CN101916965B - Short-wavelength grating surface emission quantum cascade laser structure and preparation method thereof - Google Patents

Short-wavelength grating surface emission quantum cascade laser structure and preparation method thereof Download PDF

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CN101916965B
CN101916965B CN2010102311914A CN201010231191A CN101916965B CN 101916965 B CN101916965 B CN 101916965B CN 2010102311914 A CN2010102311914 A CN 2010102311914A CN 201010231191 A CN201010231191 A CN 201010231191A CN 101916965 B CN101916965 B CN 101916965B
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grating
substrate
cap rock
silicon nitride
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CN101916965A (en
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江宇超
刘俊岐
陆全勇
张伟
郭万红
李路
刘峰奇
王利军
王占国
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Institute of Semiconductors of CAS
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Abstract

The invention relates to a short-wavelength grating surface emission quantum cascade laser structure which comprises a substrate, a lower waveguide layer, an active layer, an upper waveguide layer, a cover layer, a grating layer, a silicon dioxide layer, a front metal electrode layer and a back metal electrode layer, wherein the lower waveguide layer grows on the substrate; the active layer grows on the lower waveguide layer; the upper waveguide layer grows on the active layer; the cover layer grows on the upper waveguide layer, and the upper half part of the cover layer is provided with a two-stage distribution feedback grating; the grating layer is positioned on the cover layer and has same grating period with the grating on the cover layer; a plurality of windows are formed on the grating layer, and the depths of the windows reach the surface of the cover layer; both sides of the lower waveguide layer, the active layer, the upper waveguide layer, the cover layer and the grating layer are trapezoidal slopes; the silicon dioxide layer grows on the upper surface of the substrate, the trapezoidal slopes and the edge parts at both sides on the grating layer; the front metal electrode layer grows on the silicon dioxide layer and the edge parts at both sides of the surface of the grating layer, which are not covered by the silicon dioxide layer; and the back metal electrode layer grows under the substrate to form the short-wavelength grating surface emission quantum cascade laser structure.

Description

Short-wavelength grating surface emission quantum cascade laser structure and preparation method
Technical field
The present invention relates to the semiconductor photoelectric device technical field, relate in particular to a kind of short-wavelength grating surface emission quantum cascade laser structure and preparation method.
Background technology
Quantum cascade laser is that a kind of electronics that utilizes is at the luminous novel semi-conductor laser of intersubband transitions.Its excitation wavelength can cover 3-5 μ m middle-infrared band and two important atmospheric windows of 8-14 μ m far infrared band, has very wide application prospect in fields such as trace gas monitoring and medical diagnosis.Although conventional limit emission measure qc laser can realize the output of room-temperature continuous-wave operati and high power, but still there is the intrinsic shortcoming that beam quality is not high, far-field divergence angle is big, thereby greatly influenced the practical application of quantum cascade laser.Emitting quantum cascade laser then has the advantage of the little and single mode operation of far-field divergence angle, thereby very helps laser coupled advanced practical application such as optical system.In addition, because light vertical devices surface emitting is convenient to realize the integrated and online detection of two dimension, thereby has greatly reduced production cost that this haves a great attraction for present costliness quantum cascade laser production process consuming time.
Current emitting quantum cascade laser mainly contains grating emitting quantum cascade laser and photonic crystal emitting quantum cascade laser.Wherein, the photonic crystal emitting quantum cascade laser has characteristics symmetry, bread cast output facula, yet photonic crystal pattern needs very high thick wide ratio and accurate X-Y scheme control, this is a very big challenge to present photoetching process, and the loss of photon crystal-face transmitting laser is very big, is difficult to realize hot operation.By contrast, the grating emitting quantum cascade laser only need prepare the secondary distributed feedback grating on one dimension, therefore technology is simple relatively, becomes a focus of emitting quantum cascade laser research in the world, and has obtained deep research in the middle of in the past 10 years.
