CN104538843A - Manufacturing method of semiconductor laser chip for carbon dioxide detection - Google Patents
Manufacturing method of semiconductor laser chip for carbon dioxide detection Download PDFInfo
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- CN104538843A CN104538843A CN201410818520.3A CN201410818520A CN104538843A CN 104538843 A CN104538843 A CN 104538843A CN 201410818520 A CN201410818520 A CN 201410818520A CN 104538843 A CN104538843 A CN 104538843A
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- inp
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Abstract
A manufacturing method of a semiconductor laser chip for carbon dioxide detection comprises the steps that an InP substrate is selected, and an InP buffer layer, a lower waveguide layer, a lower limit layer, a quantum well layer, an upper limit layer, an upper waveguide layer and an InP cover layer are sequentially deposited on the substrate; Bragg grating stripes are manufactured on the upper waveguide layer and the InP cover layer; secondary epitaxy of an upper InP cladding, a first gradient layer, a second gradient layer and an InGaAs contact layer is carried out; downward etching is carried out, the etching depth reaches the surfaces of the Bragg grating stripes, the InGaAs contact layer forms a ridge-type strip structure downwards, and table faces are formed on the two sides oft the ridge-type strip structure; dielectric layers are deposited on the surface and the table faces on the two sides of the ridge-type strip structure; an electrode window is formed in the ridge-type strip structure; P-face electrodes are evaporated on the table faces with the dielectric layers deposited and in the electrode window; the InP substrate is thinned and polished; an N-face electrode is evaporated on the back face of the InP substrate; alloy is annealed, the electrodes are thickened, scribing and splitting are carried out, and manufacturing of the laser chip is completed.
Description
Technical field
The invention belongs to technical field of semiconductors, relate to particularly and grow large mismatch In (Ga) As/InP quantum-well materials by molecular beam epitaxy (MBE) or metal organic chemical vapor deposition (MOCVD), and adopting standard photoetching, etching process makes the method for carbon dioxide detection semiconductor laser chip.
Background technology
Since the mankind enter industrialization society, the demand of people to the energy is growing, the fossil fuel such as coal and oil is widely used, and the carbon dioxide content in air surges, and causes the serious environmental problems such as greenhouse effect, global warming, Melting Glaciers:, sea-level rise.Energy-saving and emission-reduction become the common recognition of countries in the world.2005, be intended to contain that the Kyoto Protocol of carbon dioxide excessive emissions comes into force, this is that form first with regulation in human history limits greenhouse-gas emissions.In actual industrial production process, detect in real time CO2 emission, control according to testing result to production process, this, to optimization production process, improves energy resource utilance very necessary.
At present, the CO based on electrochemical principle market supplied
2detector exists that such as detection accuracy is poor, result of detection is subject to other gases as shortcomings such as sulfur dioxide interference.The t unable filter (TDLAS:Tunable Diode Laser Absorption Spectroscopy) that development in recent years is got up effectively overcomes above problem.TDLAS technology is based on tunable diode laser, by controlling temperature or the Injection Current of diode laser, the fine setting of Output of laser wavelength can be carried out, the single line absorption line comprising tested gas information can be obtained and do not comprise the background spectral line of tested gas information within a scan period, thus qualitative and quantitative analysis is carried out to gas.The method has the advantages such as detection accuracy is high, antijamming capability strong, long service life, good reliability.As the absorbing window of carbon dioxide, the tunable narrow-linewidth laser being operated in 2.0 micron wavebands becomes the core component of carbon dioxide detection TDLAS technology.At present, the laser preparing this wave band mainly adopts GaSb base and InP-base I class quantum well structure.GaSb based quantum well material is because of its growth structure complexity, and the quaternary containing Sb is even difficult to control in five yuan of based compound growths and interface, is difficult to meet practical application request.The more difficult growth realizing the polynary antimonide of high-quality of the MOCVD being applicable to large-scale production and application is particularly adopted to control.Compare, InP-base In (Ga) As quantum well has many advantages in material preparation and device technology making.Except having high-quality, the backing material of low cost, InP-base laser because of the maturation process of its compatible Conventional communication laser, and easily and other device realize the advantage such as integrated and there is better application prospect.At present, due to the lattice mismatch that In (Ga) As/InP material is larger, high-quality quantum-well materials preparation is very difficult, reports that the threshold current density of In (Ga) the As/InP quantum-well laser adopting MBE and MOCVD to prepare generally is greater than 1500A/cm in the world
2, this is unfavorable for the demand of device practical application.
