CN1154155C - Method for producing III family nitride single/multiple layer heterogeneous strain film - Google Patents
Method for producing III family nitride single/multiple layer heterogeneous strain film Download PDFInfo
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- CN1154155C CN1154155C CNB011004541A CN01100454A CN1154155C CN 1154155 C CN1154155 C CN 1154155C CN B011004541 A CNB011004541 A CN B011004541A CN 01100454 A CN01100454 A CN 01100454A CN 1154155 C CN1154155 C CN 1154155C
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Abstract
The present invention relates to a manufacture method for a heterogeneous strain film with a single layer or multiple layers of III group nitride, which comprises the following preparation steps: firstly, a substrate is used, a crystal growth plane of epitaxial III group nitride on the substrate can be perpendicular to a (0001) crystal plane; secondly, epitaxial III group nitride with preset thickness is formed on substrate materials and is used as a template for the next step of epitaxial growth; thirdly, a heterogeneous strain film with a single layer or multiple layers of III group nitride is grown in an epitaxial mode on the template, and the heterogeneous strain film has a preset structure. No piezoelectric field exists in a direction which is perpendicular to the plane direction of the epitaxial film.
Description
Technical field
The present invention relates to semi-conducting material and device, be meant a kind of manufacture method of III group-III nitride single/multiple layer heterogeneous strain film especially.
Background technology
III group-III nitride single/multiple layer heterogeneous strain film relates to following content: comprise with gallium nitride that by the material branch indium gallium nitrogen, aluminum gallium nitride are the III group-III nitride of representative; Comprise with metal-organic chemical vapor deposition equipment by the growing method branch, molecular beam epitaxy, hydride gas-phase epitaxies etc. are the epitaxial growth of representative; Comprise with the energy gap difference that by epitaxial material kind branch the lattice material that do not match is the heteroepitaxy of representative.Then comprise luminescent devices such as light-emitting diode, laser diode or the like by the device function branch.
The III group-III nitride is the big direct gap semiconductor material of a kind of bandwidth adjustable extent, thereby has wide practical use.Aspect optical device, be mainly used in and make blue light, green light LED and laser, and photodetector.Light-emitting diode is the luminous semiconductor device that is widely adopted in family expenses and industry.The super brightness blue light diode that the III group-III nitride is made has broad application prospects: because trichromatic deficiency has been filled up in its appearance, satisfied the demand of making the full color outdoor display screen; Its power consumption only is 10% of an ordinary incandescent lamp, the life-span can reach 100,000 hours and brightness high, these characteristics have determined it must cause a new illumination revolution, will be used for general lighting, car light, traffic lights and instrument and meter show or the like.Adopt III group-III nitride laser to do laser head, can make the storage density of CD improve nearly four times.Document (1, S.Nakamura.M.Senoh, Jpn.J.Appl.Phys, 34, L1332 (1995); 2, S.Nakamura, M.Senoh, J.Appl.Phys, 35, L217 (1996)) this there is a more detailed explanation.Big owing to III group-III nitride energy gap aspect electronic device, can be applied to make high temperature, high power device and high mobility devices, document (3, M.A.Khan, Q.Chen, C.J.Sun, J.W.Yang, M.Blasingame, M.S.Shur, and H.Park, Appl.Phys.Lett.68,514 (1996)) this there is more detailed explanation.Because market prospects are wide, the III group-III nitride is the focus of studying in the world at present.
All can be applied to the nitride single/multiple layer heterogeneous strain film structure in above various devices, these structures can be used as active layer in device.When employing III group-III nitride single/multiple layer heterogeneous strain film was done active layer, the general form that adopts list/Multiple Quantum Well was strapped in quantum well or the base electronics, hole, thereby improved the halfwidth of recombination rate and reduction glow peak.
