WO1989007832A1 - Semiconductor superlattice heterostructures fabrication methods, structures and devices - Google Patents

Semiconductor superlattice heterostructures fabrication methods, structures and devices Download PDF

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Publication number
WO1989007832A1
WO1989007832A1 PCT/US1989/000472 US8900472W WO8907832A1 WO 1989007832 A1 WO1989007832 A1 WO 1989007832A1 US 8900472 W US8900472 W US 8900472W WO 8907832 A1 WO8907832 A1 WO 8907832A1
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substrate
superlattice
quantum well
heterostructure
thickness
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PCT/US1989/000472
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French (fr)
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Elyahou Kapon
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Bell Communications Research, Inc.
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Publication of WO1989007832A1 publication Critical patent/WO1989007832A1/en

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    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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    • H01S5/34Structure 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
    • H01S5/343Structure 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
    • H01S5/34313Structure 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 having only As as V-compound, e.g. AlGaAs, InGaAs
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    • H01S5/32Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures
    • H01S5/3202Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures grown on specifically orientated substrates, or using orientation dependent growth
    • H01S5/3203Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures grown on specifically orientated substrates, or using orientation dependent growth on non-planar substrates to create thickness or compositional variations
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    • H01S5/32Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures
    • H01S5/323Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
    • H01S5/32308Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser emitting light at a wavelength less than 900 nm
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    • H01S5/34Structure 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
    • H01S5/341Structures having reduced dimensionality, e.g. quantum wires
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    • H01S5/34Structure 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
    • H01S5/3421Structure 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 layer structure of quantum wells to influence the near/far field
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    • H01S5/34Structure 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
    • H01S5/343Structure 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
    • H01S5/34313Structure 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 having only As as V-compound, e.g. AlGaAs, InGaAs
    • H01S5/3432Structure 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 having only As as V-compound, e.g. AlGaAs, InGaAs the whole junction comprising only (AI)GaAs
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Definitions

  • This invention relates to a method for fabricating thin film semiconductor superlattice heterostructures and the resulting structures and devices obtainable thereby and more particularly to the production of quantum well structures on nonplanar substrates.
  • Such laterally patterned structures have been useful for optical wave guiding (essentially because the wavelength of light is comparable to the layer thicknesses involved).
  • Ultra-thin ( ⁇ 500 A) epitaxial layers have been grown on planar substrates.
  • quantum size effects in one dimension modify the material properties (e.g., bandgap and refractive index).
  • the thickness of the epitaxial layers it has been possible to vary the resulting superlattice (or quantum well) material properties. For example, selection of the superlattice (SL) periodicity results in selection of the material bandgap.
  • these superlattices give rise to new features, e.g., enhanced nonlinear optical properties.
  • the SL period (or layer thicknesses) in the direction of layer growth, allows one to fabricate structured materials in which the physical properties in the direction normal to the substrate plane differ based upon the SL period.
  • the production of SL or quantum well devices having superlattice structures which are more than one dimensional and/or which vary laterally in thickness is desirable in order to obtain devices having different and/or enhanced physical properties and having new and different capabilities than prior art quantum effect devices would therefore
  • a method for the production of thin ( ⁇ 500A)) epitaxially grown semi-conductor layers having a laterally varying SL periodicity comprises providing a nonplanar, e.g., a grooved, substrate on which the epitaxial semiconductor layers are grown by the usual growth techniques e.g., LPE, MBE, or OMCVD.
  • the thin SL or quantum well (QW) semiconductor layers resulting from this growth vary in thickness, and hence physical properties, laterally along the substrate plane. Such variations give rise not only to layers with varying properties but also to new device structures employing such films.
  • One characteristic of the resulting structured materials is that they may be fabricated to tailor their properties in more than one dimension.
  • FIG. 1 is a transmission electron micrograph of a cross section of a superlattice grown in an etched groove.
  • FIG. 2a-c illustrates carrier confinement induced by quantum well thickness variations.
  • FIG. 3 is an elevational view of a semiconductor wafer having an array of patterned etched depressions in one surface thereof.
  • FIG. 4 is a schematic illustration of the cross section taken across A-A or B-B of the wafer shown in FIG. 3.
  • FIG. 5 is a schematic illustration of the cross section of a patterned quantum well laser.
  • FIG. 6 is a graph showing the light output in terms of power versus the current characteristic of a patterned, 280 micron long quantum well (QW) laser with pulsed operation at room temperature.
  • QW quantum well
  • FIG. 7 shows typical far field (a) and near field (b) distributions of the patterned QW laser, measured in the junction plane.
  • FIG. 8 is a schematic illustration of a Mach-Zehnder type interferometer employing a patterned QW wire. .
  • a method for patterning semiconductor superlattice heterostructures comprises growing these superlattices on nonplanar patterned substrates to produce variations in thickness and crystallographic orientations of the grown layers in order to introduce lateral variations of the physical properties which depend on these parameters.
  • the lateral thickness variation results from the variation in the flux of the source beams across surfaces with different angular orientations and because of the different effective sticking coefficient associated with different crystal planes. If the patterned features are fine enough, semiconductor materials with reduced carrier dimensionality can be obtained.
  • GaAs substrates [(100) oriented] were patterned by using conventional photo lithography and wet chemical etching. Channels, — 3 ⁇ m wide and *-*- 2 ⁇ deep and aligned along the [Oil] direction, were etched through a photoresist mask using H2SO 4 :H 2 ⁇ 2 * *H2 ⁇ (1:8:40) preferential chemical etching solution.
