CN109166788B - Method for directly epitaxially growing germanium virtual substrate on silicon substrate - Google Patents

Method for directly epitaxially growing germanium virtual substrate on silicon substrate Download PDF

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CN109166788B
CN109166788B CN201810992194.6A CN201810992194A CN109166788B CN 109166788 B CN109166788 B CN 109166788B CN 201810992194 A CN201810992194 A CN 201810992194A CN 109166788 B CN109166788 B CN 109166788B
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substrate
silicon
germanium
silicon substrate
buffer layer
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CN109166788A (en
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芦红
苗艺
魏炼
叶佳佳
宋欢欢
陈延峰
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Nanjing University
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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
    • H01L21/02373—Group 14 semiconducting materials
    • H01L21/02381—Silicon, silicon germanium, germanium
    • 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
    • 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
    • H01L21/02439—Materials
    • H01L21/02441—Group 14 semiconducting materials
    • H01L21/0245—Silicon, silicon germanium, germanium
    • 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
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • 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
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation

Abstract

The invention discloses a method for directly epitaxially growing a germanium virtual substrate on a silicon substrate. The method comprises the following specific steps: step 1, obtaining a silicon substrate with a (100) crystal face or a silicon substrate with a (111) crystal face; step 2, treating the silicon substrate with hydrofluoric acid, and then carrying out surface treatment in a vacuum environment; step 3, growing a silicon buffer layer on the processed silicon substrate by a molecular beam epitaxy method; and 4, adjusting to a proper growth temperature, and directly epitaxially growing the germanium virtual substrate with the micron-level thickness on the silicon buffer layer. The method of the invention can directly extend the germanium virtual substrate on the silicon chip, the surface of the grown germanium virtual substrate is flat, the single crystal quality is high, the crystal lattice can be completely relaxed, and the germanium virtual substrate can replace the germanium substrate to be used for the growth of subsequent materials. The method does not need to adopt a layer-by-layer growth mode for gradually increasing the germanium content, the preparation process is simpler, and the cost can be reduced.

