CN114300551A - Graphene/plasmon polariton black silicon near-infrared detector structure and preparation method thereof - Google Patents
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Abstract
The invention discloses a graphene/plasmon polariton black silicon near-infrared detector structure and a preparation method thereof, wherein the structure comprises an n-type silicon wafer, wherein plasmon polariton black silicon is arranged in the middle of the front of the silicon wafer, a silicon dioxide layer is arranged on the peripheral side of the front of the silicon wafer, a front electrode is arranged on the silicon dioxide layer, a graphene layer is arranged on the plasmon polariton black silicon, and the peripheral side of the graphene layer extends and is in contact with the front electrode; the back surface of the silicon chip is provided with a back electrode. The invention can obviously improve the photoelectric property, broaden the response spectrum range and enhance the responsiveness.
Description
Technical Field
The invention mainly relates to the technical field of photoelectric detectors, in particular to a graphene/plasmon polariton black silicon near-infrared detector structure and a preparation method thereof.
Background
The photoelectric detector is an important component of a modern photoelectric system and is widely applied to the fields of image sensing, optical communication, industrial automation, medical diagnosis and the like. Many high performance photodetectors based on different geometries of inorganic elements and composite materials (e.g., Si, GaAs, GaP, InGaAs) have been investigated. Silicon is most widely used among these semiconductors so far, and although silicon-based photodetectors have been greatly developed at present, since the band gap of silicon is 1.12eV, the cut-off wavelength of silicon-based near-infrared light detectors is generally around 1.1 μm, resulting in a relatively narrow detection wavelength range and a low long-wavelength band responsivity. In the process of solving the problems, the graphene/silicon photoelectric detector structure is provided, and due to the ultrahigh electron mobility and the ultralow light absorption rate of a single-layer structure, the graphene is often used as a transparent electrode to be applied to the silicon photoelectric detector, so that the light responsivity of the detector is obviously improved. The typical structure is shown in fig. 1, light is incident to a photosensitive region of a graphene/planar silicon near-infrared detector, and a part of valence electrons in an n-type silicon material are transited to a conduction band after sufficient photons are absorbed, so that electron-hole pairs are generated. Subsequently, the electron-hole pairs are separated under the influence of the built-in electric field. The holes move along the direction of the built-in electric field, and the electrons move in the reverse direction and are transferred to an external circuit through the upper electrode and the lower electrode inside the graphene layer and the n-type silicon respectively, so that photocurrent is formed.
However, in the graphene/silicon photoelectric detector, the main light absorption material is silicon, and the response wavelength range of the graphene is not obviously expanded due to the introduction of the graphene. Although the graphene/planar silicon near-infrared detector has good detection performance in a visible light band, the silicon serving as a main light absorption material has inherent defects of an energy band, and the use of the silicon at a wavelength of more than 1100nm is severely restricted. Meanwhile, the surface of the untreated monocrystalline silicon wafer is smooth like a mirror, the visible light reflectivity is high and is about 40%, and the light absorption efficiency is also obviously influenced.
In addition, the photosensitive region of the conventional black silicon photoelectric detector has the problems of low carrier mobility, short service life, obvious dark current caused by surface carrier recombination and the like due to large surface area, and the improvement of the responsivity performance of the conventional black silicon photoelectric detector is limited.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the technical problems in the prior art, the invention provides a graphene/plasmon polariton black silicon near-infrared detector structure which is capable of remarkably improving the photoelectric property of the detector, wide in response spectral range and strong in responsiveness and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a graphene/plasmon polariton black silicon near-infrared detector structure comprises an n-type silicon wafer, wherein plasmon polariton black silicon is arranged in the middle of the front of the silicon wafer, a silicon dioxide layer is arranged on the periphery of the front of the silicon wafer, a front electrode is arranged on the silicon dioxide layer, a graphene layer is arranged on the plasmon polariton black silicon, and the periphery of the graphene layer extends and is in contact with the front electrode; the back surface of the silicon chip is provided with a back electrode.
As a further improvement of the above technical solution:
the front electrode and the back electrode are both metal film electrodes made of gold, aluminum or indium-gallium alloy.