The single/multiple layer heterogeneous structure of III group-III nitride all adopts epitaxial growth method, and epitaxial growth obtains on certain backing material.The main substrate that is adopted has: sapphire, carborundum (SiC), gallium nitride (GaN) monocrystalline, silicon (Si), GaAs (GaAs) or the like.These different substrates all respectively have pluses and minuses.The making of GaN single crystalline substrate is owing to need HTHP, causes cost of manufacture high and make difficulty, also do not have finished commercial prod to sell at present, also will be very high even if commercial product its price of coming out is arranged.So what adopt at present all is the heteroepitaxy of carrying out on various different substrates.Lattice mismatch between SiC substrate and the GaN epitaxial loayer is less, but its shortcoming remains too costliness of price.Though Si makes substrate some potential advantages are arranged, owing to be non-polar material, so when extension GaN, have some difficulties.Employing at present is the most extensive, uses to such an extent that the most successful backing material is a sapphire.Sapphire is cheap, and quality of materials is reliable, can obtain large batch of commercial product.Can epitaxial growth go out high-quality light-emitting diode and laser in the above.The III group-III nitride single/multiple layer heterogeneous strain film that all contains (0001) crystal face in present light-emitting diode, the laser.
Because the III group-III nitride plural layers that epitaxial growth goes out in the technology all are (0001) faces at present.So the film normal direction is all parallel with＜0001〉direction.Owing to following reason can (also being on the direction of growth of epitaxial loayer) produce very big piezoelectric field on the direction of vertical III group-III nitride (0001) crystal face, the piezoelectric modulus of (1) III group-III nitride is big.As: the e of indium nitride (InN)
31=-0.37C/m
2, the piezoelectric modulus of GaN is-0.22C/m
2With-0.49C/m
2, the piezoelectric modulus of aluminium nitride (AlN) is-0.58C/m
2With-0.6C/m
2(2) the single/multiple layer heterogeneous structure of III group-III nitride is that the binary or the ternary compound of the multilayer heterogeneity of nanometer scale formed by thickness all.Lattice constant differs greatly between the different compounds.As: GaN:a=3.189 dust, c=5.185 dust; The AlN:a=3.548 dust, the c=5.760 dust; The InN:a=3.53 dust, the c=5.69 dust.By the lattice constant of III group-III nitride and compound composition relation, determined that when the composition of nitride changes slightly the lattice constant phase missionary society between the different heterofilms is very big, then cause that lattice does not match between heterofilm, thus big strain produced.(3) because six side's nitride belong to the 6mm point group, when having strain, the stress that is produced by strain is＜0001〉will produce piezoelectric effect on the direction.Piezoelectric effect can cause very big piezoelectric field, and the magnitude of piezoelectric field is roughly MV/cm.
When occurring the heterogeneous laminate structure of strain in the device, the existence of piezoelectric field can cause many problems, and main has:
1) because the existence of piezoelectric field, can will can be with distortion in the heterogeneous thin layer, so between conduction band and valence band apart from increase and inclination.This causes the apart of electronics and hole in the device active region, thereby electronics-hole-recombination rate is descended, and causes the device internal quantum efficiency to descend, and luminosity greatly reduces.
2) have charge carrier to inject when device is worked, the charge carrier of injection can produce shielding to piezoelectric field, and conduction band and valence band spacing are dwindled.This mechanism can cause that in the luminescent device of practicality emission wavelength is along with operating voltage increases and the phenomenon of blue shift.And even the phenomenon that the emission wavelength fluctuation when voltage instability, can occur.
When 3) making laser diode, need to inject earlier a large amount of charge carriers piezoelectric field that deshields, cause laser diode threshold voltage height.Also because same reason will cause the cut-in voltage of light-emitting diode to raise.These all are unfavorable for the use of device.
Summary of the invention
The objective of the invention is to, a kind of manufacture method of III group-III nitride single/multiple layer heterogeneous strain film is provided, it is to make the not III group-III nitride multilayer strain heterofilm structure of pressurized electric field influence, is used for the active layer of luminescent device; By avoiding the influence of piezoelectric field, for making the luminescent device service of high brightness, stable, the low threshold value of emission wavelength.
Technical scheme of the present invention is: a kind of manufacture method of III group-III nitride single/multiple layer heterogeneous strain film, this method comprise and are prepared as follows step:
(1) the III group-III nitride crystal growth plane of extension can be vertical with (0001) crystal face on substrate;
(2) on backing material the III group-III nitride of extension predetermined thickness as next step epitaxial growth template;
(3) the III group-III nitride single/multiple layer heterogeneous strain film of epitaxial growth predetermined structure on template does not have piezoelectric field on the direction on vertical this epitaxial film plane.
Wherein the said substrate of step (1) is a foreign substrate; Adopt (1 102) surface sapphire to do substrate, or homo-substrate, (11 20) or (1 100) surface gallium nitride substrate etc.
