CN100344006C - Method for developing structure of LED device of InGaN/GaN quantum trap in M faces - Google Patents
Method for developing structure of LED device of InGaN/GaN quantum trap in M faces Download PDFInfo
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- CN100344006C CN100344006C CNB2005100947479A CN200510094747A CN100344006C CN 100344006 C CN100344006 C CN 100344006C CN B2005100947479 A CNB2005100947479 A CN B2005100947479A CN 200510094747 A CN200510094747 A CN 200510094747A CN 100344006 C CN100344006 C CN 100344006C
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Abstract
一种m面InGaN/GaN量子阱LED器件结构的生长方法，利用MOCVD在(100)铝酸锂衬底上合成生长GaN薄膜材料以及InGaN/GaN量子阱LED器件结构，在MOCVD系统中对生长的(100)铝酸锂衬底在500-1050℃温度下进行材料热处理，在一定500-1050℃温度范围通入载气N2，氨气以及金属有机源，在(100)铝酸锂衬底上合成生长m面的GaN材料，再在该GaN材料上以500-1050℃生长N型层M面GaN，以及分别以700-900℃和600-800℃生长层厚分别为15-20nm和5-15nm的5-10个周期的m面GaN/m面InGaN量子阱结构，最后生长一层m面P型层GaN。
A method for growing an m-plane InGaN/GaN quantum well LED device structure, using MOCVD to synthesize and grow GaN thin film materials and an InGaN/GaN quantum well LED device structure on a (100) lithium aluminate substrate. (100) The lithium aluminate substrate is subjected to material heat treatment at a temperature of 500-1050 ° C, and the carrier gas N 2 , ammonia gas and metal organic sources are passed into a certain temperature range of 500-1050 ° C, and the (100) lithium aluminate substrate is The M-plane GaN material is synthesized and grown on the GaN material, and then the N-type layer M-plane GaN is grown on the GaN material at 500-1050°C, and the layer thickness is 15-20nm and 5 nm at 700-900°C and 600-800°C respectively. -15nm m-plane GaN/m-plane InGaN quantum well structure with 5-10 periods, and finally grow a layer of m-plane P-type layer GaN.
Description
Technical field
The present invention relates on a kind of novel substrate (100) LiAlO2 material method, especially utilize the MOCVD technology M face InGaN/GaN quantum well LED device architecture of on the LiAlO2 backing material, growing with MOCVD (metal organic-matter chemical vapor phase epitaxy) technology growth m face GaN/InGaN quantum well LED.
Background technology
Be the wide direct gap semiconductor of III V family of representative with GaN because have band gap wide (E g=3.39eV), luminous efficiency height, electron drift saturated velocity height, thermal conductivity height, hardness is big, dielectric constant is little, chemical property is stable and radioresistance, characteristics such as high temperature resistant, in field of electronic devices such as opto-electronic devices such as high brightness blue light-emitting diode, blue laser and ultraviolet detector and radioresistance, high frequency, high temperature, high pressure huge application potential and vast market prospect are arranged, cause people's very big interest and extensive concern.GaN is the stock in the III group-III nitride, also is to study maximum III group nitride materials at present.The GaN material is very hard, and its chemical property is highly stable, at room temperature water insoluble, bronsted lowry acids and bases bronsted lowry, and its melting point is higher, is about 1700 ℃.The electrical properties of GaN is the principal element of decision device performance, and electronics room temperature mobility can reach 900cm at present
2/ (Vs).The GaN sample of the involuntary doping of growing on Sapphire Substrate exists higher (＞10
18/ cm3) n type background carrier concentration, the background n type carrier concentration of GaN sample can drop to 10 preferably now
16About/cm3.Because n type background carrier concentration is higher, the technical barrier of preparation p type GaN sample had once once limited the development of GaN device.Nakamura etc. adopt the thermal anneal process technology, have better realized mixing the p-typeization of the GaN sample of Mg more easily, can prepare carrier concentration at present 10
11～10
20/ cm
3P-type GaN material.Entered since the nineties, because the employing of resilient coating technology and the breakthrough that the p type mixes technology, the research boom of GaN is grown up in the world, and obtained brilliant achievement.InGaN super brightness indigo plant, green light LED has been realized commercialization.