Summary of the invention
The object of the invention is to, a kind of manufacture method of carbon dioxide detection semiconductor laser chip is provided, especially by large mismatch In (Ga) As/InP quantum-well materials lattice quality, interface, component, the accuracy controlling of doping, prepares high-quality carbon dioxide detection semiconductor laser chip.Laser room temperature threshold current density is low to moderate 1000A/cm
2below, one side power output reaches more than 5mW.
The invention provides a kind of manufacture method of carbon dioxide detection semiconductor laser chip, comprise the steps:
Step 1: select an InP substrate, deposits InP resilient coating, lower waveguide layer, lower limit layer, quantum well layer, upper limiting layer, upper ducting layer and InP cap rock over the substrate successively;
Step 2: produce Bragg grating striped by holographic exposure and lithographic method on upper ducting layer and InP cap rock;
Step 3: secondary epitaxy InP top covering, the first gradient layer, the second gradient layer and InGaAs contact layer on the substrate with Bragg grating striped;
Step 4: etch downwards on InGaAs contact layer, etching depth arrives the surface of Bragg grating striped, makes InGaAs contact layer form ridge bar structure downwards, and the both sides of this ridge bar structure form table top;
Step 5: deposit dielectric layer on the surface of ridge bar structure and the table top of both sides thereof;
Step 6: open electrode window through ray on ridge bar structure;
Step 7: evaporation p side electrode in the table top and electrode window through ray of deposit dielectric layer, forms substrate;
Step 8: by thinning for the InP substrate of substrate, polishing;
Step 9: at evaporation N face, the back side electrode of InP substrate, forms chip;
Step 10: by chip annealed alloy, add thick electrode, scribing cleavage, completes the making of laser chip.
The invention has the beneficial effects as follows, it is by the accuracy controlling to large mismatch In (Ga) As/InP quantum-well materials lattice quality, interface, component, doping, prepares high-quality carbon dioxide detection semiconductor laser chip.Laser room temperature threshold current density is low to moderate 1000A/cm
2below, one side power output reaches more than 5mW.
Accompanying drawing explanation
In order to further illustrate concrete technology contents of the present invention, be described in detail as follows below in conjunction with embodiment and accompanying drawing, wherein:
Fig. 1 is the flow chart of method;
Fig. 2 is structural representation of the present invention;
The InAs/InP quantum-well laser light power-current-voltage curve of Fig. 3 to be excitation wavelength be 2002.6nm, when illustration is 1.1 times of threshold values, the sharp of laser penetrates spectrum.
Embodiment
Refer to shown in Fig. 1, Fig. 2, the invention provides a kind of manufacture method of carbon dioxide detection semiconductor laser chip, comprise the steps:
Step 1: select an InP substrate 1, this substrate 1 deposits successively InP resilient coating 2, lower waveguide layer 3, lower limit layer 4, quantum well layer 5, upper limiting layer 6, on ducting layer 7 and InP cap rock 8.Wherein InP substrate 1 is InP single-chip, and crystal orientation is (100), and thickness is 325-375 μm, and doping content is (1-3) × 10
18cm
-3; InP resilient coating 2 growth temperature is between 600 to 660 DEG C, and doping content is between 1 × 10
17to 2 × 10
18cm
-3between; The material of quantum well layer 5 is In
xga
1-xas, wherein In component is between 60% to 100%, and this quantum well layer 5 periodicity is between 1-10, individual layer trap is thick between 1-20nm, emission wavelength is between 1900-2100nm, and the growth temperature of quantum well layer is between 450-650 DEG C, and growth atmosphere V/III is than between 0 to 100; Wherein, too high V/III is than the deterioration that can cause active area crystalline quality, and the too high Interfacial relaxation that can cause strained quantum well layer equally of growth temperature, affects the luminous efficiency of laser; Wherein the material of lower waveguide layer 3 and upper ducting layer 7 is InGaAsP or In (Al) GaAs, and the thickness of ducting layer is between 50-500nm, and growth temperature is between 550-650 DEG C, and the photic wavelength of fluorescence of room temperature is between 1000-1700nm; Wherein the material of lower limit layer 4 and upper limiting layer 6 is In (Al) GaAs, thickness is between 0-100nm, growth temperature is between 450-650 DEG C, Al component is between 0 to 80%, the introducing of Al component effectively can improve the carrier confinement effect of quantum well layer, be conducive to the temperature stability improving output characteristic of laser, but owing to being easily oxidized containing Al material, too high Al component can reduce the crystal mass of material;
Step 2: produce Bragg grating striped by holographic exposure and lithographic method on upper ducting layer 7 and InP cap rock 8; Wherein lithographic method is that wet etching or dry and wet way combine, and Bragg grating fringe depths is between 10-100nm.