The III group-III nitride single/multiple layer heterogeneous strain film of the said predetermined structure of step (3) wherein, film＜0001〉direction parallel with growth plane; Film adopts any one crystal face of vertical (0001) face, normally low index face, and on these crystal faces, III group-III nitride single/multiple layer heterogeneous strain film＜0001〉direction parallel with growth plane; The plane and＜0001 of the single/multiple layer heterogeneous strain film of (11 20) or (1100) crystal face〉direction is parallel.
Wherein the said strain film of step (3) is individual layer or multilayer; It between the adjacent layer different materials.
Description of drawings
For further specifying method step of the present invention, below in conjunction with embodiment and accompanying drawing, the present invention is done a detailed description, wherein:
Fig. 1 is the face figure according to the III group-III nitride single/multiple layer heterogeneous strain film of the embodiment of the invention.
Fig. 2 is the luminescence generated by light test spectrum that sample is carried out.
Embodiment
Make III group-III nitride single/multiple layer heterogeneous strain film＜0001〉direction parallel with growth plane, so on the direction on vertical plural layers surface, just do not have piezoelectric field, can not cause harmful effect to device performance.On any one crystal face of vertical (0001) face, piezoelectric field in the III group-III nitride single/multiple layer heterogeneous strain film is all parallel with film, for example: in the single/multiple layer heterogeneous strain film of (11 20) or (1 100) face, piezoelectric field is all parallel with thin film planar, and vertical with＜0001〉direction.Piezoelectric field just can not produce harmful effect like this.Concrete technology can adopt extension III group-III nitride on (1 102) surface sapphire.The crystal face of the III group-III nitride aufwuchsplate of extension is vertical with (0001) face on these sapphire faces.Corresponding relation sees Table 1 between crystal face between Sapphire Substrate and the epitaxial layer of gallium nitride and crystal orientation.
Table 1
| Corresponding surface | Corresponding sides | The mismatch degree |
| (0001)Al 2O 3//(0001)GaN | [01 10]Al 2O 3//[2 110]GaN | 15.3％ |
| The C surface sapphire | [ 2110]Al 2O 3//[01 10]GaN | 15.3％ |
| (11 20)Al 2O 3// (0001) GaN A surface sapphire | [01 10]Al 2O 3//[01 10]GaN [0001]Al 2O 3//[ 2110]GaN | -0.4％ 1.9％ |
| (1 102)Al 2O 3// (11 20) GaN R surface sapphire | [ 2110]Al 2O 3//[01 10]GaN [01 11]Al 2O 3//[0001]GaN | 15.3％ 1.1％ |
| (0110)Al 2O 3// (0001) GaN M surface sapphire | [2 110]Al 2O 3//[0332]GaN [0001]Al 2O 3//[2 110]GaN | -2.6％ 1.9％ |
Also can adopt other substrates (as (11 20) (1 100) surface gallium nitride substrate etc.), in the above epitaxial growth III nitride devices.As long as make piezoelectric field and epitaxial film plane parallel.
For meaning of the present invention better is described, below further explanation done in above mentioned vocabulary.
Said " III group-III nitride " comprises gallium nitride, indium nitride, aluminium nitride, InGaN, aluminium gallium nitride alloy.
Said " heterogeneous " refers to two kinds of semi-conducting materials that composition is different.Both the most essential differences are energy gap differences, promptly in two kinds of semi-conducting materials, an energy difference are arranged between the energy at the bottom of the conduction band or between the energy between the top of valence band.
Said " strain " implication is as follows: when having lattice mismatch between two kinds of different materials, if the film of two kinds of lattice mismatch materials is bonded together (no matter being to adopt methods such as epitaxial growth or bonding techniques), material at the interface in combination can produce a strain, so the material that lattice constant is big can be compressed, and the little material of lattice constant can be stretched, and exists in the material of strain and can have elastic stress.When the thickness of film during less than certain critical thickness, whole film all is in the strain regime, and stress distribution is in whole thin layer.
Said " single/multiple layer film " implication is as follows: single thin film is meant one deck and all different film of both sides, interface material.Plural layers then are index layer film structures, and every layer film is made of different materials.
