CN1900745A - High reflection ratio distribution Bragg reflective mirror structure for ultraviolet detector and growing method - Google Patents
High reflection ratio distribution Bragg reflective mirror structure for ultraviolet detector and growing method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 23
- 238000009826 distribution Methods 0.000 title claims description 22
- 239000000463 material Substances 0.000 claims description 44
- 229910002704 AlGaN Inorganic materials 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000012159 carrier gas Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000013461 design Methods 0.000 claims description 14
- 229910052594 sapphire Inorganic materials 0.000 claims description 14
- 239000010980 sapphire Substances 0.000 claims description 14
- 238000010276 construction Methods 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 7
- 238000004364 calculation method Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract 1
- 229910017083 AlN Inorganic materials 0.000 description 40
- 238000005516 engineering process Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
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Abstract
Structure of Bragg reflector from base to up part is as following: 5-50nm thick low temperature LT-GaN, 50-2000nm thick high temperature HT-GaN and/or adding high temperature HT-AlN in thickness of layer 5-100nm; finally, 10-50 periodic 15-80nm high temperature AlN/15-100nm thick high temperature AlxGal-xN, where Al component x larger than and equal to 0.3. DBR structure of ultraviolet radiation with reflected wave smaller than 360nm is as following: 5-50nm thick low temperature LT-GaN/50-2000nm thick high temperature HT-GaN and/or including 5-100nm thick high temperature HT-AlN added; finally, 10-50 periodic 15-80nm thick high temperature AlN/15-100nm thick high temperature AlxGal-xN structure.
Description
Technical field
The present invention relates to a kind of ultraviolet rays detector that is used for, high reflection ratio distribution Bragg reflective mirror (DBRs) structural design and the material growing technology of ultraviolet rays light emitting diode and ultraviolet rays laser instrument.On backing material, use MOCVD growing technology growing GaN, AlN or Al
xGa
1-xN is as cushion, again growing AIN/Al on this cushion
xGa
1-xThe multiply periodic distribution Bragg reflector of N.And this structure reflecting mirror is used for the ultraviolet rays detector, in ultraviolet rays light emitting diode and the ultraviolet rays laser structure.
Background technology
From the development process of semiconductor laser and detector, further reducing threshold value, reducing noise, improve quantum efficiency is people's pursuit always.People are in material preparation, and all many-sides such as device architecture design have been carried out a large amount of research.The active region of photoelectric device place in the Febry-Perot resonant microcavity the novel photoelectric device with GaAs and InP be representative second the band semiconductor light-emitting-diode, be applied in laser instrument and the detector.Electron device with micro-cavity structure can improve near the quantum efficiency of photoelectric device resonance wavelength greatly, improves the response speed of device, and emission or absorption spectrum are narrowed down, and improves photoemissive directivity etc.The distribution Bragg reflector of introducing high reflectance in micro-cavity structure is one of approach that addresses these problems.
At present, distribution Bragg reflector has become development light emitting diode (LEDs), the gordian technique of photo-detector and vertical cavity surface emitting laser (VCSELs).The employing of distribution Bragg reflector has greatly improved the proportion of intracavity reflecting light, has improved the output power of device.The use of high reflectance DBRs can be so that the internal quantum efficiency of these devices be greatly improved.Increase anti-principle according to multilayer film, the refringence of two kinds of semiconductor materials of composition bragg reflection mirror is big more, and the reflectivity of DBR is just high more.
Be the wide direct band-gap semicondictor of III V family of representative with GaN because have band gap wide (Eg=3.39eV), luminescence efficiency height, electron drift saturated velocity height, thermal conductivity height, hardness is big, specific inductive capacity is little, chemical property is stable and radioresistance, characteristics such as high temperature resistant, in field of electronic devices such as optoelectronic 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.AlN and GaN, InN equally belongs to the III-V compound semiconductor of broad stopband together, be a kind of important ultraviolet, blue light material, add that it has other important physical propertys such as high thermal conductivity, low thermal expansivity and piezoelectric effect and has a wide range of applications in fields such as electricity, optics.AlN and SiC, Al
2O
3And the lattice mismatch between Si is respectively 1%, 14% and 23%.The monocrystalline ALN film that obtains with the method growth of decompression metal organic chemical vapor deposition on 6H-SiC (0001) substrate, the half-peak breadth of its (0001) diffraction peak only are that the dislocation desity in 0.02 °, film is 1.81 * 10
8/ cm
2, unrelieved stress only have 109 dyne //cm
2Aluminium nitride is to be with (＜6.2eV) the wideest compound in the III-V compounds of group.It has the very high velocity of sound; Very high thermal conductivity and chemical stability; Good insulativity and very low dielectric loss; In visible light and near infrared range, have excellent photopermeability, still have very high physical strength and hardness more than 2300 ℃ in decomposition temperature; Have the low thermal coefficient of expansion close with silicon.Because the difficulty of the technology of preparing of AlN material has limited the development of AlN device.