Step 3: secondary epitaxy InP top covering 9, first gradient layer 10, second gradient layer 11 and InGaAs contact layer 12 on the substrate with Bragg grating striped; Wherein the growth temperature of InP top covering 9 is between 550-680 DEG C, and thickness is between 500nm to 2000nm, and its doping content is greater than 1E17cm
-3; First gradient layer 10 and the second gradient layer 11 are InGaAsP material, and its intrinsic wavelength is respectively 1.2 μm and 1.5 μm, and its thickness is between 5-30nm; Wherein the doping content of InGaAs contact layer 12 is greater than 5E18cm
-3, growth temperature is lower than 680 DEG C, and too high growth temperature can cause laser active district to produce annealing effect, causes its emission wavelength to produce skew.
Step 4: etch downwards on InGaAs contact layer 12, etching depth arrives the surface of Bragg grating striped, and make InGaAs contact layer 12 form ridge bar structure downwards, the both sides of this ridge bar structure form table top; Wherein corrode and carry out in two steps, the first step adopts HBr, HNO
3and H
2mixed solution corrosion InGaAs contact layer 12, first gradient layer 10 of O and the second gradient layer 11, corrosion total depth is 250 to 300nm, then adopts HCl or H
3pO
4continue to corrode InP material until arrive Bragg grating striated surface with HCl mixed solution.
Step 5: deposit dielectric layer 13 on the surface of ridge bar structure and the table top of both sides thereof; Wherein dielectric layer 13 is SiO
2material, thickness is 350nm, and it is PECVD (plasma enhanced chemical vapor deposition) or CVD (chemical vapour deposition (CVD)) method that the pad of this dielectric layer amasss method.
Step 6: open electrode window through ray 131 on ridge bar structure; By gluing, front baking, photoetching and developing process, make the SiO at ridge bar top
2layer is out exposed, then adopts HF acid as corrosive liquid, outputs electrode window through ray 131.
Step 7: evaporation p side electrode 14 in the surface of deposit dielectric layer 13 and electrode window through ray 131, forms substrate; Wherein evaporated device is electron beam evaporation equipment, and electrode 14 layer material is TiAu (titanium), and thickness is 300nm.
Step 8: by thinning for the InP substrate 1 of substrate, polishing; Between after thinning, the thickness of substrate is 140 to 160 μm, the mode that finishing method adopts mechanical polishing and chemical corrosion to combine is carried out.
Step 9: at evaporation N face, the back side electrode 15 of InP substrate 1, forms chip; Wherein N face electrode 15 is AuGeNi (gold germanium nickel) material of thermal evaporation.
Step 10: by chip annealed alloy, add thick electrode, completes the making of laser chip.Wherein alloy temperature is between 350 DEG C to 420 DEG C, and thickening electrode approach is electrogilding, and layer gold thickness is between 400 to 1000nm; Made laser chip emission wavelength is between 1900 to 2100nm.
Consult shown in Fig. 3, under Fig. 3 gives and does not carry out cavity surface film coating condition, the long laser light power in 1.5mm chamber and applying bias with the change of Injection Current (P-I-V), as seen from the figure, laser threshold current is low to moderate 45mA, and its threshold current density is only 500A/cm
2, one side light power is greater than 40mW.Under 50mA Injection Current, the sharp of laser penetrates spectrum, and it swashs penetrates peak and be positioned at 2002.6nm, is positioned at the absorption region of carbon dioxide.
The above epitaxial material growth equipment is MOCVD, and the source that epitaxial growth uses is trimethyl indium (TMIn) respectively, triethyl-gallium (TEGa), arsine (AsH
3), phosphine (PH
3), silane (SiH
4), diethyl zinc (DEZn).
The above; be only the embodiment in the present invention, but protection scope of the present invention is not limited thereto, any people being familiar with this technology is in the technical scope disclosed by the present invention; the conversion that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.
