CN1713349A - Production of silicon-base III family nitride thin-membrane without crack from self-adaption flexible layer - Google Patents
Production of silicon-base III family nitride thin-membrane without crack from self-adaption flexible layer Download PDFInfo
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- CN1713349A CN1713349A CN 200410048229 CN200410048229A CN1713349A CN 1713349 A CN1713349 A CN 1713349A CN 200410048229 CN200410048229 CN 200410048229 CN 200410048229 A CN200410048229 A CN 200410048229A CN 1713349 A CN1713349 A CN 1713349A
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Abstract
The features of the invention is: one layer or multilayer of self-adapting layer made of ternary or quaternary III family nitride is inserted into the place between the traditional Si base nitride and III family nitride. The self-adapting layer can spontaneously regulates its compositions along with stress variation in its growth to self-adapt the large lattice mismatch heteroepitaxy lattice constant or variation of heat stress, so that it can prevent generation of crack initiation at interface.
Description
Technical field
The present invention relates to semiconductor applications, particularly a kind of self-adapting flexible layer prepares the method for the silica-based III group-III nitride of flawless film.
Background technology
With GaN is the III group-III nitride semiconductor of representative owing to can be used for blue-ray LED and LD, the high-density optical storage, and high temperature, high-power and high-frequency electron device, fields such as ultraviolet detector, thereby have boundless application prospect.
Yet, be difficult to obtain high-quality GaN film owing to there is not homo-substrate.So far Zhi Bei device level GaN film obtains on Sapphire Substrate mostly.Because Sapphire Substrate hardness is big, non-conductive, and cost an arm and a leg, be difficult to produce in enormous quantities, force people to go to attempt, heat conduction, conduction, large scale modest, be easy to cleavage and be easy to growth high-quality GaN on the integrated silicon substrate of photoelectricity, to overcome the shortcoming of Sapphire Substrate at valency.
But lattice mismatch reaches 20% between Si and the GaN, and thermal mismatching is more up to 56%, and epitaxial growth GaN is highly susceptible to cracking on silicon substrate, and crackle becomes the main problem of puzzlement growth of device level high-quality GaN on the Si base.
The main method that solves crackle among the Si base GaN at present has following several:
1, in the enterprising line mask of silicon substrate or the direct horizontal extension method of etching.The artificial continuous surface with silicon of this method isolates and comes, and the GaN epitaxial growth is limited in the small window area, can effectively alleviate the stress in the big plane, stops the generation of crackle.Shortcoming is a complex process, and the flawless zone is less.
2, in GaN, insert low temperature AI N layer.By certain thickness low temperature polymorph A lN layer, can partly discharge because the stress that thermal mismatching produces is realized the flawless film.
3, adopt the AlGaN layer of gradient gradual change.Utilize the lattice constant of AlN to be slightly less than the lattice constant of GaN, make on the AlGaN layer compression to occur in the Grown GaN, the tensile stress that forms in can the partial offset temperature-fall period reduces the generation of crackle.
Above the whole bag of tricks all is difficult to grow thicker large tracts of land flawless GaN film.
On the other hand, the research of the ternary of GaN or quaternary compound semiconductor is also in deeply carrying out.The main advantage of InAlGaN quaternary compound semiconductor material is, can obtain and GaN by regulating the content of In and Al respectively, or InGaN, and the material of the lattice match of AlGaN also can be regulated and can be with poorly simultaneously, obtains the potential barrier and the potential well of design.Therefore InAlGaN is widely used in various superlattice or the quantum well structure, demonstrates very high-luminous-efficiency in ultraviolet short wavelength zone.
Research simultaneously finds that also, among InGaN or the InAlGaN phenomenon of phase separation can take place: promptly rich In district and poor In district appear in zones of different under certain condition; Or the content of In changes between growth course middle level and layer, i.e. self assembly superlattice phenomenon.The variation of In content is main relevant with the STRESS VARIATION in the epitaxial film in the growth course.
Summary of the invention
The object of the present invention is to provide a kind of self-adapting flexible layer to prepare the method for the silica-based III group-III nitride of flawless film.Refer in particular to a kind of self-adapting flexible layer that on silicon substrate, inserts, with preparation flawless III group-III nitride film, and the preparation of InAlGaN or InGaN self-adapting flexible layer and in III group-III nitride film, insert the structure of multilayer InAlGaN self-adapting flexible layer, reach 2 microns flawless III group-III nitride films with preparation thickness.