  • a superlattice consisting of five periods of alternate 100 A GaAs and
  • FIG. 1 shows a TEM cross section of a superlattice that was grown in an etched groove.
  • the MBE growth resulted in the formation of facets lying in specific crystal planes, as indicated in this Figure. It can be seen that the superlattice period 5 decreased significantly with increasing tilt angle of its growth plane relative to the horizontal
  • the "kink” in the structure o shown in FIG. 2(c) extends over 200-300 A This dimension is comparable to the diffusion length of the Ga and the Al atoms which migrate on the growth surface.
  • Table I lists the crystal planes that were identified in the TEM cross section of FIG. 1, along with the measured and calculated tilt angles ⁇ between each crystal plane and the horizontal (100) plane. Faces oriented along the ⁇ 111 ⁇ , ⁇ 411 ⁇ , and ⁇ 811 ⁇ planes were identified in other experiments of MBE growth on planar substrates as well. Table I also summarizes the superlattice periods (measured normal to the crystal planes) obtained in the present experiment. These periods should be compared to the period obtained for a o planar substrate, which was ⁇ » 200 A. It can be seen that large variations in the periods of adjacent superlattice sections can be achieved.
  • the superlattice section lying in the (554) o plane has a period of only 80 A; this is less than half the period of the adjacent section which lies in the (711) plane.
  • Table I also shows the values of ⁇ /cos ⁇ , which is a measure for the relative effective sticking coefficient, for each of the growth planes.
  • the thickness variations exhibited by the epitaxial layers give rise to lateral variations in the effective index of refraction, which can be used to define channel optical waveguides.
  • the demonstration of these thickness variations with epitaxial layers which are less than a few hundred angstroms in thickness, however, is important because of the quantum size effects exhibited by such ultrathin layer heterostructures.
  • the strong dependence of the confinement energy on the well width in quantum well heterostructures implies that lateral variation in the quantum well width gives rise to lateral variations in physical parameters which depend on this confinement energy.
  • superlattice heterostructures grown on nonplanar substrates and showing the lateral period variations described above will exhibit lateral variations in physical properties associated with the superlattice period.
  • a physical parameter which depends on the superlattice period is the refractive index.
  • the lateral variations in the superlattice period can thus be used to achieve lateral patterning of the index of refraction, which is useful for various guided-wave optics applications.
  • FIG. 2(a) shows a possible way to realize such a structure, by growing a quantum well heterostructure in a groove (see also FIG. 1).
  • a decrease in the well thickness from 100 to 50 A results in an increase in the confinement energy by more than 50 meV.
  • Such a potential step would be sufficient for achieving carrier confinement, at least at low temperatures.
  • Quantum well thickness variations of this order can clearly be obtained by MBE growth on nonplanar surfaces, as is demonstrated herein.
  • the etched grooves should be made considerably narrower (on the order of a few hundred angstroms) in order to observe quantum size effects due to lateral carrier confinement.
  • Such fine patterning can be achieved by using, e.g., electron beam lithography.
  • additional carrier confinement effects can result in the structure described in FIG. 2(c) due to the tilt in the thinner quantum well planes with respect to the thicker one.
  • Three- dimensional confinement of carriers might be obtained similarly by MBE growth on nonplanar substrates patterned with two-dimensional features.
  • the resulting structured materials now have tailored properties in more than one dimension.
  • the variation in the bandgap can be utilized in order to trap carriers in more than one dimension.
  • Prior techniques for carrier confinement in semiconductor heterostructures involved embedding a low bandgap material in high bandgap regions by using etch and regrowth steps. The method set forth herein requires only a single growth step, and does not involve physical interfaces between the high-and low- bandgap materials.
  • Applications of 3-D bandgap tailoring include semiconductor lasers* optical waveguides, diffraction gratings (e.g.
  • BSTITUTE iHEET New advantages are obtained if the lateral dimensions of the patterned o QWs (or the periods of the 3-D, 2-D SLs) are less than 500-1000 A. Then, the laterally confined carriers exhibit 2-D or 3-D quantum size effects, and the resulting structured materials exhibit quantum wire or quantum box properties (i.e., are characterized by 1-D or 0-D carriers). As such, they are expected to have new material properties; enhanced nonlinear optical properties, for example.
  • SLs will have lower thresholds, higher modulation band width and narrower line width.
  • FIG. 3 and 4 demonstrate a physical structure which gives rise to a two dimensional superlattice having varying thickness trapping the carriers to result in zero-dimensional electrons. Lateral thickness variations are obtained along the QW as defined by the ridge pattern. A one dimensional version of such a patterned structure would result in a QW wire.
  • a structure is shown for a multi ⁇ dimensional (2-D) embodiment of the invention.
  • a single crystal substrate wafter 31 e.g., GaAs
  • the substrate 31 is etched to form a fine pattern as shown in FIG. 4.
  • This fine pattern is what would be observed from a cross-section across either plane A-A or plane B-B of FIG. 3.
  • the fine pattern consists of a series of etched grooves 33 having a plurality of epitaxially grown layers thereover.
  • the first epitaxial layer 34 and the o top epitaxial layer 35 are high bandgap layers having thicknesses which may exceed 500 A.
  • a central epitaxial layer 36 of a low bandgap material is formed between the two high o bandgap layers 34 and 35.
  • This central layer 36 is less than 500 A, and typically in the o order of 100 A, and varies laterally in thickness as previously described. If the thickness of the quantum well is selected such that the width of the area 37 at the base of the groove (shown by a circle in FIG. 4) is less than the de Broglie wavelength, carriers can be trapped in this area creating a QW wire along the base of the QW layer 36.