Claims (7)
1. a manufacture method for carbon dioxide detection semiconductor laser chip, comprises the steps:
Step 1: select an InP substrate, deposits InP resilient coating, lower waveguide layer, lower limit layer, quantum well layer, upper limiting layer, upper ducting layer and InP cap rock over the substrate successively;
Step 2: produce Bragg grating striped by holographic exposure and lithographic method on upper ducting layer and InP cap rock;
Step 3: secondary epitaxy InP top covering, the first gradient layer, the second gradient layer and InGaAs contact layer on the substrate with Bragg grating striped;
Step 4: etch downwards on InGaAs contact layer, etching depth arrives the surface of Bragg grating striped, makes InGaAs contact layer form ridge bar structure downwards, and the both sides of this ridge bar structure form table top;
Step 5: deposit dielectric layer on the surface of ridge bar structure and the table top of both sides thereof;
Step 6: open electrode window through ray on ridge bar structure;
Step 7: evaporation p side electrode in the table top and electrode window through ray of deposit dielectric layer, forms substrate;
Step 8: by thinning for the InP substrate of substrate, polishing;
Step 9: at evaporation N face, the back side electrode of InP substrate, forms chip;
Step 10: by chip annealed alloy, add thick electrode, scribing cleavage, completes the making of laser chip.
2. the manufacture method of carbon dioxide detection semiconductor laser chip according to claim 1, wherein the material of quantum well layer is In
xga
1-xas, wherein In component is between 60% to 100%, and its growth temperature is between 450 DEG C to 650 DEG C.
3. the manufacture method of carbon dioxide detection semiconductor laser chip according to claim 2, wherein quantum well layer periodicity is between 1-10, and individual layer trap is thick between 1-20nm, and emission wavelength is between 1900-2100nm.
4. the manufacture method of carbon dioxide detection semiconductor laser chip according to claim 1, wherein the material of lower waveguide layer and upper ducting layer is InGaAsP or In (Al) GaAs, and the thickness of ducting layer is between 50-500nm.
5. the manufacture method of carbon dioxide detection semiconductor laser chip according to claim 1, wherein the material of lower limit layer and upper limiting layer is In (Al) GaAs, and thickness is between 0-100nm, and Al component is between 0 to 80%.
6. the manufacture method of carbon dioxide detection semiconductor laser chip according to claim 1, wherein the growth temperature of InP top covering is between 550-680 DEG C, and thickness is between 500nm to 2000nm, and its doping content is greater than 1E17cm
-3.
7. the manufacture method of carbon dioxide detection semiconductor laser chip according to claim 1, wherein the doping content of InGaAs contact layer is greater than 5E18cm
-3, growth temperature is lower than 680 DEG C.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105826814A (en) * | 2016-05-19 | 2016-08-03 | 中国科学院半导体研究所 | Method of preparing indium phosphide-based narrow-ridge waveguide semiconductor laser |
| CN108988124A (en) * | 2017-05-31 | 2018-12-11 | 中国科学院半导体研究所 | A kind of single-chip integration tunnel PN junction laser PN for microwave generating source |
| CN112687768A (en) * | 2020-12-01 | 2021-04-20 | 木昇半导体科技(苏州)有限公司 | Epitaxial material growth method capable of modulating grating array structure |
| CN114432849A (en) * | 2020-10-30 | 2022-05-06 | 株式会社电装 | Carbon dioxide recovery system and working electrode |
| CN115528537A (en) * | 2022-08-26 | 2022-12-27 | 江苏华兴激光科技有限公司 | Method for manufacturing GaAs-based narrow-linewidth red laser chip |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105826814A (en) * | 2016-05-19 | 2016-08-03 | 中国科学院半导体研究所 | Method of preparing indium phosphide-based narrow-ridge waveguide semiconductor laser |
| CN108988124A (en) * | 2017-05-31 | 2018-12-11 | 中国科学院半导体研究所 | A kind of single-chip integration tunnel PN junction laser PN for microwave generating source |
| CN108988124B (en) * | 2017-05-31 | 2020-05-19 | 中国科学院半导体研究所 | Monolithic integration tunnel junction laser for microwave oscillation source |
| CN114432849A (en) * | 2020-10-30 | 2022-05-06 | 株式会社电装 | Carbon dioxide recovery system and working electrode |
| CN112687768A (en) * | 2020-12-01 | 2021-04-20 | 木昇半导体科技(苏州)有限公司 | Epitaxial material growth method capable of modulating grating array structure |
| CN115528537A (en) * | 2022-08-26 | 2022-12-27 | 江苏华兴激光科技有限公司 | Method for manufacturing GaAs-based narrow-linewidth red laser chip |
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