CN108321243B - Black silicon nano PIN photoelectric detector structure and preparation method thereof - Google Patents
Black silicon nano PIN photoelectric detector structure and preparation method thereof Download PDFInfo
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- 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 potential barriers, e.g. phototransistors
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- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
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Abstract
The present disclosure provides a black silicon nano PIN photodetector structure and a method for manufacturing the same; wherein, black silicon nanometer PIN photoelectric detector structure includes from top to bottom in proper order: the front-surface antireflection coating comprises a front-surface metal electrode, a front-surface antireflection film, a front-surface silicon oxide film, a front-surface N-type heavily-doped region, a P-type crystalline silicon substrate, a back-surface P-type heavily-doped region and a back-surface metal electrode; wherein, the front surface N type heavily doped region adopts a black silicon nano structure. The black silicon nano PIN photoelectric detector structure and the preparation method thereof greatly improve the breakdown voltage of the detector and are beneficial to obtaining higher spectral responsivity.
Description
Technical Field
The disclosure relates to the technical field of silicon-based photoelectric detectors, in particular to a black silicon nano PIN photoelectric detector structure and a preparation method thereof.
Background
The semiconductor detector has important irreplaceable functions in military use and civil use, the product consumption is extremely large, the range is extremely wide, only a silicon-based PIN structure photoelectric detector is taken as an example, an imaging system in security check equipment widely used in Beijing subway depends on the silicon-based PIN photoelectric detector, remote controllers of refrigerator televisions and the like in families, an imaging system in CT equipment in hospitals and the like. However, the semiconductor detector in China mainly depends on import, whether high-end products or low-end products, severely restricts national defense capability in China in the military aspect, restricts exploration capability of China at the science and technology frontier in the aspect of high-technology development, and greatly increases economic burden of common people in the aspect of civilian use. Therefore, there is a need for high performance silicon-based photodetectors with proprietary intellectual property rights.
The silicon-based PIN photoelectric detector is developed from a PN junction photoelectric detector, has the characteristics of working at room temperature, high energy resolution, short pulse rise time, high detection efficiency, stable performance and the like, and plays an irreplaceable role in the fields of medical CT, baggage security inspection, container inspection, nondestructive inspection of large-scale industrial equipment, petroleum logging, radioactive detection, environmental monitoring, infrared touch screens and the like at present. Aiming at the requirements of different application fields and different detection wave bands, the quantum efficiency of the silicon-based PIN photoelectric detector in different wave bands needs to be improved or the quantum efficiency of the device is ensured while other parameters of the silicon-based PIN photoelectric detector are improved.
Disclosure of Invention
Technical problem to be solved
In order to at least partially solve the technical problems, the present disclosure provides a black silicon nano PIN photodetector structure and a method for manufacturing the same, so as to improve quantum efficiency and spectral responsivity of the detector.
(II) technical scheme
According to an aspect of the present disclosure, there is provided a black silicon nano PIN photodetector structure, comprising in order from top to bottom: the front-surface antireflection coating comprises a front-surface metal electrode, a front-surface antireflection film, a front-surface silicon oxide film, a front-surface N-type heavily-doped region, a P-type crystalline silicon substrate, a back-surface P-type heavily-doped region and a back-surface metal electrode; wherein, the front surface N type heavily doped region adopts a black silicon nano structure.
In some embodiments, a front surface P-type guard ring is formed around the front surface N-type heavily doped region.
In some embodiments, the black silicon nanostructure has a nanopore depth in the range of 100-1000 nm and a diameter in the range of 200-1000 nm.
In some embodiments, the junction depth of the N-type heavily doped region is in the range of 500-2000 nm, and the doping concentration is 1 × 1018cm-3～1×1020cm-3In the range, the junction depth of the P-type heavily doped region is within the range of 500-3000 nm, and the doping concentration is 1 × 1018cm-3～1×1020cm-3Within the range.