Although the research to the grating emitting quantum cascade laser has obtained good achievement, comprise the room temperature pulse swash penetrate with 1 ° with interior far-field divergence angle, they all mainly concentrate on wavelength long 8-14 μ m far infrared band even terahertz wave band.These long required raster size of wave band are bigger, can utilize ripe technology such as contact lithograph to realize.Yet in the short 3-5 μ m middle-infrared band of wavelength, contact lithograph can't reach required precision.Meticulous electron beam lithography then not only the time for exposure very long, cost an arm and a leg, preparation efficiency is extremely low, is not suitable for large-scale application.Because 3-5 μ m middle-infrared band is CO, N 2The peak absorbance window of pernicious gases such as O, the emitting quantum cascade laser of this wave band has comparatively urgent application demand.Based on this, this patent is invented a kind of method, can large-area preparation short wavelength surface-emitting laser.
Summary of the invention
The objective of the invention is to, a kind of short-wavelength grating surface emission quantum cascade laser structure and preparation method are provided.This method adopts the mode of two-beam interference to prepare two-grade grating, the contact lithograph required precision that is beyond one's reach can be satisfied, the shortcoming that electron beam exposure can't large-area preparation can be avoided again, cheap, good reliability can realize single mode, surface launching and the little angle of departure.
The invention provides a kind of short-wavelength grating surface emission quantum cascade laser structure, comprising:
One substrate;
One lower waveguide layer, this lower waveguide layer are grown on this substrate, and this lower waveguide layer is positioned at the middle part of substrate;
One active layer, this active layer are grown on this lower waveguide layer;
Ducting layer on one, ducting layer is grown on this active layer on this;
One cap rock, this cap rock are grown on this on ducting layer, and the first half position of this cap rock forms the secondary distributed feedback grating;
One grating layer, this grating layer be positioned at cap rock above, and this grating layer has and identical grating cycle of grating on the cap rock, is formed with a plurality of windows on this grating layer, the degree of depth of described window arrives the surface of cap rock;
The both sides of wherein said lower waveguide layer, active layer, last ducting layer, cap rock and grating layer are trapezoidal inclined-plane;
One silicon dioxide layer, this silicon dioxide layer grows on substrate and lower waveguide layer, active layer, on the trapezoidal inclined-plane that forms of ducting layer, cap rock and grating layer both sides, and edge parts at both sides above the described grating layer;
One front metal electrode layer, this front metal electrode layer are grown in the edge parts at both sides that the top of silicon dioxide layer and grating layer surface are not covered by silicon dioxide layer;
One back metal electrode layer, this back metal electrode layer be grown in substrate below, form short-wavelength grating surface emission quantum cascade laser structure.
Wherein said substrate is the InP substrate.
The material of wherein said lower waveguide layer and last ducting layer is n type InGaAs, and doping content is 1 * 10 17Cm -3-9 * 10 17Cm -3, bed thickness is 0.1-1.0 μ m.
Wherein said active layer is made up of the InGaAs/InAlAs in 10-50 cycle, and the thickness of this active layer is 0.5-2.5 μ m, and the excitation wavelength of this active layer is 3-5 μ m.
The material of wherein said cap rock is n type InP, and doping content is 1 * 10 16Cm -3-5 * 10 16Cm -3, thickness is 1-3 μ m; The material of grating layer is n type InP, and doping content is 2.5 * 10 18-1 * 10 19Cm -3, thickness is 0.1-1.0 μ m; Cap rock and grating layer have the secondary distributed feedback grating that gross thickness is 0.5-2.0 μ m, and the duty ratio at grating peak is 0.5-0.8.
