CN109920723B - Preparation method of self-supporting germanium film and germanium film - Google Patents
Preparation method of self-supporting germanium film and germanium film Download PDFInfo
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- CN109920723B CN109920723B CN201910088551.0A CN201910088551A CN109920723B CN 109920723 B CN109920723 B CN 109920723B CN 201910088551 A CN201910088551 A CN 201910088551A CN 109920723 B CN109920723 B CN 109920723B
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Abstract
The invention provides a preparation method of a self-supporting germanium film, which comprises the following steps: providing a silicon substrate; performing electrochemical etching on the silicon substrate to generate uniform and compact nano porous holes on the silicon substrate to obtain a nano porous silicon substrate; depositing a germanium film on the nano porous silicon substrate; carrying out high-temperature annealing on the nano porous silicon after the germanium film is epitaxially grown, and connecting cavities in series and in parallel at a germanium-silicon heterojunction interface; and stripping the germanium film from the nano porous silicon substrate. The embodiment of the invention provides a preparation method of a self-supporting germanium film, which is simple and feasible in preparation process and effectively reduces the cost for manufacturing the germanium film.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a preparation method of a self-supporting germanium film and the germanium film.
Background
As is well known, germanium, which is used as an infrared optical material, has the advantages of high infrared refractive index, wide infrared transmission band range, small absorption coefficient, low dispersion rate, easiness in processing, flashing, corrosion and the like, and is particularly suitable for thermal imagers, infrared radars and other infrared optical devices in military industry and major civil use; the high-purity germanium or germanium lithium is used for astronomy gamma-spectrometers, nuclear reaction energy spectrometers and plasma physical X-ray instruments; Si-Ge 10 and germanium single crystal doped with mercury, cadmium, copper and gallium are used for infrared detector. The GaAs/Ge solar cell manufactured by using germanium as a substrate has the performance close to that of a GaAs/GaAs cell, higher mechanical strength and larger area of a single cell. In the space application environment, the radiation-resistant threshold is higher than that of a silicon battery, the performance degradation is small, the application cost of the silicon battery is close to that of a silicon battery plate with the same power, and the silicon battery plate is applied to various military satellites and partial commercial satellites and gradually becomes a main space power supply. The property of germanium metal to pass infrared radiation of 2-15 microns is used in gamma radiation detectors.
The Ge material has small transmission loss in mid-infrared band light, can be used for preparing Ge-based integrated photoelectrons and has important application in the fields of medicine, biosensing and the like. Because many chemical and biological molecules have unique and strong absorption spectra in the mid-infrared band, and silicon dioxide have obvious absorption peaks in the mid-infrared band, germanium has good application prospect in the band. According to the characteristics, the germanium-based optoelectronic device and the system can be applied to the aspects of environmental pollution detection, toxic gas detection, industrial process detection, medical care, noninvasive detection (superior to blood detection), real-time seawater pollution detection and the like.
However, because the cost of the germanium thin film manufacturing process is relatively high, the germanium-based integrated photovoltaic system is mainly processed and manufactured by depositing the germanium thin film on the silicon substrate at present.
Disclosure of Invention
In order to overcome the problem that the cost of the preparation process of the germanium film is higher, the invention provides a preparation method of the self-supporting germanium film.
The invention provides a preparation method of a self-supporting germanium film, which comprises the following steps:
providing a silicon substrate;
performing electrochemical etching on the silicon substrate to generate uniform and compact nano porous holes on the silicon substrate to obtain a nano porous silicon substrate;
depositing a germanium film on the nano porous silicon substrate;
carrying out high-temperature annealing on the nano porous silicon after the germanium film is epitaxially grown, and connecting cavities in series and in parallel at a germanium-silicon heterojunction interface;
and stripping the germanium film from the nano porous silicon substrate.
Preferably, the silicon substrate is subjected to electrochemical etching, so that uniform and dense nano-porous holes are generated on the silicon substrate, and a nano-porous silicon substrate is obtained, specifically:
placing the silicon substrate at an anode of an etching device; wherein the cathode of the etching device is an inert platinum electrode; the etching solution in the etching device is a mixed solution of 49% HF solution and 98% alcohol, the volume ratio is 1:1, the anode is used for being connected with the positive pole of a power supply, and the cathode is used for being connected with the negative pole of the power supply;
and etching the silicon substrate for a preset time, so that uniform and compact nano porous holes are generated on the silicon substrate, and the nano porous silicon substrate is obtained.
Preferably, the predetermined time is 2 to 30 minutes.
Preferably, uniform and dense nano holes are formed by controlling the defect distribution, the current magnitude and the concentration of the etching solution of the silicon substrate.
Preferably, the size of the nano-pores is 5nm to 50 nm.
Preferably, the thickness of the germanium film deposited on the nanoporous silicon substrate is 1 μm.
