CN100373724C - Indium phosphide arsenic-phosphorus-including quantum cascaded laser structure and uninterrupted growth method - Google Patents
Indium phosphide arsenic-phosphorus-including quantum cascaded laser structure and uninterrupted growth method Download PDFInfo
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Abstract
The present invention relates to middle infrared InP based arsenical phosphorated quantum cascaded laser structures with low threshold current density and also relates to a preparation method of uninterrupted continuous growth. The present invention is characterized in that four middle infrared InP based arsenical phosphorated quantum cascaded laser (QCL) structures have the following characteristics: (a), all the structures comprise InP based arsenical phosphorated GaInAs/AlInAs/GaInAs/InP/InP or GaInAs/InP/GaInAs/AlInAs/InP/InP; (b), the structures only need one donor dopant of silicon; (c), the structures adopt an InP/InP composite lower waveguide surround and adopt an InP/GaInAs or a GaInAs/InP digital graded superlattice layer when the InP and the GaInAs mutually carry out transition; (d) pre-injection reinforcement layers are arranged at both sides of an active area or an injection region. The uninterrupted continuous growth method of the middle infrared InP based arsenical phosphorated quantum cascaded laser structures is characterized in that only one gas state source molecular beam epitaxy system is needed to complete the whole uninterrupted continuous growth of the InP based arsenical phosphorated quantum cascaded laser structures. The developed QCL devices have the characteristic of low threshold current density.
Description
Technical field
The present invention relates to infrared InP base arsenic-phosphorus-including quantum cascaded laser structure and uninterrupted growth preparation method continuously thereof in the low threshold value.Belong to photoelectric semiconductor material and device technology field.
Background technology
It contains 3-5 μ m to 2-14 μ middle-infrared band by what, two epochmaking atmospheric windows of 8-14 μ m, having important use in the atmosphere secure communication is worth, again by the what molecule, atomic vibration, rotation, the feature of many gases " fingerprint " the absorption line what 2-14 μ m middle-infrared band that falls, detect at trace gas, the chemical production process monitoring, medical diagnosis, biochemical poison gas monitoring has important use to be worth, therefore, the semiconductor laser that works in the 2-14 mu m waveband be applied to above-mentioned two fields must obligato important light source, the national security and the development of the national economy are all had crucial meaning.
Long-term next, the classics of ruling the semiconductor laser field swash to be penetrated theory and thinks that the sharp of semiconductor laser penetrate by being semi-conducting material conduction band electron and valence band hole-recombination, produce the p-n junction bipolar semiconductor laser of photon, its excitation wavelength is by the band gap decision of semi-conducting material, yet nature lacks the ideal semiconductor laser material of band gap place what middle-infrared band, thereby the situation of infrared semiconductor laser stagnation in causing.The only way that puts the axe in the helve is fundamentally to found new semiconductor laser theory, so Soviet Union scientist Kazarinov in 1971 and Suris propose to realize by the optical transition of quantum well intersubband the imagination of light amplification, H.C.Liu in 1988 proposed to adopt two traps coupling serial connection resonant tunneling structures by with in the intersubband optical transition realize swashing the imagination of penetrating.Through Bell Laboratory to these original physical thoughts and monoatomic layer molecular beam epitaxial growth technology 10 years of development, invented in 1994 finally work what 4.26 μ m middle-infrared bands quantum cascade laser (Quantum Cascade Laser, QCL).QCL is the epoch-making development of semiconductor laser theory and technology, has following characteristics: the sharp operation principle of penetrating of (1) QCL is based on subband optical transition in the conduction band, has only a kind of charge carrier (electronics) to participate in the optical transition ballistic phonon, is kind of an one pole type laser.The QCL excitation wavelength is also promptly to determine excitation wavelength by changing active area quantum well bed thickness by the energy difference that changes between active area excitation state, is not by semi-conductive band gap decision wavelength, therefore can cover very wide wave-length coverage.Theoretical expectation can cover from several microns to more than the 200 μ m, thereby has fundamentally solved a difficult problem that lacks mid and far infrared wave band ideal semiconductor laser material.But with the near-infrared semiconductor laser mutually quite, the new problem that infrared Radiation photograph and free carrier mutual effect brought during the QCL of work what middle-infrared band also must consider except that the operation principle difference.This shows that the appropriate design of QCL structure is crucial; (2) QCL is the product that quantum energy band cutting engineering combines with advanced person's atomic layer growth technology, and the sharp photon of penetrating that the cascading of quantum cascade laser allows the progression similar number of an electron production and cascade brings high Output optical power thus.Therefore, the monoatomic layer growth method of QCL structure and the quality control basis and the guide that are device; (3) different application is to the QCL device performance: trace gas detects and requires that tool hang down threshold value, single mode is tunable, and atmospheric communication and electrooptical countermeasures then require to work in luminous power, the Heat stability is good that room temperature, continuous and tool meet application requirements.Therefore, need the new technology of development device; (4) a series of intrinsic property of QCL tool and the extrinsic property of work what middle-infrared band, QCL quantum efficiency as single-stage is lower, threshold current is bigger, driving voltage is higher, need swash with heavy current short pulse measuring system and more special drive condition and penetrate spectrum, current-voltage, electric current-measuring light power.
