GB2202371A - Molecular beam epitaxy - Google Patents

Molecular beam epitaxy Download PDF

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GB2202371A
GB2202371A GB08706194A GB8706194A GB2202371A GB 2202371 A GB2202371 A GB 2202371A GB 08706194 A GB08706194 A GB 08706194A GB 8706194 A GB8706194 A GB 8706194A GB 2202371 A GB2202371 A GB 2202371A
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layer
plane
growth
substrate
gaas
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GB8706194D0 (en
Inventor
Toshiro Hayakawa
Takahiro Suyama
Masafumi Kondo
Kohsei Takahashi
Saburo Yamamoto
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Sharp Corp
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Sharp Corp
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Priority to DE19873709134 priority patent/DE3709134A1/en
Publication of GB8706194D0 publication Critical patent/GB8706194D0/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02387—Group 13/15 materials
    • H01L21/02392—Phosphides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02387—Group 13/15 materials
    • H01L21/02395—Arsenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02387—Group 13/15 materials
    • H01L21/02398—Antimonides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/02433—Crystal orientation
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02455—Group 13/15 materials
    • H01L21/02463—Arsenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02494—Structure
    • H01L21/02496—Layer structure
    • H01L21/0251—Graded layers
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/02546—Arsenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02576—N-type
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02579—P-type
    • H—ELECTRICITY
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Chemical & Material Sciences (AREA)
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  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Semiconductor Lasers (AREA)

Abstract

A semiconductor epitaxial layer is formed by misorienting the planar azimuth of single-crystal substrate by 0.1 to 1 degree from plane (111)B and forming the layer by molecular beam epitaxy. The method is described as applied to the fabrication of a GRIN-SCH semiconductor laser of improved quality.

