tenth nuclear island of group III-nitride is limited in nanoscale, therefore can on three-dimensional full relaxation stress, reduce strain energy; Simultaneously, numerous growth facet can either be provided in three-dimensional island growth to be in the early stage beneficial to the bending of dislocation line, to bury in oblivion, the length of misfit dislocation can be reduced again, be conducive to reducing the interaction between defect, thus obtain the epitaxial film of high-quality, low stress.But in nanoscale growth window group III-nitride close up comparatively slow, and through the growth course of micron order growth window, epitaxial loayer more easily closes up, and can obtain the epitaxial film of surface-brightening in less thickness.Therefore, the present invention adopts micrometer/nanometer compound size mask, can take into account the two advantage, in less thickness, obtain surface-brightening, and the group III-nitride epitaxial film of high-quality, low stress.
Further, carbon nano-tube mask of the present invention, except being layed in except on substrate or nucleating layer, also after grown certain thickness group III-nitride epitaxial film, can be laid carbon nano-tube mask, and then continues epitaxial growth again.This process also repeatedly can repeat according to needs, multilayer carbon nanotube mask is inserted in group III-nitride epitaxial film, form the carbon nano-tube mask of multilayer and the group III-nitride epitaxial film structure alternately of multilayer, also the periodicity mask structure on epitaxial growth direction (direction perpendicular to substrate surface) is namely formed, to improve the crystal mass of group III-nitride epitaxial film further.
Another object of the present invention is the selective area growth method providing group III-nitride epitaxial film on a kind of silicon substrate.
The selective area growth method of group III-nitride epitaxial film on silicon substrate of the present invention, comprises the following steps:
1) substrate is chosen:
Substrate adopts crystal orientation to be the silicon substrate of <111>, <110> or <100>, or adopts the thickness of epitaxial growth to be on a silicon substrate the compound substrate of the AlN nucleating layer of 10 ~ 1000nm;
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, growth group III-nitride epitaxial film:
Adopt metal-organic chemical vapor deposition equipment MOCVD or molecular beam epitaxy MBE technology growth group III-nitride epitaxial film.
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, if step 1) in employing grown the compound substrate of AlN nucleating layer, then in compound substrate, lay carbon nano-tube mask, then direct high growth temperature group III-nitride epitaxial film; If step 1) in adopt silicon substrate, then lay carbon nano-tube mask on a silicon substrate, then in step 3) in first growing AIN nucleating layer, and then high growth temperature group III-nitride epitaxial film.
Adopt MOCVD on the silicon substrate having laid carbon nano-tube mask during growing AIN nucleating layer, using hydrogen as carrier gas, using trimethyl aluminium TMAl as III source, its flow is 10 ~ 100sccm, and using ammonia as group V source, its flow is between 100 ~ 8000sccm, group V source and III source molal quantity ratio V/III are between 50 ~ 1500, temperature is between 800 ~ 1200 DEG C, and pressure is between 50 ~ 200Torr, and the thickness of AlN nucleating layer is between 10 ~ 1000nm.
During high growth temperature group III-nitride epitaxial film, using hydrogen, nitrogen or the mist of the two as carrier gas, using III metallorganic as III source, its flow is 10 ~ 200sccm, using ammonia as group V source, its flow is that 100 ~ 8000sccm, V/III are between 50 ~ 5000, temperature is between 800 ~ 1100 DEG C, and pressure is between 50 ~ 500Torr.By changing growth time, the high-quality group III-nitride epitaxial film of thickness between 10nm ~ 10 μm can be grown.
Further, in the process of high growth temperature group III-nitride epitaxial film, can repeatedly insert carbon nano-tube mask, namely in group III-nitride epitaxial film, multilayer carbon nanotube mask is inserted, the direction of growth is formed the carbon nano-tube mask of multilayer and the group III-nitride epitaxial film structure alternately of multilayer, thus form periodically mask structure, this structure can grow the group III-nitride epitaxial film that crystal mass improves further.
