CN100505166C - Method for preparing high-quality GaN single crystal thick films on heterogeneous substrates - Google Patents
Method for preparing high-quality GaN single crystal thick films on heterogeneous substrates Download PDFInfo
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- CN100505166C CN100505166C CNB2006101676055A CN200610167605A CN100505166C CN 100505166 C CN100505166 C CN 100505166C CN B2006101676055 A CNB2006101676055 A CN B2006101676055A CN 200610167605 A CN200610167605 A CN 200610167605A CN 100505166 C CN100505166 C CN 100505166C
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- 239000000758 substrate Substances 0.000 title claims abstract description 47
- 239000013078 crystal Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000010980 sapphire Substances 0.000 claims abstract description 27
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 27
- 238000005516 engineering process Methods 0.000 claims description 11
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000005336 cracking Methods 0.000 abstract description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 70
- 229910002601 GaN Inorganic materials 0.000 description 67
- 239000004065 semiconductor Substances 0.000 description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000012868 Overgrowth Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention provides a method for reducing stress between a GaN single crystal film and a heterogeneous substrate, belonging to the field of photoelectric materials and devices. The method comprises the following steps: the GaN film grows on the heterogeneous substrate such as sapphire, laser penetrates through the heterogeneous substrate such as sapphire and irradiates the GaN film growing on the substrate, and the pre-decomposed layer is obtained at the bottom of the GaN film, so that the purposes of releasing stress strain in the GaN film and reducing stress between the GaN film and the heterogeneous substrate are achieved. The invention alleviates the problem of GaN single crystal cracking due to stress and can lead to higher crystal quality material growth.
Description
Technical field
The present invention relates to photoelectric material and devices field, relate in particular to a kind of method that in heterogeneous substrate, prepares the high-quality GaN single-crystal thick films.
Background technology
Gallium nitride (GaN) base semiconductor material is owing to have very wide energy gap, favorable optoelectronic performance (higher carrier concentration, mobility, electron saturation velocities, breakdown electric field and lower dielectric constant etc.) and physical and chemical performance (high temperature resistant, corrosion-resistant etc.), being described as is the first generation Si that continues, the Ge elemental semiconductors, second generation GaAs, third generation semi-conducting material after the InP semi-conducting material, or the main representative of " back silicon device epoch material ", be to make high frequency, high temperature, high pressure, high-power integrated circuit (IC) is used microelectronic component and short wavelength, the ideal material of high-power opto-electronic device.
Because melting temperature that the GaN material is high and higher nitrogen saturated vapour pressure, method by routine prepares quite difficulty of GaN body monocrystalline, therefore the GaN base alloy material is grown in the heterogeneous substrate more at present, as sapphire, silicon, GaAs, SiC etc., especially in the majority with the cheap sapphire of economy, but because sapphire and GaN lattice mismatch are big and thermal coefficient of expansion differs bigger, cause on the one hand defect concentration height in the GaN crystal, current on sapphire the Grown GaN defect concentrations in crystals generally 10
10/ cm
2About, even if adopt technology such as epitaxial lateral overgrowth, many resilient coatings preferably also can only arrive 10 at present
6/ cm
2, the crystal mass of the GaAs material system that distance is grown in the homogeneity substrate differs also far, and this makes the excellent properties of GaN sill can not get fully playing, and the performance of corresponding GaN base optical electronic, microelectronic component has been subjected to very big restriction.
For reducing the stress in the GaN epitaxial loayer, improve crystal mass or reduce cracking, a lot of companies and research institution have adopted epitaxial lateral overgrowth technology, many resilient coatings technology, various insert layer technology or various figure base process, and applied for relevant patent, the related technical scheme of these patents is each has something to recommend him, simultaneously itself also there is the difficult point that is difficult to go beyond in each existing its advantage, especially how effectively reduce and also have a lot of problems aspect the stress in the GaN rete, this also is one of key technology of growing high-quality GaN single-crystal thick films.
Summary of the invention
The object of the present invention is to provide a kind of method that in heterogeneous substrate, prepares the high-quality GaN single-crystal thick films.
The concrete technical scheme of the present invention is as follows:
A kind of method that in heterogeneous substrate, prepares the GaN single-crystal thick films, its step is as follows:
1) at the GaN film of growth thickness in the heterogeneous substrate within 10 μ m;
2) adopt laser to see through heterogeneous substrate, irradiation obtains a predecomposition attitude layer in GaN film bottom on the GaN film, this predecomposition attitude layer is netted or point-like, its thickness range is in 100 nanometers, and described predecomposition attitude layer has reduced stress between GaN film and heterogeneous substrate;
3) diauxic growth GaN single-crystal thick films on above-mentioned GaN film.
In heterogeneous substrate, utilize technology growth GaN films such as MOCVD or MBE.
Described heterogeneous substrate is sapphire, carborundum, lithium nickelate or silicon.
