JP4575173B2 - Manufacturing method of quantum well structure - Google Patents

Description

The present invention relates to a manufacturing method capable of easily producing a high-quality quantum well structure having a large well layer of compressive strain, for example, a semiconductor laser, be used for the active layer such as a light modulation element and optical amplifier it can.

  Conventionally, by using a strained quantum well structure having a well layer with compressive strain as the active layer of a semiconductor laser, the oscillation threshold current is reduced, the oscillation spectral line width is narrowed, and the modulation frequency is increased. It has been reported that laser characteristics are remarkably improved.

  If the amount of compressive strain in the well layer can be further increased, the laser characteristics at the oscillation threshold current, modulation frequency, etc. can be further improved by the effect of reducing non-radiative recombination by Auger recombination and the effect of increasing differential gain. Known (see Non-Patent Documents 1 and 2 below).

  When growing InGaAs or InGaAsP on a substrate, so-called two-dimensional growth in which the progress of crystal growth is layered is a prerequisite for crystal growth for device formation, but the difference in lattice constant between the substrate and the growth layer That is, when the amount of strain is large, it is known that the progress of crystal growth becomes island-like, so-called three-dimensional growth. When the compressive strain of the growth layer is increased, it is known that the amount of strain at which crystal growth changes from two-dimensional growth to three-dimensional growth is about + 1.5% (see Non-Patent Document 3 below). .

  In addition, it is known that the surface diffusion (migration) of indium, which is a group III material, greatly affects the three-dimensional growth of an InGaAs or InGaAsP well layer having the compressive strain (see Non-Patent Document 4 below). See).

  Normally, when growing InGaAs or InGaAsP lattice-matched to a substrate, it is desirable to promote the surface diffusion of indium and increase the surface diffusion length in order to obtain good crystallinity. However, when the InGaAs or InGaAsP to be grown has a compressive strain with respect to the substrate, if the indium diffusion length is long, the number of indiums reaching the defects and dislocations in the film that becomes the base point of the three-dimensional growth increases. Growth is likely to occur.

  Even in the case of growing a strained multiple quantum well structure having InGaAs or InGaAsP having compressive strain on a substrate as a well layer, if the well layer has a large compressive strain as described above, non- Problems such as the occurrence of defects that become luminescent recombination centers occur.

FIG. 4 is a schematic sectional view showing a strained multiple quantum well structure manufactured by a conventional method.
This figure schematically shows a cross section when three-dimensional growth occurs in a strained multiple quantum well structure including a well layer having a large compressive strain.

  As shown in the figure, the conventional strained multiple quantum well structure 20 is formed by laminating an InGaAsP barrier layer 14 and an InGaAs well layer 15, and an InP substrate 11 and an InP buffer layer are provided on one side of the strained multiple quantum well structure 20. 12 and an InGaAsP guide layer 13 are formed, and an InGaAsP guide layer 16 and an InP cap layer 17 are formed on the other side. As an example, four barrier layers 14 and three well layers 15 are shown.

  It is known that such three-dimensional growth of the well layer 15 becomes more significant as the compressive strain of the well layer 15 increases. Furthermore, it is known that as the number of well layers 15 increases, the strain stress accumulated in the strained multi-quantum well structure 20 increases accordingly, and the influence of the three-dimensional growth increases (described below). , See Non-Patent Document 5.)

  Therefore, in the strained quantum well structure having a well layer having a strain amount of + 1.5% or more, it is necessary to suppress the three-dimensional growth in order to suppress the generation of defects and obtain a high-quality crystal.

  In order to increase the compressive strain of the well layer, it is necessary to increase the indium composition in InGaAs or InGaAsP. However, an increase in the indium composition in InGaAs or InGaAsP causes a region having a large indium composition (indium rich region) on the surface of InGaAs or InGaAsP. Further, it is known that indium is re-evaporated from InGaAs formed in the indium-rich region, so that the indium composition in InGaAs is reduced, and InGaAs having a large indium composition, that is, InGaAs having a large compressive strain cannot be grown (see below). , See Non-Patent Document 6.)

  Therefore, in order to obtain a strained quantum well structure having a well layer with a compressive strain of + 1.5% or more, it has been necessary to suppress re-evaporation of indium from InGaAs or InGaAsP.