Advantage of the present invention:
(1) although belong to selective area growth technical scheme, compared to patterned silicon substrate of the prior art and the silicon substrate with mask pattern, the advantage such as the preparation of carbon nano-tube mask to have technique simple, with low cost, environmental protection in the present invention; Compared to the mask material such as silicon dioxide, silicon nitride, carbon nano-tube material has stable chemical nature, high temperature resistant and surface cleanliness advantages of higher; In addition, carbon nano-tube mask has the size of figure, shape all flexibly and the advantage of controllable precise;
(2) with conventional flat silicon substrate epitaxy technology, and above-mentioned two kinds of selective area growth technology are compared, present invention employs carbon nano pipe array as micrometer/nanometer compound size mask, the advantage of micron order mask and nanoscale mask can be taken into account, overcome the shortcoming that the two is respective simultaneously, without the need to the prestressed layer structure of all kinds of complexity, directly can obtain high-quality group III-nitride epitaxial film, surface-brightening is obtained in less thickness, and the group III-nitride epitaxial film of high-quality, low stress;
(3) carbon nano-tube mask of the present invention except being layed in before growth except on substrate, repeatedly can also inserting in epitaxial film, to form the periodicity mask of multilayer, improves the crystal mass of group III-nitride epitaxial film further;
(4) because carbon nano-tube has thermal conductivity height and conductivity high, therefore for follow-up obtained microelectronics or opto-electronic device, the effects such as heat radiation and current expansion can be played.
Accompanying drawing explanation
Fig. 1 is the micron order growth window of the carbon nano-tube mask of the selective area growth structure of group III-nitride epitaxial film on silicon substrate of the present invention and the schematic diagram of nanoscale growth window;
Fig. 2 is the explosive view of the multilayer carbon nanotube mask formation periodicity mask of the selective area growth structure of group III-nitride epitaxial film on silicon substrate of the present invention;
Fig. 3 is the explosive view of the laying carbon nano-tube mask of the embodiment one of the selective area growth structure of group III-nitride epitaxial film on silicon substrate of the present invention;
Fig. 4 is the explosive view of the embodiment one of group III-nitride epitaxial film selective area growth structure on silicon substrate of the present invention;
Fig. 5 is the structure explosive view of the embodiment two of the selective area growth structure of group III-nitride epitaxial film on silicon substrate of the present invention;
Fig. 6 is the explosive view of the embodiment three of the selective area growth structure of group III-nitride epitaxial film on silicon substrate of 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.
As shown in Figure 2, except lay carbon nano-tube mask on substrate except, in the growth course of group III-nitride epitaxial film, re-lay multilayer carbon nanotube mask, namely in group III-nitride epitaxial film 4, insert multilayer carbon nanotube mask 2, form the periodicity mask in the direction of growth.
Embodiment one
In the present embodiment, compound substrate comprises silicon substrate and the growth AlN nucleating layer thereon in <111> crystal orientation, compound substrate is laid three layers of carbon nano-tube film as carbon nano-tube mask, preparation GaN epitaxial film.
The selective area growth method of GaN epitaxial film on the silicon substrate of the present embodiment, comprises the following steps:
1) substrate 1 adopts MOCVD technology growing AIN nucleating layer 12 on the silicon substrate 11 in <111> crystal orientation, forms compound substrate:
A) in MOCVD reative cell, in a hydrogen atmosphere, air pressure is 150Torr, is warming up to 1100 DEG C and cures 10 minutes, to carry out situ cleaning process;
B) in a hydrogen atmosphere, air pressure rises to 75Torr, and temperature is down to 1000 DEG C, and pass into trimethyl aluminium TMAl as aluminium source, the time of passing into is 15s, overlays multiple al atomic layer, to prevent from forming polycrystalline silicon nitride;
C) in a hydrogen atmosphere, air pressure is 75Torr, and temperature is 1000 DEG C, passes into TMAl as aluminium source, its flow is 25sccm, pass into ammonia as nitrogenous source, its flow is 120sccm, V/III is 100, growth thickness is the AlN film of 50nm, and then being warming up to 1100 DEG C, other conditions are constant, and regrowth thickness is the AlN film of 100nm.
2) carbon nano-tube mask 2 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 in the growth substrates of group III-nitride after being peeled off.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 pipe array 21 ~ 23 respectively as carbon nano-tube mask, carbon nano pipe array in ground floor 21 is along the direction being parallel to silicon substrate <1-10> crystal orientation, carbon nano pipe array in the second layer 22 is perpendicular to ground floor 21, carbon nano pipe array in third layer 23 perpendicular to the second layer 22, as shown in Figure 3; Final carbon nano pipe array forms bundle clustering architecture, each bundle bunch diameter be 4 μm, distance between adjacent bundle bunch is 4 μm, as micron order growth window, distance in bundle bunch between adjacent carbon nano-tube is 300nm, as nanoscale growth window, form micrometer/nanometer compound size mask.
