CN1289866A - Process for growing gallium nitride and its compound film - Google Patents
Process for growing gallium nitride and its compound film Download PDFInfo
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- CN1289866A CN1289866A CN 99119773 CN99119773A CN1289866A CN 1289866 A CN1289866 A CN 1289866A CN 99119773 CN99119773 CN 99119773 CN 99119773 A CN99119773 A CN 99119773A CN 1289866 A CN1289866 A CN 1289866A
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Abstract
A method for growing gallium nitride and its compound film features that the gallium nitride and its compound film is epitaxially grown on the non-polar c-Al2O3 substrate, or polar hexagonal crystal substrate, or polar cubic crystal substrate in metallic-organic-chemical gas phase deposition equipment by two steps.
Description
The present invention relates to a kind of epitaxial growth method of semiconductor material, be particularly related to along [000-1] crystal orientation the growth method of (that is: the atom in the nitrogen-atoms solid matter face is connected with atom in the gallium atom solid matter face with the singly-bound of vertical this face, and along this singly-bound from nitrogen-atoms the direction of sensing gallium atom) extension six side's phase gan (GaN) and compound film thereof.
Involved high preferred orientation in this patent is all represented with Miller's indices.
GaN and compound thereof have been one of Semiconductor Optoeletronic Materials with the fastest developing speed since the nineties.Owing to also do not develop GaN body material so far,, the making of various GaN base optical electronic, electron device carries out so mainly being GaN film by hetero epitaxy.The substrate that generally uses mainly is non-polar sapphire (Al at present
2O
3) crystal, its aufwuchsplate is c-face (promptly not having positive and negative (0001) face), can be abbreviated as c-Al
2O
3And with the two-step approach six side's phase GaN films of growing, make photodiode and laser diode on this basis, (see document: F.A.Ponce andD.P.Bour, Nitride-based semiconductors for blue and greenlight-emitting devices, Nature, 386 (1997) 351; Shuji Nakamura, Gerhard Fasol, The Blue Laser Diode,--GaN based light emittersand lasers ", Springer-Verlage Berlin Heidelberg, New York, (1997)).
But in the epitaxial process of nitride, nitrogen-atoms (N) is difficult to incorporate into.At first need be at Al
2O
3Substrate surface carries out high-temperature ammonolysis to be handled, and uses great ammonia (NH then
3) ratio (be V-III than) (several thousand times approximately) of flow and the organic source flux of trimethyl-gallium (TMGa).However, still exist a large amount of nitrogen rooms, the native defect of Xing Chenging has produced yellow peak therefrom.Simultaneously, in process of growth, indium (In) atom also is difficult to incorporate into nitride, even incorporate into, it is also unstable that it incorporates part into, and have high rate of decomposition.And magnesium (Mg) makes the activity ratio in its generation hole not high though atom is incorporated nitride easily into.We find that all these phenomenons all exist certain getting in touch with the nitrogen room.Therefore, the existence in nitrogen room influences and has limited the raising of nitride material characteristic and device performance.
At the problems referred to above, the method that the purpose of this invention is to provide a kind of growing gallium nitride and compound stripping thereof, it is the method along [000-1] crystal orientation epitaxy GaN and compound film thereof, can reduce nitrogen room in GaN and the compound film thereof with this method, thereby improve the characteristic of this thin-film material, and then improve the performance of the device of making based on this material.
In order to achieve the above object, growth method of the present invention is at nonpolarity c-Al
2O
3The backward crystal seed of substrate (that is, is cut Al
2O
3The surface that deviates from seed crystal during single-chip) on or on (000-1) surface that polar six side's phase crystalline substrates are arranged, or on (1-1-1) the surface that polar cube phase and square crystalline substrates are mutually arranged, by metal-organic chemical vapor deposition equipment (MOCVD) (being also referred to as gas phase epitaxy of metal organic compound (MOVPE)) equipment, with the GaN film of two-step approach epitaxy (000-1) surface orientation (below be abbreviated as (000-1) GaN).