Preferably, the high-temperature annealing adopts cyclic rapid thermal annealing, and the annealing temperature is 500-600 degrees.
Preferably, after the germanium film is epitaxially grown on the nanoporous silicon, high-temperature annealing is performed, and the cavities at the interface of the germanium-silicon heterojunction are serially connected in parallel:
through annealing, the nano holes of the nano porous silicon substrate can deform, the holes at the position close to the heterojunction can become large, and the holes are connected in series and parallel to a certain extent.
A second embodiment of the present invention provides a germanium film prepared by the method for preparing a self-supporting germanium film as described in any one of the above.
The embodiment of the invention provides a preparation method of a self-supporting germanium film, which is characterized in that after a silicon substrate is provided, the silicon substrate is etched to form a nano hole, a germanium film is generated on the nano hole and is subjected to high-temperature fire treatment, and the germanium film is made to fall off from the silicon substrate due to different thermal expansion coefficients of silicon and germanium.
Drawings
FIG. 1 is a schematic view of a manufacturing process according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a silicon substrate according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of an etching apparatus according to an embodiment of the present invention;
FIG. 4 is a schematic view of a nanopore structure on a silicon substrate according to an embodiment of the invention;
FIG. 5 is a schematic diagram of a structure of a germanium film grown on a nanopore according to an embodiment of the invention;
FIG. 6 is a schematic diagram of a series-parallel configuration of nano-holes in a silicon substrate according to an embodiment of the present invention;
FIG. 7 is a schematic diagram of a structure for stripping a germanium film on a nanoporous silicon substrate according to an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In order to overcome the problem that the cost of the preparation process of the germanium film is higher, the invention provides a preparation method of the self-supporting germanium film.
Referring to fig. 1, the present invention provides a method for preparing a self-supporting germanium film, comprising:
s101, a silicon substrate 10 is provided.
Wherein, the silicon substrate 10 has a thermal expansion coefficient of only 0.5 × 10 as shown in FIG. 2-6/℃。
S102, performing electrochemical etching on the silicon substrate 10 to generate uniform and compact nano porous holes 10 on the silicon substrate 10 to obtain a nano porous silicon substrate;
when preparing a nano porous silicon substrate, firstly, placing the silicon substrate 10 on an anode of an etching device shown in fig. 3, wherein a cathode of the etching device can adopt an inert platinum electrode, and an etching solution in the etching device is a mixed solution of 49% HF solution and 98% alcohol, and the volume ratio is 1: 1; the anode is connected with the positive pole of the power supply, and the cathode is connected with the negative pole of the power supply.
In this embodiment, when the power supply is switched on for etching, the silicon substrate 10 undergoes an oxidation reaction at the anode of the etching apparatus, loses electrons, and the inert platinum electrode undergoes a reduction reaction at the cathode of the etching apparatus, so as to obtain electrons. In this way, when the silicon substrate 10 is etched for a predetermined time, uniform and dense nanoporous holes 20 can be generated on the silicon substrate 10, i.e. the nanoporous silicon substrate as shown in fig. 4 is obtained.
Preferably, the uniform and dense nano-holes 20 can be formed by controlling the defect distribution, the current level, and the concentration of the etching solution of the silicon substrate 10.
Preferably, the predetermined time is 2 to 30 minutes.
Preferably, the size of the nano-holes 20 is 5nm to 50 nm.
In this embodiment, the size of the nano-holes on the substrate silicon is controlled by the concentration of the etching solution, the etching time and the etching current, and the etching time, the concentration of the etching solution and the etching current corresponding to the specific size of the nano-holes can be determined according to the requirements, and these schemes are all within the protection scope of the present invention.
S103, depositing a germanium film 40 on the nano-porous silicon substrate.
Wherein, as shown in fig. 5, a germanium film 40 is deposited on the nanoporous silicon substrate, and the thermal expansion coefficient of germanium is 2.45 × 10-6/℃。
Preferably, the germanium film 40 deposited on the nanoporous silicon substrate 40 has a thickness of 1 μm.
In the present embodiment, the germanium film 40 is controlled by controlling the growth time of the germanium film on the nanoporous silicon substrate, and theoretically, the thickness of the germanium film may exceed 100nm, but if the thickness is too thin, it may be broken when peeling the nanoporous silicon substrate in view of its operability, and thus, in the present preferred embodiment, the thickness of the germanium film growth is 1 μm. Of course, the thickness of the germanium film may be determined according to actual needs, and such solutions are within the scope of the present invention.
And S104, performing high-temperature annealing on the nano porous silicon epitaxial germanium film, and forming serial-parallel cavities at the germanium-silicon heterojunction interface.
Preferably, the high-temperature annealing adopts cyclic rapid thermal annealing, and the annealing temperature is 500-600 degrees.
S105, stripping the germanium film 40 from the nano-porous silicon substrate.
Preferably, after the germanium film is epitaxially grown on the nanoporous silicon, high-temperature annealing is performed, and the cavities at the interface of the germanium-silicon heterojunction are serially connected in parallel:
wherein, through annealing, the nano-pores of the nano-porous silicon substrate can deform, the pores near the heterojunction can become larger, and when the pores are connected in series to a certain extent, as shown in fig. 6, the thermal expansion coefficient of silicon is only 0.5 × 10-6V. C, the coefficient of thermal expansion of germanium is 2.45X 10-6V. C. At high temperature, the germanium-silicon interface will generate stronger stress. Meanwhile, the Ge-Si bond is easily broken at high temperature, so that the germanium film is peeled off from the nanoporous silicon substrate, thereby forming a self-supporting germanium film as shown in fig. 7.
A second embodiment of the present invention provides a germanium film prepared by the method for preparing a self-supporting germanium film as described in any one of the above.
The embodiment of the invention provides a preparation method of a self-supporting germanium film, which is characterized in that after a silicon substrate is provided, the silicon substrate is etched to form a nano hole, a germanium film is generated on the nano hole and is subjected to high-temperature fire treatment, and the germanium film is made to fall off from the silicon substrate due to different thermal expansion coefficients of silicon and germanium.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention.
Claims (8)
1. A method for preparing a self-supporting germanium film, comprising:
providing a silicon substrate;
performing electrochemical etching on the silicon substrate to generate uniform and compact nano-porous holes on the silicon substrate to obtain a nano-porous silicon substrate, wherein the size of the nano-porous holes is 5nm-50 nm;
depositing a germanium film on the nano porous silicon substrate;
carrying out high-temperature annealing on the nano porous silicon after the germanium film is epitaxially grown, and connecting cavities in series and in parallel at a germanium-silicon heterojunction interface;
and stripping the germanium film from the nano porous silicon substrate.
2. The method for preparing a self-supporting germanium film as claimed in claim 1, wherein the silicon substrate is electrochemically etched to generate uniform and dense nanoporous holes on the silicon substrate, thereby obtaining a nanoporous silicon substrate, specifically:
placing the silicon substrate at an anode of an etching device; wherein the cathode of the etching device is an inert platinum electrode; the etching solution in the etching device is a mixed solution of 49% HF solution and 98% alcohol, the volume ratio is 1:1, the anode is used for being connected with the positive pole of a power supply, and the cathode is used for being connected with the negative pole of the power supply;
and etching the silicon substrate for a preset time, so that uniform and compact nano porous holes are generated on the silicon substrate, and the nano porous silicon substrate is obtained.
3. The method of claim 2, wherein the predetermined time is 2-30 minutes.
4. The method of claim 2, wherein the uniform and dense nano-pores are formed by controlling the defect distribution, current level, and etching solution concentration of the silicon substrate.
5. The method of claim 1, wherein the germanium film deposited on the nanoporous silicon substrate has a thickness of 1 μm.
6. The method of claim 1, wherein the high temperature annealing is performed by a cyclic rapid thermal anneal at a temperature of from 500 ° to 600 °.
7. The method for preparing a self-supporting germanium film as claimed in claim 1, wherein the step of performing high temperature annealing on the nano-porous silicon after the germanium film is epitaxially grown is that the cavities are serially connected at the germanium-silicon heterojunction interface, specifically:
through annealing, the nano holes of the nano porous silicon substrate can deform, the holes at the position close to the heterojunction can become large, and the holes are connected in series and parallel to a certain extent.
8. A germanium film produced by the method of any one of claims 1 to 7.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1349204A3 (en) * | 2002-02-28 | 2007-05-02 | Interuniversitair Microelektronica Centrum ( Imec) | A method for producing a device having a semiconductor layer on a lattice mismatched substrate |
| CN1956149A (en) * | 2005-10-26 | 2007-05-02 | 国际商业机器公司 | Methods for forming germanium-on-insulator semiconductor structures and semiconductor structures formed by these methods |
| CN104377257A (en) * | 2013-09-05 | 2015-02-25 | 国家纳米科学中心 | Composite structure silicon-based germanium quantum dot material and preparation method and application thereof |
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| US20050221591A1 (en) * | 2004-04-06 | 2005-10-06 | International Business Machines Corporation | Method of forming high-quality relaxed SiGe alloy layers on bulk Si substrates |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1349204A3 (en) * | 2002-02-28 | 2007-05-02 | Interuniversitair Microelektronica Centrum ( Imec) | A method for producing a device having a semiconductor layer on a lattice mismatched substrate |
| CN1956149A (en) * | 2005-10-26 | 2007-05-02 | 国际商业机器公司 | Methods for forming germanium-on-insulator semiconductor structures and semiconductor structures formed by these methods |
| CN104377257A (en) * | 2013-09-05 | 2015-02-25 | 国家纳米科学中心 | Composite structure silicon-based germanium quantum dot material and preparation method and application thereof |
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