3) on the substrate having laid carbon nano-tube mask, adopt MOCVD technology growth GaN epitaxial film, form III nitride epitaxial film 4:
A) in MOCVD reative cell, in a hydrogen atmosphere, air pressure is 100Torr, is warming up to 1050 DEG C and cures 10 minutes, to carry out situ cleaning process;
B) in a hydrogen atmosphere, air pressure rises to 200Torr, and temperature is down to 1030 DEG C, pass into trimethyl gallium TMGa as gallium source, its flow is 65sccm, passes into ammonia as nitrogenous source, its flow is 3420sccm, V/III is 1000, and growth thickness is the GaN epitaxial film of 0.5 μm;
C) in a hydrogen atmosphere, air pressure is 200Torr, temperature is at the uniform velocity warming up to 1050 DEG C by 1030 DEG C in 1200s, pass into TMGa as gallium source, its flow is 42sccm, passes into ammonia as nitrogenous source, and its flow is 6000sccm, V/III is 3000, and growth thickness is the GaN epitaxial film of 0.6 μm;
D) in a hydrogen atmosphere, air pressure is 200Torr, and temperature is 1050 DEG C, and pass into TMGa as gallium source, its flow is 28sccm, passes into ammonia as nitrogenous source, and its flow is 8000sccm, V/III is 5000, and growth thickness is the GaN epitaxial film of 1.4 μm.
Thus obtain the high-quality GaN film that thickness is 2.5 μm, as shown in Figure 4.
Embodiment two
In the present embodiment, compound substrate comprises silicon substrate and the growth AlN nucleating layer thereon in <111> crystal orientation, compound substrate is laid two-layer carbon nano-tube film as carbon nano-tube mask, and in the growth course of GaN epitaxial film, repeat this process 2 times, make 3 layers of carbon nano-tube mask and GaN epitaxial film in the direction of growth alternately, form periodically mask, prepare high-quality GaN epitaxial film.
The selective area growth method of group III-nitride epitaxial film on the silicon substrate of the present embodiment, comprises the following steps:
1) substrate 1 adopts MOCVD technology growing AIN nucleating layer 12 on the silicon substrate 11 in <111> crystal orientation, and form compound substrate, design parameter is with the step 1 of embodiment one).
2) carbon nano-tube mask 2 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 in the growth substrates of group III-nitride after being peeled off.The carbon nano-tube formed is Single Walled Carbon Nanotube, the diameter 15nm of single-root carbon nano-tube; Substrate is laid two-layer carbon nano-pipe array column direction mutually perpendicular carbon nano-tube film respectively as carbon nano-tube mask, make it the <1-10> crystal orientation and the <001> crystal orientation that are parallel to silicon substrate respectively; Final carbon nano pipe array forms bundle clustering architecture, and the diameter of each bundle bunch is 3 μm, and the distance between adjacent bundle bunch is 3 μm, as micron order growth window, distance in bundle bunch between adjacent carbon nano-tube is 300nm, as nanoscale growth window, forms micrometer/nanometer compound mask.
3) on the substrate having laid carbon nano-tube mask, adopt MOCVD growing GaN epitaxial film, form III nitride epitaxial film 4;
A) in MOCVD reative cell, in a hydrogen atmosphere, air pressure is 100Torr, is warming up to 1050 DEG C and cures 10 minutes, to carry out situ cleaning process;
B) in a hydrogen atmosphere, air pressure is 200Torr, and temperature is 1040 DEG C, and pass into TMGa as gallium source, its flow is 65sccm, passes into ammonia as nitrogenous source, and its flow is 6000sccm, V/III is 2000, and growth thickness is the GaN epitaxial film of 0.5 μm.
4) 2 are respectively repeated steps) and step 3), to form periodically mask:
A) step 2 is repeated), lay two-layer orthogonal carbon nano pipe array respectively and form carbon nano-tube mask 2, parameters is with step 2);
B) step 3 is repeated), on carbon nano-tube mask 2, growth thickness is the GaN epitaxial film of 0.5 μm, the same step 3) of parameters.
