CN107910750B - Preparation method of semiconductor laser material - Google Patents
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- CN107910750B CN107910750B CN201710509143.9A CN201710509143A CN107910750B CN 107910750 B CN107910750 B CN 107910750B CN 201710509143 A CN201710509143 A CN 201710509143A CN 107910750 B CN107910750 B CN 107910750B
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- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000000034 method Methods 0.000 claims abstract description 59
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- 229910017115 AlSb Inorganic materials 0.000 claims description 9
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- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 7
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 claims description 7
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 3
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims description 3
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/34—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers
- H01S5/343—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
- H01S5/3434—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser with a well layer comprising at least both As and P as V-compounds
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Abstract
The invention discloses a preparation method of a semiconductor laser material, which comprises the following steps: providing a semiconductor donor substrate, epitaxially growing a buffer layer on the donor substrate, growing a sacrificial layer on the buffer layer, and growing a semiconductor thin film layer on the sacrificial layer; performing ion implantation on the side of the semiconductor thin film layer to form a defect layer in the sacrificial layer; providing a flexible substrate, and bonding the semiconductor thin film layer and the flexible substrate; and annealing the defect layer, stripping the top layer film from the donor substrate along the sacrificial layer to obtain a first substrate containing the donor substrate and a second substrate containing the flexible substrate, and removing the sacrificial layer on the second substrate to obtain the flexible substrate bonded with the semiconductor film layer. The method is a semiconductor laser material preparation method which can repeatedly utilize the donor substrate and save the thinning process.
Description
Technical Field
The invention belongs to the technical application field of semiconductor lasers, and particularly relates to a preparation method of a semiconductor laser material, wherein a donor substrate can be recycled, and a thinning process is omitted.
Background
Since the first ruby pulse semiconductor laser appeared in 1960, the semiconductor laser has been rapidly developed, and because of its wide wavelength range, simple manufacture, low cost, easy mass production, small size, light weight and long service life, its variety development is rapid, application range is wide, and it covers the whole photoelectronics field, and it has become the core technology of current photoelectronics.
The semiconductor laser has been widely used in laser ranging, laser radar, laser communication, laser simulated weapons, laser warning, laser guidance and tracking, ignition and detonation, automatic control, detection instruments and the like, and forms a broad market, and is mainly divided into an information type laser aiming at information transmission and a power type laser aiming at improving optical power.
The traditional silicon material is an indirect bandgap semiconductor, the light emitting performance is very poor, and although researchers process the silicon material into nanometer or quantum size to develop the nonlinear optical property, the performance still cannot be compared with that of a compound semiconductor. Compound semiconductors have been the subject of intense research in research and industry due to their high electron mobility and the advantage of efficient light emission from direct band gaps. However, the price of the compound semiconductor is relatively high, and the development of the later-stage integration process towards large size is very difficult, which is also a great bottleneck for the industrialization of the compound semiconductor. Therefore, a heterogeneous integration technology combining a compound semiconductor and a silicon integrated circuit becomes a research hotspot in the field of photoelectric integration and has important application in the preparation of semiconductor lasers.
In the preparation of a semiconductor laser, because a substrate has resistance, a heating phenomenon can be generated, like a high-power laser, the injection current is large, and the requirement on heating is very high, so that the thickness of an epitaxial wafer needs to be reduced from more than hundreds of micrometers to about 10 micrometers or even thinner, the resistance of ohmic contact of a chip is reduced, and the heating of a device is reduced. However, the thinning process may cause surface damage to the back surface of the substrate, and the thinned epitaxial wafer may be deformed and easily broken, thereby affecting the yield. Although the introduction of polishing process to remove the surface damage layer and eliminate the residual stress, the process is complicated, the cost is increased and the problem that the residual stress cannot be completely eliminated is still unavoidable. In addition, a general compound semiconductor substrate is a substrate of a doping type, and laser absorption of a specific wavelength is relatively large. For example, GaSb based 2 micron lasers have severe absorption of mid-infrared waves by free carriers. The heterogeneous integration can skip the thinning step, provides greater freedom for the design and preparation of devices and systems, can improve the performance of the devices, and meanwhile, the silicon substrate also serves as a heat conduction carrier and can be well applied to semiconductor laser materials.
In addition, flexible substrates have been the subject of intense research ("Lattice Engineering, Technologies and Applications" edited by)Shumin WangPan Stanford,2013, ISBN 9789814316293). Typically, lattice-mismatched epitaxial layers nucleate on the substrate surface and when the epitaxial layer exceeds a critical thickness, threading dislocations are generated throughout the epitaxial layer. If a flexible substrate material is adopted, the thickness of the epitaxial layer is larger than that of the flexible substrate when threading dislocation is generatedThe generated threading dislocation slips towards the flexible substrate, and finally, the interface dislocation is formed at the interface of the flexible film and the epitaxial layer, the threading dislocation is not generated in the epitaxial layer, the crystal quality of the material is greatly improved, and the method is greatly beneficial to the epitaxial growth of the large mismatch material. Because silicon is a good heat conduction material, the silicon-based flexible substrate can also relieve the problem of thermal mismatch between the epitaxial material and the substrate material.