The present invention also provides a kind of preparation method of short-wavelength grating surface emission quantum cascade laser structure, comprises the steps:
Step 1: growth in regular turn on the substrate have lower waveguide layer, active layer, on ducting layer, cap rock and grating layer;
Step 2: by plasma enhanced chemical vapor deposition method grown silicon nitride on grating layer;
Step 3: behind the even glue in silicon nitride layer surface, prepare the photoresist figure of secondary distributed feedback grating by the double-beam holographic exposure method;
Step 4: with the photoresist figure is mask, etches the silicon nitride figure of secondary distributed feedback grating structure in silicon nitride layer by the method for dry etching;
Step 5: with the silicon nitride figure is mask, and the method by dry etching etches secondary distributed feedback grating structure on grating layer and cap rock;
Step 6: with dilute hydrofluoric acid with dry etching after remaining silicon nitride float;
Step 7: by the method for photoetching and wet etching, with the lower waveguide layer on the substrate, active layer, the upward both sides corrosion of ducting layer, cap rock and grating layer, forming both sides is the strip structure on trapezoidal inclined-plane;
Step 8: on substrate, be the surface of the strip structure on trapezoidal inclined-plane, adopt chemical vapor deposited method in both sides, growth layer of silicon dioxide layer, and the method by photoetching and wet etching etches away the silicon dioxide layer in the middle of on the grating layer;
Step 9: adopt the method for photoetching combined belt glue evaporation, at the superficial growth front metal electrode layer of silicon dioxide layer;
Step 10: with substrate thinning, polishing;
Step 11: the back side evaporation back metal electrode layer of the substrate behind attenuate, finish the making of device.
Wherein said substrate is the InP substrate.
The material of wherein said lower waveguide layer and last ducting layer is n type InGaAs, and doping content is 1 * 10 17Cm -3-9 * 10 17Cm -3, bed thickness is 0.1-1.0 μ m.
Wherein said active layer 12 is made up of the InGaAs/InAlAs in 10-50 cycle, and the thickness of this active layer is 0.5-2.5 μ m, and the excitation wavelength of this active layer is 3-5 μ m.
The material of wherein said cap rock is n type InP, and doping content is 1 * 10 16Cm -3-5 * 10 16Cm -3, thickness is 1-3 μ m; The material of grating layer is n type InP, and doping content is 2.5 * 10 18-1 * 10 19Cm -3, thickness is 0.1-1.0 μ m; Cap rock and grating layer have the secondary distributed feedback grating that gross thickness is 0.5-2.0 μ m, and the duty ratio at grating peak is 0.5-0.8.
Description of drawings
In order to further specify feature of the present invention and effect, the present invention is described further below in conjunction with drawings and the specific embodiments, wherein:
Fig. 1 is embodiments of the invention, and it is the waveguide of INFRARED QUANTUM CASCADE LASERS in the grating surface launching and the schematic cross-section of two-grade grating structure.
Fig. 2 loss and duty ratio graph of a relation.
Fig. 3 coupling and duty ratio graph of a relation.