  • FIG. 8 there is a representation of an interferometer which makes use of such a QW wire.
  • a semiconductor device 80 includes an emitter 81 and a collector 82.
  • a QW wire 83 is formed which extends from emitter 81 to collector 82 and has a first fork 83 which diverges to form two arms 84 and 85 beyond the emitter 81 and recombines at a second fork 86 prior to or at the collector 82.
  • a base region 87 extends in the area of one arm 84 of the QW wire for modulating the phase of the carrier wave functions in that arm of the QW wire.
  • Quantum well (QW) heterostructure lasers offer a number of advantages over conventional heterostructure diode lasers, including a lower threshold current density, reduced temperature sensitivity and a potentially higher modulation bandwidth.
  • Various types of stripe geometry such as ridge waveguide and buried heterostructure configurations, have been used in the past for obtaining very low threshold QW lasers. These stripe geometries introduce the lateral patterning in the diode laser structure which is required for achieving efficient carrier and optical confinements parallel to the junction plane.
  • the method described herein which utilizes the lateral variations in the thickness of quantum wells grown on nonplanar substrates in order to achieve lateral patterning of the energy bandgap and the index of refraction can be employed to make a QW laser structure which relies on this QW patterning technique.
  • the injected carriers in this laser are laterally confined to a ⁇ - 1 ⁇ m wide QW stripe owing to the larger effective bandgap of the thinner QW layers on both sides of this stripe.
  • Room temperature threshold currents as low as 6 mA (with uncoated facets) have been obtained.
  • the schematic cross section of the patterned QW laser is shown in FIG. 5.
  • Fabrication of the lasers began by etching V-shaped grooves 51 along the [Oil] crystal direction on a (100) oriented n+ -GaAs substrate 52.
  • the grooves 51 were etched through a photoresist mask by using H 2 S0 4 : H 2 O 2 (30%) : H j O (1:8:40 by volume), and . were 10 ⁇ m wide and 7 ⁇ m deep.
  • the grooved substrates 52 Prior to the epitaxial growth, the grooved substrates 52 were cleaned by degreasing, followed by etching first in HC1 for 2 min., then in H 2 SO 4 :H 2 O 2 (30%):H 2 O (4:1:1) for 2 min. and finally in HC1 for an additional 2 min.
  • the heterostructure layers were then grown by molecular beam epitaxy (MBE) at 700°C under an arsenic-rich atmosphere.
  • MBE molecular beam
  • the layer thicknesses indicated above are for the case of a planar, (100) oriented substrate.
  • the actual grown layers exhibit lateral thickness variations in the vicinity of the groove, as is evident from scanning electron microscope (SEM) photographs (not shown) of a cleaved sample. Facets oriented parallel to the ⁇ 111 ⁇ and the ⁇ 411 ⁇ crystal planes form, and the growth rate normal to these planes is about 50 and 80 percent, respectively, of the growth rate in the ⁇ 100 ⁇ direction.
  • the grown wafers were processed into diode lasers by evaporating AuBe/Au contacts 61 on the p side, thinning the substrate and evaporating AuGe/Au n- contacts (not shown). Lateral current confinement was obtained by defining a ⁇ - 2 ⁇ m wide conductive stripe at the bottom of the groove using proton implantation (100 keV energy, 3"10 15 cm -2 dose; see FIG. 5). The lasers were tested at low duty cycle (200 nsec pulses,
  • Si doped AI Q -Gap ,As Si is amphoteric in GaAs and AlGaAs and has been shown to give rise to n-doping on the (100) planes and to p-doping on the ⁇ 111 ⁇ planes of layers grown on nonplanar substrates. Therefore, the Si doped ASQ ⁇ Ga 0 -As cladding layer in our laser structure is expected to be n-type in the ⁇ 100 ⁇ oriented sections and p-type in the ⁇ 111 ⁇ sections.
  • the patterned QW lasers exhibit low threshold currents, as low as 6 mA for 280 ⁇ m long devices. This value is comparable to the best values (5 mA) achieved with QW GaAs/AlGaAs lasers made by a single growth step, but is still larger than the lowest value that has been achieved with buried-heterostructure (BH) QW lasers (2.5 mA for uncoated lasers at room temperature).
  • BH buried-heterostructure
  • the structure described here can be used to make lasers with substantially narrower active regions using a sharper V-groove. For sufficiently narrow active regions (a few hundred Angstroms) such lasers are expected to exhibit one dimensional (quantum wire) carrier characteristics which should lead to diode lasers with interesting and useful physical properties. Similar patterned QW lasers grown on nonplanar substrates delineated by two dimensional features might yield QW lasers with zero-dimensional carriers (quantum box lasers).
  • patterned QW heterostructure injection laser grown by MBE in which the lateral carrier confinement relies on thickness and growth plane variations of the active QW layer.
  • the patterned QW GaAs/AlGaAs lasers are characterized by a low threshold current, as low as 6 mA at room temperature.
  • the patterned QW laser structure is suitable for obtaining semiconductor lasers with very small lateral dimensions, which should be useful in the fabrication of quantum wire and quantum box laser heterostructures.
  • the low absorption in the thinner QW regions in this laser structure makes it attractive for use in phase locked arrays of semiconductor lasers.

Abstract

A novel quantum well semiconductor structure is described wherein the quantum well is formed by growing a thin ( 500 Å) epitaxial layer (36) on a patterned (e.g. grooved) nonplanar substrate (31, 34) so as to achieve thickness variations along the quantum well and hence laterally varying superlattice periodicity and QW depth. Using this structure one can achieve lateral carrier confinement and real refractive index waveguiding. Index guided GaAs/Al/GaAs lasers are described.