Heterogeneous integration processes currently have two schemes: epitaxial growth and ion beam lift-off bonding techniques. For a general epitaxial method, a heteroepitaxial layer on a silicon substrate has high dislocation density, and the carrier mobility is influenced by the addition of an anti-phase domain and a self-doping effect, so that the leakage current of a device is increased. The ion beam lift-off bonding technique (see chinese patent document CN105957831A) combines the cutting technique of ion implantation defect engineering and the layer transfer technique based on wafer bonding, and is a common method for heterogeneous integration. The method cuts and transfers a thin layer on a single crystal substrate to a relatively inexpensive foreign substrate, and has certain economic benefits. For ion beam stripping techniques, the ion implantation (hydrogen or helium) first produces a gaussian distribution, forming a defect layer at a specific position parallel to the surface (where the implanted ion density is greatest or where the lattice damage is greatest), and the wafer implanted with ions will crack along the defect layer during the subsequent annealing process. However, the surface roughness caused by the delamination process brings great trouble to the subsequent work, and if the delamination layer is used as a sacrificial layer and is processed by an etching method, the number of processes is increased, and even impurity particles are easily introduced.
Disclosure of Invention
The invention provides a preparation method of a semiconductor laser material, aiming at the existing in the prior art. According to the method, an aluminum-containing compound is used as a sacrificial layer, the characteristic that the aluminum-containing compound is easy to oxidize is used after the sacrificial layer is spalled, the process of treating the sacrificial layer is simplified, the surfaces of the obtained silicon substrate material and the semiconductor substrate material are clean, a flexible substrate is provided, the thinning step is omitted, and meanwhile, the semiconductor donor substrate material can be recycled, so that the energy is saved and the environment is protected.
The preparation method of the semiconductor laser material provided by the invention comprises the following steps:
providing a semiconductor donor substrate, epitaxially growing a buffer layer on the donor substrate, growing a sacrificial layer on the buffer layer, and growing a semiconductor thin film layer on the sacrificial layer;
performing ion implantation on the side of the semiconductor thin film layer to form a defect layer in the sacrificial layer;
providing a semiconductor acceptor substrate, and bonding the semiconductor thin film layer and the semiconductor acceptor substrate;
and annealing the defect layer, and stripping the top layer film from the donor substrate along the sacrificial layer to obtain the flexible substrate bonded with the semiconductor film layer.
As a better alternative to the above method, the method further comprises growing a semiconductor laser device structure on the semiconductor thin film layer of the flexible substrate bonded with the semiconductor thin film layer.
As a better alternative to the above method, the semiconductor donor substrate is a GaSb, GaAs, InP, InAs, or InSb substrate.
Preferably, the sacrificial layer is an aluminum-containing compound and has a thickness of 100nm to 1000 nm. Those skilled in the art can further select to grow 200-, 300-, 500-, 700-, or 700-1000nm sacrificial layers as required.
As a better choice of the above method, the sacrificial layer is AlSb, AlAs, InAlAs or InAlSb.
In a more preferable embodiment of the method, the semiconductor thin film layer is GaSb, GaAs, InP, InGaAs, InAlAs, InAs, InSb, or a doped material thereof.
As a better choice of the method, the depth of the ion implantation is greater than the thickness of the semiconductor thin film layer and less than the sum of the thickness of the semiconductor thin film layer and the thickness of the sacrificial layer.
As a better alternative to the above method, the sacrificial layer is removed by natural oxidation or chemical etching in a room temperature environment.
As a better alternative to the above method, the buffer layer, the sacrificial layer and the semiconductor thin film layer are grown by an epitaxial method such as molecular beam epitaxy, chemical vapor deposition or liquid phase epitaxy.
As a better alternative to the above method, the buffer layer and the donor substrate are made of the same material and have a thickness of 100nm to 1000 nm. The skilled in the art can further select to grow the 100-200-, 200-300-, 500-700-, or 700-1000nm buffer layer according to the requirement.
As a better alternative to the above method, the semiconductor acceptor substrate is wafer-level Si or Ge.
As a better choice of the method, the ion beam for ion implantation is hydrogen ion or helium ion, the energy is between 20 keV and 180keV, and the dose of the ion beam is 1016-1017cm-2The injection temperature is room temperature.