According to another aspect of the present disclosure, there is provided a method for preparing a black silicon nano PIN photodetector structure, including: forming silicon oxide films on the front surface and the back surface of the P-type silicon substrate; opening a window on a silicon substrate covering the silicon oxide film for boron doping to form a back surface P type heavily doped region; windowing is carried out on the front surface of the boron-doped silicon substrate, and a black silicon nano structure is prepared; carrying out phosphorus doping on the region with the black silicon nano structure to form a front surface N-type heavily doped region; forming an antireflection film on the front surface of the silicon substrate subjected to phosphorus doping; and windowing the front surface and the back surface of the silicon substrate to form a front surface metal electrode and a back surface metal electrode, thereby completing the preparation of the black silicon nano PIN photoelectric detector structure.
In some embodiments, a window is opened on the silicon substrate covered with the silicon oxide film for boron doping, and a front surface P-type guard ring is further formed, wherein the front surface P-type guard ring is formed around the front surface N-type heavily doped region.
In some embodiments, the silicon oxide film is prepared by a thermal oxidation method or a PECVD method.
In some embodiments, the boron doping, phosphorus doping, or both are obtained using ion implantation or thermal diffusion methods.
In some embodiments, the black silicon nanostructure is prepared using a wet metal-catalyzed etch or a dry ion etch process.
In some embodiments, the antireflection film is prepared using a PECVD method; the metal electrode is prepared by adopting a screen printing, evaporation, sputtering or electroplating method.
(III) advantageous effects
According to the technical scheme, the structure and the preparation method of the black silicon nano PIN photoelectric detector have at least one of the following beneficial effects:
(1) the black silicon nano PIN photoelectric detector structure is provided with the front surface protection ring, so that the breakdown voltage of the detector is greatly improved, and higher spectral responsivity is favorably obtained.
(2) According to the silicon-based photoelectric detector, the black silicon nanostructure is arranged on the light incident surface of the silicon-based photoelectric detector, so that the reflectivity of the detector at a waveband of 400-1000 nm can be effectively reduced, the absorption of the detector to light is enhanced, and the spectral responsivity and the quantum efficiency of the detector are effectively improved.
(3) The method disclosed by the invention is relatively simple in process, low in equipment cost and suitable for large-scale production.
Drawings
The above and other objects, features and advantages of the present disclosure will become more apparent from the accompanying drawings. Like reference numerals refer to like parts throughout the drawings, which are not intended to be drawn to scale, emphasis instead being placed upon illustrating the principles of the disclosure.
Fig. 1 is a schematic structural view of a black silicon nano PIN photodetector according to an embodiment of the present disclosure.
Fig. 2 is a flowchart of a method for fabricating a black silicon nano PIN photodetector structure according to an embodiment of the present disclosure.
< description of symbols >
100-front surface metal electrode, 101-front surface antireflection film, 102-front surface silicon oxide film, 103-front surface guard ring, 104-front surface N-type heavily doped region, 105-P-type crystalline silicon substrate, 106-back surface P-type heavily doped region, and 107-back surface metal electrode.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
It should be noted that in the drawings or description, the same drawing reference numerals are used for similar or identical parts. Implementations not depicted or described in the drawings are of a form known to those of ordinary skill in the art. Additionally, while exemplifications of parameters including particular values may be provided herein, it is to be understood that the parameters need not be exactly equal to the respective values, but may be approximated to the respective values within acceptable error margins or design constraints. Directional phrases used in the embodiments, such as "upper," "lower," "front," "rear," "left," "right," and the like, refer only to the orientation of the figure. Accordingly, the directional terminology used is intended to be in the nature of words of description rather than of limitation.
The present disclosure provides a black silicon nano PIN photodetector structure, as shown in fig. 1, the black silicon nano PIN photodetector structure includes: in the light receiving surface direction, there are sequentially a front surface metal electrode 100 (where the front surface metal electrode is a metal gate line), a front surface antireflection film 101 (abbreviated as an antireflection film), a front surface silicon oxide film 102 (which is a silicon oxide layer and may be formed by a PECVD process), a front surface guard ring 103 (which is a P-type guard ring), a front surface N-type heavily doped region 104, a P-type crystalline silicon substrate 105, a back surface P-type heavily doped region 106, and a back surface metal electrode 107 from top to bottom. The black silicon nanostructure is arranged in the N-type heavily-doped region 104, so that the spectral response of the detector is effectively improved; the protection ring 103 is designed around the N-type heavily doped region, so that the reverse breakdown voltage of the detector is greatly improved.