Wayne W. Lui et al., "Suppression of Auger Recombination Effects in Compressively Strained Quantum-Well Lasers", IEEE JOURNAL OF QUANTUM ELECTRONICS, vol. 29, No. 6, 1993, pp. 1544-1552 Shunji Seki et al., "Theoretical Analysis of Pure Effects of Strain and Quantum Confinement on Differential Gain in InGaAsP / InP Strained-Layer Quantum-Well Lasers", IEEE JOURNAL OF QUANTUM ELECTRONICS, vol.30, No.2,1994, pp .500-510 M. Gendry et al., "Critical thicknesses of highly strained InGaAsP layers grown on InP by molecular beam epitaxy", Appl. Phys. Lett., Vol. 60, No. 18, 1992, pp. 2249-2251 N. Grandjean et al., "Epitaxial growth of highly strained InXGa1-XAs on GaAs (001): the role of surface diffusion length", JOURNAL OF CRYSTAL GROWTH, vol. 134, 1993, pp. 51-62 R.W.Glew et al., "Elimination of wavy layer growth phenomena in strain-compensated GaInAsP / GaInAsP multiple quantum well stacks", JOURNAL OF CRYSTAL GROWTH, vol.145,1994, pp.764-770 F.Bugge et al., "MOVPE growth of highly strained InGaAs / GaAs quantum wells", JOURNAL OF CRYSTAL GROWTH, vol. 183, 1998, pp.511-518 Masashi Nakao et al., “Characterization of InGaAsP / InP double-heterostructure wafers grown by metalorganic vapor phase epitaxy for semiconductor lasers by photoluminescence investigation with high-power YAG-laser excitation”, J. Appl. Phys., Vol. 63, No. .5,1988, pp.1722-1728

  As described above, there is a problem that three-dimensional island-like growth occurs in a well layer made of InGaAs or InGaAsP to which a compressive strain of + 1.5% or more in a strained quantum well structure on a substrate is applied. Furthermore, since the indium composition in InGaAs or InGaAsP is reduced by re-evaporation of indium, there is a problem that a desired amount of strain cannot be obtained.

  Therefore, in order to improve the device characteristics of a semiconductor optical device such as a semiconductor laser having a strained quantum well structure and an optical modulator device, three-dimensional growth of the well layer and re-evaporation of indium atoms can be suppressed, and a high-quality crystal is obtained. There has been a strong demand for a production method that can be used.

The present invention has been made in view of the above situation, it solves the problems of the prior art, and an object thereof is to provide a method of manufacturing a quantum well structure formed of high-quality crystal. Specifically, the generation of crystal defects can be suppressed by suppressing three-dimensional growth in the well layer (for example, formed of InGaAs or InGaAsP) having a strain amount of + 1.5% or more with the substrate. , by inhibiting the re-evaporation of indium, and an object thereof is to provide a method of manufacturing a quantum well structure that is easily controlled amount of strain of the well layer.

A method for manufacturing a quantum well structure according to the present invention that solves the above-described problem is a quantum well structure formed on an InP substrate, in which a barrier layer and a well layer having different lattice constants are stacked, A quantum well structure formed of InGaAs having a compressive strain of 1.5% or more and 1.8% or less with respect to the lattice constant of the substrate, and wherein the barrier layer is formed of InGaAs , is formed by metal organic vapor phase epitaxy, molecular In the manufacturing method of the quantum well structure formed by the crystal growth method of any one of the line epitaxy method, the gas source molecular beam epitaxy method, and the chemical beam epitaxy method, the well layer is formed so that the three-dimensional growth of the well layer is suppressed . By keeping the supply rate of As raw material constant and controlling the amount of strain by controlling the Group III raw material supply ratio, the growth rate is controlled by controlling the Group III raw material supply amount to the As raw material. The main feature is that the film is formed at 0.4 nm / second or more and 0.83 nm / second or less.

The well layer and the barrier layer can be formed by, for example, a crystal growth method such as metal organic vapor phase epitaxy, molecular beam epitaxy, gas source molecular beam epitaxy, or chemical beam epitaxy. Moreover, the well layer or barrier layer, for example, can each be more formed InGaAs s.