The invention provides a kind of structure of inserting the self-adapting flexible layer, growing flawless III group-III nitride film on silicon substrate of utilizing.This method technology is simple, by the adaptive InGaN of composition or the InAlGaN flexible layer of growth in advance, can effectively eliminate the crackle in the silica-based GaN film in the large tracts of land; By inserting multilayer self-adapting flexible layer, can grow obtains about 2 microns of thickness, the flawless III group-III nitride film that device can be used.The process window broad of this invention simultaneously, to the dependence of appointed condition a little less than, be a kind of method of the pervasive silica-based GaN crackle of elimination.
In order to achieve the above object, according to the present invention's growing flawless III group-III nitride film on silicon substrate, it is characterized in that: according to a conventional method behind growing AIN resilient coating on the silicon substrate, before growth III group-III nitride, insert one deck self-adapting flexible layer, this layer self-adapting flexible layer comprises InAlGaN or InGaN, and the thickness of flexible layer is between 50-500nm.
Owing between silicon and the III group-III nitride very big lattice mismatch and thermal mismatching are arranged, when silicon face epitaxial growth self-adapting flexible layer, can produce bigger internal stress, the self-adapting flexible layer can be regulated the In constituent content according to the size adaptation of internal stress, lattice constant is gradually changed, thereby slow down lattice mismatch stress; On the other hand, with in one deck because stress distribution is inhomogeneous, be directed at and form rich In district and poor In district, owing to the In-N key by force a little less than, rich In district is the absorption portion thermal stress effectively, plays the effect of certain flexibility layer.So the present invention is with this insert layer called after " self-adapting flexible layer ".
Comprise the In component of 2% to 20% ratio, the Al component of 10% to 90% ratio according to self-adapting flexible layer InGaN of the present invention or InAlGaN, and In, Al and Ga component, or the ratio summation of In and Ga component is 100%.
Self-adapting flexible layer InAlGaN, wherein the ratio of In component is more than or equal to 10%.
The method for preparing InGaN or InAlGaN self-adapting flexible layer according to the present invention comprises that InGaN or InAlGaN carry out crystal growth under 800 ℃ to 950 ℃ growth temperature, and wherein ammonia, trimethyl gallium, trimethyl indium and trimethyl aluminium are as unstrpped gas.
Prepare according to the present invention in the method for InGaN or InAlGaN self-adapting flexible layer, the flow velocity of ammonia is 4L/min, the flow velocity of trimethyl gallium is 2umol/min to 20umol/min, the flow velocity of trimethyl indium adduct is 20umol/min to 60umol/min, and the flow velocity of trimethyl aluminium is 1umol/min to 10umol/min.
Prepare multilayer according to the present invention and insert the self-adapting flexible layer, grow thickness and reach the 2 microns silica-based III group-III nitride of flawless films, its feature comprises:
Growth one layer thickness is about the III group-III nitride film of 100-500nm on ground floor self-adapting flexible layer, the second layer self-adapting flexible layer of growing then, regrowth III group-III nitride film on it, the structure of alternately inserting the layer flexible layer like this.
The growth temperature of each layer self-adapting flexible layer, bed thickness and In, the component of Al can be inequality, but all within the scope of claim 4 and claim 5.
Description of drawings
Detailed introduction that below provides and the accompanying drawing that only provides by explanation can make the present invention be easier to understand fully, but are not to limit the present invention thus, wherein:
Fig. 1 is the structural representation that self-adapting flexible layer of the present invention prepares the silica-based III group-III nitride of large tracts of land flawless film;
Fig. 2 be according to the present invention prepare multilayer insert (In, Al) GaN flexible layer growth thickness reaches the structural representation of the 2 microns silica-based III group-III nitride of flawless films;
Fig. 3 is the comparison diagram that inserts self-adapting flexible layer a and do not insert the silica-based GaN epitaxial film of self-adapting flexible layer b surface topography;
Fig. 4 is the comparison diagram that inserts self-adapting flexible layer a and do not insert the silica-based GaN epitaxial film of self-adapting flexible layer b PL spectrum;
Hereinafter, to introduce the self-adapting flexible layer InAlGaN structure of on silicon substrate, inserting in advance of the present invention in detail and come growing flawless III group-III nitride film, and prepare its method and adopt multilayer to insert the example that InAlGaN self-adapting flexible layer structure come 2 microns flawless III of growth thickness group-III nitride film.