Invented first low temperature from 1994, [J.Faist since the infrared QCL in the 4.6 μ m multimodes of pulsed operation, F.Capasso, D.L.Sivco, C.Sirtori, A.L.Hutchinson, and A.Y.Cho, " Quantum cascade laser; " Science 264,553 (1994) .], the breakthrough that obtained milestone in short ten years: developed first room temperature infrared QCL[M.Beck among the 9.0 μ m of output continuously in 1998, D.Hofstetter, T.Aellen, J.Faist, U.Oesterle, M.Ilegams, E.Gini, H.Melchior, " Continuous wave operation of a mid-infrared semiconductor laser at roomtemperature ", Science 295,301 (1998) .], reported first 5.4 μ m and 8 μ m room temperatures in 1997, the tunable distributed feed-back QCL[J.Faist of pulse single mode, C.Gmachl, F.Capasso, C.Sirtori, D.L.Sivco, J.Baillargeon, and A.Y.Cho, " Distributed feedback quantumcascade lasers ", Appl.Phys.Lett 70 (20), and 2670 (1997) .], reported first 5.4 μ m room temperature in 2005, the tunable distributed feed-back QCL[S.Blaser of the single mode of continuous operation, D.A.Yarckha, L.Hvozdara, Y.Bonetti, A.Muller, M.Giovannini and J.Faist, " Room-temperature, continuous-wave, single-mode quantum-cascade lasers at λ～5.4 μ m ", Appl.Phys.Lett.86 (4), 041109 (2005) .].The room temperature pulse multimode QCL[that developed first watt level power in 1998 is C.Gmachl 1., A.Tredicucci, F.Capasso, A.L.Hutchinson, D.L.Sivco, J.N.Baillargeon, and A.Y.Cho, " Higu-power λ～8 μ mcascade lasers with near optimum performance ", Appl.Phys.Lett.72,3130 (1998). 2. C.Sirtori, J.Faist, F.Capasso, D.L.Sivco, A.L.Hutchinson, and A.Y.Cho, " Mid-infrared (8.5 μ m) semiconductor lasers operating at room temperre ", IEEE Photonics Technol.Lett.9,294 (1997) .].At present, the InP base AlInAs/GaInAs quantum cascade laser with ternary system waveguide material or the development of binary system waveguide material has covered 3.5-25 μ m middle-infrared band widely.QCL becomes first running continuously under 〉=room temperature, single mode is adjustable〉infrared semiconductor laser among the 4 μ m, become first at room temperature running, watt level power output continuously〉infrared semiconductor laser among 5 μ m, at first enter the practicability experimental stage, but that device will reach is real stable, reliable, practicality still has many preparation methods and Technology Need to be situated between to determine and develop.
Existing InAlAs/InGaAs quantum cascade laser structure is grown directly upon on the substrate, transit directly to AlGaInAs from InP, when adopting InP to do the waveguide integument, then transit directly to InP and do the cap layer with InP by InGaAsP, such structure can cause fault of construction to increase, the difficult ready-made problem of ohmic contact.The InAlAs/InGaAs quantum cascade laser structure of existing preparation InP base arsenic-phosphorus-including adopts the interruption growing method usually: (1) contains arsenic earlier with Solid State Source molecular beam epitaxy (SSMBE) equipment growth that contains solid-state arsenic source ternary system compound, take out and put into the phosphorous material of another SSMBE equipment that contains solid state of phosphorous source continuation epitaxial growth.Or (2) contain earlier the ternary system compound of arsenic with Solid State Source molecular beam epitaxy (SSMBE) equipment growth that contains solid-state arsenic source, epitaxial wafer taken out from SSMBE equipment put into the phosphorous material of another metallo-organic compound (MOCVD) equipment continuation epitaxial growth.This interruption growth method not only exists interface quality, growth background difference, and cost doubles.Therefore, the uninterrupted growth method of the InAlAs/InGaAs quantum cascade laser structure of development new construction and preparation InP base arsenic-phosphorus-including is exactly a purpose of the present invention with Jie's existing problem of determining.Use the present invention, successfully develop a series of room temperature pulses of 5-10 mu m waveband and quasi-continuous AlInAs/GaInAs middle-infrared band InP base unit weight qc laser.
Summary of the invention
Infrared low-threshold power current density InP base arsenic-phosphorus-including quantum cascaded laser structure and uninterrupted growth preparation method continuously thereof in the object of the present invention is to provide.The middle-infrared band InP base InAlAs/InGaAs quantum cascade laser structure and the uninterrupted growth preparation method continuously thereof of four kinds of arsenic-phosphorus-includings specifically, are provided.
One, InP base arsenic-phosphorus-including quantum cascaded laser structure
In Fabry-Perot (F-P) the chamber multimode of invention in 1994 the INFRARED QUANTUM CASCADE LASERS structure as shown in Figure 1, it is growth InGaAs and an AlInAs epitaxial material on the InP substrate.This classical architecture is removed the InP substrate, and epitaxial loayer only contains arsenide, does not have a difficult problem of switching with V family interface, can be by Solid State Source or the growth of gas source molecular beam epitaxy method.But by what AlInAs in this classical architecture, the InGaAs thermal conductance is low and cause the QCL device heating serious, and thermal characteristics is undesirable.Be to improve QCL device thermal characteristics, the real Nan Nan of 1997-1998 Bel Experience chamber proposed as shown in Figure 2 with thermal conductivity InP substitute for Al InAs preferably, InGaAs strengthens limiting layer and cap layer as last waveguide integument, plasma.Researched and developed again after 1997 as shown in Figure 3 and Figure 4 the ternary system waveguide and the distribution as unimodal feedback quantity qc laser (DFB-QCL) of binary system waveguide.Arsenic but also phosphorous QCL had not only been contained for epitaxial loayer, adopted MBE to be interrupted growth method in the world, after having grown the structure that contains arsenic another MBE equipment that contains the solid state of phosphorous source being put in the material taking-up grows, also there is the people then after the structure that contains arsenic of having grown with MBE, to take out, uses metal-organic chemical vapor deposition equipment method (MOCVD) continued growth InP layer thereon.This interruption growing method will not only be brought secondary environmental pollution, and by interrupting and improve interfacial state and reduce interface quality, make the complicated increase cost of technology in the what interface.