Description

Method for directly epitaxially growing germanium virtual substrate on silicon substrate
Technical Field
The invention relates to a method for directly epitaxially growing a germanium virtual substrate on a silicon substrate, in particular to optimization of growth conditions of a directly epitaxial high-quality germanium virtual substrate on the silicon substrate, which comprises the processes of substrate processing, buffer layer growth and germanium virtual substrate growth temperature optimization.
Background
Silicon (Si) and germanium (Ge) are the most common semiconductor materials and are also important electronic component materials. The silicon-based germanium epitaxial material can be used as a new material for silicon-based high-speed circuit research and is a preferred material for silicon-based long-wavelength photodetectors.
In addition, the germanium is matched with the GaAs material in lattice mode, and the silicon-based germanium epitaxial material can be used as a virtual substrate of materials such as silicon-based GaAs and the like, and has important application prospects in the aspects of silicon-based photoelectric integration, silicon-based high-efficiency solar cell development and the like.
But the lattice mismatch degree of germanium and silicon is more than 4%, so that the realization difficulty of the silicon-based Ge virtual substrate technology is high. From the main technical specifications of Ge epilayers obtained by direct epitaxy on silicon substrates, the following problems exist:
1) the surface roughness of the Ge epitaxial layer is large, so that the growth of a III-V group heterostructure on a subsequent Ge buffer layer is not facilitated;
2) the dislocation density of the Ge epitaxial layer is high, so that the performance of the device is degraded when the Ge epitaxial layer is applied to a photoelectric device.
And the germanium substrate is expensive. Therefore, the development and optimization of the process for preparing the high-quality Ge epitaxial layer on the silicon substrate have important application value.
The existing method for extending a germanium virtual substrate on a current silicon substrate is as follows: firstly, growing a germanium-silicon alloy with low germanium content on a silicon wafer, and then continuously increasing the layer-by-layer growth mode of the germanium content. The method is complex to operate, needs to change the germanium-silicon ratio continuously, and is time-consuming and high in cost.
Disclosure of Invention
The invention aims to provide a method for directly epitaxially growing a germanium virtual substrate on a silicon substrate, and the growing method has the advantages of simpler preparation process and lower cost.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for directly epitaxially growing a germanium virtual substrate on a silicon substrate comprises the following specific steps:
step 1, obtaining a silicon substrate with a (100) crystal face or a silicon substrate with a (111) crystal face;
step 2, treating the silicon substrate with hydrofluoric acid, and then carrying out surface treatment in a vacuum environment;
step 3, growing a silicon buffer layer on the silicon substrate after surface treatment by a molecular beam epitaxy method;
and 4, adjusting to a proper growth temperature, and directly epitaxially growing the germanium virtual substrate with the micron-level thickness on the silicon buffer layer.
Preferably, in the step 2, the surface treatment is performed on the silicon substrate with the (100) crystal plane at the temperature of 500-600 ℃. The treatment time is 5-10 minutes.
Preferably, in the step 2, the surface treatment is carried out on the silicon substrate with the (111) crystal face at the temperature of 800-1000 ℃. The treatment time is 5-10 minutes.
Further, in the step 3, the growth thickness of the silicon buffer layer is 20-50 nm. The growth temperature of the silicon buffer layer is 400-600 ℃.
Further, in the step 4, a suitable growth temperature is 200 ℃.
The invention provides a novel preparation method of the germanium virtual substrate by directly epitaxially growing the germanium virtual substrate on the silicon substrate, and has the following advantages:
(1) the germanium virtual substrate prepared by the method has flat surface and high single crystal quality, can be completely relaxed, can replace a germanium substrate, and is used for the growth of subsequent materials.
(2) Both silicon (100) and silicon (111) substrates treated by the method of the present invention can achieve atomic level flatness.
(3) The mode of low-temperature (200 ℃) growth is beneficial to reducing stress caused by thermal mismatch among different films, so that the defect generation is reduced.
(4) The surface of the germanium virtual substrate prepared by the method is flat, the roughness of the silicon (100) epitaxial germanium virtual substrate is 988pm, and the roughness of the silicon (111) epitaxial germanium virtual substrate is 880 pm; and the interface between the silicon substrate and the germanium virtual substrate is clear.
(5) The method can directly epitaxially grow the germanium virtual substrate on the silicon substrate without growing in a layer-by-layer growth mode of gradually increasing the germanium content, so that the preparation process is simpler and the cost is lower.
Drawings
FIG. 1 is a schematic structural diagram of a germanium dummy substrate epitaxially grown directly on a silicon substrate according to the present invention.
FIG. 2 is an X-ray diffraction pattern of (a) a germanium virtual substrate grown epitaxially directly on a silicon (100) substrate in an embodiment of the present invention; (b) the X-ray diffraction pattern of a germanium dummy substrate was epitaxially grown directly on a silicon (111) substrate.
FIG. 3 is an atomic force microscope image of (a) a virtual substrate of germanium grown epitaxially directly on a silicon (100) substrate in an embodiment of the present invention; (b) atomic force microscopy images of germanium virtual substrates were grown epitaxially directly on silicon (111) substrates.
Fig. 4 is an X-ray reversed spatial diffraction pattern of a germanium dummy substrate grown epitaxially directly on a silicon (100) substrate in an embodiment of the present invention.
FIG. 5 is a cross-sectional scanning electron microscope image of (a) a germanium virtual substrate grown epitaxially directly on a silicon (100) substrate in an embodiment of the present invention; (b) cross-sectional scanning electron microscopy of a germanium dummy substrate grown epitaxially directly on a silicon (111) substrate.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The invention provides a method for directly epitaxially growing a germanium virtual substrate on a silicon substrate through molecular beam epitaxy. Fig. 1 is a schematic structural diagram of a germanium virtual substrate in this embodiment, and a specific preparation method is as follows:
the (100) and (111) crystal plane silicon substrates are first surface-treated by solid-state source molecular beam epitaxy. Conveying the silicon substrate treated by hydrofluoric acid into a vacuum chamber, keeping the substrate rotating, and raising the substrate heater to 500-600 ℃ for the silicon (100) substrate and keeping the temperature for 5-10 minutes; for a silicon (111) substrate, the substrate heater was raised to 800-.
And then growing a 30nm thick silicon buffer layer on the processed silicon substrate by a molecular beam epitaxy method. The growth temperature of a silicon buffer layer on a silicon (100) substrate is 400 ℃; the growth temperature of the silicon buffer layer on the silicon (111) substrate was 550 ℃. The silicon source furnace used in this example was an electron beam evaporation source, and the growth rate of silicon was changed by changing the excitation current.
And finally, growing a germanium virtual substrate on the silicon buffer layer by a molecular beam epitaxy method. The growth temperature here is chosen to be 200 ℃ and the growth rate is
Figure BDA0001781040200000031
The Ge source furnace is a thermal evaporation source furnace, and the growth rate of Ge is changed by changing the temperature of the source furnace.
The X-ray diffraction patterns of this example for direct epitaxial growth of germanium virtual substrates on silicon (100) and silicon (111) substrates are shown in fig. 2(a) and (b), respectively. The peak of the germanium virtual substrate in the X-ray diffraction pattern is symmetrical and the intensity is high. The full width at half maximum of the germanium peak in fig. 2(a) is 0.1412 °, and the full width at half maximum of the germanium peak in fig. 2(b) is 0.0556 °, which indicates that the quality of the germanium virtual substrate single crystal grown in this embodiment is high. FIGS. 3(a) and (b) are atomic force microscope images of the germanium virtual substrate directly epitaxially grown on the silicon (100) and silicon (111) substrates in this example, respectively, and it can be seen that the surface waviness of both samples is of pm order, wherein the roughness of the silicon (100) epitaxial germanium virtual substrate is 988pm, and the roughness of the silicon (111) epitaxial germanium virtual substrate is 880 pm; this indicates that the germanium dummy substrate surface is very flat.
Fig. 4 is an X-ray reversed spatial diffraction pattern of a germanium growth dummy substrate directly epitaxially on a silicon (100) substrate, the germanium dummy substrate shown in a fully relaxed state.
FIGS. 5(a) and (b) are cross-sectional scanning electron microscope images of the germanium dummy substrate of the present embodiment epitaxially grown directly on a silicon (100) substrate and a silicon (111) substrate, respectively, in which it can be seen that the thickness of the germanium dummy substrate epitaxial with silicon (100) is 1.21 μm; the thickness of the silicon (111) epitaxial germanium virtual substrate is 1.11 μm, reaching the micrometer scale.
According to the characteristics, the germanium virtual substrate directly epitaxially grown on the silicon chip has good quality and smooth surface, is completely relaxed, and can replace the germanium substrate for the growth of subsequent materials.