Specifically, the depth of the nano-pores of the black silicon nano-structure is within the range of 100-1000 nm, and the diameter of the nano-pores is within the range of 200-1000 nm.
The junction depth of the N-type heavily doped region is within the range of 500-2000 nm, and the doping concentration is 1 × 1018cm-3～1×1020cm-3Within the range.
The junction depth of the P-type heavily doped region is within the range of 500-3000 nm, and the doping concentration is 1 × 1018cm-3～1×1020cm-3Within the range.
The thickness of the antireflection film is within the range of 50-120 nm, and the refractive index is within the range of 1.9-2.4.
The present disclosure also provides a method for manufacturing a black silicon nano PIN photodetector structure, as shown in fig. 2, the method for manufacturing a black silicon nano PIN photodetector structure includes the following steps:
s1, carrying out standard RCA cleaning on the P-type crystalline silicon substrate;
s2, preparing silicon oxide films on the two sides of the cleaned silicon substrate;
s3, forming boron diffusion windows on the front surface and the back surface of the silicon substrate covered with the silicon oxide film, and doping boron to form a front surface guard ring (namely, a front surface boron doping guard ring) and a back surface P + heavily-doped region;
s4, forming a phosphorus diffusion window on the front surface of the silicon substrate after boron doping is completed, and preparing a black silicon nano structure;
s5, carrying out phosphorus doping on the black silicon nano structure region to form an N + heavily doped region (namely a front surface phosphorus doped black silicon nano N + region);
s6, removing the phosphorosilicate glass (formed in the diffusion process) in the phosphorus doped region, and preparing an antireflection film on the front surface of the silicon substrate subjected to phosphorus doping;
and S7, opening windows on the front and back surfaces of the silicon substrate to prepare metal electrodes.
Specifically, boron diffusion windows are formed around the back surface and the front surface, and boron diffusion is carried out to form a heavily doped P + + layer; then, a phosphorus diffusion window is formed on the front surface of the silicon substrate, the preparation of the black silicon nanostructure is carried out, and then phosphorus diffusion is carried out to form an N + + heavily doped layer; then removing the phosphorus-silicon glass in the phosphorus diffusion area and preparing Si3N4An emission reducing film; and finally, respectively windowing the front surface phosphorus diffusion area and the back surface boron diffusion area, and finishing the preparation of the metal electrode.
Specifically, the silicon oxide film is prepared by a thermal oxidation method, a PECVD method and the like.
The boron doping is obtained by adopting methods such as ion implantation or thermal diffusion, and the phosphorus doping is also obtained by adopting methods such as ion implantation or thermal diffusion.
The black silicon nano structure is prepared by adopting methods such as wet metal catalytic corrosion or dry ion etching.
The antireflection film is prepared by adopting a PECVD method.
The metal electrode is prepared by adopting methods such as screen printing, evaporation, sputtering or electroplating. The metal electrode material is one or the combination of aluminum, gold, silver, chromium, titanium or platinum.
In the step S3, the boron doping depth is in the range of 500-3000 nm, and the doping concentration is 1 × 1018cm-3～1×1020cm-3Within the range.
In the step S4, the depth of the nano-pores of the black silicon nano-structure is within 100-1000 nm, and the diameter is within 200-1000 nm.
In the step S5, the P-doped junction depth is in the range of 500-2000 nm, and the doping concentration is 1 × 1018cm-3～1×1020cm-3Within the range.
In the step S6, the antireflection film has a thickness of 50 to 120nm and a refractive index of 1.9 to 2.4.
In the step S7, the metal electrode is prepared by screen printing, evaporation, sputtering or electroplating; the metal electrode material is one or the combination of aluminum, gold, silver, chromium, titanium or platinum.