The present invention is directed to the problems referred to above, the middle-infrared band InP base InAlAs/InGaAs quantum cascade laser structure of four kinds of arsenic-phosphorus-includings shown in Fig. 5-8 has been proposed, wherein Fig. 5,6 is Fabry-Perot multimode QCL, and Fig. 7,8 tunable distributed feed-back QCL structure that is single mode.It is characterized in that: (1) Fig. 5,7 structures are GaInAs/AlInAs/InP/InP, and its characteristics are gently mixed the multi-functional InP resilient coating of silicon for containing, and reduce the influence from substrate, reduce the wastage; There are digital alternation superlattice to assist the injection region at active area and both sides, injection region, are beneficial to the raising injection efficiency.(2) Fig. 6,8 structures are GaInAs/InP/GaInAs/AlInAs/InP/InP, its characteristics are for to do the cap layer with low energy gap InGaAs, do plasma with InP binary system material and strengthen limiting layer, the last waveguide coating layer of InP, and with gently mixing the multi-functional InP resilient coating of silicon, and add the auxiliary injection region of digital alternation superlattice in active area and both sides, injection region, the main distinction of the structure of multimode and single mode QCL strengthens the thickness of limiting layer at plasma, and this layer thickness of single mode DFBQCL is that grating etching depth (200-300nm) adds 300-350nm and is beneficial to the raising injection efficiency.Four kinds of structures of the present invention material select and structural design on have Wall around improving the population inversion main line, in the reduction infrared Radiation penetrate, reduce non-Radiation penetrate the complex centre, improve material thermal conductance and device thermal characteristics, reduce that optical loss improves the gain of light, improves electron injection efficiency, the characteristics of reduction threshold current density.Fig. 9 is the relation of GaInAs refractive index under the present invention the studies different donor concentrations and wavelength, from Fig. 9 as seen, along with donor concentration and wavelength increase and wavelength, is absorbed to increase fast by the what free carrier and causes refractive index to be badly in need of descending.Make that the photon restriction weakens, loss increases.This result of study has been applied to the selection of Fig. 5 of the present invention-6 parameter and has optimized.
The characteristics of four kinds of structure QCL of the invention described above are: (1) every kind of structure all contains arsenide and phosphide simultaneously; (2) adopt InP substrate and extension InP resilient coating to form compound waveguide integument down, described InP substrate is mixed sulphur; (3) between InP resilient coating and GaInAs lower limit layer, mutually adopt InP/GaInAs or GaInAs/InP numeral alternation superlattice layer during transition; (4) add pre-injection region auxiliary layer in active area/both sides, injection region; (5) when reducing the ducting layer loss and improving the gain of light, counted the relation of semi-conducting material refractive index and wavelength and free carrier concentration; (6) described active area undopes, and all epitaxial loayers except that described active area only adopt a kind of donor dopant of silicon, and existing report all adopts silicon, two kinds of donor dopants of tin simultaneously.
Two, the uninterrupted growth preparation method continuously of InP base arsenic-phosphorus-including quantum cascaded laser structure
The InAlAs/InGaAs quantum cascade laser structure of arsenic-phosphorus-including usually adopts the interruption growing method of two kinds of combinations: (1) first kind is interrupted the assembled growth method is to grow with Solid State Source molecular beam epitaxy (SSMBE) equipment that contains solid-state arsenic source earlier to contain the ternary system compound of arsenic, cooling stops growing then, epitaxial wafer is taken out from SSMBE equipment put into the phosphorous material of another SSMBE equipment that contains solid state of phosphorous source continuation epitaxial growth.(2) second kinds are interrupted the assembled growth method is to grow with Solid State Source molecular beam epitaxy (SSMBE) equipment that contains solid-state arsenic source earlier to contain the ternary system compound of arsenic, cooling stops growing then, epitaxial wafer is taken out from SSMBE equipment put into the phosphorous material of another metallo-organic compound (MOCVD) equipment continuation epitaxial growth.What the present invention adopted is the uninterrupted continuous growing method of gas source molecular beam epitaxy (GSMBE), be characterized in once finishing the growth of entire I nP base arsenic-phosphorus-including quantum cascaded laser structure material, guaranteed that each layer of QCL of being made up of layer up to a hundred and even thousands of layers of arsenic-phosphorus-including epitaxial loayer all is in identical background background with each interface, stable optimal conditions, stable growth conditions is growth down, can not bring interface quality to change because of being interrupted growth.And only needing an equipment, fund input is low, steady quality, good reliability.
Uninterrupted growth preparation method continuously of the present invention is to adopt the uninterrupted grown InP base arsenic-phosphorus-including quantum cascaded laser structure material continuously of gas source molecular beam epitaxy (GSMBE).Device therefor is the V80H GSMBE system that is produced by Britain VG MBE company that is disposed voluntarily by the inventor shown in Figure 10.The characteristics of this system configuration are: V family gaseous source is high-purity arsine (AsH
3) and phosphine (PH
3), pressure control and high pressure cracking rather than quality control and catalytic pyrolysis are adopted in its beam intensity control, and contaminating impurity and the lysis efficiency to system and epitaxial loayer of having avoided the mass flowmenter dead angle to bring are degenerated; The electron gun stove of gallium and indium is the tantalum resistance furnace that the dual heating zones of particular design is formed; The electron gun stove of aluminium and dopant is the tantalum resistance furnace of normal structure; The beam intensity of aluminium, gallium, indium is monitored by the decision of electron gun stove heating-up temperature and by the on-line measurement ion flow; The background residual gas of system is monitored by online quadrupole mass spectrometer; The reflection high energy electron diffraction instrument (RHEED) that the surface texture of substrate and epitaxial loayer is produced with German Staib Instrucmente company.The architectural characteristic of epitaxial loayer, electrology characteristic and optical characteristics are respectively by the X-ray double crystal diffraction, and Hall electrical testing and Fu Li leaf photoluminescent method characterize.