Description

SEMICONDUCTOR SUPERLATTICE HETE OSTRUCTURES FABRICATION METHODS, STRUCTURES AND DEVICES
BACKGROUND OF THE TNVENTTON
Field of Invention This invention relates to a method for fabricating thin film semiconductor superlattice heterostructures and the resulting structures and devices obtainable thereby and more particularly to the production of quantum well structures on nonplanar substrates.
Description of the Prior Art o "Thick" (>500 A) epitaxial layers have been grown on nonplanar substrates by various growth techniques, e.g., liquid phase epitaxy (LPE), molecular beam epitaxy (MBE), and organometallic chemical vapor deposition (OMCVD). In all cases, the nonplanarity of the substrate gives rise to lateral thickness variations in the epitaxial layers.
Such laterally patterned structures have been useful for optical wave guiding (essentially because the wavelength of light is comparable to the layer thicknesses involved). o Ultra-thin (<500 A) epitaxial layers have been grown on planar substrates. For such thin layers (i.e. layers whose thickness is comparable to the deBroglie wavelength of charge carriers) quantum size effects in one dimension (along the growth direction) modify the material properties (e.g., bandgap and refractive index). Hence, by tailoring the thickness of the epitaxial layers, it has been possible to vary the resulting superlattice (or quantum well) material properties. For example, selection of the superlattice (SL) periodicity results in selection of the material bandgap. In addition, these superlattices give rise to new features, e.g., enhanced nonlinear optical properties. Furthermore it has been shown that the SL period (or layer thicknesses) in the direction of layer growth, allows one to fabricate structured materials in which the physical properties in the direction normal to the substrate plane differ based upon the SL period. Devices which rely not only upon the new properties of the SL materials, but also on quantum size effects that occur in the individual layers, have also been demonstrated, e.g., quantum well lasers, resonant tunneling devices, quantum-confined Stark effect modulators, etc. The production of SL or quantum well devices having superlattice structures which are more than one dimensional and/or which vary laterally in thickness is desirable in order to obtain devices having different and/or enhanced physical properties and having new and different capabilities than prior art quantum effect devices would therefore
SUBSTITUTE SHEET be desirable.
Summary of the Invention
A method for the production of thin (<500A)) epitaxially grown semi-conductor layers having a laterally varying SL periodicity is described. The method comprises providing a nonplanar, e.g., a grooved, substrate on which the epitaxial semiconductor layers are grown by the usual growth techniques e.g., LPE, MBE, or OMCVD.
The thin SL or quantum well (QW) semiconductor layers resulting from this growth vary in thickness, and hence physical properties, laterally along the substrate plane. Such variations give rise not only to layers with varying properties but also to new device structures employing such films. One characteristic of the resulting structured materials is that they may be fabricated to tailor their properties in more than one dimension.
Brief Description of the Drawings FIG. 1 is a transmission electron micrograph of a cross section of a superlattice grown in an etched groove.
FIG. 2a-c illustrates carrier confinement induced by quantum well thickness variations.
FIG. 3 is an elevational view of a semiconductor wafer having an array of patterned etched depressions in one surface thereof.
FIG. 4 is a schematic illustration of the cross section taken across A-A or B-B of the wafer shown in FIG. 3.
FIG. 5 is a schematic illustration of the cross section of a patterned quantum well laser. FIG. 6 is a graph showing the light output in terms of power versus the current characteristic of a patterned, 280 micron long quantum well (QW) laser with pulsed operation at room temperature.
FIG. 7 shows typical far field (a) and near field (b) distributions of the patterned QW laser, measured in the junction plane. FIG. 8 is a schematic illustration of a Mach-Zehnder type interferometer employing a patterned QW wire. .
Detailed Description of the Invention
Generally, a method for patterning semiconductor superlattice heterostructures comprises growing these superlattices on nonplanar patterned substrates to produce variations in thickness and crystallographic orientations of the grown layers in order to introduce lateral variations of the physical properties which depend on these parameters. The lateral thickness variation results from the variation in the flux of the source beams across surfaces with different angular orientations and because of the different effective sticking coefficient associated with different crystal planes. If the patterned features are fine enough, semiconductor materials with reduced carrier dimensionality can be obtained. By proper selection of the features in the pattern, "artificial" materials useful
5 in high speed electronics and optical signal processing can be produced.
By way of example, GaAs substrates [(100) oriented] were patterned by using conventional photo lithography and wet chemical etching. Channels, — 3 μm wide and *-*- 2 μ deep and aligned along the [Oil] direction, were etched through a photoresist mask using H2SO4:H2θ2**H2θ (1:8:40) preferential chemical etching solution. The
10 photoresist mask was then removed, and the patterned substrates were cleaned by degreasing, followed by etching for 45 seconds in H2SO4:H2θ2-H2O (4:1:1) solution and for 4 minutes in HC1. Finally, the samples were rinsed and blown dry. The resulting grooves had rounded profiles because of the etching in the (4:1:1) solution.
A superlattice consisting of five periods of alternate 100 A GaAs and
15 100 A A1Q VGH -As layers, preceded by a thick GaAs buffer layer, was grown on the patterned samples by MBE. (The layer thicknesses are the ones obtained for a planar substrate.) The growth was carried out at 100°C above the oxide desorption temperature, typically 680°C, and the As/Ga beam equivalent pressure ratio was — 3. The substrates were rotated at 20 rpm during the growth. The superlattice growth features were studied by 0 using transmission electron microscopy (TEM) to examine (011) cross sections of the grown samples.