5) again respectively repeat steps 2 and step 3), to form periodically mask:
A) step 2 is repeated), lay two-layer orthogonal carbon nano pipe array respectively and form carbon nano-tube mask 2, parameters is with step 2);
B) step 3 is repeated), on carbon nano-tube mask 2, growth thickness is the GaN epitaxial film of 1.5 μm, and wherein V/III changes to 5000, the same step 3) of other parameters.
Thus obtain the high-quality GaN epitaxial film that thickness is 2.5 μm, as shown in Figure 5.
Embodiment three
In the present embodiment, substrate adopts the silicon substrate in <110> crystal orientation, substrate is laid single-layer carbon nano-tube film as carbon nano-tube mask, and in the growth course of GaN epitaxial film, repeat this process 2 times, make 3 layers of carbon nano-tube mask and GaN epitaxial film in the direction of growth alternately, form periodically mask, prepare high-quality GaN epitaxial film.
The selective area growth method of group III-nitride epitaxial film on the silicon substrate of the present embodiment, comprises the following steps:
1) substrate 1 is the silicon substrate in <110> crystal orientation;
2) on the silicon substrate of <110> crystal orientation, ground floor carbon nano-tube mask 2 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 in the growth substrates of group III-nitride after being peeled off.The carbon nano-tube formed is Single Walled Carbon Nanotube, the diameter 20nm of single-root carbon nano-tube; Substrate lays single-layer carbon nano-tube film as carbon nano-tube mask along the direction being parallel to silicon substrate <1-10> crystal orientation; Final carbon nano-tube forms the structure of bundle bunch, and often the diameter of bundle bundle bunch is 2 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 mask.
3) on the substrate having laid carbon nano-tube mask, MOCVD technology growth AlN nucleating layer 5 is adopted:
A) in MOCVD reative cell, in a hydrogen atmosphere, air pressure is 150Torr, is warming up to 1100 DEG C and cures 10 minutes, to carry out situ cleaning process;
B) in a hydrogen atmosphere, air pressure is down to 100Torr, and temperature is down to 1000 DEG C, and pass into trimethyl aluminium TMAl as aluminium source, the time of passing into is 20s, overlays multiple al atomic layer, to prevent from forming polycrystalline silicon nitride;
C) in a hydrogen atmosphere, air pressure is down to 75Torr, and temperature is 1000 DEG C, passes into TMAl as aluminium source, its flow is 25sccm, pass into ammonia as nitrogenous source, its flow is 120sccm, V/III is 100, growth thickness is the AlN film of 50nm, and then being warming up to 1100 DEG C, other conditions are constant, and growth thickness is the AlN film of 250nm.
4) on the substrate that grown nucleating layer, adopt MOCVD technology growth GaN epitaxial film, form III nitride epitaxial film 4:
A) in MOCVD reative cell, in a hydrogen atmosphere, air pressure is 100Torr, is warming up to 1050 DEG C and cures 10 minutes, to carry out situ cleaning process;
B) in a hydrogen atmosphere, air pressure rises to 200Torr, and temperature is down to 1030 DEG C, pass into trimethyl gallium TMGa as gallium source, its flow is 65sccm, passes into ammonia as nitrogenous source, its flow is 3420sccm, V/III is 1000, and growth thickness is the GaN epitaxial film of 0.5 μm.
5) in above-mentioned GaN epitaxial film, second layer carbon nano-tube mask 2 is laid;
A) step 2 is repeated), single-layer carbon nano-tube film is laid as carbon nano-tube mask in the direction along the <001> crystal orientation being parallel to silicon substrate, and other parameters are with step 2).
6) 4 are respectively repeated steps) and step 5);
A) step 4 is repeated), growth thickness is the GaN epitaxial film of 0.5 μm, the same step 4) of parameters;
B) step 5 is repeated), single-layer carbon nano-tube film is laid as carbon nano-tube mask in the direction along the <1-10> crystal orientation being parallel to silicon substrate, the same step 5) of other parameters.
7) MOCVD technology growth GaN epitaxial film is adopted.