Described have polar six side's phase crystalline substrates to be meant the 6H-silicon carbide (6H-SiC) of (000-1) surface orientation, zinc oxide (ZnO) crystal of (000-1) surface orientation, described have polar cube phase and a square crystalline substrates mutually, is meant (1-1-1) gallium arsenide of surface orientation (GaAs) and (1-1-1) spinel (MgAl of surface orientation respectively
2O
4) crystal.
(000-1) thickness of GaN buffer layer is greater than the roughness of substrate surface.
Below in conjunction with accompanying drawing the present invention is described further as after, wherein:
Fig. 1 (a) is six side's phase GaN atomic structure schematic diagrams in [0001] crystal orientation up, and wherein, black circles is represented the Ga atom, and white circle is represented the N atom.And Fig. 1 (b) is six side's phase GaN atomic structure schematic diagrams in [000-1] crystal orientation up.(a) and (b) the arrow indication is GaN extension direction in.
Fig. 2 is the present invention (000-1) GaN/Al
2O
3Epitaxially grown orientation synoptic diagram, wherein, B is Al
2O
3Backward crystal seed during crystal-pulling, A are to seed face.
Fig. 3 (a) takes (000-1) GaN film cross section picture in transmission electron microscope, (b) be the wide-angle convergent beams diffraction of determining its [000-1] crystal orientation.
Fig. 4 (a) takes (0001) GaN film cross section picture in transmission electron microscope, (b) be the wide-angle convergent beams diffraction of determining its [0001] crystal orientation.
Fig. 5 is the temperature variant relation of carrier concentration, and wherein 2 and 1 represents respectively to (000-1) GaN film with to the result of (0001) GaN films test.
Fig. 6 is the temperature variant relation of resistivity, and wherein 2 and 1 represents respectively to (000-1) GaN film with to the result of (0001) GaN films test.
Fig. 7 is the temperature variant relation of electronic mobility, and wherein 2 and 1 represents respectively to (000-1) GaN film with to the result of (0001) GaN films test.
Fig. 8 is the temperature variant relation of Hall (Hall) coefficient, and wherein 2 and 1 represents respectively to (000-1) GaN film with to the result of (0001) GaN films test.
Fig. 9 relation that to be photoluminescence intensity change with emission wavelength, wherein 2 and 1 represents respectively to (000-1) GaN film with to the result of (0001) GaN films test.
Except nitrogen has this principal element of high vapour pressure, it will be argued that the polarity atomic structure of GaN is difficult for capturing nitrogen-atoms when it is grown along [0001] crystal orientation, also be that nitrogen-atoms is difficult to one of reason of incorporating into (0001) GaN.Along [0001] crystal orientation, shown in Fig. 1 (a), gallium atom (Ga) is connected with nitrogen-atoms N with singly-bound, and span is big (about 0.4nm), and N is connected with Ga with triple bond, span less (about 0.1nm).Otherwise along [000-1] crystal orientation, shown in Fig. 1 (b), Ga is connected with N with triple bond, span less (about 0.1nm), and N is connected with Ga with singly-bound, span is big (about 0.4nm).Therefore, Ga captures N with singly-bound among (0001) GaN relatively, and in the process of growth of (000-1) GaN, Ga captures N with triple bond and just seems relatively easily, and then just can reduce the N room in (000-1) GaN film.In addition,, that is to say that (0001) GaN surface is to be terminal with the Ga atom, and (000-1) the GaN surface is to be terminal with the N atom because semiconductor surface disconnects at the singly-bound place often.With the N atom is that the surface of terminal often is difficult for reacting with impurity atomss such as airborne oxygen, carbon, thereby has reduced pickup such as surface oxidation, has increased the stability and the reliability of technology behind the nitride device.