FIG. 1 shows a TEM cross section of a superlattice that was grown in an etched groove. The MBE growth resulted in the formation of facets lying in specific crystal planes, as indicated in this Figure. It can be seen that the superlattice period 5 decreased significantly with increasing tilt angle of its growth plane relative to the horizontal
(100) plane. This period variation arises from the difference in the growth rate, measured perpendicular to the crystal planes associated with the different planes. The difference in the growth rate results both from the variation in the flux of the source beams across planes with different orientation as well as from different sticking coefficients of the Ga and the Al 0 atoms for different crystal planes. The asymmetry in the structure shown in FIG. 1 is probably due to a slight misalignment of the etched grooves with respect to the [011] direction.
Magnified TEM cross sections of the regions where superlattices of different periods intersect, show the change in the superlattice period is mostly smooth and o 5 occurs within <100 A. The transition between the superlattices oriented along the (711) and the (554) planes, however, exhibits a "kink." This is believed to be a result of migration of the source atoms, after reaching the surface of the substrate, to more "favorable" crystal planes. Atoms reaching the (554) plane, close to the intersection with the (711) plane, migrated to the neighboring (711) plane, which resulted in even smaller growth rate along the (554) plane in that region. Note also that the GaAs layers (the dark stripes in FIG. 1) are thinner than the AlGaAs ones in the "kink" region, which indicates that this migration effect is stronger for the Ga atoms than it is for the Al ones. The "kink" in the structure o shown in FIG. 2(c) extends over 200-300 A This dimension is comparable to the diffusion length of the Ga and the Al atoms which migrate on the growth surface.
Table I lists the crystal planes that were identified in the TEM cross section of FIG. 1, along with the measured and calculated tilt angles θ between each crystal plane and the horizontal (100) plane. Faces oriented along the {111}, {411}, and {811} planes were identified in other experiments of MBE growth on planar substrates as well. Table I also summarizes the superlattice periods (measured normal to the crystal planes) obtained in the present experiment. These periods should be compared to the period obtained for a o planar substrate, which was ~» 200 A. It can be seen that large variations in the periods of adjacent superlattice sections can be achieved. The superlattice section lying in the (554) o plane has a period of only 80 A; this is less than half the period of the adjacent section which lies in the (711) plane. Table I also shows the values of Λ/cos θ , which is a measure for the relative effective sticking coefficient, for each of the growth planes. The planes
(411), (111), (811), and (711) have similar effective sticking coefficients and thus the growth rate on these planes is determined mainly by their tilt angle. The effective sticking coefficient for the (554) plane, on the other hand, is considerably smaller.
The use of the features of MBE growth on patterned substrates in the fabrication of optoelectronic devices has already been pointed out. In particular, the thickness variations exhibited by the epitaxial layers give rise to lateral variations in the effective index of refraction, which can be used to define channel optical waveguides. The demonstration of these thickness variations with epitaxial layers which are less than a few hundred angstroms in thickness, however, is important because of the quantum size effects exhibited by such ultrathin layer heterostructures. The strong dependence of the confinement energy on the well width in quantum well heterostructures implies that lateral variation in the quantum well width gives rise to lateral variations in physical parameters which depend on this confinement energy. Therefore, it is expected that superlattice heterostructures grown on nonplanar substrates and showing the lateral period variations described above will exhibit lateral variations in physical properties associated with the superlattice period. One example of a physical parameter which depends on the superlattice period is the refractive index. The lateral variations in the superlattice period can thus be used to achieve lateral patterning of the index of refraction, which is useful for various guided-wave optics applications.
Another example of an application of these patterned superlattices is the use of the difference in the effective band gap of quantum wells of different thickness to induce carrier confinement in more than one dimension. Consider the quantum well heterostructure whose cross section is described schematically in FIG. 2(a). The quantum well is thicker near the center of the structure. Consequently, the lowest lying bound states have a higher energy on both sides of the structure [FIG. 2(b)]. Therefore, the resulting steps in the carrier energies provide an effective potential well in the lateral direction, which can serve to achieve lateral carrier confinement. FIG. 2(c) shows a possible way to realize such a structure, by growing a quantum well heterostructure in a groove (see also FIG. 1). For a GaAs/Al0 Ga0 -As quantum well heterostructure, a decrease in the well thickness from 100 to 50 A results in an increase in the confinement energy by more than 50 meV. Such a potential step would be sufficient for achieving carrier confinement, at least at low temperatures. Quantum well thickness variations of this order can clearly be obtained by MBE growth on nonplanar surfaces, as is demonstrated herein. However, the etched grooves should be made considerably narrower (on the order of a few hundred angstroms) in order to observe quantum size effects due to lateral carrier confinement. Such fine patterning can be achieved by using, e.g., electron beam lithography. It should be noted that additional carrier confinement effects can result in the structure described in FIG. 2(c) due to the tilt in the thinner quantum well planes with respect to the thicker one. Three- dimensional confinement of carriers might be obtained similarly by MBE growth on nonplanar substrates patterned with two-dimensional features.
The resulting structured materials now have tailored properties in more than one dimension. For example, the variation in the bandgap can be utilized in order to trap carriers in more than one dimension. Prior techniques for carrier confinement in semiconductor heterostructures involved embedding a low bandgap material in high bandgap regions by using etch and regrowth steps. The method set forth herein requires only a single growth step, and does not involve physical interfaces between the high-and low- bandgap materials. Applications of 3-D bandgap tailoring include semiconductor lasers* optical waveguides, diffraction gratings (e.g. gain modulation distributed feedback lasers: the periodic corrugations in the substrates are maα such that Λ = λo/2n, where Λ is the period, m is an integer, λo is the vacuum wavelength, and n is the refractive index. Then, in addition to the periodic variation in the real part of the refractive index, the imaginary part is also modulated due to the QW thickness modulation. This leads to single frequency emission.)