Embodiment
See also shown in Figure 1ly, the invention provides a kind of short-wavelength grating surface emission quantum cascade laser structure, comprising:
One substrate 10, this substrate 10 is the InP substrate;
One lower waveguide layer 11, this lower waveguide layer 11 is grown on this substrate 10, and this lower waveguide layer 11 is positioned at the middle part of substrate 10;
One active layer 12, this active layer 12 are grown on this lower waveguide layer 11, and described active layer 12 is made up of the InGaAs/InAlAs in 10-50 cycle, and the thickness of this active layer 12 is 1.0-5 μ m, and the excitation wavelength of this active layer 12 is 3-5 μ m;
Ducting layer 13 on one, and ducting layer 13 is grown on this active layer 12 on this;
The material of described lower waveguide layer 11 and last ducting layer 13 is n type InGaAs, and doping content is 1 * 10 17Cm -3-9 * 10 17Cm -3, bed thickness is 0.1-1.0 μ m;
One cap rock 14, this cap rock 14 are grown on this on ducting layer 13, and the first half position of this cap rock 14 forms the secondary distributed feedback grating, and the material of cap rock 14 is n type InP, and doping content is 1 * 10 16Cm -3-5 * 10 16Cm -3, thickness is 1-3 μ m; The material of grating layer 15 is n type InP, and doping content is 2.5 * 10 18-1 * 10 19Cm -3, thickness is 0.1-1.0 μ m; Cap rock 14 and grating layer 15 have the secondary distributed feedback grating that gross thickness is 0.5-2.0 μ m, and the duty ratio at grating peak is 0.5-0.8;
One grating layer 15, this grating layer 15 be positioned at cap rock 14 above, and this grating layer 15 has and identical grating cycle of grating on the cap rock 14, is formed with a plurality of windows 151 on this grating layer 15, the degree of depth of described window 151 arrives the surface of cap rock 14;
One silicon dioxide layer 16, this silicon dioxide layer 16 be grown in substrate 10 top and lower waveguide layer 11, active layer 12, go up on the trapezoidal inclined-plane that ducting layer 13, cap rock 14 and grating layer 15 both sides form and edge parts at both sides above the described grating layer 15;
One front metal electrode layer 17, this front metal electrode layer 17 are grown in the edge parts at both sides that top and grating layer 15 surfaces of silicon dioxide layer 16 are not covered by silicon dioxide layer 16;
One back metal electrode layer 18, this back metal electrode layer 18 be grown in substrate 10 below, form short-wavelength grating surface emission quantum cascade laser structure.
Please consult shown in Figure 1ly again, the invention provides a kind of preparation method of short-wavelength grating surface emission quantum cascade laser structure, comprise the steps:
Step 1: growth in regular turn on the substrate 10 have lower waveguide layer 11, active layer 12, on ducting layer 13, cap rock 14 and grating layer 15;
Step 2: by plasma enhanced chemical vapor deposition method grown silicon nitride on grating layer 15;
Step 3: behind the even glue in silicon nitride layer surface, prepare the photoresist figure of secondary distributed feedback grating by the double-beam holographic exposure method;
Step 4: with the photoresist figure is mask, etches the silicon nitride figure of secondary distributed feedback grating structure in silicon nitride layer by the method for dry etching;
Step 5: with the silicon nitride figure is mask, and the method by dry etching etches secondary distributed feedback grating structure on grating layer 15 and cap rock 14;
Step 6: with dilute hydrofluoric acid with dry etching after remaining silicon nitride float;
Step 7: by the method for photoetching and wet etching, with the lower waveguide layer on the substrate 10 11, active layer 12, the upward both sides corrosion of ducting layer 13, cap rock 14 and grating layer 15, forming both sides is the strip structure on trapezoidal inclined-plane;
Step 8: on substrate 10, in both sides is the surface of the strip structure on trapezoidal inclined-plane, adopt chemical vapor deposited method, growth layer of silicon dioxide layer 16, and the method by photoetching and wet etching etches away the silicon dioxide layer 16 in the middle of on the grating layer 15;
Step 9: adopt the method for photoetching combined belt glue evaporation, at the superficial growth front metal electrode layer 17 of silicon dioxide layer 16;
Step 10: with substrate 10 attenuates, polishing;
Step 11: the back side evaporation back metal electrode layer 18 of the substrate 10 behind attenuate, finish the making of device.
Grating emitting quantum cascade laser and the preparation method of embodiment 4.6 μ m
Fig. 1 is the waveguide of grating emitting quantum cascade laser of wavelength 4.6 μ m and the schematic cross-section of two-grade grating structure.At n type InP substrate 10 (3 * 10 17Cm -3) on be followed successively by InGaAs lower waveguide layer 11 (the n type mixes, 6 * 10 17Cm -3, thickness 0.3 μ m), (doping content of injection region is 2.5 * 10 to 30 grades of InGaAs/InAlAs active layers 10 17Cm -3, thickness 1.51 μ m), the last ducting layer 13 of InGaAs (the n type mixes, 6 * 10 17Cm -3, thickness 0.3 μ m), InP cap rock 14 (the n type mixes, 2.2 * 10 16Cm -3, thickness 2.1 μ m) and InP heavily doped layer 15 (the n type mixes, and 2.5 * 10 18-1 * 10 19Cm -3, thickness 0.5 μ m).