The invention also discloses a preparation method of the graphene/plasmon polariton black silicon near-infrared detector structure, which comprises the following steps:
1) selecting an n-type monocrystalline silicon wafer;
2) oxidizing the two sides of the silicon wafer to form a silicon dioxide layer;
3) photoetching the front surface of a silicon wafer for the first time to form a photosensitive area, and forming a light trapping structure through a black silicon preparation process;
4) depositing an ultrathin metal layer on the front surface of the silicon wafer integrally, performing heat treatment to form a nano metal structure, and forming plasmon polariton black silicon together with the black silicon;
5) photoetching the front side of the silicon wafer for the second time to form an annular electrode area, and preparing a front electrode;
6) removing the silicon dioxide layer on the back of the silicon chip and evaporating a back electrode;
7) preparing a graphene layer by a chemical vapor deposition method and transferring the graphene layer to the surface of plasmon black silicon;
8) and photoetching the front side of the silicon wafer for the third time, and etching the redundant graphene layer by a dry method.
As a further improvement of the above technical solution:
the ultrathin metal in the step 4) is a metal material with obvious plasmon effect in a visible light to near infrared wave band; the thickness of the ultrathin metal is controlled within the range of 1-50 nm, so that the prepared film is ensured to be in an island forming stage, and a continuous film is not formed.
And 7) preparing the graphene in the step 7) by a chemical vapor deposition method, and transferring the graphene to the plasmon black silicon through polymethyl methacrylate.
The preparation process of the plasmon black silicon comprises the following steps: synthesizing pyramid-shaped black silicon by adopting a simple alkali etching method and forming LSPR-B-Si by matching with heat treatment of the ultrathin gold film, wherein the method specifically comprises the following steps:
firstly, removing micro dust on the surface of a substrate of an n-type lightly doped silicon wafer;
then forming a window by a photoetching method, immersing the substrate in etching solution to remove the insulating layer in the window, taking out the substrate after etching, and washing residual etching solution;
then placing the silicon pyramid array into the mixed solution, etching for a certain time, and forming a silicon pyramid array on the exposed silicon window area through anisotropic etching;
and preparing an ultrathin gold film on the surface of the black silicon, and performing vacuum heat treatment to finally obtain the plasmon black silicon.
The mixed solution is a mixed solution of 5-30 g of sodium hydroxide, 5-50 ml of isopropanol and 95 ml of deionized water.
The preparation process of the transferable graphene layer comprises the following steps:
by chemical vapor deposition with gaseous CH4And H2Preparing a large-area graphene film at 900-1000 ℃ by using a copper foil with the thickness of 25 mu m as a catalyst;
after growth, spin-coating PMMA with the mass concentration of 5% on the upper surface of the copper foil with the graphene film grown on the surface at the rotating speed of 2000-3000 rpm, and then putting the copper foil into CuSO4In solution;
and after the graphene film is completely stripped from the copper foil substrate, placing the graphene film attached to the PMMA surface into deionized water for several times of cleaning, so as to obtain the transferable graphene film.
The CuSO4The solution reagent solution comprises the following components in percentage by weight: CuSO4：HCl：H2O＝10g：50ml：50ml。
The black silicon preparation process in the step 3) comprises a conventional wet etching black silicon process or a dry etching black silicon process.
Compared with the prior art, the invention has the advantages that:
the graphene/plasmon polariton black silicon near-infrared detector structure has the working principle similar to that of a typical graphene/planar silicon near-infrared detector, and is characterized in that the photosensitive region on the front side is graphene/plasmon polariton black silicon, and due to the introduction of the plasmon polariton black silicon, the device can realize the absorption detection of light above the silicon forbidden band width, so that the response spectrum range of the graphene/planar silicon near-infrared detector is widened, meanwhile, the graphene transparent electrode prepared on the surface of the plasmon polariton black silicon improves the collection efficiency of photon-generated carriers, overcomes the defects of low carrier mobility and short service life of the plasmon polariton black silicon, and finally, the performance of the graphene/silicon photoelectric detector is obviously improved.
Drawings
Fig. 1 is a schematic structural diagram of a conventional graphene/planar silicon near-infrared detector.
Fig. 2 is a schematic structural diagram of an embodiment of the near-infrared detector of the present invention.
FIG. 3 is a flow chart of a method for manufacturing a near infrared detector according to an embodiment of the present invention.
Illustration of the drawings: 1. a graphene layer; 2. a front electrode; 3. a silicon dioxide layer; 4. plasmonic black silicon; 5. a silicon wafer; 6. a back electrode.
Detailed Description
The invention is further described below with reference to the figures and the specific embodiments of the description.