A) in MOCVD reative cell, in a hydrogen atmosphere, air pressure is 100Torr, is warming up to 1050 DEG C and cures 10 minutes, to carry out situ cleaning process;
B) in a hydrogen atmosphere, air pressure rises to 200Torr, and temperature is down to 1040 DEG C, pass into trimethyl gallium TMGa as gallium source, its flow is 28sccm, passes into ammonia as nitrogenous source, its flow is 8000sccm, V/III is 5000, and growth thickness is the GaN epitaxial film of 1.5 μm.
Thus obtain the high-quality GaN epitaxial film that thickness is 2.5 μm, 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. the selective area growth method of group III-nitride epitaxial film on silicon substrate, it is characterized in that, described selective area growth method comprises the following steps:
1) substrate is chosen:
Substrate adopts crystal orientation to be the silicon substrate of <111>, <110> or <100>, or adopts the thickness of epitaxial growth to be on a silicon substrate the compound substrate of the AlN nucleating layer of 10 ~ 1000nm;
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, growth group III-nitride epitaxial film:
Adopt metal-organic chemical vapor deposition equipment MOCVD or molecular beam epitaxy MBE technology growth group III-nitride epitaxial film.
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, it is characterized in that, if step 1) in employing grown the compound substrate of AlN nucleating layer, then in compound substrate, lay carbon nano-tube mask, then in step 3) in direct high growth temperature group III-nitride epitaxial film.
5. selective area growth method as claimed in claim 1, it is characterized in that, if step 1) middle employing silicon substrate, then lay carbon nano-tube mask on a silicon substrate, then in step 3) in first growing AIN nucleating layer, and then high growth temperature group III-nitride epitaxial film.
6. selective area growth method as claimed in claim 1, it is characterized in that, further, in the process of high growth temperature group III-nitride epitaxial film, repeatedly insert carbon nano-tube mask, namely in group III-nitride epitaxial film, insert multilayer carbon nanotube mask, the direction of growth is formed the carbon nano-tube mask of multilayer and the group III-nitride epitaxial film structure alternately of multilayer, thus form periodically mask structure.
7. the selective area growth structure of group III-nitride epitaxial film on silicon substrate, it is characterized in that, described selective area growth structure comprises: substrate, carbon nano-tube mask and group III-nitride epitaxial film; 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; Described carbon nano-tube mask grows group III-nitride epitaxial film.
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, comprise multilayer carbon nanotube mask further, multilayer carbon nanotube mask is inserted in group III-nitride epitaxial film, epitaxial growth direction is formed the carbon nano-tube mask of multilayer and the group III-nitride epitaxial film structure alternately of multilayer, thus forms periodically mask structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510050080.6A CN104637795B (en) | 2015-01-30 | 2015-01-30 | The selective area growth method and structure of group III-nitride epitaxial film on silicon substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510050080.6A CN104637795B (en) | 2015-01-30 | 2015-01-30 | The selective area growth method and structure of group III-nitride epitaxial film on silicon substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104637795A true CN104637795A (en) | 2015-05-20 |
| CN104637795B CN104637795B (en) | 2018-03-30 |
Family
ID=53216396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510050080.6A Active CN104637795B (en) | 2015-01-30 | 2015-01-30 | The selective area growth method and structure of group III-nitride epitaxial film on silicon substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104637795B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711024A (en) * | 2016-12-30 | 2017-05-24 | 东莞市中镓半导体科技有限公司 | Method for preparing high-electron-mobility field effect transistor on silicon substrate |
| CN106783547A (en) * | 2016-12-30 | 2017-05-31 | 东莞市中镓半导体科技有限公司 | Method for preparing high electron mobility field-effect transistor on a silicon substrate |
| CN110911274A (en) * | 2019-10-25 | 2020-03-24 | 北京大学 | III-nitride epitaxial film and selective area growth method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080194085A1 (en) * | 2002-04-30 | 2008-08-14 | University Of Louisville | Growth of textured gallium nitride thin films and nanowires on polycrystalline substrates |