The concrete growth technique of QCL structure: before the epitaxial growth, indium is at 890-910 ℃, and aluminium is at 1200-1220 ℃, gallium is at 1050-1100 ℃, silicon is at 1250-1280 ℃, V family pyrolysis furnace 1030-1160 ℃ respectively growth room's degasification 15-30 minute, used temperature when reducing to growth then.Open box promptly use (English for epi-ready) mix sulphur n type InP single crystalline substrate (English be epi-readysubstrate) earlier in pretreatment chamber at 200-250 ℃ of degasification 1-3 hour, slough the aqueous vapor of surface adsorption, and then be sent on growth room's specimen holder, the heated sample heater, when rising to 300 ℃, feed PH
3To the growth room, this moment, the pressure of growth room was 3 * 10
-5Torr is to protect substrate surface and to keep stoichiometric proportion.The desorption situation of under high electron energy diffractometer (RHEED) monitoring, observing InP substrate temperature-rise period surface adsorption gas and oxide.For low-resistance n type InP substrate, desorption temperature is at 460-480 ℃ usually.When surface texture transfers 4 * 2 to by 2 * 2, show the CO of substrate surface absorption
2With the oxide desorb of phosphorus, kept 2-5 minute at desorption temperature, reduce the about 40-70 of underlayer temperature ℃ or 60-90 ℃ then, close RHEED, to prevent the damage of high energy electron to substrate surface and epitaxial loayer.The growth temperature of InP is 380-420 ℃, the growth temperature of AlInAs and GaInAs is 400-440 ℃, when growth AlInAs, GaInAs, keep identical indium electron gun furnace temperature, indium stove shutter is in normally open, when switching AlInAs, GaInAs, only need ON/OFF aluminium stove or gallium stove shutter, Si dopant temperature is decided according to required doping content during growth, V family pyrolysis furnace maintains 1000 ℃, and the growth room leads to PH
3The time, the pressure of growth room is 2.2-3 * 10
-5Torr, the growth room leads to AsH
3The time, the pressure of growth room is 1.5-2 * 10
-5Torr.The growth rate of four kinds of epitaxial materials is 0.7-1.0 μ m/ hour, and the rotary speed of specimen holder is 10 rev/mins during growth.After treating that underlayer temperature is stable, press the layer of structure order epitaxial growth of Fig. 5-8, epitaxial growth finishes the back substrate heater and reduces to 100 ℃, and 900-1000 ℃ of In reduced to by the Al stove and the Ga stove is reduced to 650-700 ℃, V family pyrolysis furnace maintains 1000 ℃, with residual A sH in the assurance system
3And PH
3Fully cracking can not enter pretreatment chamber when slice, thin piece is come out of the stove.F-P chamber InP shown in Figure 5 base AlInAs/GaInAsQCL ternary system waveguiding structure is to be that substrate and resilient coating are formed compound waveguide integument down to mix sulphur InP, be GaInAs/InP numeral alternation superlattice layer then, improvement is carried out the transition to the defective of GaInAs lower limit layer by InP, regrowth GaInAs lower limit layer on GaInAs/InP numeral alternation superlattice layer, it is pre-injection region auxiliary layer thereafter, prevent that electronics is injected with the source region electrons spread, what continue is AlInAs/GaInAs active area and injection region, and the thickness at its trap and base has determined the excitation wavelength of QCL.The pre-injection region of the AlInAs/GaInAs auxiliary layer of then growing is strengthened electronics and is injected with the source region.Be GaInAs upper limiting layer (photon and the electronics of upper and lower limit preparative layer restriction active area and injection region) then.Regrowth GaInAs/AlInAs numeral alternation superlattice layer improves the interface that is carried out the transition to AlInAs by GaInAs.The AlInAs that grows then goes up the waveguide integument, and regrowth AlInAs/GaInAs numeral alternation superlattice layer improves the interface that is carried out the transition to GaInAs by AlInAs, and regrowth GaInAs plasma increases limiting layer, the GaInAs cap layer of growing at last.F-P chamber multimode InP shown in Figure 6 base AlInAs/GaInAsQCL binary system waveguiding structure is to be that substrate and resilient coating are formed compound waveguide integument down to mix sulphur InP, be GaInAs/InP numeral alternation superlattice layer then, improvement is carried out the transition to the defective of GaInAs lower limit layer by InP, regrowth GaInAs lower limit layer on GaInAs/InP numeral alternation superlattice layer, it is pre-injection region auxiliary layer thereafter, prevent that electronics is injected with the source region electrons spread, what continue is AlInAs/GaInAs active area and injection region, and the thickness at its trap and base has determined the excitation wavelength of QCL.The pre-injection region of the AlInAs/GaInAs auxiliary layer of then growing is strengthened electronics and is injected with the source region.Be GaInAs upper limiting layer (photon and the electronics of upper and lower limit preparative layer restriction active area and injection region) then.Regrowth GaInAs/InP numeral alternation superlattice layer improves the interface that is carried out the transition to InP by GaInAs.Waveguide integument on the grown InP then, the InP plasma increases limiting layer, the GaInAs cap layer of growing at last.DFB single mode InP shown in Figure 7 base AIInAs/GaInAsQCL ternary system waveguiding structure is to be that substrate and resilient coating are formed compound waveguide integument down to mix