At present, because the difficulty of material growth, in the preparation of most of AlGaN series semiconductor laser instruments and photodetector structure material, the bragg reflection mirror adopts GaN/Al more
xGa
1-xThe semiconductor material of N (x≤0.3) alternating growth.But, limited the development of the low band ultraviolet device below the 360nm because al composition is low excessively.
Summary of the invention
The present invention seeks to: with transfer matrix method calculation Design high reflection ratio distribution Bragg reflective mirror structure, the i.e. structure of AlGaN/AlN catoptron; Utilize the AlGaN/AlN semiconductor multi layer film DBRs catoptron of low-pressure MOCVD method growth wavelength below 360nm, grow in order to the optimization that has realized material, and the application aspect laser instrument.
The technology of the present invention solution is: the high reflection ratio distribution Bragg reflective mirror structure and the growing method that are used for ultraviolet detector: its structure from the substrate to top be the thick high temperature HT-GaN of 5-50nm thick low temperature LT-GaN, 50-2000nm and or add the high temperature HT-AlN that a layer thickness is 5-100nm; Be the 15-80nm high temperature AlN/15-100nm high temperature AlxGa1-xN in 10-50 cycle, wherein Al component x 〉=0.3 at last; Growing method is: at first, with the structure (result as above) of transfer matrix method calculation Design AlGaN/AlN catoptron, determine the material structure of DBR; Carry out the material structure growth then; In the MOCVD system, the Sapphire Substrate of growth is carried out material heat treatment under 500-1100 ℃ of temperature, then or feed ammonia and carry out surfaces nitridedly, feed carrier gas N at certain temperature range 500-1100 ℃ again
2Ammonia and metal organic source, by the control carrier gas, parameters such as source gas flow and growth temperature, synthetically grown thickness is at low temperature and the high temperature GaN material of 50-2000nm on Sapphire Substrate, or the high temperature AlN insert layer of growth one deck 5-10nm on this GaN material again, then be respectively the distribution Bragg reflector of AlN/AlGaN sandwich construction in 5-50 the cycle of 15-80nm and 15-100nm with 1000-1300 ℃ of growth bed thickness.Wherein metal organic source comprises trimethyl aluminium or trimethyl gallium or adopts HCL carrier gas metal Ga that the gallium source is provided.
Mechanism of the present invention and technical characterstic:
With the structure of transfer matrix method calculation Design AlGaN/AlN catoptron, determine the material structure of DBR.The structure of the present patent application be the thick high temperature HT-GaN/ of the thick low temperature LT-GaN/50-2000nm of 5-50nm and or comprise that adding a layer thickness is that the high temperature HT-AlN/ of 5-100nm is the 15-80nm high temperature AlN/15-100nm high temperature AlxGa1-xN in 10-50 cycle, wherein Al component x 〉=0.3 at last; According to this structure control reflection wavelength less than 360nm; Carry out the material structure growth then.Concrete structure is seen shown in the figure; In the MOCVD system, the Sapphire Substrate of growth is carried out material heat treatment under 500-1100 ℃ of temperature, then or feed ammonia and carry out surfaces nitridedly, feed carrier gas N at certain temperature range 500-1100 ℃ again
2Ammonia and metal organic source (or source metal), by the control carrier gas, parameters such as source gas flow and growth temperature, synthetically grown thickness is at low temperature and the high temperature GaN material of 50-2000nm on Sapphire Substrate, or the high temperature AlN insert layer of growth one deck 5-100nm on this GaN material again, then be respectively the distribution Bragg reflector of AlN/AlGaN sandwich construction in 10-50 the cycle of 15-80nm and 15-100nm with 1000-1300 ℃ of growth bed thickness.