Backing material is very big for the crystal mass influence of heteroepitaxy GaN, to the Performance And Reliability generation significant effects of device.Shortage is one of main difficulty that influences GaN device maturation with the suitable backing material of GaN lattice match and heat compatibility.The most widely used at present C surface sapphire (c-plane-Al
2O
3) the lattice mismatch rate of substrate and GaN is up to 13.6%.Though can improve the coupling of epitaxial film and substrate by resilient coating, this serious lattice mismatch still can cause epitaxial film middle-high density generation of defects, and the life-span of device and performance are descended greatly.Though it is tempting to carry out the homoepitaxy prospect on the GaN substrate, grow large scale GaN monocrystal and need time, seeking other desirable backing material also is one of effective way of dealing with problems.LiAlO
2Very good with GaN coupling, the lattice mismatch rate of it and GaN has only 1.4% respectively, is the backing material of very promising growing GaN.With C face LiAlO
2Do backing material, adopt MBE, the work of technology synthetically grown M face GaN such as HVPE has a lot of bibliographical informations, and utilizes the MOCVD growing technology to exist) synthetically grown InGaN/GaN quantum-well materials and LED thereof do not appear in the newspapers as yet on the lithium aluminate substrate.
The present invention utilizes MOCVD growing technology synthetically grown M face InGaN/GaN quantum-well materials and LED device architecture material on (100) lithium aluminate substrate.LiAlO2 does backing material with the C face, adopt MBE, the work of technology synthetically grown M face GaN such as HVPE has a lot of bibliographical informations, and utilizes MOCVD growing technology synthetically grown M face InGaN/GaN quantum-well materials and LED thereof on (100) lithium aluminate substrate not to appear in the newspapers as yet.The applicant utilizes MOCVD growing technology synthetically grown M face GaN thin-film material and M face InGaN/GaN quantum well LED device architecture on (100) lithium aluminate substrate first.This application adopts MOCVD (metal organic-matter chemical vapor phase epitaxy) technology synthetically grown M face InGaN/GaN quantum well LED device architecture on (100) lithium aluminate substrate, belong to first technically.The employing of M face InGaN/GaN quantum well is not owing to there is the spontaneous polarization effect of general C face InGaN/GaN quantum well LED structure might improve the internal quantum efficiency of LED device, thereby improves the luminous efficiency of device.
Summary of the invention
The present invention seeks to: on (100) lithium aluminate substrate, adopt MOCVD (metal organic-matter chemical vapor phase epitaxy) technology synthetically grown high brightness M face InGaN/GaN quantum well LED device architecture.
Technical solution of the present invention: (100) the lithium aluminate substrate to growth in the MOCVD system carries out material heat treatment under 500-1050 ℃ of temperature, then or feed ammonia and carry out surfaces nitridedly, feeds carrier gas N in certain 500-1050 ℃ of temperature range again
2, ammonia and metal organic source, by the control carrier gas, parameters such as source gas flow and growth temperature, the GaN material of synthetically grown m face on (100) lithium aluminate substrate, growth one deck doping content reaches 5*10 on this GaN material again
18Cm
-3M face N type GaN, then be respectively the m face GaN/m face InGaN quantum well in 5-10 the cycle of 15-20nm and 5-15nm respectively with 700-900 ℃ and 600-800 ℃ of growth bed thickness, one deck doping content of growing at last reaches 3*10
17Cm
-3The LED device architecture of m face P type GaN layer.And to this structure in the activation of annealing of 600-800 ℃ of temperature and 0.1-1 hour annealing time.
Mechanism of the present invention and technical characterstic:
A kind of growing method of m face InGaN/GaN quantum well LED device architecture is utilized MOCVD growing technology synthetically grown GaN thin-film material and InGaN/GaN quantum well LED device architecture on (100) lithium aluminate substrate.(100) lithium aluminate substrate to growth in the MOCVD system carries out material heat treatment under 500-1050 ℃ of temperature, then or feed ammonia and carry out surfaces nitridedly, feed carrier gas N in certain 500-1050 ℃ of temperature range again
2Ammonia and metal organic source, by the control carrier gas, parameters such as source gas flow and growth temperature, the GaN material of synthetically grown m face on (100) lithium aluminate substrate, again on this GaN material with 500-1050 ℃ of growth N type layer M face GaN and the m face GaN/m face InGaN quantum well structure that is respectively 5-10 the cycle of 15-20nm and 5-15nm respectively with 700-900 ℃ and 600-800 ℃ growth bed thickness, the LED device architecture of one deck m face P type GaN that grows at last.N type layer M face GaN concentration is 5*10
18Cm
-3, P type layer M face GaN concentration is 3*10
17m
-3And to this structure in the activation of annealing of 600-800 ℃ of temperature and 0.1-1 hour annealing time.
Wherein, (100) thermal anneal process before the growth of the employing of lithium aluminate substrate, and lithium aluminate substrate, the thermal annealing temperature, growth back P type layer annealing activationary temperature and time, the temperature control of growth material and the growth and the concentration of m face GaN/m face InGaN quantum well structure are 5*10
18Cm
-3N type layer M face GaN, concentration is 3*10
17Cm
-3P type layer M face GaN is a key of the present invention.
The present invention's optimization growth conditions scope of growing GaN and InGaN/GaN quantum well LED device architecture on (100) lithium aluminate substrate is shown in Table 1.Growth high brightness m face InGaN/GaN quantum well LED device architecture.