Description

Semiconductor device BACKGROUND OF THE INVENTION 1. Field of the Invention: This invention relates to a semiconductor device fabricated by forming a high-quality epitaxial layer on a single-crystal substrate by MBE (molecular beam epitaxy) method.
2. Prior Art: Recently progress of MBE growth technology is remarkable, and it is possible to control an extremely: th-in-epitaxial layer in the order of monomolecular layer order of 10 or less. This progress in MBE growth technology is also seen in the field of semiconductor devices, and has enabled fabrication of semiconductor device utilizing a new effect based on an element structure having an extremely thin layer which was hard to fabricated in the conventional liquid phase epitatial growth (LPE) process. As typical example, GaAs/AlGaAs quantum well (QW) laser is known.
This QW laser depends on the phenomenon that an quantization order is formed in the active layer by controlling the active layer thickness under 100 A as compared with more than several hundred in the conventional double hetero junction (DH) laser, and it has many advantages, such as lower threshold current than in the conventional DH laser, good temperature characteristic, and excellent transient characteristic.
The following references are known concerning this technology: (1) W. T. Tsang, Physics Letters, vol. 39, No. 10, p. 786 (1981).
(2) N. K. Dutta, Journal of Applied Physics, vol. 53, No. 11, p. 7211 (1982).
(3) H. Iwamura, T. Saku, T. Ishibashi, K. Otsuka, Y.
Horikoshi, Electronics Letters, vol. 19, No. 5, p. 180 (1983).
Another representative semiconductor device fabricated by the MBE method is a field effect transistor (FET) utilizing the high mobility characteristic of secondary electron gas formed on the boundary of GaAs and AlGaAs (T. Mimura, et al., Japn. J. Appl.
Phys., vol. 19, p. L225, 1980). When fabricating these semiconductor devices by MBE method, it is known that the crystalline property of growth layer significantly affects the element characteristic. Especially in the element of GaAs/AlGaAs compound, since the crystalline property of AlGaAs including Al greatly depends on the growth condition, it is important to improve the crystalline property of AlGaAs (W. T. Tsang, et al., Appl. Phys. Lett., vol. 36, p. 118, 1980).
SUMMARY OF THE INVENTION In the light of the above-discussed situation, this invention is intended to present a semiconductor device small in threshold current and excelling in temperature characteristic and transient characteristic by improving the crystalline property of the epitaxial layer developed by epitaxial growth employing the MBE method.
The present inventors, with the purpose of im-proving the crystalline property of epitaxial layer grown by MBE method, evaluated the crystalline property of epitaxial layer by developing AlxGa1-xAs (x = 0.2 to 0.8) on GaAs substrates differing in planar azimuth.
As a result, it was found that, a high quality epitaxial growth layer of a perfect mirror-smooth surface was obtained on the conventionally used plane (001) at substrate temperature of 7200C or higher, only an unsmooth growth layer was obtained on the planes (011) and (111)B. Furthermore, on the substrate of plane (111)B, as shown in FIG. 1, at the time of etching with mixed solution of sulfuric acid, aqueous hydrogen peroxide and water before growth, runs were formed in the peripheral area of substrate, and an off plane with the angle continuously misoriented from the plane (111)B was formed, and a similar growth was developed. At this time, a similar growth was made on an exactly (001)-oriented substrate, and the both were compared.As shown in FIG. 2, an Alo.#Gao.3As layer 32 of 2 ijm in thickness was grown on a GaAs substrate 31, a GaAs quantum well layer 33 of 80 in thickness was formed on it, and further an Alo.7Gao.3As layer 34 of 1000 in thickness was grown on it, and the crystalline form of Alo.7Gao.3As layer 32 was evaluated from the luminescent characteristic of the quantum well layer 33.
As far as the misorientation angle from the plane (111)B of the planar azimuth of GaAs substrate 31 was in a range of 0.1 to 1 degree, a growth surface homology of a perfectly mirror-smooth surface was obtained, but out of this range, whether at greater side or smaller side, only unsmooth surfaces were obtained. By exciting with Ar laser beam of 514.5 nm, when the efficiency of photoluminescence at room temperature was measured in the quantum well layer 33, as shown in FIG. 3, as far as the misorientation angle was in a range of 0.1 to 1 degree, a luminescent efficiency higher by one order or more than that of other regions was obtained, and it has been confirmed that the growth layer of this portion possesses a high quality.At the same time, by growing on the substrate of plane (001), a mirror-smooth growth was obtained, but the intensity of luminescence from the quantum well layer 33 was in the same order as that of the unsmooth growth layer on the plane (111), and it has been found that the luminescence is outstandingly excellent in the mirrorsmooth growth portion on the plane misoriented from the plane (111)B. That the luminescent efficiency of the unsmooth growth part on the plane (111)B is relatively high, being nearly equal to that on the plane (001), is because the unsmooth surface is caused by formation of local surface defects, and the surface is perfectly mirror-smooth except for such surface defect parts, and the luminescence on this surface is strong.
It has been thus found possible to grow at high quality on the plane misorietnted 0.1 to 1 degree from the plane (111)3, and high quality epitaxial growth was possible on the peripheral part of the substrate on which runs were formed, regardless of the direction.
From this it has been known that the direction of misorientation does not matter.
This invention is to obtain, being based on the above discovery, a high-performance device by using an epitaxial layer of MBE growth on a substrate of which planar azimuth is misoriented 0.1 to 1 degree form the plane (111)B.