BSTITUTE iHEET New advantages are obtained if the lateral dimensions of the patterned o QWs (or the periods of the 3-D, 2-D SLs) are less than 500-1000 A. Then, the laterally confined carriers exhibit 2-D or 3-D quantum size effects, and the resulting structured materials exhibit quantum wire or quantum box properties (i.e., are characterized by 1-D or 0-D carriers). As such, they are expected to have new material properties; enhanced nonlinear optical properties, for example. Semiconductor lasers made of such 3-D (or 2-D)
SLs will have lower thresholds, higher modulation band width and narrower line width.
New electrical transport properties of these materials are also expected.
In addition, the ability to create quantum wires and quantum boxes with this technique opens the door for a new generation of electronic devices, relying on what may be called "guided-wave electronics." Creating a single "wire" of low bandgap material surrounded by high bandgap material and thinner QWs results in one-dimensional electrons guided by the wire. For example, FIG. 3 and 4 demonstrate a physical structure which gives rise to a two dimensional superlattice having varying thickness trapping the carriers to result in zero-dimensional electrons. Lateral thickness variations are obtained along the QW as defined by the ridge pattern. A one dimensional version of such a patterned structure would result in a QW wire.
Referring to FIG. 3 and 4, a structure is shown for a multi¬ dimensional (2-D) embodiment of the invention. Here, a single crystal substrate wafter 31, e.g., GaAs, is etched to form a plurality of spaced depressions 32 which may have circular, square or other cross sections when viewed from the top of the substrate. In addition to the depressions, the substrate 31 is etched to form a fine pattern as shown in FIG. 4. This fine pattern is what would be observed from a cross-section across either plane A-A or plane B-B of FIG. 3. Referring to FIG. 4, the fine pattern consists of a series of etched grooves 33 having a plurality of epitaxially grown layers thereover. The first epitaxial layer 34 and the o top epitaxial layer 35 are high bandgap layers having thicknesses which may exceed 500 A.
A central epitaxial layer 36 of a low bandgap material is formed between the two high o bandgap layers 34 and 35. This central layer 36 is less than 500 A, and typically in the o order of 100 A, and varies laterally in thickness as previously described. If the thickness of the quantum well is selected such that the width of the area 37 at the base of the groove (shown by a circle in FIG. 4) is less than the de Broglie wavelength, carriers can be trapped in this area creating a QW wire along the base of the QW layer 36.
In FIG. 8 there is a representation of an interferometer which makes use of such a QW wire. Here, a semiconductor device 80 includes an emitter 81 and a collector 82. A QW wire 83 is formed which extends from emitter 81 to collector 82 and has a first fork 83 which diverges to form two arms 84 and 85 beyond the emitter 81 and recombines at a second fork 86 prior to or at the collector 82. A base region 87 extends in the area of one arm 84 of the QW wire for modulating the phase of the carrier wave functions in that arm of the QW wire. In operation, carriers are injected from the emitter into the QW wire in the region of the emitter, the carrier wave functions (initially of the same phase) are split into the two arms 84 and 85 at the fork 83. By applying an appropriate signal to the base region, a modulated phase shift can be obtained in arm 84 relative to arm 84. When the carrier wave functions recombine at the second fork 86, the current in the QW wire will be modulated in accordance with the phase modulation in the arm 84 (i.e. constructive or destructive recombination). It should be noted that this configuration can be used for light modulation as well as current modulation where the QW wire is in a laser structure and supports laser transmission.
Quantum well (QW) heterostructure lasers offer a number of advantages over conventional heterostructure diode lasers, including a lower threshold current density, reduced temperature sensitivity and a potentially higher modulation bandwidth. Various types of stripe geometry, such as ridge waveguide and buried heterostructure configurations, have been used in the past for obtaining very low threshold QW lasers. These stripe geometries introduce the lateral patterning in the diode laser structure which is required for achieving efficient carrier and optical confinements parallel to the junction plane.
The method described herein which utilizes the lateral variations in the thickness of quantum wells grown on nonplanar substrates in order to achieve lateral patterning of the energy bandgap and the index of refraction can be employed to make a QW laser structure which relies on this QW patterning technique. By growing an otherwise conventional GaAs/AlGaAs single QW laser heterostructure on a grooved substrate, we obtain an effectively buried QW laser. The injected carriers in this laser are laterally confined to a ~- 1 μm wide QW stripe owing to the larger effective bandgap of the thinner QW layers on both sides of this stripe. Room temperature threshold currents as low as 6 mA (with uncoated facets) have been obtained.