The optimization growth conditions scope of table 1. growing GaN on (302) lithium aluminate substrate
| Grown layer | Growth temperature (℃) | Pressure (Torr) | The V/III ratio | Material |
| Nucleating layer | 500-1050 | 0-500 | - | The lithium aluminate substrate |
| Resilient coating | 500-1050 | 0-500 | 500-3000 | M face GaN |
| N type layer | 500-1050 | 0-500 | 500-3000 | M face N type GaN |
| Grown layer | M face GaN700-900 | 0-500 | 500-3000 | The sub-trap of m face GaN/InGaN |
| M face InGaN600-800 | 0-500 | 500-3000 | ||
| P type layer | 800-1100 | 0-500 | 500-3000 | M face P type GaN |
| P type layer activates in the annealing of 600-800 ℃ of temperature and 0.1-1 hour annealing time | ||||
Description of drawings
Fig. 1 is InGaN/GaN quantum well LED device architecture figure of the present invention.In this structure, with (100) lithium aluminate as backing material, on this substrate, grow m face GaN as being resilient coating, on this resilient coating, grow again N type layer M face GaN and InGaN/GaN Multiple Quantum Well, the LED device architecture of one deck M face P type GaN that grows at last.Wherein the InGaN/GaN multi-quantum pit structure is: the m face InGaN Multiple Quantum Well of the m face GaN in 5-10 cycle and 15-20nmm.
The XRD scintigram of the m face GaN that Fig. 2 grows on (100) lithium aluminate substrate for the present invention.As can be seen from the figure, (100) LiAlO2 substrate peak is at 34.66 degree.Lattice constant is a=5.1687 in its face, c=6.2679.The XRD peak position of sample is that crystal orientation is the m face monocrystalline GaN of [1-100] at 32.26 degree, illustrates that the GaN film that grows is the GaN film with m face.Fine through the lattice match of calculating LiAlO2 (302) substrate and M face GaN film, be respectively 0.3% and 1.7%.
The m face GaN with growth that Fig. 3 grows on (100) lithium aluminate substrate for the present invention is the XRC figure of the InGaN/GaN quantum well LED device architecture material of resilient coating.As can be seen from the figure tangible quantum well satellites.Prove that the InGaN/GaN quantum well LED device architecture quality that we develop is better.
What Fig. 4 grew on (100) lithium aluminate substrate for the present invention is the InGaN/GaN quantum well LED device architecture LED tube core luminous photo and the electroluminescent graph of resilient coating with what grow with m face GaN.Our development is that the InGaN/GaN quantum well LED device architecture LED tube core electroluminescence spectrum of resilient coating is at the 517.2nm wave band with m face GaN as we can see from the figure.
Embodiment
The present invention utilizes MOCVD growing technology synthetically grown GaN thin-film material and InGaN/GaN quantum well LED device architecture on (100) lithium aluminate substrate.Specifically comprise following a few step:
1, (100) the lithium aluminate substrate to growth carries out material heat treatment under 500-1050 ℃ of temperature in the MOCVD system, and probable back feeds ammonia and carries out surfaces nitrided.
2, feed carrier gas N 500-1050 ℃ of temperature range again
2, ammonia and metal organic source are by control carrier gas, parameters such as source gas flow and growth temperature, the GaN material of synthetically grown or m face on (100) lithium aluminate substrate.
3, again on this GaN material with 500-1050 ℃ of growth N type layer M face GaN, then respectively with 700-900 ℃ and
600-800 ℃ of growth bed thickness is respectively the m face GaN/m face InGaN quantum well structure in 5-10 the cycle of 15-20nm and 5-15nm, the LED device architecture of one deck P type of growing at last GaN layer.Wherein, the employing of (100) lithium aluminate substrate, and the thermal anneal process before the growth of lithium aluminate substrate, the control of thermal annealing temperature, the temperature control of growth material, and growth concentration is 5*10
18Cm
-3N type layer M face GaN, concentration is 3*10
17Cm
-3P type layer M face GaN, the m face GaN/m face InGaN quantum well LED device architecture in 5-10 cycle of growth is a key of the present invention on growth back P type layer annealing activationary temperature and time and the lithium aluminate substrate.
The method of mixing silicon or mixing magnesium of the preparation utilization routine of N type layer and P type layer GaN is finished.Ni/AuTi/A among Fig. 1] be metal electrode.
Make the GaN material of substrate developing m face in the MOCVD system of (100) lithium aluminate, (100) the lithium aluminate substrate to growth in the MOCVD system carries out material heat treatment under 500-1050 ℃ of temperature, and the time is 10,30,60 minutes indifferences.