Embodiment:
With the metal-organic chemical vapor deposition equipment method is example
1) as shown in Figure 1, after the high temperature AlN resilient coating 3 of Al layer 2 and 20～30nm has been grown on silicon substrate 1 surface according to a conventional method, be cooled to about 850 ℃, carrier gas is changed to nitrogen, feed unstripped gass such as ammonia, trimethyl gallium, trimethyl indium and trimethyl aluminium, growth InAlGaN or InGaN self-adapting flexible layer 4, the thickness of this layer is regulated according to the flow velocity and the temperature of unstripped gas, can in 50～500nm scope, change the certain thickness III group-III nitride film 5 of growing at last.
2) as shown in Figure 2, after the high temperature AlN resilient coating 3 of Al layer 2 and 20～30nm has been grown on silicon substrate 1 surface according to a conventional method, be cooled to about 850 ℃, carrier gas is changed to nitrogen, feed unstripped gass such as ammonia, trimethyl gallium, trimethyl indium and trimethyl aluminium, growth InAlGaN self-adapting flexible layer 4, the III group-III nitride film 5 of growing then.Self-adapting flexible layer 4 and III nitride epitaxial layers 5 alternating growths can be two-layer or more multi-layered.The growth temperature of self-adapting flexible layer is controlled between 800～900 ℃, and the growth temperature of III nitride epitaxial layers is then between 1020～1080 ℃.Two layers of thickness must be controlled in the 500nm, to avoid the generation of crackle.
The present invention has utilized InGaN and the intrinsic characteristic of InAlGaN compound: the spontaneous adjusting of various internal stresss that its component can produce according to when growth, lattice mismatch in the big mismatch heteroepitaxy of self adaptation, simultaneously In-N key key by force a little less than, the experiment of rich In district is found obviously to alleviate the strain that thermal mismatching produces, and reduces the generation and the expansion of crackle.
Compare with other technology of growing silica-based flawless III group-III nitride epitaxial film, present technique does not need other ancillary techniques such as mask, photoetching, need not introduce polycrystalline/monocrystalline interface yet, technology is simple, can the big mismatch heteroepitaxy of spontaneous adjusting, its principle has universality applicable to multiple epitaxy technology (comprising MOCVD, MBE and HVPE etc.) and multiple material system.Compare with conventional method simultaneously, (In, Al) luminescent properties of GaN flexible layer Grown GaN has obvious enhancing (accompanying drawing 4), illustrates that the performance of Si base GaN has clear improvement to adopt self adaptation.
Implement main method of the present invention and comprise various semiconductor film membrane preparation methods, as metal organic-matter chemical vapour phase epitaxy (MOCVD), molecular beam epitaxy (MBE), hydride gas-phase epitaxy (HVPE) and ion sputtering etc., to different semiconductor film preparing systems, various growth parameter(s)s are adjusted as the case may be.
The III group-III nitride comprises: the structural material that thin-film material such as gallium nitride, aluminum gallium nitride, indium gallium nitrogen, aluminium gallium nitrogen or they are combined to form.
Embodiment 1:
With the metal-organic chemical vapor deposition equipment mocvd method is example.
1) be substrate with monocrystalline silicon Si (111) face;
2) be warmed up to 1000～1100 ℃, feed trimethyl aluminium TMAl, form thin Al layer at silicon face; Feed ammonia then, form the AlN layer about 30nm;
3) cool to 800～900 ℃, growth InAlGaN self-adapting flexible layer.Unstripped gas is that ammonia, trimethyl gallium, trimethyl indium and trimethyl aluminium are used as unstrpped gas: wherein the flow velocity of ammonia is 4L/min, the flow velocity of trimethyl gallium is 10umol/min, the flow velocity of trimethyl indium adduct is 30umol/min, and the flow velocity of trimethyl aluminium is 5umol/min.The thickness of this layer is 300nm;
4) be warmed up to 1000～1100 ℃ high temperature, growing GaN epitaxial film 700nm makes the epitaxial film gross thickness reach 1um.