Claims (3)

1. A method for directly epitaxially growing a germanium virtual substrate on a silicon substrate is characterized by comprising the following specific steps: step 1, obtaining a silicon substrate with a (100) crystal face or a silicon substrate with a (111) crystal face; step 2, treating the silicon substrate with hydrofluoric acid, and then carrying out surface treatment in a vacuum environment; step 3, growing a silicon buffer layer on the silicon substrate after surface treatment by a molecular beam epitaxy method; the growth thickness of the silicon buffer layer is 20-50 nm; step 4, adjusting the silicon buffer layer to a proper growth temperature, and then directly epitaxially growing a germanium virtual substrate with a micron-level thickness on the silicon buffer layer; growing a germanium virtual substrate on the Si buffer layer by a molecular beam epitaxy method, wherein the selected growth temperature is 200 ℃; in the step 2, the surface treatment is carried out on the silicon substrate with the (100) crystal face at 500-600 ℃, and the surface treatment is carried out on the silicon substrate with the (111) crystal face at 800-1000 ℃; in the step 3, for the silicon substrate with the (100) crystal plane and the silicon substrate with the (111) crystal plane, the growth temperature of the silicon buffer layer is 400-600 ℃.
2. The method for directly epitaxially growing a germanium virtual substrate on a silicon substrate according to claim 1, wherein the surface treatment time is 5 to 10 minutes for the (100) crystal plane silicon substrate.
3. The method for directly epitaxially growing a germanium dummy substrate on a silicon substrate as claimed in claim 1, wherein the surface treatment time is 5 to 10 minutes for the (111) plane silicon substrate.
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Citations (2)

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US20020185686A1 (en) * 2001-06-12 2002-12-12 International Business Machines Corporation Relaxed SiGe layers on Si or silicon-on-insulator substrates by ion implantation and thermal annealing
CN101459061A (en) * 2009-01-07 2009-06-17 清华大学 Preparation for relaxation thin SiGe virtual substrate

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US20020185686A1 (en) * 2001-06-12 2002-12-12 International Business Machines Corporation Relaxed SiGe layers on Si or silicon-on-insulator substrates by ion implantation and thermal annealing
CN101459061A (en) * 2009-01-07 2009-06-17 清华大学 Preparation for relaxation thin SiGe virtual substrate

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Surfactant-Controlled Solid Phase Epitaxy of Germanium on Silicon;H. J. Osten et.al;《PHYSICAL REVIEW LETTERS》;19920720;第69卷(第3期);第450-453页 *
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