Wherein, the 15-80nm high temperature AlN/15-100nm high temperature AlxGa1-xN sandwich construction that has the 10-50 cycle in the structure, the employing of AlN and high Al component AlxGa1-xN (Al component 〉=0.3), and the number of plies amount of sandwich construction, the thickness of each layer, and the thermal anneal process before the growth, the thermal annealing temperature, the temperature of growth material is controlled and is key of the present invention.
The present patent application people uses the transfer matrix method design first and utilizes MOCVD growing technology synthetically grown on Sapphire Substrate to can be used for the low band ultraviolet detector, the AlN/AlGaN distribution Bragg reflector structured material of ultraviolet laser and ultraviolet light-emitting diode.Adopt AlN and high Al component AlGaN material to improve the low band ultraviolet detector greatly in dbr structure, the quantum efficiency of ultraviolet laser and ultraviolet light-emitting diode device, response speed and making absorb and emission spectrum narrows down has improved device performance.
Obtained reflectivity up to 93.5%, centre wavelength and emissivity be all near the dbr structure material of theoretical value.And material structure and optical property made further research.
On Sapphire Substrate, adopt MOCVD (metal organic-matter chemical vapour phase epitaxy) technology synthetically grown AlN/AlGaN distribution Bragg reflector.Improve the low band ultraviolet detector, the quantum efficiency of ultraviolet laser and ultraviolet light-emitting diode device, response speed and making absorb and emission spectrum narrows down improves device performance.
Description of drawings
It is as shown below that the present invention designs the characteristic of the sandwich construction DBR of growth and this catoptron.
Fig. 1 is AlN/AlGaN multilayer dbr structure figure of the present invention.With the structure of transfer matrix method calculation Design AlGaN/AlN catoptron, determine the material structure of DBR.Structure of the present invention be the thick high temperature HT-GaN/ of the thick low temperature LT-GaN/50-2000nm of 5-50nm and or comprise that adding a layer thickness is that the high temperature HT-AlN/ of 5-100nm is the 15-80nm high temperature AlN/15-100nm high temperature AlxGa1-xN in 10-50 cycle, wherein Al component x 〉=0.3 at last; Determine that according to this structure the reflection wavelength of dbr structure is less than 360nm;
Fig. 2 for the present invention with a kind of design wavelength of MOCVD equipment growth 30 cycle AlN/AlGaN multilayer dbr structure stereoscan photograph figure that have at 320nm.Can clearly be seen that the stratum boundary of dbr structure from figure, and the interface of growing as can be seen is smooth, each layer thickness is consistent with calculated value.
Fig. 3 is of the present invention based on the DBR theoretical modeling value of optical delivery matrix method and the comparison of measured value, is 1.05 with refractive index ratio during simulation, and the two coincide fine.
Fig. 4 is of the present invention based on the DBR theoretical modeling spectrum of optical delivery matrix method and the comparison of measuring spectrum, the ratio of the refractive index of the AlN of this structure choice and AlGaN material is 1.05, the ultraviolet reflectance wavelengths centered peak of design is at 320nm, and the actual measurement peak position is in 313nm; The reflectivity of the DBR of design is R98%, and the DBR actual measured value that grows is 93%.It is relatively good to have reflected that actual measured value and design load meet.
Embodiment
The present invention determines the material structure of DBR with the structure of transfer matrix method calculation Design AlGaN/AlN catoptron.This transmission matrix is expressed as follows:
N in the formula
SubAnd n
rRepresent substrate and reflection horizon r respectively
ThReflection coefficient; d
rThe geometric thickness of corresponding cycle logarithm; λ
dIt is the target wavelength at high reflection configuration peak.Therefore, reflectivity can be determined by following formula:
The structure of the present patent application be the thick high temperature HT-GaN/ of the thick low temperature LT-GaN/50-2000nm of 5-50nm and or comprise that adding a layer thickness is that the high temperature HT-AlN/ of 5-100nm is the 15-80nm high temperature AlN/15-100nm high temperature AlxGa1-xN in 10-50 cycle, wherein Al component x 〉=0.3 at last; According to this structure control reflection wavelength less than 360nm; Carry out the material structure growth then.