sulphur InP, be GaInAs/InP numeral alternation superlattice layer then, improvement is carried out the transition to the defective of GaInAs lower limit layer by InP, regrowth GaInAs lower limit layer on GaInAs/InP numeral alternation superlattice layer, it is pre-injection region auxiliary layer thereafter, prevent that electronics is injected with the source region electrons spread, what continue is active area and injection region, and the thickness at its trap and base has determined the excitation wavelength of QCL.The pre-injection region of the AlInAs/GaInAs auxiliary layer of then growing is strengthened electronics and is injected with the source region.Be GaInAs upper limiting layer (photon and the electronics of upper and lower limit preparative layer restriction active area and injection region) then.Regrowth GaInAs/AlInAs numeral alternation superlattice layer improves the interface that is carried out the transition to AlInAs by GaInAs.The AlInAs that grows then goes up the waveguide integument, regrowth AlInAs/GaInAs numeral alternation superlattice layer improves the interface that is carried out the transition to GaInAs by AlInAs, and regrowth GaInAs plasma increases limiting layer, this layer thickness lacks 300-350nm, the GaInAs cap layer of growing at last approximately than multimembrane.DFB single mode InP shown in Figure 8 base AlInAs/GaInAsQCL binary system waveguiding structure is to be that substrate and resilient coating are formed compound waveguide integument down to mix sulphur InP, be GaInAs/InP numeral alternation superlattice layer then, improvement is carried out the transition to the defective of GaInAs lower limit layer by InP, regrowth GaInAs lower limit layer on GaInAs/InP numeral alternation superlattice layer, it is pre-injection region auxiliary layer thereafter, prevent that electronics is injected with the source region electrons spread, what continue is AlInAs/GaInAs active area and injection region, and the thickness at its trap and base has determined the excitation wavelength of QCL.The pre-injection region of the AlInAs/GaInAs auxiliary layer of then growing is strengthened electronics and is injected with the source region.Be GaInAs upper limiting layer (photon and the electronics of upper and lower limit preparative layer restriction active area and injection region) then.Regrowth GaInAs/InP numeral alternation superlattice layer improves the interface that is carried out the transition to InP by GaInAs.Waveguide integument on the grown InP then, the InP plasma increases limiting layer, and this layer thickness is than the thin 300-350nm of multimembrane, the GaInAs cap layer of growing at last.
Description of drawings
Fig. 1 is the InP base AlInAs/GaInAs ternary system waveguide F-P chamber QCL structure (J.Faist et al, " Quantum cascade laser, " Science264,553 (1994)) of the classics of bibliographical information.
Fig. 2 is the InP base AlInAs/GaInAs binary system waveguide F-P chamber QCL structure (C.Sirtori et al, IEEE Photonics Technol.Lett.9,294 (1997)) of the classics of bibliographical information.
Fig. 3 is the InP base AlInAs/GaInAs ternary system waveguide DFB-QCL structure (J.Faist etal, Appl.Phys.Lett70 (20), 2670 (1997)) of the classics of bibliographical information.
Fig. 4 is the DFB InP base AlInAs/GaInAs QCL binary system waveguiding structure (J.Faist et al, IEEE Journal of Quantum Electronics, 34 (2), 336 (1998)) of the classics of bibliographical information.
Fig. 5 is a multimode F-P provided by the invention chamber InP base AlInAs/GaInAs QCL ternary system waveguiding structure.
Fig. 6 is an InP base AlInAs/GaInAs multimode F-P chamber binary system waveguide QCL structure provided by the invention.
Fig. 7 is an InP base AlInAs/GaInAs ternary system waveguide DFB-QCL structure provided by the invention.
Fig. 8 is a single mode DFB InP base AlInAs/GaInAs QCL binary system waveguiding structure provided by the invention.
Fig. 9 (a) GaInAs, AlInAs, the Zhe She of InP are Shuaied the Sui wavelength change; (b) the Zhe She of GaInAs is Shuaied the Sui wavelength change under different carrier concentrations.
Figure 10 is the V80H gas source molecular beam epitaxy system that is used for grown InP base arsenic-phosphorus-including quantum cascaded laser structure material.
Figure 11 (a) is for reaching uninterruptedly the sharp spectrogram of penetrating of the quantum cascade laser of the GSMBE material development of growth preparation method growth continuously with Fig. 5 GaInAs/GaInAs/AlInAs/InP/InP triple-well coupling QCL structure of the present invention; (b) be that 2mm, ridge wide are QCL naked pipe device electric current-luminous power characteristic at room temperature of 20 microns for grid are long.
Figure 12 (a) is the sharp spectrogram of penetrating with the F-P chamber quantum cascade laser of the GSMBE material development of Fig. 6 GaInAs/InP/GaInAs/AlInAs/InP/InP triple-well coupling QCL structure of the present invention and the growth of uninterrupted growth preparation method continuously thereof; (b) for grid are long be 18 microns the QCL naked pipe device relation of the electric current of QCL device-luminous power characteristic and duty ratio at room temperature for 2mm, ridge wide.
Figure 13 (a) is the sharp spectrogram of penetrating with the anti-cloth feedback quantity of the triple-well coupling single mode qc laser DFB-QCL of the present invention's development; (b) be that 2mm, ridge wide are the electric current-luminous power characteristic of DFB-QCL naked pipe device QCL device under different temperatures of 20 microns for grid are long.