Therefore, according to this invention, the epitaxial layer may be improved in quality, and a semiconductor device possessing excellent characteristics such as small threshold current may be obtained.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic sectional view of a GaAs substrate used for investigating the dependency of substrate of epitaxial layer on the planar azimuth; FIG. 2 is a schematic sectional view of a structure grown for evaluation of epitaxial layer; FIG. 3 is an explanatory diagram to show the dependency on misorientation angle from the plane plane of the photoluminescent efficiency from a quantum well layer; FIG. 4 is a schematic sectional view of a semiconductor laser fabricated as an embodiment of this invention; ; FIG. 5 (a) shows a threshold current density distribution of a semiconductor laser fabricated on the 0.5-degree off plane (111)B as an embodiment of this invention and (b) shows, for reference, a threshold current density distribution of a semiconductor layer fabricated simultaneously on a conventional substrate of plane (100); and FIG. 6 is a schematic sectional view of a semiconductor layer in another embodiment of this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now to the drawings, some of the embodiments of this invention are described below.
As one of the embodiments of the present invention, a sectional structural drawing of GRIN-SCH (graded index separate confinement heterostructure) type semiconductor layer is shown in FIG. 4. On an n-GaAs substrate (Si: 1018cm'3 dope) 1 misoriented by 0.5 degree from the plane (111)B to the plane (110), n-GaAs buffer layer 2 (0.5 pom), n-AlyGa #yAs compositionally grated buffer layer 12 iy, continuously increasing from 0.1 to 0.7, 0.2 m), n-Al0.7Ga0.3As clad layer 3 (1 pom), undoped AlxGa1#xAs optical guide layer 4 (0.15 pom), undoped GaAs quantum well layer 5 (70 A), undoped AlxGa1-xAs optical guide layer 6 (0.15 m), pAlo.#Ga0.s Ga clad layer 7 (1 m), and p-GaAs cap layer 8 (0.5 pm) were formed continuously by MBE growth. The dopant was Si=101 8 cm for type and Be=1018 cm for p-type.
The maximum clad speed was 1.4 pm/h in the clad layer.
The group V/III flux ratio was 3. By way of comparison, n-GaAs substrates of just planes (100), (111)B were glued to Mo holders, and grown simultaneously to compare with the embodiment.
The optical guide layers 4 and 6 were varied so that the Al mixing ratio could change in parabollic distribution from 0.7 to 0.2, from the clad layers 3 and 7 to the quantum well layer 5. After the growth, an ohmic electrode was formed by evaporating and alloying AuGe-Ni layer 11 to the n-side and AnZn layer 10 to the p-side. From these wafers, a full surface electrode type laser having resonator length of 490 pm and width of 150 to 200 pm was fabricated. FIG. 5 (a) shows the distribution of threshold current density per bar of the element on (111)B 0.5-degree off plane substrate in the embodiment of this invention, and FIG. 5 (b) shows that of the element on the substrate of plane (100) fabricated by way of comparison.The mean threshold current density Jth was 178 A/cm2 on the (111)B 0.5-degree off plane, which was lower than 201 A/cm2 on plane (100). The minimum Jth on the (111)3 0.5-degree off plane was 166 A/cm2, which was the lowest value ever reported.
For reference, the following values have been reported about the resonator length L of similar structure.
1) Jth = 170 A/cm2 (L = 500 pm): R. I. Burnham, W.
streifer, T. L. Paoli, and N. Holonyok, Jr., J.
Crystal Growth, vol. 68, p. 370 (1984).
2) Jth = 175 A/cm2 (L - 450 m): T. Fuji, S.
Hiyamizu, S. Yamakoshi, and T. Ishikawa, J.
Vac. Sci. Technol. vol. B3, p. 776 (1985).
In these example, the quantum well width was narrow, that is, 60 , and the present inventors obtained Jth = 166 A/cm2 at quantum well width of 60 A on the (100) just substrate, so that a further lower threshold value will be obtained by decreasing the quantum well width on the 0.5-degree off substrate of plane (111)B.
Incidentally, in all elements on the (111)B just plane, the Jth was over 300 A/cm2, and the surface was not smooth.
As other embodiment of this invention, a schematic sectional view of an electrode stripe type semiconductor layer is shown in FIG. 6. Similar to the above embodi ment, on an n-GaAs substrate 1 misoriented 0.5 degree from the plane (111)B, n-GaAs buffer layer 2 (0.5 pm), n-AlyGa1#yAs compositionally grated buffer layer 12 (y = 0.1 to 0.7, 0.2 pm), n-Alo.#Gao.sAs clad layer 3 (1 m), undoped AlxGa1#xAs optical guide layer 4 (x = 0.7 to 0.2, 0.2 pom), undoped multiple quantum well region 21, undoped AlxGa1#xAs optical guide layer 5 (x = 0.2 to 0.7, 0.2 pm), pAlo.#Gao.3As clad layer 7 (1 pm), p-GaAs cap layer 8 (0.5 pom), and n-Alo.#Gao.sAs current blocking layer 9 (0.8 pm) were formed continuously by MBE growth. By way of comparison, a similar growth was simultaneously formed on the substrate of plane (100). The dopants and growth conditions were same as in the previous embodiment. The MQW multiple quantum well region is composed of four GaAs quantum layers of 70 in width and three Al0.2Ga0.8As barrier layers of O 40 A in width. After growth, the current blocking layer 9 was selectively removed in a stripe form of 5 pm in width by hydrofluoric acid (he), and current stripes 20 were formed, and an ohmic electrode was formed by evaporating and alloying AuGe-Ni layer 11 to the n-side and AuZn layer 10 to the p side.This laser, in the case of resonator length of 250 pm, oscillated at a low threshold current Ith = 49 - 58 mA (as converted to full surface electorde, Jth = 375 to 444 A/cm2). The element on the plane (100) was high in threshold current, that is, Ith = 60 - 75 mA (as converted to full surface electron=, Jth = 460 - 574 A/cm2).
As clear from the embodiments illustrated hereabove, by this invention, the threshold current of quantum well semiconductor layer was notably decreased as compared with that of the conventional plane (100) substrate.
The above embodiments related to examples of AlGaAs type quantum well semiconductor laser, but the fundamental phenomenon of this invention is based on the essential growth mechanism of MBE growth of group III-V compound semiconductor, and this invention can be applied to any other group III-V semiconductor devices fabricated by MBE growth. For example, this example may be applied to GaAs/AlGaAs fabricated on GaAs substrate, two-dimensional electron gas field effect transistor, InAlAs/InGaAs layer in Inp substrate, etc.
Having described specific embodiments of this invention, it is believed obvious that modification and variation of this invention are possible in the light of above technique.