Concrete structure is seen shown in the figure; In the MOCVD system, the Sapphire Substrate of growth is carried out material heat treatment under 500-1100 ℃ of temperature, then or feed ammonia and carry out surfaces nitrided (3-15min), feed carrier gas N at certain temperature range 500-1100 ℃ again
2Ammonia and metal organic source (wherein metal organic source comprises trimethyl aluminium or trimethyl gallium or adopts HCL carrier gas metal Ga that the gallium source is provided), by the control carrier gas, parameters such as source gas flow and growth temperature, synthetically grown thickness is at low temperature 500-1100 ℃ and high temperature 800-1100 ℃ of GaN material of 50-2000nm on Sapphire Substrate, or the high temperature 800-1100 ℃ of AlN insert layer of growth one deck 5-100nm on this GaN material again, then be respectively the distribution Bragg reflector of AlN/AlGaN sandwich construction in 10-50 the cycle of 15-80nm and 15-100nm with 1000-1300 ℃ of growth bed thickness.The present invention's optimization growth conditions scope of dbr structure on Sapphire Substrate is shown in Table 1.
Wherein, the 15-80nm high temperature AlN/15-100nm high temperature AlxGa1-xN sandwich construction that has the 10-50 cycle in the structure, the employing of AlN and high Al component AlxGa1-xN (Al component 〉=0.3), and the number of plies amount of sandwich construction, the thickness of each layer, and the thermal anneal process before the growth, the thermal annealing temperature, the temperature of growth material and temperature control are keys of the present invention.
The optimization growth conditions scope of table 1. growing AIN/AlGaN dbr structure on Sapphire Substrate
| Grown layer | Growth temperature (℃) | Pressure (Torr | The V/III ratio | Material |
| Nucleating layer | 500-1100 | 0-500 | -- | Backing material |
| Cushion | 500-1100 | 0-500 | 50-3000 | Low temperature GaN |
| Cushion | 800-1100 | 0-500 | 50-3000 | High temperature GaN |
| Catoptron | AlN，1000-1300 | 0-500 | 50-3000 | The long layer of 10-50 week period interval |
| AlGaN，1000-1300 | 0-500 | 50-3000 |
Specifically comprise following a few step:
1. in the MOCVD system Sapphire Substrate of growth is carried out material heat treatment under 500-1100 ℃ of temperature, probable back feeds ammonia and carries out surfaces nitrided.
2. feed carrier gas N 500-1100 ℃ of temperature range then
2, ammonia and metal organic source are by control carrier gas, parameters such as source gas flow and growth temperature, the GaN cushioning layer material of synthetically grown low temperature and high temperature 5-100nm on Sapphire Substrate.
Again on this GaN material with the 500-1300 ℃ of growth thick AlN/15-100nm of 15-80nm thick Al
xGa
1-xN, the mirror layer in the 10-50 cycle of x0.3.Wherein, the 15-80nm high temperature AlN/15-100nm high temperature AlxGa1-xN sandwich construction that has the 10-50 cycle in the structure, the employing of AlN and high Al component AlxGa1-xN (Al component 〉=0.3), and the number of plies amount of sandwich construction, the thickness of each layer, and the thermal anneal process before the growth, the thermal annealing temperature, the temperature of growth material and temperature control are keys of the present invention.
Wherein V/III represents atomic ratio in the flow of element al in V valency source than III price ratio than the element (Ga, N) in expression V valency carrier gas or source.V/III among the present invention is 50-3000,500-1100 ℃ of thermal annealing temperature, and the time is 10-40min.
Add metal organic source trimethyl aluminium and nitrogen during growing AIN, growth Al
xGa
1-xTrimethyl aluminium or trimethyl gallium or employing HCL carrier gas metal Ga provide gallium source and nitrogen carrier gas during N, and throughput ratio satisfies above-mentioned condition.
High reflection ratio distribution Bragg reflective mirror structure is at ultraviolet laser, the application in ultraviolet light-emitting diode and the ultraviolet detector.