Embodiment
Further specifying substantive distinguishing features of the present invention and obvious improvement in conjunction with the accompanying drawings below by embodiment, but limit the present invention absolutely not, also is that the present invention absolutely not only is confined to embodiment.
The step of the concrete growth of InP base arsenic-phosphorus-including quantum cascaded laser structure is:
1. will be contained in the Sample Room that sulphur n type InP single crystalline substrate is put into the GSMBE system of mixing that box is promptly used (epi-ready) of opening in the molybdenum holder.Vacuumize with turbomolecular pump.
2.InP substrate degasification: treat that Sample Room vacuum degree reaches 10
-6During Torr, will mix sulphur n type InP single crystalline substrate and be passed on the heating station of pretreatment chamber of GSMBE system, at 200-250 ℃ of degasification 1-3 hour, slough the aqueous vapor of surface adsorption, reduce to 50-100 ℃ then in pretreatment chamber.
3. electron gun degasification: the InP substrate is in pretreatment chamber's degasification, growth room's electron gun material must finish before epitaxial growth in degasification: indium is at 890-910 ℃, aluminium is at 1200-1220 ℃, gallium is at 1050-1100 ℃, silicon is at 1250-1280 ℃, V family pyrolysis furnace respectively growth room's degasification 15-30 minute, is reduced to used temperature when growing at 1030-1160 then.
4. epitaxial growth: will except that the InP substrate transfer of intact gas to the sample heating station of GSMBE system growth room, when the heated sample heter temperature rises to 300 ℃, feed PH
3To the growth room, this moment, the pressure of growth room was 3 * 10
-5Torr is to protect substrate surface and to keep stoichiometric proportion.The desorption situation of under high electron energy diffractometer (RHEED) monitoring, observing InP substrate temperature-rise period surface adsorption gas and oxide.For low-resistance n type InP substrate, desorption temperature is at 460-480 ℃ usually.When surface texture transfers 4 * 2 to by 2 * 2, show the CO of substrate surface absorption
2With the oxide desorb of phosphorus, kept 2-5 minute at desorption temperature, reduce the about 40-70 of underlayer temperature ℃ or 60-90 ° of C then, close RHEED, to prevent the damage of high energy electron to substrate surface and epitaxial loayer.The growth temperature of InP is 380-420 ℃, the growth temperature of AlInAs and GaInAs is 400-440 ℃, when growth AlInAs, GaInAs, keep identical indium electron gun furnace temperature, indium stove shutter is in normally open, when switching AlInAs, GaInAs, only need ON/OFF aluminium stove or gallium stove shutter, Si dopant temperature is decided according to required doping content during growth, V family pyrolysis furnace maintains 1000 ℃, and the growth room leads to PH
3The time, the pressure of growth room is 2.2-3 * 10
-5Torr, the growth room leads to AsH
3The time, the pressure of growth room is 1.5-2 * 10
-5Torr.The growth rate of three kinds of epitaxial materials is o.7-1.0 μ m/ hour.After treating that underlayer temperature is stable, press the layer of structure order epitaxial growth of Fig. 4-6, the rotary speed of specimen holder is 10 rev/mins during growth.Epitaxial growth finishes the back substrate heater and reduces to 100 ℃, and the Al stove is reduced to 900-1000 ℃, and In and Ga stove are reduced to 650-700 ℃, and V family pyrolysis furnace maintains 1000 ℃, with residual A sH in the assurance system
3And PH
3Fully cracking can not enter pretreatment chamber when slice, thin piece is come out of the stove.
5. the QCL epitaxial wafer is passed to pretreatment chamber in regular turn from the growth room, closes the main valve between growth room and pretreatment chamber; V family pyrolysis furnace is reduced to 600 ℃ from 1000 ℃; The QCL epitaxial wafer is passed to Sample Room again, takes out epitaxial wafer, carry out surface topography observation and preparation of QCL device and test.
Show structure of the present invention and uninterrupted growth preparation method continuously thereof feasibility at preparation hundreds of infrared QCL material and low-threshold power current density QCL device to thousands of layers.
Embodiment 1:
Figure 11 (a) is the QCL structure that is coupled with Fig. 5 GaInAs/GaInAs/AlInAs/InP/InP triple-well of the present invention
And the sharp spectrogram of penetrating of the quantum cascade laser of the GSMBE material development of uninterrupted growth preparation method continuously growth, be 8.0 microns from scheming visible its excitation wavelength.Figure 11 b is that grid are long for 2mm, ridge wide are QCL naked pipe device electric current-luminous power characteristic at room temperature of 20 microns, from Figure 11 b visible threshold current density 1.75KA/cm only
-3
Embodiment 2:
Figure 12 (a) is the sharp spectrogram of penetrating of the F-P chamber quantum cascade laser of the GSMBE material development of growing with Fig. 6 GaInAs/InP/GaInAs/AlInAs/InP/InP triple-well coupling QCL structure of the present invention and uninterrupted growth preparation method continuously thereof, and its excitation wavelength is 7.6 microns under the visible room temperature of Figure 12 a.Figure 12 b is that grid are long for 2mm, ridge wide are 18 microns the QCL naked pipe device relation of the electric current of QCL device-luminous power characteristic and duty ratio at room temperature, from Figure 12 b visible threshold current density 1.75KA/cm only
-3
Embodiment 3:
Figure 13 (a) is the sharp spectrogram of penetrating with the anti-cloth feedback quantity of the triple-well coupling single mode qc laser DFB-QCL of the present invention development, from Figure 12 a as seen under 80K its excitation wavelength be 7.6 microns.Figure 13 b is that grid are long for 2mm, ridge wide are the electric current-luminous power characteristic of DFB-QCL naked pipe device QCL device under different temperatures of 20 microns, from Figure 13 b visible threshold current density 574A/cm only
-3Demonstrate the low threshold current density feature.