As shown in fig. 2, the graphene/plasmon black silicon near-infrared detector structure according to the embodiment of the invention includes an n-type silicon wafer 5, wherein plasmon black silicon 4 is disposed in the middle of the front surface of the silicon wafer 5, a silicon dioxide layer 3 is disposed on the periphery of the front surface of the silicon wafer 5, a front electrode 2 is disposed on the silicon dioxide layer 3, a graphene layer 1 is disposed on the plasmon black silicon 4, and the periphery of the graphene layer 1 extends and contacts with the front electrode 2; the back side of the silicon wafer 5 has a back electrode 6. The front electrode 2 and the back electrode 6 are made of metal thin film electrodes and can form ohmic contact with graphene, and the materials are gold (Au), aluminum (Al), indium-gallium alloy (In-Ga) and the like.
The graphene/plasmon black silicon near-infrared detector structure has the working principle similar to that of a typical graphene/planar silicon near-infrared detector, and is different in that the photosensitive region on the front side is the graphene/plasmon black silicon 4, and due to the introduction of the plasmon black silicon 4, the device can realize the absorption detection of light above the silicon forbidden band width, so that the response spectrum range of the graphene/planar silicon near-infrared detector is widened, meanwhile, the graphene transparent electrode prepared on the surface of the plasmon black silicon 4 improves the collection efficiency of photo-generated carriers, makes up the defects of low carrier mobility and short service life of the plasmon black silicon 4, and finally obviously improves the performance of the graphene/silicon photoelectric detector.
As shown in fig. 3, the method for manufacturing the graphene/plasmon black silicon near-infrared detector structure according to the embodiment of the present invention includes:
1) selecting n-type monocrystalline silicon;
2) oxidizing the double surfaces of the monocrystalline silicon to form a silicon dioxide layer 3 (protective layer);
3) photoetching the front side for the first time to form a photosensitive area, and forming a light trapping structure through a black silicon preparation process;
4) depositing an ultrathin metal layer on the front surface of the substrate, performing heat treatment to form a nano metal structure, and forming plasmon polariton black silicon 4 with black silicon;
5) forming an annular electrode area by front-side second photoetching to prepare a front-side electrode 2;
6) removing the silicon dioxide layer 3 on the back surface and evaporating a back electrode 6;
7) preparing graphene by a chemical vapor deposition method and transferring the graphene to the surface of plasmon black silicon 4;
8) and carrying out third photoetching on the front surface, and carrying out dry etching on the redundant graphene.
In a specific embodiment, the black silicon preparation process in step 3) includes a conventional wet black silicon etching process, a dry black silicon etching process, and the like.
In a specific embodiment, the ultra-thin metal in step 4) is a metal material having a significant plasmon effect in a visible light to near-infrared band, such as a metal material of gold (Au), silver (Ag), or the like. The thickness of the ultrathin metal is controlled within the range of 1-50 nm, so that the prepared film is ensured to be in an island forming stage, and a continuous film is not formed. The purpose of the heat treatment is to enable the prepared ultrathin metal film to be agglomerated to form nano metal particles, and excite the surface plasmon polariton of the nano metal particles to enhance the light absorption performance.
In a specific embodiment, the graphene in step 7) is prepared by a chemical vapor deposition method, and then is transferred onto the plasmon black silicon 4 through polymethyl methacrylate (PMMA).
In one embodiment, the preparation process of the plasmon black silicon 4 comprises the following steps: synthesizing pyramid-shaped black silicon by adopting a simple alkali etching method and forming LSPR-B-Si by matching with heat treatment of the ultrathin gold film, wherein the method specifically comprises the following steps:
firstly, removing micro dust on the surface of a substrate of an n-type lightly doped silicon wafer;
then forming a window by a photoetching method, immersing the substrate in etching solution to remove the insulating layer in the window, taking out the substrate after etching, and washing residual etching solution;
then placing the silicon pyramid array into the mixed solution, etching for a certain time, and forming a silicon pyramid array on the exposed silicon window area through anisotropic etching;
and preparing an ultrathin gold film on the surface of the black silicon, and performing vacuum heat treatment to finally obtain the plasmon black silicon 4.
In a specific embodiment, the preparation process of the transferable graphene layer 1 is as follows:
by chemical vapor deposition with gaseous CH4And H2Preparing a large-area graphene film at 900-1000 ℃ by using a copper foil with the thickness of 25 mu m as a catalyst;
after growth, spin-coating PMMA with the mass concentration of 5% on the upper surface of the copper foil with the graphene film grown on the surface at the rotating speed of 2000-3000 rpm, and then putting the copper foil into CuSO4In solution;
and after the graphene film is completely stripped from the copper foil substrate, placing the graphene film attached to the PMMA surface into deionized water for several times of cleaning, so as to obtain the transferable graphene film.