As a better alternative to the above method, the bonding temperature is between room temperature and 200 ℃.
As a better choice of the method, the annealing temperature is between 150 and 300 ℃.
After the annealing step, the top layer film is stripped from the donor substrate along the sacrificial layer, the sacrificial layer is an easily-oxidized aluminum-containing compound and is extremely easy to process, so that a silicon-based heteroepitaxial structure with a clean surface and capable of serving as a flexible substrate and a reusable semiconductor donor substrate structure with a clean surface can be obtained, and a semiconductor laser device structure continues to grow epitaxially on the flexible substrate, so that the thinning step can be omitted in the later process.
The invention adopts the ion beam stripping technology, takes the easily oxidized aluminum-containing compound as the sacrificial layer, has simple and easy realization, and can be used in the preparation method of the conventional semiconductor laser material. By adopting the method, the semiconductor film can be successfully transferred to the silicon substrate, the process is further simplified, the size is large, the flexible substrate is provided, the substrate thinning step is omitted, the heat dissipation of the device is improved, and the donor substrate can be recycled.
According to the preparation method of the semiconductor laser device material, an ion beam stripping method is adopted, an easily-oxidized aluminum-containing compound is used as a sacrificial layer, the surfaces of a donor substrate and an acceptor substrate after the layer splitting are clean and flat, the donor substrate is recycled, and the energy is saved and the environment is protected; secondly, the semiconductor film on the surface of the receptor substrate serves as a flexible substrate, so that residual stress in a subsequent epitaxial layer is reduced, and the crystal quality is improved; thirdly, the silicon substrate has good thermal conductivity, so that heat generated by the laser can be effectively taken away, and the service life of the device is prolonged; and finally, a substrate thinning step is omitted in the later-stage process, so that the process is further simplified, the heat generation is reduced, the surface damage and the participation stress caused by the later-stage thinning process are avoided, and the cost is greatly reduced.
Drawings
FIG. 1 is a schematic diagram of a method for preparing a novel semiconductor laser material according to the present invention;
fig. 2 is a schematic diagram of a laser device prepared by the method.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example one
The following process of growing a semiconductor laser by heterointegration of GaSb and a silicon-based substrate is taken as an example to illustrate the process steps of recycling a donor substrate by using an aluminum-containing compound which is easily oxidized in the air as a sacrificial layer, and the structures and the preparation steps can be directly popularized to other types of semiconductor laser processes, and the specific structure of the structure can be shown in fig. 2. The specific process steps are as follows:
(1) growing a 550nm GaSb buffer layer on a GaSb substrate;
(2) growing a 600nm AlSb sacrificial layer on the buffer layer;
(3) 200nm of n-type doping (doping concentration of Te 5X 10) is grown on the sacrificial layer18cm-3) The GaSb thin film layer; please refer to fig. 1A, thisThe formed structure sequentially comprises an n-type doped GaSb thin film cover layer, an AlSb sacrificial layer, a GaSb buffer layer and a GaSb substrate (donor substrate) from top to bottom;
(4) hydrogen ion implantation was performed from the top, at an energy of 75keV and at a dose of 5x1016cm-2(up to 660nm implant depth); referring to fig. 1B, the structure formed at this time is, from top to bottom, an n-type doped GaSb thin film cap layer, an AlSb sacrificial layer containing defects, a GaSb buffer layer, and a GaSb substrate (donor substrate) in sequence;
(5) bonding the silicon substrate and the structure at room temperature; referring to fig. 1C, the structure formed at this time sequentially includes, from top to bottom, a Si substrate, an n-type doped GaSb thin film cap layer, an AlSb sacrificial layer, a GaSb buffer layer, and a GaSb substrate (donor substrate);
(6) annealing the structure at 250 ℃;
(7) carrying out spalling after annealing, placing the sacrificial layer in air, and carrying out spalling by using an air pump after the sacrificial layer is automatically oxidized; referring to fig. 1D, in the structure formed at this time, the upper half portion is, from top to bottom, sequentially provided with a Si substrate, an n-type doped GaSb thin film cap layer, an AlSb sacrificial layer, and the lower half portion is, from top to bottom, sequentially provided with an AlSb sacrificial layer, a GaSb buffer layer, and a GaSb substrate (donor substrate);
(8) referring to fig. 1F, 200nm n-type doping (doping concentration of Te 5 × 10) is epitaxially grown on the surface-treated flexible substrate18cm-3) The GaSb buffer layer;
(9) a growth-limiting layer of 1.5 μm thick Al on the GaSb layer0.9Ga0.1As0.07Sb0.93(n-side doped with Te);
(10) growing non-doped Al with the total thickness of 0.8 mu m on the structure0.25Ga0.75As0.02Sb0.98A waveguide layer containing two 9nm wide quantum well structures In0.34Ga0.66As0.06Sb0.94As an active region, a waveguide layer structure with 18.5nm of distance between two quantum wells;
(11) continuing to grow 1.5 μm Al on the waveguide layer0.9Ga0.1As0.07Sb0.93A confinement layer (p-edge doped Be);
(12) finally, a 200nm thick p-type doped GaSb layer (doping concentration of Be 3x 10) was grown on the above structure19cm-3)。
Referring to FIG. 2, two Al layers with p-GaSb cap layer can be obtained according to the above method0.9Ga0.1As0.07Sb0.93、Al0.25Ga0.75As0.02Sb0.98Waveguide layer (which comprises two Ins)0.34Ga0.66As0.06Sb0.94An active region of a quantum well), an n-GaSb buffer layer, an n-GaSb thin film layer and a Si substrate.