In general, at the InGaA lattice strain of s or Ranaru well layer + 1.5% or more to above occurs three-dimensional island growth, it is difficult to further applications Debaisuhe to crystal defects occur It was. In addition, when the strain amount is + 1.5% or more, re-evaporation of indium becomes remarkable and it becomes difficult to increase the indium composition. Therefore, it is difficult to apply a strain amount of + 1.5% or more to the well layer. there were.

However, as will be described in detail in the first embodiment, if the growth rate when growing the well layer is set to 0.4 nm or more and 0.83 nm or less per second, indium which causes three-dimensional growth is promoted. it is possible to suppress the surface diffusion, it is possible to suppress the three-dimensional growth of InGaAs s or Ranaru well layer. As a result, even if the amount of compressive strain increases, a high-quality quantum well structure having an interface between a flat well layer and a barrier layer can be obtained.

Furthermore, as will be described in detail in the second embodiment, the re-evaporation of indium can be suppressed by setting the growth rate when growing the well layer to 0.4 nm or more and 0.83 nm or less per second. , even in the quantum well structure having a InGaAs s or Ranaru well layer having a compressive strain of 1.8% or less 1.5% or more, it is possible to easily control the amount of strain of the well layer.

In the conventional method for producing a strained quantum well structure having a well layer with a strain amount of + 1.5% to 1.8%, there is no regulation regarding the growth rate of the well layer, and in particular, metal organic vapor phase epitaxy method (MOVPE method) However, no method has been taken to suppress the generation of crystal defects by the growth rate of the well layer.

On the other hand, in the present invention, a quantum well having a well layer having a strain amount of + 1.5% to 1.8% by increasing the film thickness grown per second to 0.4 nm to 0.83 nm. Also in the structure, it is possible to obtain a crystal having a flat well layer / barrier layer interface and few defects (three-dimensional growth is suppressed). Further, the strain amount of the well layer can be easily controlled. If the growth rate is 0.4 nm / second or more, it is considered that these effects can be achieved. As for the upper limit value, the film formation limit value resulting from the film formation method is currently the upper limit value. Therefore, for example, in the MOVPE method, which is considered to have the highest film formation speed among the current film formation methods, the upper limit is about 3 nm / second. However, the upper limit value is attributed to the film forming method, and does not mean that the above effect is not obtained when the upper limit value is exceeded. In the future, when a film forming method, a film forming apparatus, or the like having a film forming performance equal to or higher than the upper limit is developed, it is considered that the above-described effect can be obtained even at a film forming speed higher than about 3 nm / second.

  According to the present invention, it is possible to easily produce a quantum well structure having a well layer having a high compressive strain of + 1.5% or more, which has been difficult to produce in the past, and having suppressed three-dimensional growth, This structure is extremely useful for improving device characteristics such as increasing the speed of a laser using the structure and reducing the oscillation threshold current.

<First embodiment>
FIG. 1 is a schematic sectional view showing a strained multiple quantum well structure according to an embodiment of the present invention. The first embodiment of the present invention using InGaAs having compressive strain as the well layer and InGaAs as the barrier layer will be described with reference to FIG.

  As shown in the figure, the strained multiple quantum well structure 10 according to the present embodiment is formed by laminating an InGaAs barrier layer 4 and an InGaAs well layer 5, and one of the strained multiple quantum well structures 10 includes an InP substrate 1 and An InP buffer layer (thickness 200 nm) 2 and an InGaAsP guide layer (band gap wavelength 1.3 μm, thickness 100 nm) 3 lattice-matched to the InP substrate 1 are formed, and the InGaAsP guide lattice matched to the InP substrate 1 is formed on the other side. A layer (band gap wavelength 1.3 μm, film thickness 100 nm) 6 and an InP cap layer (film thickness 100 nm) 7 are formed. This figure shows an example in which the barrier layer 4 has four layers and the well layer 15 has three layers.

As the InGaAs well layer 5, an InGaAs layer having a compressive strain and having a thickness of 10 nm was used. As the InGaAs barrier layer 4, an InGaAs layer having a tensile strain of -0.1% and a thickness of 18.5 nm was used. Crystal growth is performed by metal organic vapor phase epitaxy, and the growth temperature is 700 ° C. Further, trimethylindium (TMIn) and triethylgallium (TEGa) were used as Group III materials, and arsine (AsH ₃ ) and phosphine (PH ₃ ) were used as Group V materials.