Claims (8)
1. indium phosphide arsenic-phosphorus-including quantum cascaded laser structure is characterized in that described quantum cascade laser structure is any one in following four kinds:
1. F-P chamber multimode InP base AlInAs/GaInAsQCL ternary system waveguiding structure;
2. F-P chamber multimode InP base AlInAs/GaInAsQCL binary system waveguiding structure;
3. DFB single mode InP base AlInAs/GaInAsQCL ternary system waveguiding structure;
4. DFB single mode InP base AlInAs/GaInAsQCL binary system waveguiding structure;
Described quantum cascade laser structure feature is that (a) every kind of structure all contains arsenide and phosphide simultaneously; (b) adopt InP substrate and extension InP resilient coating to form compound waveguide integument down, described InP substrate is mixed sulphur; (c) between Inp resilient coating and GaInAs lower limit layer, mutually adopt InP/GaInAs or GaInAs/InP numeral alternation superlattice layer during transition; (d) in active area/both sides, injection region pre-injection region auxiliary layer is arranged; (e) described active area undopes, and all epitaxial loayers except that described active area only adopt a kind of donor dopant of silicon;
The F-P chamber is the abbreviation of Fabry-Perot in described four kinds of structures, and QCL represents quantum cascade laser, and DFB represents distributed feed-back.
2. by the described indium phosphide arsenic-phosphorus-including quantum cascaded laser structure of claim 1, it is characterized in that described F-P chamber multimode InP base AlInAs/GaInAsQCL ternary system waveguiding structure is to form compound waveguide integument down with InP substrate and InP resilient coating, be GaInAs/InP numeral alternation superlattice layer then, to improve the defective that carries out the transition to the GaInAs lower limit layer by InP; Regrowth GaInAs lower limit layer on GaInAs/InP numeral alternation superlattice layer, it is pre-injection region auxiliary layer thereafter, prevent that electronics is injected with the source region electrons spread, what continue is AlInAs/GaInAs active area and injection region, and the thickness at its trap and base has determined the excitation wavelength of QCL; The pre-injection region of the AlInAs/GaInAs auxiliary layer of then growing is strengthened electronics and is injected with the source region; Be the GaInAs upper limiting layer then, regrowth GaInAs/AlInAs numeral alternation superlattice layer improves the interface that is carried out the transition to AlInAs by GaInAs; The AlInAs that grows then goes up the waveguide integument, and regrowth AlInAs/GaInAs numeral alternation superlattice layer improves the interface that is carried out the transition to GaInAs by AlInAs, and regrowth GaInAs plasma increases limiting layer, the GaInAs cap layer of growing at last.
3. by the described indium phosphide arsenic-phosphorus-including quantum cascaded laser structure of claim 1, it is characterized in that described F-P chamber multimode InP base AlInAs/GaInAsQCL binary system waveguiding structure is to form compound waveguide integument down with InP substrate and InP resilient coating, be GaInAs/InP numeral alternation superlattice layer then, to improve the defective that carries out the transition to the GaInAs lower limit layer by InP, regrowth GaInAs lower limit layer on GaInAs/InP numeral alternation superlattice layer, it is pre-injection region auxiliary layer thereafter, prevent that electronics is injected with the source region electrons spread, what continue is AlInAs/GaInAs active area and injection region, and the thickness at its trap and base has determined the excitation wavelength of QCL; The pre-injection region of the AlInAs/GaInAs auxiliary layer of then growing is strengthened electronics and is injected with the source region; Be the GaInAs upper limiting layer then, regrowth GaInAs/InP numeral alternation superlattice layer is to improve the interface that is carried out the transition to InP by GaInAs; Waveguide integument on the grown InP then, the InP plasma increases limiting layer, the GaInAs cap layer of growing at last.
4. by the described indium phosphide arsenic-phosphorus-including quantum cascaded laser structure of claim 1, it is characterized in that described DFB single mode InP base AlInAs/GaInAsQCL ternary system waveguiding structure is to form compound waveguide integument down with InP substrate and InP resilient coating, be GaInAs/InP numeral alternation superlattice layer then, to improve the defective that carries out the transition to the GaInAs lower limit layer by InP, regrowth GaInAs lower limit layer on GaInAs/InP numeral alternation superlattice layer, it is pre-injection region auxiliary layer thereafter, prevent that electronics is injected with the source region electrons spread, what continue is active area and injection region, and the thickness at its trap and base has determined the excitation wavelength of QCL; The pre-injection region of the AlInAs/GaInAs auxiliary layer of then growing is strengthened electronics and is injected with the source region; Be the GaInAs upper limiting layer then, regrowth GaInAs/AlInAs numeral alternation superlattice layer improves the interface that is carried out the transition to AlInAs by GaInAs; The AlInAs that grows then goes up the waveguide integument, and regrowth AlInAs/GaInAs numeral alternation superlattice layer improves the interface that is carried out the transition to GaInAs by AlInAs, and regrowth GaInAs plasma increases limiting layer, the GaInAs cap layer of growing at last.