The characteristics of this structure are: (1) cap rock 14 and top layer 15 adopt the InP material, compare early stage employing InAlAs cap rock, and the thermal conductivity of InP is better, helps the hot operation of device; (2) top layer 15 is heavily doped layers, has not only greatly reduced refractive index, light field can be limited in the ducting layer better, and be beneficial to the surface electrical injection.In addition, top layer 15 and cap rock 14 also have the surface plasma enhancement effect, can further add the high light restriction.
Cap rock 14 and the high layer 15 of mixing have the air/semiconductor two-grade grating that gross thickness is 1 μ m, and the grating peak is 0.5 in the duty ratio in a grating cycle.The enough big grating degree of depth and duty ratio can obtain higher coupling coefficient and face coupling efficiency, thereby improve the performance of grating surface-emitting laser.
The secondary distributed feedback grating cycle is satisfied Λ=λ/n.In this example, design wavelength lambda=4.6 μ m, effective refractive index n is 3-3.2, so the design two-grade grating cycle is 1.48-1.5 μ m.
17 both sides that cover grating layer 15 surfaces of front metal electrode layer.The advantage of this structure is: both avoided metal absorption loss bigger in the waveguide, can allow lateral current to inject again.
For obtaining the optical grating construction of above-mentioned deep erosion, big space rate, the concrete preparation process of the described two-grade grating of this example is:
(1) with the plasma reinforced chemical vapour deposition method height mix the layer 15 on the growth 180nm silicon nitride;
(2) photoresist S1805 and diluent are matched well dilution with 1: 1 volume, be spin-coated on the silicon nitride layer surface.The sol evenning machine rotating speed is 4000 rev/mins, and the whirl coating time is 30 seconds, can get the thin glue of the uniform 200nm of thickness.
(3) the 30 seconds holographic exposure time.Tetramethylammonium hydroxide original solution and deionized water with 1: 5 volume proportion, are made developer solution.Developing time 60 seconds can obtain the glue pattern that grating peak duty ratio reaches 0.5-0.6;
(4) utilize the photoresist figure as being mask, in the CF4 atmosphere, do to carve glue pattern is transferred on the silicon nitride.
(5) utilize the silicon nitride figure as mask, in the atmosphere of SiCl4/Ar, do to carve figure transfer is mixed in layer 15 and the cap rock 14 to height.Etching depth can reach 1 μ m.
(6), finish the two-grade grating preparation of required deep erosion, big space rate successively with photoresist and the silicon nitride of acetone and diluted hydrofluoric acid flush away sample surfaces remnants.
The waveguiding structure and the two-grade grating structure Design main points of the above-mentioned short wavelength's emitting quantum cascade laser that provides below are provided in detail.