  In general, the photoluminescence (PL) emission intensity in a laser wafer is closely related to the oscillation threshold current density, and it is known that the laser oscillation threshold current density increases as the photoluminescence emission intensity decreases. (See Non-Patent Document 7 above.) Therefore, in order to obtain good device characteristics, it is necessary to set the growth rate of the well layer in a range in which the reduction of the photoluminescence emission intensity does not occur.

  FIG. 2 is a diagram showing an example of the relationship between PL (photoluminescence) emission intensity and the growth rate of the well layer (growth film thickness per second). Regarding the strained multiple quantum well structure according to this example, FIG. It is the result of measuring the well layer growth rate dependence of photoluminescence luminescence intensity. In the figure, the horizontal axis is the growth rate (nm / second) of the well layer, and the vertical axis is the photoluminescence emission intensity (logarithmic arbitrary scale) of the strained multiple quantum well structure. The compressive strain of the well layer at this time was set to + 1.65%.

  As is clear from the figure, the photoluminescence emission intensity changes abruptly at a growth rate of 0.4 nm / second, and is weak emission intensity at a growth rate of less than 0.4 nm / second, whereas 0.4 nm / second. Strong light emission intensity is maintained at a growth rate of 2 seconds or more. Therefore, it was confirmed that if the growth rate of the well layer 5 is set to 0.4 nm / second or more, a decrease in photoluminescence intensity is prevented and a high emission intensity can be obtained.

  Furthermore, when the strain rate of the InGaAs well layer 5 is set to 0.68 nm / second and the amount of compressive strain in the InGaAs well layer 5 is increased to form the strained multi-quantum well structure 10, X-ray diffraction (XRD) and photoluminescence From the observation results, it was confirmed that a high-quality strained multiple quantum well structure was obtained without three-dimensional growth.

  On the other hand, when the well layer is grown at a growth rate of 0.35 nm / sec (0.4 nm / sec or less), the interface between the InGaAs well layer and the InGaAs barrier layer deteriorates due to the three-dimensional growth of the well layer. This was confirmed by X-ray diffraction. Furthermore, photoluminescence emission could not be confirmed. When the well layer grows three-dimensionally in this way, defects serving as non-radiative recombination centers are generated, the light emission intensity in photoluminescence is significantly reduced, and it is difficult to obtain sufficient light emission intensity.

  However, as shown in this embodiment, the three-dimensional growth in the well layer 5 can be suppressed by growing the well layer 5 at a growth rate of 0.4 nm / second or more, and as a result, the generation of crystal defects can be suppressed. Therefore, a crystal having sufficient photoluminescence emission intensity can be obtained.

  In the study in this example, the case where the growth rate of the well layer 5 was up to 0.83 nm / second was shown (see FIG. 2). Obviously, a similar effect can be obtained.

  In the study in this example, InGaAs was used as the well layer 5. However, even when InGaAsP is used as the well layer, similarly, if the growth rate of the well layer 5 is less than 0.4 nm / second, it is 3 due to strain applied to the crystal. It was confirmed that dimensional growth occurred. Then, it was confirmed that good results were obtained as in this example by setting the growth rate of the InGaAsP well layer to 0.4 nm / second or more as in this example. In this example, an InGaAs layer was used as the barrier layer, but the same effect as in this example was obtained even when an InGaAsP layer was used.

  In this example, arsine and phosphine were used as Group V materials, but the same effect was obtained using tertiary butylarsine (TBAs) and tertiary butylphosphine (TBP), which are organometallic materials. .

  In this example, each layer was grown by metal organic vapor phase epitaxy, but the same effect was obtained by using any of molecular beam epitaxy, gas source molecular beam epitaxy, and chemical beam epitaxy. .

<Second embodiment>
In the strained multiple quantum well structure according to this example, InGaAs having compressive strain is used as the well layer, InGaAsP having a tensile strain of −0.1% is used as the barrier layer, the well layer has three layers, and the barrier layer has It has a strained multiple quantum well structure with four layers and is grown by metal organic vapor phase epitaxy. Each layer portion (such as an InP substrate) other than the strained multiple quantum well structure is the same as in the first embodiment.