Aiming at the modification of a silicon material, the black silicon of the silicon surface light trapping structure and the metal nanoparticles for enhancing infrared absorption are combined and introduced into the graphene/silicon photoelectric detector structure, so that the light absorption efficiency and the wavelength range of the graphene/silicon photoelectric detector structure are greatly improved, and the performance of the photoelectric detector is improved. In addition, the combination of black silicon/nano metal particles/graphene is also mutually beneficial, and the graphene improves the defects of low carrier mobility and life defect of the black silicon; the nano metal particles attached to the surface of the black silicon have a stronger light field action environment, so that the LSPR effect is increased, the absorption efficiency is greatly improved, and the wavelength range of light absorbed by the black silicon is widened.
The above preparation process is further illustrated below with reference to a complete embodiment:
the whole process is as follows: firstly, preparing plasmon black silicon 4 on the front surface of a silicon wafer 5, then, carrying out secondary photoetching to define an annular top electrode of a device by adopting a photoetching alignment process, using gold with the thickness of 200-500 nm prepared by an electron beam evaporation system as the top electrode, and using In-Ga alloy with the thickness of 300-500 nm as a bottom electrode. And then transferring the prepared graphene to LSPR-B-Si to form a heterojunction, standing at room temperature for 6 hours, then putting the device into acetone to soak for 2 hours, and removing the PMMA on the surface. On the basis, negative photoresist is adopted for third photoetching (the size of a single window is 600 microns multiplied by 600 microns), and the graphene outside the window is etched by RIE (reactive ion etching), so that the graphene/plasmon black silicon 4 photodetector is obtained.
Preparation method of plasmon black silicon 4 (LSPR-B-Si): pyramid-shaped black silicon is synthesized by a simple alkali etching method and is matched with a heat treatment ultrathin gold film to form LSPR-B-Si.
First, an n-type lightly doped (100) silicon wafer (1-10. omega. cm)-1) Sequentially carrying out ultrasonic treatment in ethanol, acetone and deionized water for about 15 minutes to remove micro dust on the surface of the substrate, wherein SiO is2The thickness of the insulating layer is 100 to 300 nm. Then forming a window with the size of 400 microns multiplied by 400 microns through a photoetching method, and then immersing the substrate in BOE etching solution for 2-5 minutes to remove SiO in the window2Insulating layer (BOE solution: 30% strength HF solution 3ml, 5g NH)4F and 7mlH2And O), taking out the etching solution after etching, and washing the residual BOE etching solution by deionized water.
And then, adding a mixed solution of 5-30 g of sodium hydroxide (NaOH), 5-50 ml of isopropanol and 95 ml of deionized water, etching for 30 minutes in an oven at 50-90 ℃, and forming a silicon pyramid array on the exposed silicon window area through anisotropic etching. And preparing an ultrathin gold film with the thickness of 5-10 nm on the surface of the black silicon by an electron beam evaporation system, and then carrying out vacuum heat treatment at the temperature of 400-500 ℃ for half an hour to finally obtain the plasmon black silicon 4.
The preparation method of the transferable graphene film comprises the following steps: by Chemical Vapor Deposition (CVD) of gas CH4(40 to 60sccm) and H2(20-30 sccm), and preparing the large-area graphene film at 900-1000 ℃ by using a copper foil with a thickness of 25 mu m as a catalyst. After growth, spin-coating PMMA with the mass concentration of 5% on the upper surface of the copper foil with the graphene film grown on the surface at the rotating speed of 2000-3000 rpm, and then putting the copper foil into CuSO4In solution. CuSO4The solution reagent solution has the ratio of (CuSO)4：HCl：H2O10 g:50ml:50 ml). And after the graphene film is completely stripped from the copper foil substrate, placing the graphene film attached to the PMMA surface into deionized water, and washing for 5 minutes for several times to obtain the transferable graphene film.
The essence of the black silicon preparation technology is a processing means of a micro-nano light trapping structure on the surface of a silicon substrate, common preparation methods comprise metal auxiliary etching, acid-base corrosion, electrochemical etching, reactive ion etching, femtosecond laser etching and the like, and the prepared black silicon has absorption of more than 90% in visible light to near infrared after heavy doping. The metal localized surface plasmon polariton resonance realizes super-absorption of light by preparing a micro-nano metal structure on the surface of a silicon material, the enhancement effect of the metal localized surface plasmon polariton resonance depends on an external matching environment, and the wide spectrum absorption of visible light and even terahertz wave bands can be realized by designing the structure of the metal localized surface plasmon polariton resonance.