Another embodiment is, feeds ammonia then and carry out surfaces nitridedly after above-mentioned heat treatment, and the time is also not have marked difference in 10,30,60 minutes.After treatment, feed carrier gas H 500-1050 ℃ of temperature range then
2With or N
2, ammonia and metal organic gallium source and indium source, wherein the indium source flux remains unchanged, by control carrier gas, parameters such as gallium source gas flow, the GaN material of synthetically grown m face on (100) lithium aluminate substrate.
Organic gallium source is that trimethyl gallium stream is 1-50sccm, and the organo indium source is that trimethyl indium stream is 50-200sccm.According to this apparatus features, adopt the trimethyl gallium (indium) of different flow not have significantly difference, the speed of growth is different.Carrier gas flux is 2-8slm.The ammonia flow that is added directly to substrate is 1-15slm.NH
3Flow is 3-8slm, and growth temperature is 500-1050 ℃.
The further control of carrier band gas is H
2Or N
2Or H
2And N
2Mist is as diluent gas, NH
3Gas is as nitrogenous source.H
2Or N
2Or H
2And N
2Air-fuel mixture enleanment throughput 2500-3500sccm, NH
3Gas 500-7000sccm, the conversion zone temperature also can be 500-1050 ℃, growth time is can obtain A face GaN film completely under the condition of 8-20min.V/III refers to the mol ratio of N and Ga, referring to subordinate list than being 500-3000.Gas flow control is controlled by mass flowmenter.
(100) thermal anneal process before the growth of the employing of lithium aluminate substrate, and lithium aluminate substrate, the temperature control of control of thermal annealing temperature and growth material is key of the present invention.
The present invention feeds carrier gas H
2, or N
2, also can be H
2, and N
2Mist, ammonia and metal organic gallium source provide nitrogenous source and gallium source, by the control carrier gas, parameters such as gallium source gas flow, the embodiment of the invention shows: the GaN material of synthetically grown m face on (100) lithium aluminate substrate easily.The thickness of film is controlled by growth time.
Claims (2)
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| CNB2005100947479A CN100344006C (en) | 2005-10-13 | 2005-10-13 | Method for developing structure of LED device of InGaN/GaN quantum trap in M faces |
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| CN100344006C true CN100344006C (en) | 2007-10-17 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010113238A1 (en) * | 2009-04-03 | 2010-10-07 | パナソニック株式会社 | Nitride semiconductor element and method for manufacturing same |
| WO2010116703A1 (en) * | 2009-04-06 | 2010-10-14 | パナソニック株式会社 | Nitride semiconductor element and method for production thereof |
| US20120085986A1 (en) * | 2009-06-18 | 2012-04-12 | Panasonic Corporation | Gallium nitride-based compound semiconductor light-emitting diode |
| CN101901758B (en) * | 2010-06-24 | 2012-05-23 | 西安电子科技大学 | MOCVD growth method of non-polar m-plane GaN thin film based on m-plane SiC substrate |
| CN101931037A (en) * | 2010-08-03 | 2010-12-29 | 上海半导体照明工程技术研究中心 | GaN based LED epitaxial wafer, chip and device |
| CN102931229B (en) * | 2012-11-06 | 2016-01-20 | 中国电子科技集团公司第五十五研究所 | A kind of AlGaN/GaN/InGaN double heterojunction material and production method thereof |
| CN104600162B (en) | 2014-03-24 | 2016-01-27 | 上海卓霖半导体科技有限公司 | Based on the preparation method of the nonpolar blue-ray LED epitaxial wafer of LAO substrate |
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| US20030024472A1 (en) * | 2001-08-01 | 2003-02-06 | Crystal Photonics, Incorporated | Wafer produced thereby, and associated methods and devices using the wafer |
| US20050026399A1 (en) * | 2003-08-02 | 2005-02-03 | Fen-Ren Chien | Light emitting diode structure and manufacture method thereof |
| US20050040385A1 (en) * | 2002-04-15 | 2005-02-24 | Craven Michael D. | Non-polar (Al,B,In,Ga)N quantum well and heterostructure materials and devices |
| CN1599031A (en) * | 2004-07-21 | 2005-03-23 | 南京大学 | Method of preparing high quality non-polar GaN self-support substrate |
-
2005
- 2005-10-13 CN CNB2005100947479A patent/CN100344006C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030024472A1 (en) * | 2001-08-01 | 2003-02-06 | Crystal Photonics, Incorporated | Wafer produced thereby, and associated methods and devices using the wafer |
| US20050040385A1 (en) * | 2002-04-15 | 2005-02-24 | Craven Michael D. | Non-polar (Al,B,In,Ga)N quantum well and heterostructure materials and devices |
| US20050026399A1 (en) * | 2003-08-02 | 2005-02-03 | Fen-Ren Chien | Light emitting diode structure and manufacture method thereof |
| CN1599031A (en) * | 2004-07-21 | 2005-03-23 | 南京大学 | Method of preparing high quality non-polar GaN self-support substrate |
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