Preparation is also adopted a kind of III group-III nitride single/multiple layer heterogeneous strain film, and this method comprises the steps:
1. the material growth plane of extension is vertical with (0001) face on substrate, and this backing material can be any backing material, as long as make the III group-III nitride growth plane of extension on this substrate vertical with (0001) face.
On backing material the gallium nitride of extension predetermined thickness as next step epitaxially grown template.
3. the III group-III nitride single/multiple layer heterogeneous strain film of epitaxial growth predetermined structure again, this heterofilm can adopt the single or multiple lift structure; It between the adjacent layer different materials.
III group-III nitride single/multiple layer heterogeneous strain film can be used for active luminescent layer in designs.Can adopt once in the device or several.
Embodiment:
Seeing also Fig. 1, is the face figure of the III group-III nitride single/multiple layer heterogeneous strain film of present embodiment.The preparation method of this structure comprises following process:
1. adopt (1 102) surface sapphire (R-Al
2O
3) 1 make substrate.
2. the resilient coating 2 of epitaxial growth one deck gallium nitride on (1 102) surface sapphire substrate, resilient coating 10-200nm is thick, and growth temperature is 450-600 ℃.
On resilient coating the growth certain thickness gallium nitride 3, growth temperature 1000-1100 ℃, thickness is the 0.5-10 micron.
4. growth III group-III nitride single/multiple layer heterogeneous structure 4 on gallium nitride template, the structure of concrete growth conditions and multilayer film is decided on designed structure.
Substrate in the step 1 removes (1 102) surface sapphire (R-Al
2O
3) outside, gallium nitride (GaN) monocrystalline of vertical (0001) face of crystal face, silicon single crystal (Si), spinelle (MgAl
2O
4), carborundum (SiC), aluminium nitride (AlN), zinc oxide (ZnO), growth aluminium oxide compound substrate (Al on the silicon
2O
3/ Si), various compound substrate of developing zinc oxide compound substrate (ZnO/Si) and AlN/SiC or the like on growing aluminum nitride compound substrate (AlN/Si), the silicon on the silicon.In a word, as long as can make the plane and＜0001 of the III group-III nitride single/multiple layer heterogeneous strain film of extension on this substrate〉direction is parallel.Though extension can obtain same effect on multiple substrate, we think that to do substrate with (1 102) surface sapphire at present best, and this substrate is compared with other substrates has cheapness, the advantage that is easy to obtain.
The epitaxial growth method of each material employing MOVPE method is present best mode among the step 2-4.
III group-III nitride single/multiple layer heterogeneous strain film in the step 4 can be that individual layer can be a multilayer also, and the number of plies is not limit, and each layer thickness is that 1 nanometer is to 500 nanometers.Can be different materials between the different layers, for example A, the B that is indicated among the figure, C represent different dissimilar materials layers respectively; Also can be same material between the different layers.For example the A layer is identical with the C layer different with the B layer again, thereby constitutes a double-heterostructure.The growth plane and＜0001 of this III group-III nitride single/multiple layer heterogeneous strain film〉direction is parallel.So on the direction of vertical plane, just there is not the existence of piezoelectric field.When with such III group-III nitride single/multiple layer heterogeneous strain film during as the active layer of luminescent device, the harmful effect that can avoid the piezoelectric field on vertical thin-film plane to cause.The luminescent device of making will have high luminous efficiency, stable emission wavelength and low cut-in voltage (threshold voltage).
Fig. 2 is the luminescence generated by light test spectrum that a sample to our made carries out.Sample is at (1 102) surface sapphire (R-Al
2o
3) go up the GaN/InGaN plural layers of epitaxial growth (1120) crystal face, this plural layers have constituted Multiple Quantum Well, can be used as the luminescent layer of luminescent device.Increase under the situation of two orders of magnitude in excitation intensity as can be seen from test result, the wavelength of luminous spectrum does not change.And if with plural layers epitaxial growth on (0001) surface sapphire of spline structure, its luminescence generated by light summit of so resulting sample is moved along with the variation of excitation intensity.
Compared with prior art, this invention has following meaning:
In gallium nitride (blue and green) light-emitting diode and laser diode preparation in the past, adopting all is the material of (0001) crystal face.The III group-III nitride plural layers that adopt in the device active layers also all are (0001) faces.So the film normal direction is all parallel with＜0001〉direction.There is very big piezoelectric field in (also being on the direction of growth of epitaxial loayer) on the direction of vertical III group-III nitride (0001) crystal face.The existence of piezoelectric field can cause many problems, and main has:
1) because the existence of piezoelectric field, can will can be with distortion in the heterogeneous thin layer, so between conduction band and valence band apart from increase and inclination.This causes the apart of electronics and hole in the device active region, thereby electronics-hole-recombination rate is descended, and causes the device internal quantum efficiency to descend, and luminosity greatly reduces.