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. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention.
Claims (10)
1. The graphene/plasmon polariton black silicon near-infrared detector structure is characterized by comprising an n-type silicon wafer (5), wherein plasmon polariton black silicon (4) is arranged in the middle of the front face of the silicon wafer (5), a silicon dioxide layer (3) is arranged on the periphery of the front face of the silicon wafer (5), a front electrode (2) is arranged on the silicon dioxide layer (3), a graphene layer (1) is arranged on the plasmon polariton black silicon (4), and the periphery of the graphene layer (1) extends and is in contact with the front electrode (2); the back surface of the silicon chip (5) is provided with a back electrode (6).
2. The graphene/plasmonic black silicon near-infrared detector structure of claim 1, wherein the front electrode (2) and the back electrode (6) are both metal thin film electrodes made of gold, aluminum or indium-gallium alloy.
3. A method for preparing the graphene/plasmonic black silicon near-infrared detector structure of claim 1 or 2, comprising the steps of:
1) selecting an n-type monocrystalline silicon wafer (5);
2) oxidizing the two sides of the silicon wafer (5) to form a silicon dioxide layer (3);
3) photoetching the front surface of the silicon wafer (5) for the first time to form a photosensitive area, and forming a light trapping structure through a black silicon preparation process;
4) an ultrathin metal layer is integrally deposited on the front surface of the silicon wafer (5), a nano metal structure is formed through heat treatment, and plasmon black silicon (4) is formed with the nano metal structure and the black silicon;
5) photoetching the front surface of the silicon wafer (5) for the second time to form an annular electrode area, and preparing a front electrode (2);
6) removing the silicon dioxide layer (3) on the back surface of the silicon wafer (5) and evaporating a back electrode (6);
7) preparing a graphene layer (1) by a chemical vapor deposition method and transferring the graphene layer (1) to the surface of plasmon black silicon (4);
8) and photoetching the front surface of the silicon wafer (5) for the third time, and etching the redundant graphene layer (1) by a dry method.
4. The preparation method according to claim 3, wherein the ultra-thin metal in the step 4) is a metal material having a significant plasmon effect in a visible light to near infrared band; the thickness of the ultrathin metal is controlled within the range of 1-50 nm, so that the prepared film is ensured to be in an island forming stage, and a continuous film is not formed.
5. The method according to claim 3, wherein the graphene in step 7) is transferred to the plasmonic black silicon (4) by polymethyl methacrylate after being prepared by chemical vapor deposition.
6. Preparation method according to claim 3 or 4 or 5, characterized in that the plasmonic black silicon (4) is prepared by: synthesizing pyramid-shaped black silicon by adopting a simple alkali etching method and forming LSPR-B-Si by matching with heat treatment of the ultrathin gold film, wherein the method specifically comprises the following steps:
removing the dust on the surface of the substrate of the n-type lightly doped silicon wafer;
then forming a window by a photoetching method, immersing the substrate in etching solution to remove the insulating layer in the window, taking out the substrate after etching, and washing residual etching solution;
then placing the silicon pyramid array into the mixed solution, etching for a certain time, and forming a silicon pyramid array on the exposed silicon window area through anisotropic etching;
and preparing an ultrathin gold film on the surface of the black silicon, and performing vacuum heat treatment to finally obtain the plasmon black silicon (4).
7. The preparation method according to claim 6, wherein the mixed solution is a mixed solution of 5 to 30 g of sodium hydroxide, 5 to 50ml of isopropanol and 95 ml of deionized water.
8. The method for preparing according to claim 3 or 4 or 5, characterized in that the graphene layer (1) is prepared by:
by chemical vapor deposition with gaseous CH4And H2Preparing a large-area graphene film at 900-1000 ℃ by using a copper foil with the thickness of 25 mu m as a catalyst;
after growth, spin-coating PMMA with the mass concentration of 5% on the upper surface of the copper foil with the graphene film grown on the surface at the rotating speed of 2000-3000 rpm, and then putting the copper foil into CuSO4In solution;
and after the graphene film is completely stripped from the copper foil substrate, placing the graphene film attached to the PMMA surface into deionized water for several times of cleaning, so as to obtain the transferable graphene film.
9. The method of claim 8, wherein the CuSO is applied to a substrate4The solution reagent solution comprises the following components in percentage by weight: CuSO4：HCl：H2O＝10g:50ml:50ml。
10. The method according to claim 3, 4 or 5, wherein the black silicon preparation process in step 3) comprises a conventional wet etching black silicon process or a dry etching black silicon process.
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