The schematic cross section of the patterned QW laser is shown in FIG. 5. Fabrication of the lasers began by etching V-shaped grooves 51 along the [Oil] crystal direction on a (100) oriented n+ -GaAs substrate 52. The grooves 51 were etched through a photoresist mask by using H2S04 : H2O2(30%) : HjO (1:8:40 by volume), and . were 10 μm wide and 7 μm deep. Prior to the epitaxial growth, the grooved substrates 52 were cleaned by degreasing, followed by etching first in HC1 for 2 min., then in H2SO4:H2O2(30%):H2O (4:1:1) for 2 min. and finally in HC1 for an additional 2 min. The heterostructure layers were then grown by molecular beam epitaxy (MBE) at 700°C under an arsenic-rich atmosphere. The single quantum well, separate confinement laser heterostructure
18 -3 ° consisted of a 0.5μmGaAs buffer layer 53 (Si, n=2'10 cm ) 5 periods of a 150 A -| θ *I
GaAs/150 A A1Q 5GaQ 5As buffer superlattice 54 (Si, n=* 10iOcm ), a 1.25 μm AIQ jGa0 -As cladding layer 55 (Si,
Figure imgf000010_0001
a 0.2 μm Al Ga., As waveguide layer 56 with x linearly graded from 0.5 to 0.2, performed by rapid switching of the Al shutter
17 -.**. °
(Si, n=1 0 cm ), a 70 A undoped GaAs active layer 57, a 0.2 μm AlχGal χAs waveguide layer 58, x-0.2-0.5 (Be, p=l°10 cm" ), a 1.25 μm A1Q jGa0 -As cladding layer
59 (Be, p=ri018cm"3), and a 0.2 μm GaAs contact layer 60 (Be, p=51018 cm"3). The layer thicknesses indicated above are for the case of a planar, (100) oriented substrate. The actual grown layers exhibit lateral thickness variations in the vicinity of the groove, as is evident from scanning electron microscope (SEM) photographs (not shown) of a cleaved sample. Facets oriented parallel to the {111} and the {411} crystal planes form, and the growth rate normal to these planes is about 50 and 80 percent, respectively, of the growth rate in the {100} direction. Transmission electron microscopy studies show that the thicker o (-7 A), (100) oriented GaAs QW at the center of the structure is bounded by thinner (~40 o A), (111) oriented QW layers on both sides. The width of the (100) oriented QW stripe is
~- 1 μm. It is interesting to note the existence of lateral tone variations along the Si doped
AIQ ζGa.-, ,As layer visible in the SEM's probably represent doping type variations.
The grown wafers were processed into diode lasers by evaporating AuBe/Au contacts 61 on the p side, thinning the substrate and evaporating AuGe/Au n- contacts (not shown). Lateral current confinement was obtained by defining a ~- 2 μm wide conductive stripe at the bottom of the groove using proton implantation (100 keV energy, 3"10 15 cm -2 dose; see FIG. 5). The lasers were tested at low duty cycle (200 nsec pulses,
1kHz repetition rate). Their optical field patterns were evaluated by employing a video camera and a video analyzer. Below threshold, spontaneous emission emanated mainly from the (100) oriented QW stripe at the center of the structure. Weaker spontaneous emission occurred at the (100) oriented regions at the "shoulders" of the structure, probably due to current leakage. Above threshold, the device lased in a single, almost circular spot, with lateral full width at half maximum (FWHM) of — 2 μm. The threshold current was as low as 6 mA (for uncoated devices) and the differential efficiency was 35 percent. The light
(power output) versus current characteristics were linear up to more than four times the threshold current (see FIG. 6) . In this range of currents the spectrum of the laser exhibits a o few (3-4) longitudinal modes and is centered about λ. = --8450 A.
Typical far field and near field distributions of the patterned QW laser, measured in the junction plane, are given in FIG. 7 a & b, respectively. Stable fundamental mode operation was observed up to four times the threshold current. o The patterned QW lasers lased in a single spatial spot at λ = —8450 A up to about four times the threshold currents. At higher currents, two additional lasing spots appeared at the "shoulders" of the structure where the spontaneous emission due to current leakage had been observed. The wavelength for these additional lasing spots was o also at ~8450 A which is consistent with the fact that the QW layers at the (100) stripe in the center as well as in the (100) shoulders have a similar thickness. At still higher diode currents, lasing occurred at the {411} oriented regions (see FIG. 5), for which the emission o o wavelength was —8150 A This wavelength corresponds to the thinner (—55 A) QW at the
{411} oriented sections of the active layer. Lasing from the thinnest, {111} oriented QW's has not been observed at this time.
These observations indicate that carriers which are injected into the (100) oriented QW stripe at the center of the laser are laterally confined to this stripe, which is — 1 μm wide. This lateral dimension is considerably smaller than the carrier diffusion length. The lateral carrier confinement is achieved probably due to the effective lateral potential barriers which result from the reduced thickness (and possibly the different orientation) of the {111} oriented QW's.
The absence of lasing from the {111} oriented QW's could be the result of the peculiar doping distribution observed in the Si doped AIQ -Gap ,As. Si is amphoteric in GaAs and AlGaAs and has been shown to give rise to n-doping on the (100) planes and to p-doping on the {111} planes of layers grown on nonplanar substrates. Therefore, the Si doped ASQ ςGa0 -As cladding layer in our laser structure is expected to be n-type in the {100} oriented sections and p-type in the {111} sections. This should result in the relocation of the p-n junction to the substrate-Alp -Gag -As interface, and hence an elimination of carrier injection into the QW, at the {111} oriented sections. The far field distribution of the patterned QW lasers (FIG. 7(a)) and their spectral characteristics show that their optical field is predominantly index guided. The built-in lateral distribution of the refractive index results from the lateral variation in the thickness of the epitaxial layers (including the QW layer) , and their nonplanar configuration. It should be noted that the higher bandgap of the thinner QW's surrounding the active (100) oriented QW stripe makes these regions transparent at the laser wavelength. This reduces the threshold current and increases the differential efficiency. Furthermore, the absence of substantial interband absorption in the {111} oriented QW's results in real index guiding of the optical field which, in spite of its very narrow near field distribution, exhibits a single lobe far field distribution (see FIG. 7) . The patterned QW lasers exhibit low threshold currents, as low as 6 mA for 280 μm long devices. This value is comparable to the best values (5 mA) achieved with QW GaAs/AlGaAs lasers made by a single growth step, but is still larger than the lowest value that has been achieved with buried-heterostructure (BH) QW lasers (2.5 mA for uncoated lasers at room temperature). However, lower threshold currents and higher differential efficiencies should be achievable with the patterned QW laser configuration by reducing the current leakage and optimizing the laser structure. In particular, the structure described here can be used to make lasers with substantially narrower active regions using a sharper V-groove. For sufficiently narrow active regions (a few hundred Angstroms) such lasers are expected to exhibit one dimensional (quantum wire) carrier characteristics which should lead to diode lasers with interesting and useful physical properties. Similar patterned QW lasers grown on nonplanar substrates delineated by two dimensional features might yield QW lasers with zero-dimensional carriers (quantum box lasers).