Claims (5)

  1. CLAIMS:
    (1) A semiconductor device fabricated by forming an epitaxial layer on a single-crystal substrate by molecular beam epitaxy method, wherein the planar azimuth of said single-crystal substrate is misoriented from plane (111)B in a range of 0.1 to 1 degree.
  2. (2) A semiconductor device as set forth in claim 1, wherein said single-crystal substrate is composed of any one of GaAs, GaSb, InAs, InP, GaP, and InSb.
  3. (3) A semiconductor device as set forth in claim 1, wherein said epitaxial layer is a group III--IV compound semiconductor.'
  4. 4. A semiconductor device substantially as hereinbefore described with reference to figure 4 of the accompanying drawings.
  5. 5. A semiconductor device substantially as hereinbefore described with reference to figure 6 of the accompanying drawings.
GB8706194A 1985-10-14 1987-03-16 Semiconductor device Expired GB2202371B (en)

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JP60229382A JPS6288318A (en) 1985-10-14 1985-10-14 Semiconductor device
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DE19873709134 DE3709134A1 (en) 1985-10-14 1987-03-20 SEMICONDUCTOR COMPONENT

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0402136A2 (en) * 1989-06-07 1990-12-12 Sharp Kabushiki Kaisha Semiconductor device having multiple epitaxial layers
CN100453690C (en) * 2006-07-21 2009-01-21 哈尔滨工业大学 Molecular beam epitaxy process of growing GaAs-base InSb film

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2708156B2 (en) * 1987-07-27 1998-02-04 シャープ株式会社 Method for manufacturing semiconductor device
JP2750856B2 (en) * 1987-11-12 1998-05-13 シャープ株式会社 Semiconductor device
JP2674043B2 (en) * 1987-12-11 1997-11-05 ソニー株式会社 Epitaxial growth method
JP3129112B2 (en) * 1994-09-08 2001-01-29 住友電気工業株式会社 Compound semiconductor epitaxial growth method and InP substrate therefor
DE102011087628A1 (en) * 2011-12-02 2013-06-06 Bosch Mahle Turbo Systems Gmbh & Co. Kg loader

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0214610A2 (en) * 1985-09-03 1987-03-18 Daido Tokushuko Kabushiki Kaisha Epitaxial gallium arsenide semiconductor wafer and method of producing the same
GB2180689A (en) * 1985-07-20 1987-04-01 Plessey Co Plc Method of producing a heterostructure device

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
US3325314A (en) * 1961-10-27 1967-06-13 Siemens Ag Semi-conductor product and method for making same
US3379584A (en) * 1964-09-04 1968-04-23 Texas Instruments Inc Semiconductor wafer with at least one epitaxial layer and methods of making same
US3476592A (en) * 1966-01-14 1969-11-04 Ibm Method for producing improved epitaxial films

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2180689A (en) * 1985-07-20 1987-04-01 Plessey Co Plc Method of producing a heterostructure device
EP0214610A2 (en) * 1985-09-03 1987-03-18 Daido Tokushuko Kabushiki Kaisha Epitaxial gallium arsenide semiconductor wafer and method of producing the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0402136A2 (en) * 1989-06-07 1990-12-12 Sharp Kabushiki Kaisha Semiconductor device having multiple epitaxial layers
EP0402136A3 (en) * 1989-06-07 1991-01-16 Sharp Kabushiki Kaisha Semiconductor device having multiple epitaxial layers
US5027169A (en) * 1989-06-07 1991-06-25 Sharp Kabushiki Kaisha Semiconductor device with substrate misorientation
CN100453690C (en) * 2006-07-21 2009-01-21 哈尔滨工业大学 Molecular beam epitaxy process of growing GaAs-base InSb film

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GB2202371B (en) 1991-03-20
DE3709134A1 (en) 1988-09-29
GB8706194D0 (en) 1987-04-23
JPS6288318A (en) 1987-04-22

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