Embodiment 2
Adopt multilayer InAlGaN self-adapting flexible layer growth 2 micron thickness flawless III group-III nitride films, preceding four steps are identical with embodiment 1, and the thickness of just will grow InAlGaN flexible layer and GaN epitaxial film all is decided to be 500 nanometers, and subsequent was the 5th step:
5) with 3) growth 500 nanometer InAlGaN self-adapting flexible layers;
6) same 4) growth 500 nanometer GaN places prolong film.
The surface topography that inserts the self-adapting flexible layer and do not insert 1 micron silica-based GaN epitaxial film of self-adapting flexible layer is adopted in contrast, shown in the accompanying drawing 3, found that Fig. 3 b has many parallel to each other with conventional method Grown GaN surface, crisscross crackle, through behind certain process optimization, can in 10um * 10um square range, there be crackle to produce greatly; And the growth of InAlGaN self-adapting flexible layer method is inserted in Fig. 3 a employing, and by the GaN of identical technology growth same thickness, the quantity of its face crack has reduction significantly, seldom can find crackle in the range of observation shown in Fig. 3 a.Because the GaN film is mainly used in photoelectric device, thus with photic fluorescence Spectra (PL spectrum) optical property of GaN epitaxial film is tested, as shown in Figure 4.Found that curve a inserts the GaN thin-film light emitting intensity that the luminous strength ratio curve b of growing GaN film behind the InAlGaN self-adapting flexible layer do not insert the self-adapting flexible layer and significantly improves, luminous intensity approximately improves about ten times, therefore the luminescent properties with InAlGaN self-adapting flexible layer method Grown GaN film improves significantly, and the half-breadth of PL spectrum does not significantly reduce, and illustrates that the crystal mass with InAlGaN self-adapting flexible layer method Grown GaN does not significantly reduce.
The present invention compares with technology in the past, and this invention has following meaning:
1) be applicable to all kinds of epitaxial growth equipments commonly used at present, as metal organic-matter chemical vapour phase epitaxy (MOCVD), molecular beam epitaxy (MBE), hydride gas-phase epitaxy (HVPE) and ion sputtering etc.
2) InGaN and the intrinsic characteristic of InAlGaN compound have been utilized: the spontaneous adjusting of various internal stresss that its component can produce according to when growth, lattice mismatch in the big mismatch heteroepitaxy of self adaptation, simultaneously In-N key key by force a little less than, the experiment of rich In district is found obviously to alleviate the strain that thermal mismatching produces, and reduces the generation and the expansion of crackle.
3) do not need other ancillary techniques such as mask, photoetching, also need not introduce polycrystalline/monocrystalline interface, technology is simple, and cost is low, need not add any new process equipment and can finish.
4) can reach 2 microns flawless silicon based gallium nitride film by growth thickness.
Claims (8)
1. the structure of a self-adapting flexible layer, its structure is as follows: behind silicon substrate 1 superficial growth Al layer 2 and the AlN resilient coating 3, growth InAlGaN or InGaN self-adapting flexible layer 4, the certain thickness III group-III nitride film 5 of growing at last.
2. the generation method of the structure of a self-adapting flexible layer, its step is as follows:
After the high temperature AlN resilient coating 3 of Al layer 2 and 20～30nm has been grown on silicon substrate 1 surface according to a conventional method, be cooled to about 850 ℃, carrier gas is changed to nitrogen, feed ammonia, trimethyl gallium, trimethyl indium and trimethyl aluminium unstripped gas, growth InAlGaN or InGaN self-adapting flexible layer 4, the thickness of this layer is regulated according to the flow velocity and the temperature of unstripped gas, can change in 50～500nm scope, the certain thickness III group-III nitride film 5 of growing at last.
3. according to the structure of the self-adapting flexible layer of claim 1, with the silica-based III group-III nitride of preparation flawless film, its feature comprises:
In the middle of traditional nitride resilient coating and III group-III nitride, insert one deck self-adapting flexible layer, the spontaneous adjusting of various internal stresss that this its component of self-adapting flexible layer can produce according to when growth, lattice mismatch and thermal mismatching in the big mismatch heteroepitaxy of self adaptation, it mainly acts on is generation and the expansion that stops the Interface Crack source.