The present invention has the advantage of the following aspects:
(1) the predecomposition attitude layer that forms at the interface at sapphire and GaN of laser irradiation, can reduce in the growth course because the stress between heterogeneous substrate such as sapphire and the GaN monocrystalline, can reduce the mismatch stress between epitaxial loayer and substrate, cause the more material growth of high-crystal quality.
(2) laser irradiation is at the predecomposition attitude layer that sapphire and GaN form at the interface, can reduce in the growth course because the stress between heterogeneous substrate such as sapphire and the GaN monocrystalline is alleviated the problem because the GaN monocrystalline that stress causes ftractures.
(3) the present invention can obtain suitable predecomposition state by regulating laser energy, laser facula size, sweep span etc., and process controllability is strong, and repeatability is high, is suitable for industrialization and produces in batches.
Description of drawings
Below in conjunction with accompanying drawing the present invention is illustrated in further detail:
Fig. 1 is the embodiment of the invention one schematic diagram; Wherein, Grown GaN film in the heterogeneous substrate of Fig. 1 a; Fig. 1 b laser irradiation prepares GaN predecomposition attitude; The quick growth of GaN single-crystal thick films on Fig. 1 cGaN film; Fig. 1 d GaN film thick film separates from substrate automatically, obtains the GaN single-crystal thick films.
Embodiment
The present invention proposes a kind of technical method that is used to reduce stress between GaN single crystal film and heterogeneous substrate, and this method can lump together with GaN growing technologies combinations such as HVPE, MOCVD, preparation high-quality GaN single-crystal thick films.Core of the present invention is that the method by laser irradiation reduces the stress between heterogeneous substrate such as sapphire and the GaN single-crystal thick films, adopt photon energy greater than the band gap of GaN less than the laser of substrate band gap such as sapphire from sapphire one side incident, sapphire all sees through laser, and GaN material for laser light strong absorption, therefore sapphire and GaN GaN at the interface just raise fast because of its local temperature of absorption to laser photon, along with the rising of temperature can cause 100 nanometers at the interface with the decomposition of interior GaN or be in the predecomposition state, the energy density of control laser can realize the reduction of stress between heterogeneous substrates such as GaN single crystal film and sapphire.
Below with reference to accompanying drawing of the present invention, more detailed description goes out most preferred embodiment of the present invention.
With reference to figure 1, the present invention adopts laser irradiation to be reduced in the stress of GaN rete in the heterogeneous substrate 1 such as sapphire, preparation large tracts of land GaN high quality single crystal thick film 2.
Utilize technology growth high-quality GaN films such as MOCVD or MBE in heterogeneous substrates such as sapphire, thickness is within 10 μ m, as Fig. 1 a;
Select the laser of photon energy between substrate band gap such as GaN and sapphire (as the KrF excimer laser etc.) from sapphire one side irradiation, locality ground heating sapphire interface place 100 nanometer range GaN retes, make 100 nanometer range GaN experience high temperature and be in local predecomposition state, discharge the ess-strain in the GaN rete, obtain the weak articulamentum 3 of GaN bottom.
Sample stage can constitute that laser irradiation is used by a cover four-dimension by high accuracy electronic control translation stage and the rotating platform that computer realization is controlled automatically, it is motionless that the position of laser facula keeps, its position is by the decision of laser output light path, by the automatic scan of mobile realization laser facula on sample of computer control sample stage.The mode of scanning can be progressive scan mode or rotary scanning, application number 200410009840.0 patents that the detailed technology method can have been applied for referring to the inventor.Can obtain to be the predecomposition attitude layer of netted or spot distribution by the interval on sample, scanned of control laser facula (generally in the 2mm), shown in Fig. 1 b;
The predecomposition attitude layer of GaN has discharged the ess-strain in the GaN rete, reduces stress between GaN film and heterogeneous substrate.
The weak heterogeneous substrates of handling through laser irradiation such as GaN/ sapphire that connect that have, carry out diauxic growth surface treatment before, comprise the removal of organic washing and oxide layer;
With the weak heterogeneous substrates such as GaN/ sapphire that connect are carried out the growth of GaN single-crystal thick films in quick growth apparatus such as HVPE the diauxic growth that has that cleans up, in GaN single-crystal thick films growth course, because the thermal mismatching of GaN single-crystal thick films and substrate and the internal stress that lattice mismatch produces have been alleviated in the weak connection of predecomposition, avoid crooked, cracking, obtain large-area high quality GaN single-crystal thick films 4, as Fig. 1 c;
The present invention can also be used to preparing self-supporting GaN substrate, as above-mentioned embodiment, in the step after obtaining large-area high quality GaN single-crystal thick films 4, when GaN single-crystal thick films thickness is more than 0.1 millimeter, during growth ending, in temperature-fall period, because the thermal coefficient of expansion of GaN material and sapphire material is different, the normal force of generation makes the GaN single-crystal thick films separate automatically on the articulamentum a little less than GaN with predecomposition state and the sapphire, obtain the GaN single crystal substrates, Fig. 1 d.