The preparation process of the black silicon nano PIN photoelectric detector structure of the present disclosure is described in further detail below.
Firstly, standard RCA cleaning is carried out on P type crystalline silicon, organic contamination and metal particles on the surface of the crystalline silicon are removed, after cleaning is finished, a silicon oxide film is prepared on two sides, PECVD growth can be carried out, a thermal oxidation method can also be used for growth, the silicon oxide film is a passivation layer on the surface of the P type crystalline silicon and a doping barrier layer, the thickness of the silicon oxide film can be determined according to the subsequent process requirements such as doping, after the silicon oxide film is grown, windows are formed on the front surface and the back surface of a crystalline silicon substrate by utilizing a photoetching technology or other graphical technologies, then boron doping is carried out, a front surface protection ring (also called a front surface boron doping protection ring) and a back surface P + heavily doped region are formed, the doping depth is within the range of 500-3000 nm, and the doping concentration is 1 × 1018cm-3～1×1020cm-3In this context, boron doping may be accomplished by ion implantation or diffusion. The boron-doped guard ring can greatly improve the breakdown voltage of the detector and is beneficial to obtaining higher spectral responsivity.
And after boron doping is finished, a window is formed on the front surface of the crystalline silicon, and the black silicon nanostructure is prepared. Several methods for preparing the black silicon nano structure include dry ion etching, wet metal catalytic corrosion and the like. Taking the metal silver catalytic corrosion as an example, firstly, a silicon wafer is implanted with HF and AgNO with a certain concentration and proportion3In the mixed solution, after several seconds, randomly distributed metallic silver nanoparticles are formed on the silicon substrate. Then it is put intoImplanting HF and H with a certain concentration ratio2O2In the mixed solution, metal silver particles on the surface of a silicon wafer are used as a cathode, silicon is used as an anode, a micro electrochemical reaction channel is formed on the surface of the silicon wafer, and a silicon substrate is quickly etched below the metal particles to form a black silicon nano-pore structure. The black silicon nano structure can effectively reduce the reflectivity of the detector in a 400-1000 nm wave band, enhance the absorption of the detector to detection light, and further effectively improve the spectral responsivity and quantum efficiency of the detector.
Finally adopting HNO3And (5) soaking to remove the metal silver particles in the nanopores. The depth of the nanometer hole of the black silicon nanometer structure is within the range of 100-1000 nm, the diameter is within the range of 200-1000 nm, and the specific depth and diameter can be determined by the subsequent phosphorus doping process and the optimal reflectivity of a detector. Although the present disclosure exemplifies the preparation of black silicon nanostructures by metallic silver catalyzed etching, the scope of the practice of the present disclosure is not limited thereto.
Then, phosphorus doping is carried out on the black silicon nano structure, the doping depth is within the range of 500-2000 nm, and the doping concentration is 1 × 1018cm-3～1×1020cm-3In this context, the phosphorus doping may be performed by ion implantation or diffusion. After the phosphorus doping is finished, diluted HF is adopted to remove the phosphorosilicate glass on the surface, and then an antireflection film is grown on the front surface of the silicon substrate, wherein the antireflection film can be MgF2，TiO2Or Si3N4. With Si3N4For example, a PECVD system is used to grow Si3N4Film by adjusting SiH of reaction gas4And NH3The concentration ratio of (a) is controlled to be within a range of 1.9-2.4. The thickness of the antireflection film is within the range of 50-120 nm. Although the present disclosure is illustrated with a silicon nitride film, the scope of the present disclosure is not limited thereto.
And then, opening a metal electrode window on the antireflection film, removing borosilicate glass on the back surface of the silicon substrate, and preparing a metal electrode. The metal electrode can be prepared by adopting methods such as screen printing, thermal evaporation, electron beam evaporation, magnetron sputtering or electroplating. The electrode material is one or the combination of aluminum, gold, silver, chromium, titanium or platinum.