Claims (6)
1, the high reflection ratio distribution Bragg reflective mirror structure that is used for ultraviolet detector: it is characterized in that the structure from the substrate to top is, the high temperature HT-GaN that low temperature LT-GaN, the 50-2000nm that 5-50nm is thick is thick and or add the high temperature HT-AlN that a layer thickness is 5-100nm; Be the 15-80nm high temperature AlN/15-100nm high temperature AlxGa1-xN in 10-50 cycle, wherein Al component x 〉=0.3 at last.
2, by the high reflection ratio distribution Bragg reflective mirror structure of the described ultraviolet detector of claim 1: it is characterized in that to the dbr structure of reflection wavelength less than the ultraviolet rays of 360nm; This structure comprises: the thick high temperature HT-GaN/ of the low temperature LT-GaN/50-2000nm that 5-50nm is thick and or comprise that adding a layer thickness is that the high temperature HT-AlN/ of 5-100nm is the 15-80nm high temperature AlN/15-100nm high temperature AlxGa1-xN structure in 10-50 cycle, wherein Al component x 〉=0.3 at last.
3, by the high reflection ratio distribution Bragg reflective mirror structure of the described ultraviolet detector of claim 1: the 15-80nm high temperature AlN/15-100nm high temperature AlxGa1-xN sandwich construction that it is characterized in that having in the structure 10-50 cycle, AlN and high Al component AlxGa1-xN, Al component 〉=0.3.
4, the growing method two that is used for the high reflection ratio distribution Bragg reflective mirror structure of ultraviolet detector is characterized in that: at first, with the structure of transfer matrix method calculation Design AlGaN/AlN catoptron, determine the material structure of DBR; Carry out the material structure growth then; In the MOCVD system, the Sapphire Substrate of growth is carried out material heat treatment under 500-1100 ℃ of temperature, or feed ammonia again and carry out surfaces nitrided; Feed carrier gas N at certain temperature range 500-1100 ℃ again
2Ammonia and metal organic source, by the control carrier gas, source gas flow and growth temperature, synthetically grown thickness is at low temperature and the high temperature GaN material of 50-2000nm on Sapphire Substrate, or the high temperature AlN insert layer of growth one deck 5-10nm on this GaN material again, then be respectively the distribution Bragg reflector of AlN/AlGaN sandwich construction in 5-50 the cycle of 15-80nm and 15-100nm with 1000-1300 ℃ of growth bed thickness; Wherein metal organic source comprises trimethyl aluminium or trimethyl gallium or adopts HCL carrier gas metal Ga that the gallium source is provided.
5, by the described growing method that is used for the high reflection ratio distribution Bragg reflective mirror structure of ultraviolet detector of claim 4: it is characterized in that: 500-1100 ℃ of the thermal anneal process thermal annealing temperature before the growth.
6, claim 1-5 be used for ultraviolet detector high reflection ratio distribution Bragg reflective mirror structure at ultraviolet laser, the application in ultraviolet light-emitting diode and the ultraviolet detector.
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| CN103199164A (en) * | 2013-04-07 | 2013-07-10 | 中国科学院半导体研究所 | Ultraviolet light-emitting diode with distributed bragg reflector (DBR) and preparation method thereof |
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| CN105914266A (en) * | 2016-05-05 | 2016-08-31 | 映瑞光电科技(上海)有限公司 | Preparation method of GaN-based light emitting diode |
| CN108461568A (en) * | 2018-03-27 | 2018-08-28 | 扬州乾照光电有限公司 | A kind of multijunction solar cell and preparation method thereof with Bragg mirror |
| WO2019196292A1 (en) * | 2018-04-10 | 2019-10-17 | 北京创昱科技有限公司 | Nitride thin-film solar cell |
| CN109950792A (en) * | 2019-03-29 | 2019-06-28 | 钟祥博谦信息科技有限公司 | The distributed bragg reflector mirror of gallium nitride and the preparation method of resonant cavity |
| CN110716260A (en) * | 2019-09-12 | 2020-01-21 | 南京工程学院 | Communication chip of homogeneous integrated laser, reflector and detector and preparation method |
| CN110716260B (en) * | 2019-09-12 | 2020-07-07 | 南京工程学院 | Communication chip of homogeneous integrated laser, reflector and detector and preparation method |
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