4. according to the structure of the self-adapting flexible layer of claim 1 or 3, it is characterized in that the self-adapting flexible layer comprises InAlGaN, InGaN comprises:
The Al component of the In component of 2% to 20% ratio, 10% to 90% ratio, and In, Al and Ga component, or the ratio summation of In and Ga component is 100%; The thickness of this self-adapting flexible layer is the 50-500 nanometer.
5. according to the structure of the self-adapting flexible layer of claim 1 or 3, it is characterized in that, self-adapting flexible layer InAlGaN, wherein the ratio of In component is more than or equal to 10%.
6. according to the generation method of the structure of the self-adapting flexible layer of claim 2, it is characterized in that: wherein self-adapting flexible layer InAlGaN or InGaN carry out crystal growth under 800 ℃ to 950 ℃ growth temperature, and wherein ammonia, trimethyl gallium, trimethyl indium and trimethyl aluminium are as unstrpped gas.
7. according to the generation method of the structure of the self-adapting flexible layer of claim 2, it is characterized in that, wherein the flow velocity of ammonia is 4L/min, the flow velocity of trimethyl gallium is 2umol/min to 20umol/min, the flow velocity of trimethyl indium adduct is 20umol/min to 60umol/min, and the flow velocity of trimethyl aluminium is 1umol/min to 10umol/min.
8. a multilayer is alternately inserted the structure of self-adapting flexible layer, and preparation thickness reaches the 2 microns silica-based III group-III nitride of flawless films, and its feature comprises:
Growth one layer thickness is about the III group-III nitride film of 100-500 nanometer on ground floor self-adapting flexible layer, the second layer self-adapting flexible layer of growing then, regrowth III group-III nitride film on it, the structure of alternately inserting multilayer self-adapting flexible layer like this;
The growth temperature of each layer self-adapting flexible layer, bed thickness and In, the component of Al can be inequality, but all within claim 4,5 or 6 scope.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100437910C (en) * | 2006-07-27 | 2008-11-26 | 中国科学院半导体研究所 | Method for epitaxy InAlGaN monocrystal film using MBE |
| CN102923636A (en) * | 2012-10-30 | 2013-02-13 | 上海丽恒光微电子科技有限公司 | Semiconductor structure and manufacturing method thereof |
| CN103415915A (en) * | 2011-07-25 | 2013-11-27 | 东芝技术中心有限公司 | Nucleation of aluminum nitride on a silicon substrate using an ammonia preflow |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5798537A (en) * | 1995-08-31 | 1998-08-25 | Kabushiki Kaisha Toshiba | Blue light-emitting device |
| US5828684A (en) * | 1995-12-29 | 1998-10-27 | Xerox Corporation | Dual polarization quantum well laser in the 200 to 600 nanometers range |
| KR19990014304A (en) * | 1997-07-30 | 1999-02-25 | 아사구사 나오유끼 | Semiconductor laser, semiconductor light emitting device and manufacturing method thereof |
| JP3726252B2 (en) * | 2000-02-23 | 2005-12-14 | 独立行政法人理化学研究所 | Ultraviolet light emitting device and method for producing InAlGaN light emitting layer |
| US6958497B2 (en) * | 2001-05-30 | 2005-10-25 | Cree, Inc. | Group III nitride based light emitting diode structures with a quantum well and superlattice, group III nitride based quantum well structures and group III nitride based superlattice structures |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100437910C (en) * | 2006-07-27 | 2008-11-26 | 中国科学院半导体研究所 | Method for epitaxy InAlGaN monocrystal film using MBE |
| CN103415915A (en) * | 2011-07-25 | 2013-11-27 | 东芝技术中心有限公司 | Nucleation of aluminum nitride on a silicon substrate using an ammonia preflow |
| US9617656B2 (en) | 2011-07-25 | 2017-04-11 | Toshiba Corporation | Nucleation of aluminum nitride on a silicon substrate using an ammonia preflow |
| US10174439B2 (en) | 2011-07-25 | 2019-01-08 | Samsung Electronics Co., Ltd. | Nucleation of aluminum nitride on a silicon substrate using an ammonia preflow |
| CN102923636A (en) * | 2012-10-30 | 2013-02-13 | 上海丽恒光微电子科技有限公司 | Semiconductor structure and manufacturing method thereof |
| CN102923636B (en) * | 2012-10-30 | 2015-11-25 | 上海丽恒光微电子科技有限公司 | Semiconductor structure and preparation method thereof |
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