  As a well layer having a strained multiple quantum well structure, InGaAs having a thickness of 10 nm grown at a growth rate of 0.35 nm / second (comparative example), 0.42 nm / second, and 0.68 nm / second was used. At this time, the supply ratio of trimethylindium and triethylgallium, which are Group III materials (Group III material supply ratio (TMIn / TEGa)) is changed from 4 to 7, and the growth rate of the well layer is controlled to control the samples. Produced. The raw materials used are the same as in the first example.

  Explaining the control of the growth rate of the well layer, the flow rate of arsine is kept constant, the trimethylindium supply amount is increased, and further, the triethylgallium supply amount is adjusted so as to be a predetermined group III raw material supply amount ratio. , Controlled the growth rate. That is, the indium composition was controlled (strain control) by the group III source supply ratio, and the film formation rate was controlled by the group III source supply to arsine. First, the growth rate in the embodiment is also controlled by the same method.

  FIG. 3 is a diagram showing an example of the relationship between the amount of compressive strain in the well layer and the supply ratio of trimethylindium and triethylgallium during the growth of the well layer. This figure shows the results for a strained multiple quantum well structure in which a well layer is grown at growth rates of 0.35 nm / second, 0.42 nm / second, and 0.68 nm / second.

  Basically, at any growth rate, the amount of compressive strain in the well layer tends to increase by increasing the group III raw material supply amount ratio and increasing the indium composition. However, when the growth rate of the well layer is 0.35 nm / second, the amount of compressive strain can be increased up to + 1.5%, while the amount of strain of + 1.5% or more increases the supply amount of the group III material. It can be seen that even if the ratio of trimethylindium in the ratio is further increased, the amount of compressive strain cannot be increased.

  On the other hand, when the growth rate of the well layer is 0.42 nm / second, a well layer having a compressive strain of + 1.65% can be obtained when the group III raw material supply amount ratio is 5.6. Furthermore, when the growth rate of the well layer is increased to 0.68 nm / second, the strain amount of the well layer can be further increased by further increasing the ratio of trimethylindium in the ratio of the group III raw material supply amount. It was confirmed that it was possible.

  Therefore, by setting the growth rate of the well layer to 0.4 nm / second or more, even if the compressive strain amount of the well layer is + 1.5% or more, the strain multiquantum in which the compressive strain amount of the well layer is easily controlled. It was confirmed that a well structure can be formed.

1 is a schematic cross-sectional structure diagram showing a strained multiple quantum well structure according to an embodiment of the present invention. It is a figure which shows an example of the relationship between PL (photoluminescence) light emission intensity and the growth rate of a well layer. It is a figure which shows an example of the relationship between the amount of compressive strains of a well layer, and the supply amount ratio of trimethylindium and triethylgallium at the time of well layer growth. It is a schematic sectional drawing which shows the strain multiple quantum well structure produced by the conventional method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 InP substrate 2 InP buffer layer 3 InGaAsP guide layer 4 InGaAs barrier layer 5 InGaAs well layer 6 InGaAsP guide layer 7 InP cap layer 10 Strained multiple quantum well structure 11 InP substrate 12 InP buffer layer 13 InGaAsP guide layer 14 InGaAsP barrier layer 15 InGaAs Well layer 16 InGaAsP guide layer 17 InP cap layer 20 Strained multiple quantum well structure

Claims (1)

A quantum well structure formed on an InP substrate and formed by laminating a barrier layer and a well layer, each having a different lattice constant, wherein the well layer is 1.5% to 1.8% of the lattice constant of the substrate. % Of the quantum well structure formed of InGaAs having a compressive strain of less than 1% , and the barrier layer is formed of InGaAs. Metalorganic vapor phase epitaxy, molecular beam epitaxy, gas source molecular beam epitaxy, or chemical beam epitaxy In the method of manufacturing a quantum well structure formed by any one of the crystal growth methods,
In order to suppress the three-dimensional growth of the well layer , the supply amount of the As raw material is kept constant, the strain amount is controlled by the Group III raw material supply ratio, and the Group III raw material supply amount to the As raw material is controlled. A method for producing a quantum well structure, characterized by being formed at a growth rate of 0.4 nm / second or more and 0.83 nm / second or less by controlling .

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