2) have charge carrier to inject when device is worked, the charge carrier of injection can produce shielding to piezoelectric field, and conduction band and valence band spacing are dwindled.This mechanism can cause that in the luminescent device of practicality emission wavelength is along with operating voltage increases and the phenomenon of blue shift.And even the phenomenon that the emission wavelength fluctuation when voltage instability, can occur.
When 3) making laser diode (LD), need to inject earlier a large amount of charge carriers piezoelectric field that deshields, cause LD threshold voltage height.Also because same reason will cause the cut-in voltage of light-emitting diode (LED) to raise.These all are unfavorable for the use of device.By contrast, the present invention has avoided the harmful effect of piezoelectric field.The luminescent device that adopts the present invention to do active layer will have high luminous efficiency, stable emission wavelength and low cut-in voltage (threshold voltage).
Claims (4)
1. the manufacture method of an III group-III nitride single/multiple layer heterogeneous strain film is characterized in that, this method comprises and is prepared as follows step:
(1) uses a substrate, make the III group-III nitride crystal growth plane of extension on this substrate can be vertical with (0001) crystal face;
(2) on backing material the III group-III nitride of extension predetermined thickness as next step epitaxial growth template;
(3) the III group-III nitride single/multiple layer heterogeneous strain film of epitaxial growth predetermined structure on template does not have piezoelectric field on the direction on vertical this epitaxial film plane.
2. the manufacture method of a kind of III group-III nitride single/multiple layer heterogeneous strain film according to claim 1 is characterized in that, wherein the said substrate of step (1) is a foreign substrate; Adopt (1102) surface sapphire to do substrate, or homo-substrate, (1120) or (1100) surface gallium nitride substrate etc. adopted.
3. the manufacture method of a kind of III group-III nitride single/multiple layer heterogeneous strain film according to claim 1, it is characterized in that, the III group-III nitride single/multiple layer heterogeneous strain film of the said predetermined structure of step (3) wherein, film＜0001〉direction parallel with growth plane; Film adopts any one crystal face of vertical (0001) face, normally low index face, and on these crystal faces, III group-III nitride single/multiple layer heterogeneous strain film＜0001〉direction parallel with growth plane; (1120) or the plane and＜0001 of the single/multiple layer heterogeneous strain film of (1100) crystal face direction is parallel.
4. the manufacture method of a kind of III group-III nitride single/multiple layer heterogeneous strain film according to claim 1 is characterized in that, wherein the said strain film of step (3) is individual layer or multilayer; It between the adjacent layer different materials.
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| JP3947443B2 (en) * | 2002-08-30 | 2007-07-18 | Ｔｄｋ株式会社 | Electronic device substrate and electronic device |
| CN100377371C (en) * | 2003-12-05 | 2008-03-26 | 鸿富锦精密工业（深圳）有限公司 | Light-emitting diode |
| CN1313654C (en) * | 2004-06-02 | 2007-05-02 | 中国科学院半导体研究所 | Method for growing high-resistance gallium nitride epitaxial film |
| CN1313655C (en) * | 2004-06-02 | 2007-05-02 | 中国科学院半导体研究所 | Method for growing high-mobility gallium nitride epitaxial film |
| CN100336942C (en) * | 2004-06-02 | 2007-09-12 | 中国科学院半导体研究所 | Method for growing high crystal quality indium nitride single-crystal epitaxial film |
| US7804100B2 (en) * | 2005-03-14 | 2010-09-28 | Philips Lumileds Lighting Company, Llc | Polarization-reversed III-nitride light emitting device |
| CN100549243C (en) * | 2006-07-05 | 2009-10-14 | 武汉华灿光电有限公司 | A kind of on saphire substrate material epitaxy Al xGa 1-xThe method of N monocrystal thin films |
| US9368582B2 (en) * | 2013-11-04 | 2016-06-14 | Avogy, Inc. | High power gallium nitride electronics using miscut substrates |
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