Compared with the traditional silicon-based PIN photoelectric detector, the black silicon nano photoelectric detector can effectively reduce leakage current, increase reverse breakdown voltage, greatly reduce the reflectivity of a short waveband, solve the problem of low spectral response of the short waveband and effectively improve the spectral responsivity of the detector. The process steps involved in the disclosure are simple and low in cost.
So far, the embodiments of the present disclosure have been described in detail with reference to the accompanying drawings. From the above description, those skilled in the art should clearly recognize the present disclosure.
It is to be noted that, in the attached drawings or in the description, the implementation modes not shown or described are all the modes known by the ordinary skilled person in the field of technology, and are not described in detail. In addition, the definitions of the elements are not limited to the specific structures, shapes or modes mentioned in the embodiments, and those skilled in the art may easily modify or replace them.
Similarly, it should be appreciated that in the foregoing description of exemplary embodiments of the disclosure, various features of the disclosure are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various disclosed aspects. However, the disclosed method should not be interpreted as reflecting an intention that: that is, the claimed disclosure requires more features than are expressly recited in each claim. Rather, as the following claims reflect, disclosed aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this disclosure.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.
Claims (7)
1. The utility model provides a black silicon nanometer PIN photoelectric detector structure for reduce photoelectric detector and be 400 ~ 1000nm light wave band's of wavelength reflectivity, top-down includes in proper order: the front surface silicon oxide film, the front surface N-type heavily doped region, the P-type crystalline silicon substrate, the back surface P-type heavily doped region and the back surface metal electrode;
forming a front surface antireflection film on the front surface silicon oxide film and the front surface N-type heavily doped region;
wherein the front surface N-type heavily doped region adopts a black silicon nano structure; forming a front surface P-type guard ring around the front surface N-type heavily doped region;
the black silicon nano structure is obtained by metal catalytic corrosion and diffusion doping.
2. The black silicon nano-PIN photodetector structure of claim 1, wherein the black silicon nano-structure has a nanopore depth in the range of 100 to 1000nm and a diameter in the range of 200 to 1000 nm.
3. The black silicon nano PIN photodetector structure of claim 1, wherein the junction depth of the N-type heavily doped region is in the range of 500-2000 nm, and the doping concentration is 1 × 1018cm-3～1×1020cm-3In the range, the junction depth of the P-type heavily doped region is within the range of 500-3000 nm, and the doping concentration is 1 × 1018cm-3～1×1020cm-3Within the range.
4. A preparation method of a black silicon nano PIN photoelectric detector structure comprises the following steps:
forming silicon oxide films on the front surface and the back surface of the P-type silicon substrate;
opening a window on a silicon substrate covered with the silicon oxide film for boron doping to form a back surface P-type heavily-doped region and a front surface P-type protection ring;
windowing is carried out on the front surface of the boron-doped silicon substrate, and a black silicon nano structure is prepared by adopting a wet metal catalytic corrosion method;
carrying out phosphorus doping on the region of the black silicon nano structure to form a front surface N-type heavily doped region, wherein the front surface P-type guard ring is positioned around the front surface N-type heavily doped region;
forming an antireflection film on the front surface of the silicon substrate subjected to phosphorus doping; and
windowing is carried out on the front surface and the back surface of the silicon substrate to form a front surface metal electrode and a back surface metal electrode, so that the preparation of the black silicon nano PIN photoelectric detector structure is completed;
the black silicon nano PIN photoelectric detector structure is used for reducing the reflectivity of the photoelectric detector to a light wave band with the wavelength of 400-1000 nm.
5. The method for preparing a black silicon nano PIN photodetector structure as claimed in claim 4, wherein the silicon oxide thin film is prepared by thermal oxidation or PECVD.
6. The method for preparing the black silicon nano PIN photodetector structure as claimed in claim 4, wherein the boron doping and the phosphorus doping are obtained by ion implantation or thermal diffusion.
7. The method for preparing a black silicon nano PIN photodetector structure as claimed in claim 4, wherein the anti-reflective film is prepared by PECVD method; the metal electrode is prepared by adopting a screen printing, evaporation, sputtering or electroplating method.
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