Therefore, growth (000-1) GaN and compound film thereof can suitably reduce V/III ratio in process of growth by this method, reduce cost.GaN that grows and the N room in the compound film thereof reduce greatly, and film quality is improved, and the quality of the device of making of its also can correspondingly be improved.So the characteristic of epitaxially grown (000-1) GaN and compound film thereof is better than the characteristic of epitaxially grown under the same conditions (0001) GaN and compound film thereof.
But, Al
2O
3Be not show polar on crystallography, the experiment of open report at present shows, at c-Al
2O
3Just (0001) GaN film that last epitaxy is come out, therefore, be at non-polar Al
2O
3The growth that realizes (000-1) GaN on the substrate is seemingly impossible.Yet, Al
2O
3In combination between the atom mainly be by covalent linkage (rather than ionic linkage), these characteristics make when drawing its monocrystalline, deviate from the seed crystal direction and on the seed crystal direction its valence link produced some difference.Though this difference also can't directly be differentiated at present, finds after deliberation, can come epitaxy to have the GaN film of opposed orientation by it.Usually our Al of using
2O
3Substrate is that it (that is, is cut Al to seed face
2O
3During single-chip towards the surface of seed crystal) polish, and on this surface epitaxy GaN film.The GaN that grows out like this, its surface is (0001) often, that is: the face normal of this face is consistent with the pole axis forward; And at Al
2O
3On the backward crystal seed of monocrystalline, we find can epitaxy (000-1) GaN and compound film thereof, that is: the face normal of this face is consistent with the pole axis negative sense.Though the residual impairment of this substrate surface is big, pattern is comparatively coarse, but still can epitaxy go out (000-1) GaN film more excellent than (0001) GaN.
We adopt MOCVD (also claiming MOVPE) method to come epitaxy (000-1) GaN film, use TMGa as Ga source, high-purity N H
3As the N source, High Purity Hydrogen (H
2) as carrier gas, c-Al
2O
3As substrate, and make its backward crystal seed B up, and to seed face A down, as shown in Figure 2, be B face conduct (000-1) GaN epitaxial surface of 40nm, and carry out epitaxy with two-step approach with the roughness.With c-Al
2O
3The backward crystal seed of substrate is through three chloroethene selenium, acetone, sulfuric acid+nitric acid (HS
2O
4+ HNO
3) mixed solution clean, with sulfuric acid+phosphoric acid (HS
2O
4+ HPO
3) mixed solution corrosion, again with ethanol, get the ionized water ultrasonic cleaning, after the vacuum hydro-extraction, the reaction chamber of packing into; Again at H
2Under the atmosphere, high temperature 1000-1100 ℃ is carried out cleaning surfaces and handled 20 minutes; Then, cool to 500-650 ℃ of growth (000-1) GaN buffer layer 20-80nm, be warmed up to 1000-1100 ℃ of growth (000-1) GaN monocrystal thin films (i.e. two one-step growth methods) again.
We are to (000-1) GaN film and (0001) the GaN film of growing in same stove simultaneously by the inventive method growth, the research of transmission electron microscopy, the test of Hall (Hall) effect and the test of photoluminescence (PL) have been carried out, its result represents with 2 and 1 respectively, and contrasts as follows:
One, determined the polarity of GaN:
Shown in Fig. 3 (a) and 4 (a), all exist a large amount of threading dislocations in two GaN films, but do not find antiphase domain.Their polarity is by wide-angle convergent beams diffraction, measures at the dislocation-free place, and many places checking in same film.Fig. 3 (b) central authorities are white (0000) transmissive disks, the dark-coloured striped (horizontal line is heavier) of cruciform is arranged in its top airy's disk, and a dark-coloured striped of erectting arranged in the airy's disk of below, according to relevant bibliographical information, can calibrate respectively airy's disk up and down and be (000-2) and (0002) with this asymmetric striped, that is: among Fig. 3 (a) the GaN film along [000-1] direction extension.In contrast, the top of (0000) transmissive disk is to contain the garden dish of erectting dark-coloured striped in Fig. 4 (b), and its below is the garden dish that contains the dark-coloured striped of cruciform, with in like manner last, can calibrate to (0002) respectively and (000-2), that is: the middle GaN film of Fig. 4 (a) is along [0001] direction extension to airy's disk up and down.