| CN102610718A (en) * | 2011-01-24 | 2012-07-25 | 清华大学 | Substrate used for growing epitaxial structure and using method thereof |
| CN102723352A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Epitaxial structure body |
| CN102723407A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Preparation method for epitaxial structure body |
| CN102723406A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Semiconductor epitaxial structure |
-
2015
- 2015-01-30 CN CN201510050080.6A patent/CN104637795B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080194085A1 (en) * | 2002-04-30 | 2008-08-14 | University Of Louisville | Growth of textured gallium nitride thin films and nanowires on polycrystalline substrates |
| CN102610718A (en) * | 2011-01-24 | 2012-07-25 | 清华大学 | Substrate used for growing epitaxial structure and using method thereof |
| CN102723352A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Epitaxial structure body |
| CN102723407A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Preparation method for epitaxial structure body |
| CN102723406A (en) * | 2011-03-29 | 2012-10-10 | 清华大学 | Semiconductor epitaxial structure |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711024A (en) * | 2016-12-30 | 2017-05-24 | 东莞市中镓半导体科技有限公司 | Method for preparing high-electron-mobility field effect transistor on silicon substrate |
| CN106783547A (en) * | 2016-12-30 | 2017-05-31 | 东莞市中镓半导体科技有限公司 | Method for preparing high electron mobility field-effect transistor on a silicon substrate |
| CN106711024B (en) * | 2016-12-30 | 2020-08-21 | 东莞市中镓半导体科技有限公司 | Method for preparing high electron mobility field effect transistor on silicon substrate |
| CN106783547B (en) * | 2016-12-30 | 2020-08-21 | 东莞市中镓半导体科技有限公司 | Method for preparing high electron mobility field effect transistor on silicon substrate |
| CN110911274A (en) * | 2019-10-25 | 2020-03-24 | 北京大学 | III-nitride epitaxial film and selective area growth method thereof |
| CN110911274B (en) * | 2019-10-25 | 2022-12-30 | 北京大学 | III-nitride epitaxial film and selective area growth method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104637795B (en) | 2018-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11450528B2 (en) | Process for growing nanowires or nanopyramids on graphitic substrates | |
| Tomioka et al. | Selective-area growth of vertically aligned GaAs and GaAs/AlGaAs core–shell nanowires on Si (111) substrate | |
| CN101910050B (en) | Nanowire growth on dissimilar material | |
| CN102142454B (en) | Semiconductor device and manufacturing method thereof | |
| CN103348447A (en) | Semiconductor wafer comprising gallium nitride layer having one or more silicon nitride interlayer therein | |
| CN103952683A (en) | Preparation method of semi-polar m-plane GaN base semiconductor device containing SiNx insertion layer | |
| CN111785610A (en) | Heat dissipation enhanced diamond-based gallium nitride material structure and preparation method thereof | |
| US9515222B2 (en) | Gallium nitride on 3C—SiC composite wafer | |
| CN107210195B (en) | Semiconductor wafer comprising a monocrystalline group IIIA nitride layer | |
| US8168517B2 (en) | Method for epitaxial growth and epitaxial layer structure using the method | |
| CN104637795B (en) | The selective area growth method and structure of group III-nitride epitaxial film on silicon substrate | |
| Ryu et al. | Two-dimensional material templates for van der Waals epitaxy, remote epitaxy, and intercalation growth | |
| TWI457271B (en) | Method for making semiconductor epitaxial structure | |
| CN103094078A (en) | Gallium nitride extension preparation method for semiconductor device | |
| CN104637788A (en) | Selective area growing method for III-nitride micro graphic structure and structure | |
| CN108394857A (en) | A kind of preparation method of nucleocapsid GaN nano wire array | |
| TWI474966B (en) | A method for making epitaxial structure | |
| CN103757693B (en) | A kind of growing method of GaN nano wire | |
| CN102881570A (en) | Method for manufacturing semiconductor material | |
| JP2006324512A (en) | Nitride semiconductor thin film and its manufacturing method | |
| KR20110115105A (en) | Electronic device and manufacturing method thereof | |
| CN103325677A (en) | Method for preparing polar c surface GaN-base semiconductor device with SiNx inserting layer | |
| Rishinaramangalam et al. | Three-dimensional GaN templates for molecular beam epitaxy of nonpolar InGaN/GaN coaxial light-emitting diodes | |
| JP6527667B2 (en) | Method of manufacturing nitride semiconductor substrate | |
| CN103320764B (en) | Based on the preparation method of InN semiconducter device on a face GaN buffer layer on the 6H-SiC substrate of a face |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |