CN112002784B - Self-filtering visible blind silicon compatible infrared photoelectric detector - Google Patents
Self-filtering visible blind silicon compatible infrared photoelectric detector Download PDFInfo
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
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- H01L31/035218—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
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Abstract
The invention discloses a self-filtering visible blind silicon compatible infrared photoelectric detector, which has the structure that: taking a monocrystalline silicon substrate as a base, and etching the upper surface of the monocrystalline silicon substrate into a silicon micropore array structure; transferring a layer of graphene film on the lower surface of the monocrystalline silicon substrate to form a silicon-graphene Schottky junction; and a quantum dot layer is arranged on the lower surface of the graphene film. The photoelectric detector has the advantages of self-driving, visible light blindness, near-infrared narrow-band response, high response speed and the like, and also has the advantages of strong compatibility, high stability, easiness in preparation, low cost and the like.
Description
Technical Field
The invention relates to a self-filtering visible blind silicon compatible infrared photoelectric detector, and belongs to the technical field of semiconductor photoelectric devices.
Background
In recent years, no exception exists in advanced technologies such as artificial intelligence, unmanned driving and intelligent medical treatment, which require participation of photoelectric detection process, and the photoelectric detection technology becomes a foundation stone for building future scientific buildings. In the near infrared band, due to the strong penetrability and stability, the near infrared band has great application value in the aspects of clinical medicine, optical imaging and the like. However, the near infrared short band (780-1100 nm) as the non-visible light region which people find at first is very easily interfered by visible light (400-780 nm). In some special applications such as clinical medicine, a special-band narrow-band detector with the characteristics of high sensitivity, high speed, stability and the like is urgently needed. Currently, one implementation strategy of a narrow-band photodetector is to add a filter structure on the basis of a wide-spectrum photodetector, and implement narrow-band detection by designing layers of optical filters to filter light in non-target bands. This strategy limits the miniaturization of the device, increases the difficulty of device design and manufacture, and at the same time, the high quality filter doubles the manufacturing cost of the device. More and more reports are beginning to begin from the perspective of device materials and structures, and high-performance photoelectric detector preparation schemes are explored. Such as narrow band detectors (f.cao; j.chen; h.zeng; et al. However, these detector materials are not inherently stable, e.g., perovskite materials are extremely susceptible to oxidation and are incompatible with conventional silicon processes, which presents new challenges for the design and fabrication of narrow-band photodetectors.
Due to the property of tunable band gap, quantum dot materials have been increasingly used to prepare photodetectors, for example (y.yu; y.zhang; h.zhang; et al.acs photonics.2017,4(4), 950.). Chalcogenide lead quantum dot materials are of great interest because of their unique optical, electrical and chemical properties. Taking lead sulfide as an example, it has a narrow band gap (0.4 eV) and an exciton bohr radius of 18nm width, so that the lead sulfide quantum dots can be continuously adjusted in the band gap range of 0.4-2.0eV, thereby bringing excellent properties of adjustable size, exciton effect, higher spectral absorption and excitation, and being increasingly used for preparing novel nano electronic and photoelectric devices.
Disclosure of Invention
On the basis of the prior art, the invention aims to provide a self-filtering visible blind silicon compatible infrared photoelectric detector, and the technical problem to be solved is to obtain the infrared photoelectric detector with the advantages of high response speed, high detectivity, strong visible light interference resistance and the like by combining a silicon micropore array and quantum dots and reasonably designing a device structure.
In order to solve the technical problem, the invention adopts the following technical scheme:
the utility model provides a self-filtering visible blind silicon compatible infrared photoelectric detector which characterized in that: the near infrared photoelectric detector takes a monocrystalline silicon substrate as a base, and the upper surface of the monocrystalline silicon substrate is etched into a silicon micropore array structure; transferring a layer of graphene film on the lower surface of the monocrystalline silicon substrate to form a silicon-graphene Schottky junction; a quantum dot layer is arranged on the lower surface of the graphene film;
the top electrode is arranged on the upper surface of the monocrystalline silicon substrate, the bottom electrode is arranged on the lower surface of the graphene film, the top electrode and the monocrystalline silicon substrate form ohmic contact, and the bottom electrode and the graphene film form ohmic contact.
Further, the thickness of the monocrystalline silicon substrate is 100-500 μm.
Further, the parameters of the silicon micropore array structure are as follows: the diameter of the silicon micropore is 50-100 μm, the depth of the silicon micropore is 5-20 μm, and the distance between adjacent silicon micropores is 100-300 μm.
Further, the top electrode and the bottom electrode are Au electrodes or Ag electrodes, and the thickness of the top electrode and the bottom electrode is 20nm-300 nm.
Furthermore, lead sulfide quantum dots or lead telluride quantum dots are arranged in the quantum dot layer, and the average grain diameter of the quantum dots is 3-5 nm.
The invention relates to a preparation method of a self-filtering visible blind silicon compatible infrared photoelectric detector, which comprises the following steps:
a. forming a silicon micropore array on the upper surface of the monocrystalline silicon substrate through photoetching and inductively coupled plasma etching;
b. transferring a layer of graphene film on the lower surface of the monocrystalline silicon substrate to form a silicon-graphene Schottky junction;
c. quantum dots are coated on the surface of the graphene film in a spinning mode and serve as a photosensitive layer to increase near infrared light absorption;
d. the method comprises the steps that a bottom electrode is arranged on a graphene film on the lower surface of a monocrystalline silicon substrate, a top electrode is arranged on the upper surface of the monocrystalline silicon substrate, the top electrode and the bottom electrode cover partial areas of the corresponding surfaces, ohmic contact is formed between the top electrode and the monocrystalline silicon substrate, ohmic contact is formed between the bottom electrode and graphene, and then the self-filtering visible blind silicon compatible infrared photoelectric detector is manufactured.
Light is attenuated in a conductive medium, and light with different wavelengths is attenuated in silicon to different degrees. For the visible band, light is completely absorbed before reaching the junction and does not contribute to photocurrent, corresponding to the lower absorption limit of the spectrum. The silicon substrate and the graphene film form Schottky contact, and for light which can reach a junction region, photo-generated electrons and holes move in a reverse direction under the action of an electric field, namely carrier separation is accelerated, and photocurrent is improved. Photons with energies below the forbidden band width of silicon are not absorbed and silicon is quite transparent to these lights, so there is an upper limit on the absorption wavelength. Therefore, the device structure realizes the design of the absorption waveband. Meanwhile, by regulating the size of the silicon micropore array and utilizing the light trapping effect, light is reflected and refracted for multiple times in the hole, and the quantum efficiency of the whole device is finally improved. Graphene and silicon form Schottky contact, under the action of an internal electric field, electron holes are separated to form photo-generated electromotive force, and an external circuit is connected to form current. The Schottky device belongs to a multi-sub device, and accumulation does not exist, so that the Schottky device has the characteristics of high response speed and less carrier recombination. The lead sulfide or lead telluride quantum dot has the characteristic of adjustable band gap, and the absorption of a near-infrared band can be enhanced by adding the lead sulfide (lead telluride) quantum dot layer. In conclusion, under the synergistic effect of the structures of all parts, the silicon-based photoelectric detector has the characteristics of visible blindness, enhanced infrared absorption and high-speed stability.
Compared with the prior art, the invention has the beneficial effects that:
the photoelectric detector has the advantages of self-driving, visible light blindness, near-infrared narrow-band response, high response speed and the like, has the advantages of strong compatibility, high stability, easiness in preparation, low cost and the like, and has a wide application prospect in research and development of detectors with low cost, high speed, stability, spectral sensitivity and high integration level.
Drawings
FIG. 1 is a schematic plane view of a self-filtering visible-blind silicon compatible infrared photodetector according to the present invention;
FIG. 2 is a normalized spectral response curve of the photodetector prepared in example 1;
FIG. 3 is a time response curve of the photodetector prepared in example 1;
reference numbers in the figures: 1 is a top electrode; 2 is a monocrystalline silicon substrate; 3 is a graphene film; 4 is quantum dot layer; and 5, a bottom electrode.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
As shown in fig. 1, the infrared photodetector compatible with the self-filtering visible blind silicon in this embodiment is based on a monocrystalline silicon substrate 2, and the upper surface of the monocrystalline silicon substrate is etched to form a silicon micropore array structure; a layer of graphene film 3 is transferred on the lower surface of the monocrystalline silicon substrate 2 to form a silicon-graphene schottky junction; a quantum dot layer 4 is arranged on the lower surface of the graphene film 3;
a top electrode 1 is arranged on the upper surface of a monocrystalline silicon substrate 2, a bottom electrode 5 is arranged on the lower surface of a graphene film 3, the top electrode 1 and the monocrystalline silicon substrate 2 form ohmic contact, and the bottom electrode 5 and the graphene film 3 form ohmic contact.
Specifically, in this embodiment: the thickness of the used monocrystalline silicon substrate 2 is 300 μm; the diameter of the silicon micropore is about 100 μm, the depth of the silicon micropore is about 10 μm, and the distance between adjacent silicon micropores is 300 μm; the top electrode and the bottom electrode are both Ag electrodes with the thickness of 100 nm; the quantum dot layer 4 is internally provided with lead sulfide quantum dots, and the average grain diameter of the quantum dots is about 3.2 nm.
The preparation method of the self-filtering visible blind silicon compatible infrared photoelectric detector comprises the following steps:
a. placing the cleaned silicon wafer on a spin coater turntable for tightly sucking, uniformly dripping two drops of photoresist in the center of the silicon wafer by using a rubber head dropper, starting the spin coater turntable, firstly rotating at a low speed of 500rpm for 10s, then rotating at a high speed of 3000rpm for 20s, placing the silicon wafer on a drying table for drying for 5min after the photoresist is homogenized, and then repeating the steps of dripping the photoresist, homogenizing and drying once.
And (3) placing the silicon wafer subjected to secondary spin coating and drying in the middle of a workbench of an exposure machine, tightly absorbing the silicon wafer, aligning the silicon wafer with a mask, turning on a xenon light source, and exposing for 100 s. And after the exposure is finished, the silicon wafer is placed into a developing solution to be soaked for 5 minutes.
And (3) putting the developed silicon wafer into a vacuum chamber, closing a chamber door to carry out vacuum pumping operation, starting a mechanical pump to carry out pre-pumping, simultaneously opening a molecular pump and achieving a stable rotating speed of 27000rpm, closing a pre-pumping valve when the indication value of a vacuum gauge is reduced to be below 3.5Pa, and carrying out high vacuum pumping on an etching chamber. In order to ensure the vacuum reaction environment, the pressure of the vacuum chamber reaches 5 multiplied by 10 -3 Pa is needed. Introduction of SF 6 As etching gas, when the gas flow meter reaches 40sccm, the power supplies 1 and 2 are turned on, the amplitude of the power supplies is set to 300W and 80W respectively, and the depth of the micropore is regulated and controlled by controlling the electrifying time (30 min). And after etching, removing the photoresist on the surface of the silicon by using a positive photoresist stripping agent, thereby completing the preparation of the silicon micropore array.
b. And transferring a layer of graphene film on the lower surface of the monocrystalline silicon substrate to form a silicon-graphene Schottky junction.
c. Lead sulfide quantum dots with the average diameter of about 3.2nm are coated on the surface of the graphene film in a spin mode and serve as a photosensitive layer to increase near infrared light absorption. Meanwhile, a corner position is reserved for manufacturing a subsequent bottom electrode.
d. And coating silver paste with the thickness of about 100nm on the graphene film on the lower surface of the monocrystalline silicon substrate to serve as a bottom electrode, and coating silver paste with the thickness of about 100nm on the upper surface of the monocrystalline silicon substrate to serve as a top electrode, so that the preparation of the self-filtering visible blind silicon compatible infrared photoelectric detector is completed.
Fig. 2 is a normalized spectral response curve of the photodetector prepared in this embodiment, and it can be seen that the device has an obvious optical response to 960-1400nm near infrared light, but has substantially no obvious optical response to visible light, and has a partial band enhancement at 1200nm, because the lead sulfide quantum dots have an absorption enhancement effect on the band.
Fig. 3 is a time response curve of the photodetector prepared in this example, and it can be seen that the device has a stable response under 20Hz near infrared pulse illumination, and the rise time/fall time is about 0.48 μ s/0.88 μ s, respectively, indicating that the device has a high response speed.
In conclusion, the photodetector prepared by the embodiment realizes high-speed stable response of the near-infrared band completely shielded by visible light.
Example 2
As shown in fig. 1, the infrared photodetector compatible with the self-filtering visible blind silicon in the present embodiment is based on a monocrystalline silicon substrate 2, and the upper surface of the monocrystalline silicon substrate is etched to form a silicon micro-pore array structure; a layer of graphene film 3 is transferred on the lower surface of the monocrystalline silicon substrate 2 to form a silicon-graphene schottky junction; a quantum dot layer 4 is arranged on the lower surface of the graphene film 3;
the top electrode 1 is arranged on the upper surface of the monocrystalline silicon substrate 2, the bottom electrode 5 is arranged on the lower surface of the graphene film 3, the top electrode 1 and the monocrystalline silicon substrate 2 form ohmic contact, and the bottom electrode 5 and the graphene film 3 form ohmic contact.
Specifically, in this embodiment: the thickness of the used monocrystalline silicon substrate 2 is 300 μm; the diameter of the silicon micropore is about 100 μm, the hole depth is about 10 μm, and the distance between adjacent silicon micropores is 300 μm; the top electrode and the bottom electrode are both Ag electrodes with the thickness of 100 nm; the quantum dot layer 4 is internally provided with lead telluride quantum dots, and the average grain diameter of the quantum dots is about 3.6 nm.
The preparation method of the self-filtering visible blind silicon compatible infrared photoelectric detector comprises the following steps:
a. placing the cleaned silicon wafer on a spin coater turntable for sucking tightly, uniformly dripping two drops of photoresist on the center of the silicon wafer by using a rubber head dropper, starting the spin coater turntable, firstly rotating at a low speed of 500rpm for 10s, then rotating at a high speed of 3000rpm for 20s, placing the silicon wafer on a drying table for drying for 5min after the spin coating is finished, and then repeating the steps of dripping the photoresist, spin coating and drying once again.
And (3) placing the silicon wafer after the secondary spin coating and drying in the middle of a workbench of an exposure machine, tightly absorbing the silicon wafer, aligning the silicon wafer with a mask, turning on a xenon light source, and exposing for 100 s. And after the exposure is finished, the silicon wafer is placed into a developing solution to be soaked for 5 minutes.
Placing the developed silicon wafer into a vacuum chamber, closing a chamber door to perform vacuum pumping operation, starting a mechanical pump to perform pre-pumpingWhen the molecular pump is started and reaches the stable rotating speed of 27000rpm, the pre-pumping valve is closed when the indication value of the vacuum meter is reduced to be below 3.5Pa, and the etching chamber is pumped to be in high vacuum. In order to ensure the vacuum reaction environment, the pressure of the vacuum chamber reaches 5 x 10 -3 Pa. Introduction of SF 6 As etching gas, when the gas flow meter reaches 40sccm, power supplies 1 and 2 are switched on, the amplitude values of the power supplies are respectively set to 300W and 80W, and the depth of the micropores is regulated by controlling the electrifying time (30 min). And after etching, removing the photoresist on the silicon surface by using a positive photoresist stripping agent, thus finishing the preparation of the silicon micropore array.
b. And transferring a layer of graphene film on the lower surface of the monocrystalline silicon substrate to form a silicon-graphene Schottky junction.
c. And spin-coating lead telluride quantum dots with the average diameter of about 3.6nm on the surface of the graphene film to be used as a photosensitive layer to increase near infrared light absorption. Meanwhile, a corner position is reserved for manufacturing a subsequent bottom electrode.
d. And coating silver paste with the thickness of about 100nm on the graphene film on the lower surface of the monocrystalline silicon substrate to serve as a bottom electrode, and coating silver paste with the thickness of about 100nm on the upper surface of the monocrystalline silicon substrate to serve as a top electrode, so that the preparation of the self-filtering visible blind silicon compatible infrared photoelectric detector is completed.
Through tests, the performance parameters of the device prepared by the embodiment are very close to those of the device listed in the embodiment 1, the response range is about 950 nm-1400 nm, a stronger absorption peak exists at 1100nm and 1250nm respectively, the light response to visible light is basically not obvious, and the response speed is in the same order of magnitude as that of the embodiment 1.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. The utility model provides a self-filtering visible blind silicon compatible infrared photoelectric detector which characterized in that: the infrared photoelectric detector takes a monocrystalline silicon substrate (2) as a base, and the upper surface of the monocrystalline silicon substrate is etched into a silicon micropore array structure; a graphene film (3) is transferred on the lower surface of the monocrystalline silicon substrate (2) to form a silicon-graphene schottky junction; a quantum dot layer (4) is arranged on the lower surface of the graphene film (3); lead sulfide quantum dots or lead telluride quantum dots are arranged in the quantum dot layer (4), and the average grain diameter of the quantum dots is 3-5 nm;
a top electrode (1) is arranged on the upper surface of the monocrystalline silicon substrate (2), a bottom electrode (5) is arranged on the lower surface of the graphene thin film (3), the top electrode (1) and the monocrystalline silicon substrate (2) form ohmic contact, and the bottom electrode (5) and the graphene thin film (3) form ohmic contact;
the parameters of the silicon micropore array structure are as follows: the diameter of the silicon micropore is 50-100 μm, the depth of the silicon micropore is 5-20 μm, and the distance between adjacent silicon micropores is 100-300 μm.
2. The self-filtering visible-blind silicon-compatible infrared photodetector of claim 1, wherein: the thickness of the monocrystalline silicon substrate (2) is 100-500 mu m.
3. The self-filtering visible-blind silicon-compatible infrared photodetector of claim 1, characterized in that: the top electrode (1) and the bottom electrode (5) are Au electrodes or Ag electrodes, and the thickness of the top electrode and the bottom electrode is 20nm-300 nm.
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