Two, improved the electrical properties of nitride:
(a) as shown in Figure 5, (000-1) the carrier concentration N in the GaN film
2Generally be lower than the carrier concentration N in (0001) GaN film
1Though they all increase with the rising of temperature, N
2Vary with temperature slowly, and N
1Vary with temperature then greatlyyer, and a flex point that obviously increases is arranged at the 490K place.When temperature when 100K brings up to 580K, N
2Only from really-7 * 10
16/ cm
3Increase to-3 * 10
17/ cm
3, and N
1Then from-1.6 * 10
17/ cm
3Increase to-1.7 * 10
18/ cm
3
(b) as shown in Figure 6, (000-1) electricalresistivity in the GaN film
2Generally be higher than the electricalresistivity in (0001) GaN film
1At the ρ of 490K place
1Intrinsic conduction appears, N among this and Fig. 1
1Unexpected increase under same temperature is corresponding; And do not see ρ yet at the 580K place
2Show intrinsic conduction.Therefore, the nitride device that constitutes with (000-1) GaN film obviously has higher use temperature and life-span.
(c) as shown in Figure 7, (000-1) mobility [mu] in the GaN film
2Generally exceed the mobility [mu] in (0001) GaN film
1About 40cm
2More than/the V.s.At room temperature, μ
2=320cm
2/ V.s, μ
1=260cm
2/ V.s; And their peak value is respectively μ
2=477cm
2/ V.s (when 184K) and be μ
1=439cm
2/ V.s (when 200K).
(d) as shown in Figure 8 Hall (Hall) coefficients R in (000-1) GaN film
H2Generally greater than the Hall coefficients R in (0001) GaN film
H1, and when being lower than 100K, have higher numerical value.
Three, improved the optical property of nitride:
As shown in Figure 9, (000-1) photoluminescence of GaN film surface (PL) intensity is greater than the photoluminescence intensity of (0001) GaN film surface, and the former yellow peak then is weaker than the latter.
Certainly, the present invention is applicable to that also other surface orientation of epitaxy is the nitride of (000-1), as (000-1) InGaN and (000-1) AlGaN.Remove non-polar Al
2O
3Outside the substrate, be used as the substrate of epitaxy (000-1) nitride, can also be other have (000-1) surface orientation polarity six side's phase crystal are arranged, as (000-1) 6H-SiC, (000-1) ZnO; Can also be that other has that (1-1-1) surface orientation has polarity cube phase and a square crystal mutually, as (1-1-1) GaAs, or (1-1-1) MgAl
2O
4
Claims (3)
1, the method for a kind of growing gallium nitride and compound film thereof, it is the growth along [000-1] crystal orientation extension six side's phase GaN and compound film thereof, this method is used metal-organic chemical vapor deposition equipment, at non-polar c-Al
2O
3On the substrate or on having on polar six side's phase crystalline substrates or polar cube phase and square crystalline substrates are mutually being arranged, use the two-step approach epitaxy; It is characterized in that: described nonpolarity c-Al
2O
3Backward crystal seed when the epitaxial surface of substrate is meant its crystal-pulling; Described the epitaxial surface of polar six side's phase crystalline substrates is arranged is its (000-1) face, and described the epitaxial surface of polar cube phase and square crystalline substrates is mutually arranged is its (1-1-1) face.
2, according to the method for described a kind of growing gallium nitride of claim 1 and compound film thereof, it is characterized in that: wherein said polar six side's phase crystalline substrates are arranged is (000-1) 6H-SiC, (000-1) ZnO crystal, and described polar cube phase is arranged is respectively (1-1-1) GaAs, (1-1-1) MgAl with square crystalline substrates mutually
2O
4Crystal.