The foregoing description is of the present invention giving an example, although disclose most preferred embodiment of the present invention and accompanying drawing for the purpose of illustration, 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 replacements, variation and modification all are possible.Therefore, the present invention should not be limited to most preferred embodiment and the disclosed content of accompanying drawing.
Claims (5)
1, a kind of method that in heterogeneous substrate, prepares the GaN single-crystal thick films, its step is as follows:
1) at the GaN film of growth thickness in the heterogeneous substrate within 10 μ m;
2) adopt laser to see through heterogeneous substrate, irradiation growth obtains a predecomposition attitude layer at suprabasil GaN film in GaN film bottom, and this predecomposition attitude layer is netted or point-like, its thickness range is in 100 nanometers, and described predecomposition attitude layer has reduced stress between GaN film and heterogeneous substrate;
3) diauxic growth GaN single-crystal thick films on above-mentioned GaN film.
2, the method for preparing the GaN single-crystal thick films in heterogeneous substrate as claimed in claim 1, it is characterized in that: step 2 further comprises: the photon energy range that adopts laser is between GaN and heterogeneous substrate band gap.
3. the method for preparing the GaN single-crystal thick films in heterogeneous substrate as claimed in claim 1 or 2, it is characterized in that: step 2 further comprises: the energy density of control laser irradiation is at 200-500mJ/cm
2Between.
4, the method for preparing the GaN single-crystal thick films in heterogeneous substrate as claimed in claim 1 is characterized in that: utilize MOCVD or MBE technology growth GaN film in heterogeneous substrate.
5, the method for preparing the GaN single-crystal thick films in heterogeneous substrate as claimed in claim 1 is characterized in that: described heterogeneous substrate is sapphire, carborundum, lithium nickelate or silicon.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101676055A CN100505166C (en) | 2006-12-19 | 2006-12-19 | Method for preparing high-quality GaN single crystal thick films on heterogeneous substrates |
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| CNB2006101676055A CN100505166C (en) | 2006-12-19 | 2006-12-19 | Method for preparing high-quality GaN single crystal thick films on heterogeneous substrates |
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| CN100505166C true CN100505166C (en) | 2009-06-24 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101556914B (en) * | 2008-04-08 | 2011-07-27 | 北京大学 | Method for preparing semiconductor gallium nitride (GaN) extending thin film substrate |
| JP6144630B2 (en) * | 2012-08-30 | 2017-06-07 | 日本碍子株式会社 | Method for producing composite substrate, method for producing functional layer made of group 13 element nitride |
| CN102962588B (en) * | 2012-12-12 | 2015-04-22 | 东莞市中镓半导体科技有限公司 | Method for fabricating invisibly structured substrate |
| CN107170668B (en) * | 2017-06-01 | 2020-06-05 | 镓特半导体科技（上海）有限公司 | Preparation method of self-supporting gallium nitride |
| JP7117690B2 (en) * | 2017-09-21 | 2022-08-15 | 国立大学法人大阪大学 | Method for producing group III-V compound crystal and method for producing semiconductor device |
| CN108265329A (en) * | 2018-01-22 | 2018-07-10 | 东莞市中晶半导体科技有限公司 | Fixed-point localized laser stripping device |
| CN108315823A (en) * | 2018-02-07 | 2018-07-24 | 山东大学 | A method of utilizing laser treatment substrate growth low stress Free-standing GaN monocrystalline |
| CN108538784B (en) * | 2018-06-19 | 2023-12-01 | 南通中铁华宇电气有限公司 | Laser stripping device for patterned epitaxial structure |
| CN111584689B (en) * | 2020-05-13 | 2021-10-08 | 深圳市华星光电半导体显示技术有限公司 | Micro LED mass transfer device and micro LED mass transfer method |
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| US4318752A (en) * | 1980-05-16 | 1982-03-09 | Bell Telephone Laboratories, Incorporated | Heterojunction semiconductor laser fabrication utilizing laser radiation |
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| CN1661817A (en) * | 2004-02-27 | 2005-08-31 | 炬鑫科技股份有限公司 | Gallium nitride-based vertical light-emitting diode structure and method for separating substrate and film |
| CN1779900A (en) * | 2004-11-23 | 2006-05-31 | 北京大学 | Large-area, low-power laser lift-off method for GaN-based epitaxial layers |
| CN1794419A (en) * | 2005-11-04 | 2006-06-28 | 南京大学 | Improved laser stripped method of preparing self-supporting gallium nitride substrate |
| CN1797795A (en) * | 2004-12-27 | 2006-07-05 | 北京大学 | Preparation method of LED chip with two-dimensional natural light-scattering surface |
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2006
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4318752A (en) * | 1980-05-16 | 1982-03-09 | Bell Telephone Laboratories, Incorporated | Heterojunction semiconductor laser fabrication utilizing laser radiation |
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