Two-grade grating distributed feed-back vertical launching quantum cascade laser utilize two-grade grating to the vertical diffraction of light and obtain Vertical Launch, the coupling coefficient of its grating has directly determined the performance of device.And the size of coupling coefficient depends primarily on two factors, i.e. the difference of the pattern effective refractive index at grating bottom and grating top and the overlapping degree of light field and grating.According to the coupled mode theory of the long structure in the theoretical and limited chamber of the Floquet-Bloch of unlimited chamber long periodicity structure, the duty ratio at grating peak influences the surface radiation loss and the coupling coefficient of two-grade grating distributed feed-back vertical launching quantum cascade laser strongly in cap rock 14 and the grating layer 15.As shown in Figure 2, when duty ratio less (duty ratio is less than 0.3), because semi-conductive ratio is less in the grating, cause the overlapping between light field and grating less, so surface radiation loss and substrate loss are all smaller, thereby vertical coupled efficient is very little.When duty ratio excessive (duty ratio is greater than 0.8), though bigger semiconductor ratio has guaranteed bigger light field and the overlapping between grating in the grating layer, but the pattern effective refractive index difference of place, grating top and grating bottom this moment waveguiding structure is along with the formed perturbation intensity of grating cyclic variation is very little, and both cancel out each other and cause less surface radiation loss.Thereby duty ratio is taken at and can obtains bigger surface radiation loss between the 0.5-0.8, and total waveguide loss increase is less relatively, makes that like this face coupling efficiency of light is higher.For the coupling coefficient of two-grade grating distributed feed-back vertical launching quantum cascade laser, as shown in Figure 3, when duty ratio hour, coupling coefficient is less, it is less that this comes from the grating layer semiconductor ratio, makes a little less than the Bragg diffraction effect of grating pair light field.Along with the grating duty ratio increases, it is big that coupling coefficient becomes, and reach when duty ratio is 0.65 left and right sides greatly, begins again subsequently to reduce.To sum up, in order to obtain big surface radiation loss and coupling coefficient, the grating duty ratio should be chosen between the 0.5-0.8 in cap rock 14 and the grating layer 15.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (2)

1. the preparation method of a short-wavelength grating surface emission quantum cascade laser structure comprises the steps:
Step 1: growth in regular turn on the substrate have lower waveguide layer, active layer, on ducting layer, cap rock and grating layer;
Step 2: by plasma enhanced chemical vapor deposition method grown silicon nitride on grating layer;
Step 3: behind the even glue in silicon nitride layer surface, prepare the photoresist figure of secondary distributed feedback grating by the double-beam holographic exposure method;
Step 4: with the photoresist figure is mask, etches the silicon nitride figure of secondary distributed feedback grating structure in silicon nitride layer by the method for dry etching;
Step 5: with the silicon nitride figure is mask, and the method by dry etching etches secondary distributed feedback grating structure on grating layer and cap rock;
Step 6: with dilute hydrofluoric acid with dry etching after remaining silicon nitride float;
Step 7: by the method for photoetching and wet etching, with the lower waveguide layer on the substrate, active layer, the upward both sides corrosion of ducting layer, cap rock and grating layer, forming both sides is the strip structure on trapezoidal inclined-plane, this active layer is made up of the InGaAs/InAlAs in 10-50 cycle, the thickness of this active layer is 0.5-2.5 μ m, the excitation wavelength of this active layer is 3-5 μ m, and the material of this cap rock is n type InP, and doping content is 1 * 10 16Cm -3-5 * 10 16Cm -3, thickness is 1-3 μ m; The material of grating layer is n type InP, and doping content is 2.5 * 10 18-1 * 10 19Cm -3, thickness is 0.1-1.0 μ m; Cap rock and grating layer have the secondary distributed feedback grating that gross thickness is 0.5-2.0 μ m, and the duty ratio at grating peak is 0.5-0.8;
Step 8: on substrate, be the surface of the strip structure on trapezoidal inclined-plane, adopt chemical vapor deposited method in both sides, growth layer of silicon dioxide layer, and the method by photoetching and wet etching etches away the silicon dioxide layer in the middle of on the grating layer;
Step 9: adopt the method for photoetching combined belt glue evaporation, at the superficial growth front metal electrode layer of silicon dioxide layer;
Step 10: with substrate thinning, polishing;
Step 11: the back side evaporation back metal electrode layer of the substrate behind attenuate, finish the making of device.
2. by the preparation method of the described short-wavelength grating surface emission quantum cascade laser structure of claim 1, the material of wherein said lower waveguide layer and last ducting layer is n type InGaAs, and doping content is 1 * 10 17Cm -3-9 * 10 17Cm -3, bed thickness is 0.1-1.0 μ m.
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