3, according to the method for described a kind of growing gallium nitride of claim 1 and compound film thereof, it is characterized in that: wherein the thickness of (000-1) GaN buffer layer is greater than the roughness of substrate surface.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119773 CN1113113C (en) | 1999-09-28 | 1999-09-28 | Process for growing gallium nitride and its compound film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119773 CN1113113C (en) | 1999-09-28 | 1999-09-28 | Process for growing gallium nitride and its compound film |
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| Publication Number | Publication Date |
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| CN1289866A true CN1289866A (en) | 2001-04-04 |
| CN1113113C CN1113113C (en) | 2003-07-02 |
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|---|---|---|---|
| CN 99119773 Expired - Fee Related CN1113113C (en) | 1999-09-28 | 1999-09-28 | Process for growing gallium nitride and its compound film |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100435281C (en) * | 2006-01-17 | 2008-11-19 | 北京大学 | Method for preparing GaN base diluted magnetic semiconductor material |
| CN100465356C (en) * | 2001-06-08 | 2009-03-04 | 克利公司 | High surface quality GaN wafer and method of fabricating same |
| CN1957447B (en) * | 2004-05-18 | 2010-11-03 | 住友电气工业株式会社 | III nitride semiconductor crystal and manufacturing method thereof, III nitride semiconductor device and manufacturing method thereof, and light emitting device |
| CN101066583B (en) * | 2006-05-01 | 2011-01-19 | 住友电气工业株式会社 | Method of processing a surface of group III nitride crystal and group III nitride crystal substrate |
| CN101988213A (en) * | 2009-06-25 | 2011-03-23 | 阿莫诺公司 | Method of obtaining bulk mono-crystalline gallium-containing nitride, bulk mono-crystalline gallium-containing nitride, substrates manufactured thereof and devices manufactured on such substrates |
| CN101308896B (en) * | 2007-05-17 | 2011-12-07 | 住友电气工业株式会社 | Gan substrate, and epitaxial substrate and semiconductor light-emitting device employing the substrate |
| CN101519799B (en) * | 2008-02-27 | 2012-11-21 | 中国科学院半导体研究所 | Method for preparing non-polar GaN thick film on sapphire substrate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8598685B2 (en) | 2009-09-04 | 2013-12-03 | Sumitomo Electric Industries, Ltd. | GaN single crystal substrate and method of manufacturing thereof and GaN-based semiconductor device and method of manufacturing thereof |
-
1999
- 1999-09-28 CN CN 99119773 patent/CN1113113C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465356C (en) * | 2001-06-08 | 2009-03-04 | 克利公司 | High surface quality GaN wafer and method of fabricating same |
| CN1957447B (en) * | 2004-05-18 | 2010-11-03 | 住友电气工业株式会社 | III nitride semiconductor crystal and manufacturing method thereof, III nitride semiconductor device and manufacturing method thereof, and light emitting device |
| CN100435281C (en) * | 2006-01-17 | 2008-11-19 | 北京大学 | Method for preparing GaN base diluted magnetic semiconductor material |
| CN101066583B (en) * | 2006-05-01 | 2011-01-19 | 住友电气工业株式会社 | Method of processing a surface of group III nitride crystal and group III nitride crystal substrate |
| CN101308896B (en) * | 2007-05-17 | 2011-12-07 | 住友电气工业株式会社 | Gan substrate, and epitaxial substrate and semiconductor light-emitting device employing the substrate |
| CN101519799B (en) * | 2008-02-27 | 2012-11-21 | 中国科学院半导体研究所 | Method for preparing non-polar GaN thick film on sapphire substrate |
| CN101988213A (en) * | 2009-06-25 | 2011-03-23 | 阿莫诺公司 | Method of obtaining bulk mono-crystalline gallium-containing nitride, bulk mono-crystalline gallium-containing nitride, substrates manufactured thereof and devices manufactured on such substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1113113C (en) | 2003-07-02 |
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