5. by the described indium phosphide arsenic-phosphorus-including quantum cascaded laser structure of claim 1, it is characterized in that described DFB single mode InP base AlInAs/GaInAsQCL binary system waveguiding structure is to form compound waveguide integument down with InP substrate and InP resilient coating, be GaInAs/InP numeral alternation superlattice layer then, to improve the defective that carries out the transition to the GaInAs lower limit layer by InP, regrowth GaInAs lower limit layer on GaInAs/InP numeral alternation superlattice layer, it is pre-injection region auxiliary layer thereafter, prevent that electronics is injected with the source region electrons spread, what continue is AlInAs/GaInAs active area and injection region, and the thickness at its trap and base has determined the excitation wavelength of QCL; The pre-injection region of the AlInAs/GaInAs auxiliary layer of then growing is strengthened electronics and is injected with the source region; Be the GaInAs upper limiting layer then, regrowth GaInAs/InP numeral alternation superlattice layer is to improve the interface that is carried out the transition to InP by GaInAs; Waveguide integument on the grown InP then, the InP plasma increases limiting layer, the GaInAs cap layer of growing at last.
6. by the described indium phosphide arsenic-phosphorus-including quantum cascaded laser structure of any claim in the claim 2 to 5, it is characterized in that the photon and the electronics of described upper limiting layer and described lower limit layer restriction active area and injection region.
7. by the uninterrupted growth preparation method of any described indium phosphide arsenic-phosphorus-including quantum cascaded laser structure of claim among the claim 2-5, it is characterized in that only finishing the uninterrupted growth continuously of entire I nP base arsenic-phosphorus-including quantum cascaded laser structure with a gas source molecular beam epitaxy system; Its concrete growth technique: before the epitaxial growth, indium is at 890-910 ℃, and aluminium is at 1200-1220 ℃, gallium is at 1050-1100 ℃, silicon is at 1250-1280 ℃, V family pyrolysis furnace 1030-1160 ℃ respectively growth room's degasification 15-30 minute, used temperature when reducing to growth then; Open box promptly usefulness mix sulphur n type InP single crystalline substrate earlier in pretreatment chamber at 200-250 ℃ of degasification 1-3 hour, slough the aqueous vapor of surface adsorption, and then be sent on growth room's specimen holder, the heated sample heater when rising to 300 ℃, feeds PH
3To the growth room, this moment, the pressure of growth room was 3 * 10
-5Torr is to protect substrate surface and to keep stoichiometric proportion; The desorption situation of under the high electron energy diffractometer monitoring, observing InP substrate temperature-rise period surface adsorption gas and oxide; For low-resistance n type InP substrate, desorption temperature is at 460-480 ℃; When surface texture transfers 4 * 2 to by 2 * 2, show the CO of substrate surface absorption
2Oxide desorb with phosphorus, kept 2-5 minute at desorption temperature, reduce underlayer temperature 40-70 ℃ or 60-90 ℃ then, close high electron energy diffractometer, the growth temperature of InP is 380-420 ℃, the growth temperature of AlInAs and GaInAs is 400-440 ℃, when growth AlInAs, GaInAs, keep identical indium electron gun furnace temperature, indium stove shutter is in normally open, when switching AlInAs, GaInAs, only need ON/OFF aluminium stove or gallium stove shutter, Si dopant temperature is decided according to required doping content during growth, V family pyrolysis furnace maintains 1000 ℃, and the growth room leads to PH
3The time, the pressure of growth room is 2.2-3 * 10
-5Torr, the growth room leads to AsH
3The time, the pressure of growth room is 1.5-2 * 10
-5Torr; The growth rate of four kinds of epitaxial materials is 0.7-1.0 μ m/ hour, and the rotary speed of specimen holder is 10 rev/mins during growth; After treating that underlayer temperature is stable, hierarchical sequence epitaxial growth by any described indium phosphide arsenic-phosphorus-including quantum cascaded laser structure of claim among the claim 2-5, epitaxial growth finishes the back sample heating device and reduces to 100 ℃, the Al stove is reduced to 900-1000 ℃, In and Ga stove are reduced to 650-700 ℃, V family pyrolysis furnace maintains 1000 ℃, with residual A sH in the assurance system
3And PH
3Fully cracking is passed to pretreatment chamber in regular turn with the QCL epitaxial wafer from the growth room, close the main valve between growth room and pretreatment chamber, V family pyrolysis furnace is reduced to 600 ℃ from 1000 ℃, the QCL epitaxial wafer is passed to Sample Room again, takes out epitaxial wafer, carry out preparation of devices.
8. by the described uninterrupted growth preparation method of claim 7, the electron gun stove that it is characterized in that gallium and indium is the tantalum resistance furnace that dual heating zones is formed; The electron gun stove of aluminium and dopant is the tantalum resistance furnace of normal structure; The beam intensity of aluminium, gallium and indium is monitored by the decision of electron gun stove heating-up temperature and by the on-line measurement ion flow; The background residual gas of system is monitored by online quadrupole mass spectrometer.
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| JPH08279647A (en) * | 1994-04-04 | 1996-10-22 | At & T Corp | Unipolar semiconductor laser |
| EP0964488A2 (en) * | 1998-06-12 | 1999-12-15 | Lucent Technologies Inc. | Improved quantum cascade laser |
| US20040161009A1 (en) * | 2003-02-13 | 2004-08-19 | Hamamatsu Photonics K.K. | Quantum cascade laser |
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| WO2005057746A1 (en) * | 2003-12-08 | 2005-06-23 | Teraview Limited | A laser |
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| JPH08279647A (en) * | 1994-04-04 | 1996-10-22 | At & T Corp | Unipolar semiconductor laser |
| EP0964488A2 (en) * | 1998-06-12 | 1999-12-15 | Lucent Technologies Inc. | Improved quantum cascade laser |
| US6829269B2 (en) * | 2002-05-21 | 2004-12-07 | University Of Massachusetts | Systems and methods using phonon mediated intersubband laser |
| US20040161009A1 (en) * | 2003-02-13 | 2004-08-19 | Hamamatsu Photonics K.K. | Quantum cascade laser |
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