In conclusion, we have demonstrated a patterned QW heterostructure injection laser grown by MBE in which the lateral carrier confinement relies on thickness and growth plane variations of the active QW layer. This results in an effectively buried heterostructure laser than can be fabricated by a single crystal growth step. The patterned QW GaAs/AlGaAs lasers are characterized by a low threshold current, as low as 6 mA at room temperature. Furthermore, the patterned QW laser structure is suitable for obtaining semiconductor lasers with very small lateral dimensions, which should be useful in the fabrication of quantum wire and quantum box laser heterostructures. Furthermore, the low absorption in the thinner QW regions in this laser structure makes it attractive for use in phase locked arrays of semiconductor lasers.
SUBSTITUTE SHEET

Claims

What is claimed is:
1. A method for producing a thin epitaxial superlattice layer on a single crystal substrate having a thickness which varies laterally over the surface of said substrate comprising 1) patterning a planar substrate to form a nonplanar micro pattern on the surface thereof;
2) depositing an epitaxial film having a thickness of ≤500 A on said patterned substrate in a manner so as to form a superlattice having a periodicity or quantum well depth which varies laterally over said substrate. . 2. The method recited in Claim 1 wherein said pattern is etched into said substrate.
3. The method recited in Claim 2 wherein said film is deposited by molecular beam epitaxy.
4. The method recited in Claim 3 wherein said etched pattern comprises one or more grooves in the surface of said substrate causing lateral variation of growth atom flux density on said surface as well as a variation of exposed crystal planes.
5. The method recited in Claim 2 wherein a multidimensional superlattice structure is formed.
6. The method recited in Claim 5 wherein a two dimensional superlattice is formed in a manner so as to form a quantum well wire.
7. A thin superlattice heterostructure comprising a nonplanar single crystal substrate having a patterned surface and a superlattice epitaxial film of a thickness of less than about 50θA on said substrate, said superlattice characterized by a laterally varying periodicity over the pattern portion of said substrate.
8. The heterostructure recited in Claim 7 including a quantum well region capable of confining charge carriers therein.
9. The heterostructure recited in Claim 7 comprising a thin quantum well epitaxial region of low bandgap material surrounded by a higher bandgap on either side thereof.
10. The heterostructure recited in Claim 7 having multidimensional superlattice periodicity.
11. The heterostructure recited in Claim 10 having two dimensional periodicity.
12. The heterostructure recited in Claim 8 comprising a plurality of epitaxial layers having laterally varying thickness and wherein a quantum well region is provided into which charge carriers injected therein cause lasing action in said confined region of said quantum well.
13. An interferometer comprising a superlattice heterostructure on a nonplanar structure, said superlattice having a two-dimensional varying periodicity including a laterally varying periodicity to form a charge carrier confined quantum well wire, means for injecting carriers into said quantum well wire, said wire branching into two forks into
5 which said carriers are divided, said forks reunited at or before a carrier collector region, and phase modulator means coupled to at least one of said forks.
14. A heterostructure comprising a nonplanar single crystal substrate having a patterned surface and a thin epitaxial film of a thickness of less than —500 A on said substrate, said structure characterized by a laterally varying thickness in one direction
ΪΘ) along the plane of the substrate and of essentially uniform thickness in the orthogonal dfrectϊσn so as to result in a quantum well wire in said orthogonal direction.
SUBST Tϋ i «s SHEET
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US5233205A (en) * 1989-09-25 1993-08-03 Hitachi, Ltd. Quantum wave circuit
US5105232A (en) * 1989-09-26 1992-04-14 Massachusetts Institute Of Technology Quantum field-effect directional coupler
EP0423535A2 (en) * 1989-10-02 1991-04-24 Kabushiki Kaisha Toshiba Semiconductor device made by an epitaxial growth technique and method for the making of the same
EP0423535A3 (en) * 1989-10-02 1991-12-04 Kabushiki Kaisha Toshiba Semiconductor device made by an epitaxial growth technique and method for the making of the same
US5093696A (en) * 1989-10-02 1992-03-03 Kabushiki Kaisha Toshiba Semiconductor heterojunction device made by an epitaxial growth technique
EP0506453A1 (en) * 1991-03-28 1992-09-30 Sharp Kabushiki Kaisha A quantum wire structure and a method for producing the same
EP0507516A1 (en) * 1991-03-28 1992-10-07 Sharp Kabushiki Kaisha A quantum wire laser
US5280493A (en) * 1991-03-28 1994-01-18 Sharp Kabushiki Kaisha Quantum wire laser
WO1999066562A1 (en) * 1998-06-19 1999-12-23 The Secretary Of State For Defence Quantum wire field-effect transistor and method of making the same
US6753593B1 (en) 1998-06-19 2004-06-22 Qinetiq Limited Quantum wire field-effect transistor and method of making the same

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