Example two
The embodiment is consistent with the method and the embodiment except that the substrate is GaAs, the semiconductor film layer is GaAs and the sacrificial layer is AlAs, and the rest is a common laser structure on the GaAs substrate.
EXAMPLE III
In the embodiment, except that the substrate is InP, the semiconductor thin film layer is InP and the sacrificial layer is InAlAs, the rest is a common laser structure on the InP substrate, and the method is consistent with the embodiment.
Example four
In the embodiment, except that the substrate is InAs, the semiconductor thin film layer is InAs and the sacrificial layer is AlSb, the rest is a common laser structure on the InAs substrate, and the method and the embodiment are consistent.
EXAMPLE five
The method is consistent with the embodiment except that the substrate is InSb, the semiconductor thin film layer is InSb, the sacrificial layer is InAlSb, and the rest is the common laser structure on the InSb substrate.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A preparation method of a semiconductor laser material comprises the following steps:
providing a semiconductor donor substrate, epitaxially growing a buffer layer on the donor substrate, growing a sacrificial layer on the buffer layer, and growing a semiconductor thin film layer on the sacrificial layer;
performing ion implantation on the side of the semiconductor thin film layer to form a defect layer in the sacrificial layer;
providing a semiconductor acceptor substrate, and bonding the semiconductor thin film layer and the semiconductor acceptor substrate;
annealing the defect layer, stripping the top layer film from the donor substrate along the sacrificial layer to obtain a first substrate containing the donor substrate and a second substrate containing the semiconductor film layer, and removing the sacrificial layer on the second substrate to obtain a flexible substrate bonded with the semiconductor film layer;
the semiconductor donor substrate is a GaSb, GaAs, InP, InAs or InSb substrate;
the sacrificial layer is AlSb, AlAs, InAlAs or InAlSb;
the semiconductor thin film layer is made of doping materials of GaSb, GaAs, InP, InGaAs, InAlAs, InAs, InSb or the substances above;
the semiconductor receptor substrate is wafer-level Si or Ge;
the depth of the ion implantation is larger than the thickness of the semiconductor film layer and smaller than the sum of the thickness of the semiconductor film layer and the thickness of the sacrificial layer.
2. A method of fabricating a semiconductor laser material as claimed in claim 1 wherein: the method further includes growing a semiconductor laser device structure on the semiconductor thin film layer of the flexible substrate bonded with the semiconductor thin film layer.
3. A method of preparing a semiconductor laser material as claimed in claim 1 or 2 wherein: and the sacrificial layer is removed by natural oxidation or chemical etching under the room temperature environment.
4. A method of fabricating a semiconductor laser material as claimed in claim 2 wherein: the buffer layer, the sacrificial layer and the semiconductor thin film layer are grown by a molecular beam epitaxy, chemical vapor deposition or liquid phase epitaxy method.
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| CN109192670A (en) * | 2018-08-17 | 2019-01-11 | 中国科学院上海微系统与信息技术研究所 | Flexible semiconductor laminated film and preparation method thereof |
| CN110600417B (en) * | 2019-08-02 | 2022-11-18 | 中国科学院微电子研究所 | Epitaxial transfer method on GaAs substrate and manufactured semiconductor device |
| CN110739604B (en) * | 2019-10-24 | 2021-03-09 | 厦门乾照半导体科技有限公司 | Semiconductor epitaxial structure based on flexible substrate, VCSEL and manufacturing method |
| CN111262127B (en) * | 2020-02-04 | 2022-06-10 | 中国科学院上海微系统与信息技术研究所 | Preparation method of silicon-based InGaAs laser substrate, substrate and laser |
| CN111564756B (en) * | 2020-04-14 | 2022-03-25 | 中国科学院上海微系统与信息技术研究所 | Silicon-based non-phosphorus laser and preparation method thereof |
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